摘要:

ii. 146 ABSTRACTS OF CHEMICAL PAPERS. An alg t i c a1 Chemistry . Extraction Apparatus. HENRY J. CARY-CURR (J. I r ~ d . Erzg. CI~srn. 1912 4 535).-This apparatus consists of a short metallic spiral-tube reflux condenser t h e inlet arid outlet tubes of which project through a metal plate which serves the double purpose of a support for * and Gazxelta 1913 43 i 36-38.ANALYTICAL CHEMISTRY. ii. 147 the condenser and a closure for the glass extraction flask. The flask is of somewhiit conical form with a long neck and flat bottom. A porcelain Gooch crucible is suspended from the conderiser (in the neck of the flask) by means of platinum wire fastened into two holes bored on opposite sides of its upper rim and in i t is placed the material to be extracted The whole apparatus is only six inches high and three inches wide.F. 121. G. M Alundum not Constant in Weight. E. €3. FORBES (J. I n d . Eng. Chem. 1912 4 544-545).-1t is found that the porous earthenware material '' alundum " in use for extraction vessels does not remain of constant weight when heated in contact with water; one of its constit>uents combines with water forming a compound which is stable at 160° but destroyed at considerably below 1000° whilst a second factor which results in a gain of weight is also present. F. M. G. 31. A Modification of the Frary Electrodynamic Stirring Device. J. M. KNOTE and W. R. WORKE (J. Ind. i3)Lg. Cheni. 1912 4 534).-The use of a solenoid in the rapid electrolytic estimation of metals has been proposed by Frary (A 1908 ii 68) and the essential improvement now described consists in putting the coil of the solenoid round an iron core covering the top with a suitable material and placing the beaker containing the electrolyte on i t ; whilst the use of electrodes with bent stems fastened to a block which can be raised facilitates inspection during the course of the reaction.F. 31. G. M. Apparatus for Testing Water by Measurement of its Electrical Conductivity. LEONARD ARCHBUTT (Analpst 19 12 37 538-542).-The apparatus described is known as the Digby and Biggs' '' Dionic " water-tester and its usefulness depends on the fact t h a t the conductivity of pure water is extreniely small whilst the presence of any sdt acid or base in solution at once increases the conductivity. The water to be tested is filled into a U-tube the two electrodes being fitted into the tops of the two limbs respectively.The current is supplied by a hand-driven dynamo provided with a constant-speed friction clutch which maintairis a constant E. M.F. of 100 volts. The current passing through the water is measured by a direct-reading conductivity meter. Boiled distilled water shows a conductivity of about 1.5 ; ,distilled water saturated with carbon dioxide 44 ; Glasgow (Loch Katrine) water 34 ; spriug water of 38.4 hardness 552. The author gives results of many experiments and mentions instances The standard temperature of testing is 20'. where the apparatus would be of practical use. w. P. s. Cslour Reactions of Hydrogen. JOSE GIRAL PEREIRA (Anal. Pis. Quinz. 19 12 10 570-381).-Hydrogen gas rapidly at 80" more slowly in the cold produces a blue coloration on passiug into 2 C.C.of saturated phobphomolybdic acid 1 C.C. of 1% palladium chloride and 3 e.c. of water. In the cold the reaction is slower. With 2 C.C. ofii. 148 ABSTRACTS OF CHEMICAL PAPERS. 10% sodium tungstate 2 C.C. of glacial acetic acid and 2 drops of palladium chloride a blue colour is given similarly and in both cases finely divided palladium is separated. The presence of niiich free strong acid the use of a saturated solution of phosphomolybdic acid or the addition of too large a propor- tion of palladium ail retard or reduce the iutensity of the reaction. Carbon monoxide reduces less readily and does not give a pure blue coloration. G. D. L. Use of Selenic Acid in Ghe Estimation of Bromine Asvociated with Chlorine in Haloid Salts FRANK A.GOOCH and PHILIP L. BLUMENTEIAL(AWL~T. J . Sci. 1913 [IV] 55 54-62).-Ahout 0 07 gram of the mixed salt is distilled in a n atmosphere of carbon dioxide with 30 C.C. of water aud 5 C.C. of 40% selenic acid or a mixture of 1.8 grams of sodium selenate and 3 C.C. of dilute sulphuric acid (1 1). The vapours are conducted into a relay flask contailling 2.5 C.C. of selenic acid and 10-15 C.C. of water or 0.2-0.3 gram of the selenate and 1-2 C.C. of the dilute sulphriric acid ; this flabk is placed in at1 oil-bath heated at 110-115°. The vapour is then absorbed in a special receiver containing 4 grams of potassium iodide dissolved in 250 C.C. of slightly acid water and surrounded by cold water.When the liquid in the distilling flask has boiled down to about 10-15 c.c. the boiling is stopped; and a mDderately strong current of carbon dioxide passed to preveut regurgitation. The iodine liberated by the bromine eet free is then titrated as usual. L. de K. Preparation of Selenic Acid and Sodium Selenate Used in the Estimation of Bromine in Haloid Salts. PHILIP LEE BLUMENTHAL (Arrter. J . Sci. 19 13 [iv] 35 93-dC).-Srlenic acid is best piepartd by oxidising selrniuin dioxide with nitric acid and potassium bromate. After the bromine liberated has been completely expelled the solution is made slightly ammoniacal and precipitated at boiling heat wit ti barium chloride. Tha precipitate when heated with a calculabed amount of sulphuric acid yields selenic acid.Sodium selenate may be prepared by mixing 1 part of selenium with 5 parts of sodium peroxide and heating this by degrees in a nickel crucible. The mass is dissolved in water evnporated to a pasty condition and most of the sodium hydroxlde removed by extraction with alcohol. The residue consisting of sodium selenate and carbonate is dissolved in water and carefully rieutralised with sulphuric acid; on evaporation sodium sulphate crystallises first then a mixture of this with sodium selenate which after being dried a t 108" is then tested as to its true selenate content. The salt may also be prepared by fusing barium selenate with a n insufficiency of sodium carbonate and recrystallising the product from Oxygen in Brass TIIOMAS TURNER (J. I n s t . Metals 1912 8 248-257).-1t is not possible to estimate oxygen accurately in brass by heating i n a current of bydrogen.Some zinc is always reduced volatilised and again oxidised at n lower temperature by the water water. L. DE I(.ANALYTICAL CHEMISTRY. ii. 149 vapoiir which thus does not reach the drying tube. observed when hydrogen is passed over zinc oxide at 1000". This effect is also C. H. D. Comparison of Some Methods for the Estimation of Sul- phur in Vulcanised Caoutchouc with Especial Rbference to Electrolytic Oxidation. DAVID SPENCE and J. YOUNG (J. I n d . Eng. C h m . 1912 4 413-416).-As a result of the comparison of numerous methods for estimating combined sulphur in caoutchouc wlth a standard C$rius method a moditication of the electrolytic oxidation method introduced by Gasparini (A.19U7 ii 650) is advocated as being exceedingly accurate simple aud rapid. About 0-5 gram of the sample in a 200 C.C. beaker is covered with nitric acid (D 1*4) and gently warmed until soltition is complete; about 30 C.C. of nitric acid (D 1.5) are added and a current of about 3 amperes with a potential of 6-8 volts passed through the solution between elect,rodes of platinum foil until oxidation is complete (one to four hours). A diagram of the electrical connexions is given and the further simplification by introducing a subsequent volumetric process (Pennock and Morton A 1904 ii 206) for estimating the sulphur is discussed in the original. Estimation of Sulphurous Acid in Sugar Cane and Beetroot Products. HENRI PELLET (Bull. Assoc.chim. sucre fitst. 1912 30 33?-338).-The apparatus described for the estimation of sulphurous acid in sugar products consists essentially of a cylinder bearing marks which indicitte the quantity of sugar solution to be taken for the estimation the volume of acid etc. to be added for neutralisation the quantity of indicator and the volume of standard iodine solution MAURICE DUYK (Ann. Chim. anal. 1912 17 445-447).-One hundred C.C. of the water are aciditied with 20 C.C. of 10% hydrochloric acid 4 grams of potassium hydrogen carbonate are added in small quantities at a time a crystal of potass- ium iodide is then introduced and after the further addition of 1 gram of potassium hydrogen carbonate the liberated iodiue is titrated with thiosulphate solution. The addition of the potassium hydrogen carbonate is for the purpose of expelling air from the water and vessel in which the experiment is carried out; the liberated nitric oxide is also expelled and there is therefore no risk of the latter combining with oxygen and reacting further with the potassium iodide.w. P. s. Detection of Nitric Acid in Presence of Nitroue Acid. V. N. IVANOV (J. Buss. Yhya. Chem. Soc. 1912,44,17'72-1775*).-As little as 0.0001 gram of nitric acid may be detected in presence of one hundred times as much nitrous acid by the blue coloration which it yields with a quadrivalent iridium compound. The reagent may be prepared conveniently from 0.025 gram of iridium in the form of * and Chem. Zeit. 1913 37 157. F. M. G. M. required to oxidise the sulphurous acid.w. P. s. Estimation of Nitrites in Water. VOL. civ. ii. 11ii. 150 ABSTRACTS OF CHEMICAL PAPERS. iridichloride or dioxide which is dissolved in 3-5 C.C. of water 100 C.C. of concentrated sulphriric acid (98-99%) being then added to the solu- tion with constant stirring. The liquid is heated to boiling toede- colorise it and when cold is stored in a well-stoppered bottle It should contain 96-96.5% of sulphuric acid. To make a test 5 C.C. of the reagent are heated to incipient boiling and the substance t o be tested which must be in the solid state quickly added. If for example a water is to he examined i t is first evaporated to dryness with a slight excess of alkali. The test-tube is not heated while the substance is being added owing t o the danger of converting t’he nitrous acid into nitric acid ; on the other hand i f the reagent is insuBciently heated a yellow and not a blue coloration is obtained.With a large amount of nitrous acid a coloration may appear after a time as a result of the reaction between nitrogen peroxide and water-vapour N20 + H20 = HNO + HNO,. By means of a tube fitted with a ground stopper and with two side-tubes for the passage of a current of carbon dioxide the gas formed is rapidly removed and satibfactory results are obtained. T. H. P. A n a l y s i s of M i x t u r e s of Nitric Acid Carbamide and Water. A. MASSINK (Chem. Wepkblad 1912 9 1000-1(i02).-To estimate nitric acid In presence of carbamide the author titratm with potas.-ium hydroxide and methyl-orange. The carbamide is estimated by evapo- rating the neutralised liquid to drynes removing the last traces of water by iepeated evaporation with 96% alcohol and weighing the residual carbarnide and potassium nitrate.The amount of nitrate preserit in the mixture is calculated from the volume of alkali employed in the titration. The method is rapid and accurate. A. J. W. Detection and E s t i m a t i o n of Free W h i t e Phosphorus in Phosphorus Set quisulphide. THEOPRILE SCHL~SIR’ G j iin. (Cumpi. (rend. 19 12 155 1461-1464).-The phosphorus sesquisulphide is shaken for several minutes with sufficient light petroleum (b. p. (45’) to dissolve any free phosphorus present the liquid quickly filtered aud a n aliquot portion taken and quickly evaporated in a vacuum at 15-20’. The residue is oxidised with nitric acid and the sulphur arid phosphorus estimated according t o Berger’s method (compare A.1907 ii 129). I n order simply t o detect the presence of phosphorus the residue after evaporating off the petroleum is shaken with some fino sand in a flask i n the dark and carefully examined for any phosphorescent glow which is given by minute traces of free phosphorus. w. G. Reduction of Manganese Dioxide by Nitrous Acid. Applica- tion of t h i s Reaction in t h e E s t i m a t i o n of P h o s p h o r u s in Iron a n d Steel without Separation of Silicon. EUGEN R. E. MULLER (Chem. Zzit. 1912 36 1490).-A slight modification of the author’s process described previously (A. 191 1 ii 1 132). Instead of reducing the manganese dioxide formed by means of sodium peroxide 0.5 C.C.of absolute alcohol and 1 C.C. of 10% sodiumANALYTICAL CHEMISTRY. ii. 151 nitrite are added which causes the liquid rapidly to clear. After adding 1 C.C. of ammonia and boiling for a short time the solution is ready for the molybdate precipitation. PAUL FRELJNDLER (Bull. Soc. chim. 1912 [iv] 11 1041-1043).-Two to three grams of lecithin are heated with 50 C.C. of fuming nitric acid in a 500 C.C. flask on a water-bath. After two to three hours the reaction stops; 25-30 C.C. of water are then added and 25-35 grams of finely powdered permanganate in portions of one gram a t a time. When the oxidation is complete the solution is diluted t o 150-200 c.c. the manganese dioxide dissolved with sodium nitrite and the whole evaporated to a syrup t o expel the excess of acid. The phosphorus is then precipitated without it being necesqary t o filter the liquid with ammonium molybdate in the presence of ammonium nitrate and estimated in the usual way.The method is accurate and preferable L. DE K. The Estimation of Phosphorus in Lecithin. to that described by Bordas (A. 1902 ii 587). T. s. P. Accurate Volumetric Estimation of Phosphoric Acid in Phoaphate Rock. JOEN G . PAIRCHILD ( J . Ind. Bag. Chem. 19 12 4 520-522).-A modification of Pemberton’s (Pharm. 2entr.-h. 191 1 50 1288) method of estimating phosphoric acid by titration with alkali hydroxide in which Sutton’s (Volumetric Analpis) suggestion of first precipitating the phosphoric acid with barium chloride is carried out. This method is claimed to be accurate and very rapid as after allowing twenty minutes for the solution of the rock about one hour is needed to finish the experiment.F. M. G. M. Use of ‘( Activated ’’ Aluminium in the Detection of Arsenic EMILE KOHN-ABREST (Ann. FcdsijC 1912 5 384-388. Compare A. 1912 ii 768).-The hydrogen required in the Marsh test for the detection of arsenic may be obtained by the action of water on activated aluminium foil and the following method of carrying out the test is recommended Four grams of aIuminium foil in small pieces are cleaned with nitric acid and then immersed for three or four minutes in 25 C.C. of a 1% mercuric chloride solution. The pieces of foil are now washed with water and introduced together with 220 C.C. of water into the flask of the Marsh apparatus.At the end of about two hours the solution to be tested for arsenic is added; the latter solution should be neutral in reaction and measure about 20 C.C. w. P. s. Detection and Estimation of Arsenic in the Earth of a Cemetery. GINO ZUCCARI (Gazxettn 19 12 42 ii 633-638).-1n view of the fact that in cases of suspected poisoning it has been suggested that arsenic may have reached a corpse from the soil of the cemetery in which it was buried the author has made experiments on the soil of a cemetery known to contain arsenic. From samples of the soil extracts were made with water aqueous ammonia (l%) aqueous sodium carbonate (l%) and sulphuric acid. I n all these extracts small quantities of arsenic could be detected by Bressanin’s method ( A t t i R. 11-2‘ii.152 ABSTRACTS OF CEEMICAL PAPERS. 1st. Yen. 8. L. A 1911 70 951) the organic matter being previously removed by Breteau’s method (A 1911 ii 226). x. v. s. Estimation of Arsenic in Pyrites. E. SCH~RMANN and WILHELiu BOTTCHER (Chem. Zeit. 1913 37 k9-51).-Three grams of the sample are heated in a reflux apparatus with 12 grams of chromic acid and 30 C.C. of dilute sulphuric acid (1 1) for four hours at boiling heat. When cold 50 C.C. of water are added and then 1.1 gram of cuprous chloride. After further addition of two grams of potassium bromide and 100 C.C. of fuming hydrochloric acid the arsenic is distilled off in a current of hydrogen chloride and collected in a n Erlenmeyer flask containing 150 C.C. of water and cooled by means of ice and salt. When two-thirds of the liquid has distilled over the arsenic has generally passed over completely.This reduction with cuprous chloride is preferable to the use of sulphur dioxide. The arsenic is now precipitated as sulphide by means of hydrogen sulphide. This is then converted in the usual manner into silver arsenate. To effect complete precipitation the authors add a little ammonium acetate so as to remove free nitric acid or the sulphide may be converted into arsenious acid which is then titrated with iodine. L. DE I(. Phenolphthalein as a Double Indicator in the Estimation of Carbon in Castings Steel and Alloys by Direct Combustion. P. B R ~ S (Mon. Sci. 1912 [v] 2 501-502).-The carbon dioxide obtained in the ordinary combustion process is absorbed in a U-tube one limb of which is filled with a mixture consisting of soda-lime SO grams sawdust 20 grams potassium hydroxide solution D 1.18 20 c.c.and phenolphthalein 0.3 gram. This mixture is colourless but a red coloration develops as the carbon dioxide is absorbed by the soda-lime and the course of the absorption may thus be observed. The other limb of the U-tube is filled with calcium chloride t o prevent loss of moisture from the first limb. Any escape of unabsorbed carbon dioxide may be detected by subsequently passing the gases through a solution containing 1 part per 100,000 of potassium hydroxide and a small quantity of phenolphthalein; 10 C.C. of this solution are decolorised by as little as 0*0002 gram of carbon dioxide. w. P. x. Phenolphthalein as an Indicator of the Presence of Sodium Carbonate in Sodium Hydrogen Carbonate.R. RICHTER. (Phawn. Zeit. 1912 57 998-999).-According to the author phenol- phthalein is an untrustworthy indicator for the detection of sodium carbonate in sodium hydrogen carbonate as the latter itself exhibits an alkaline reaction when the indicator is concentrated. At the same time the presence of less than 4% of the normal carbonate in the hydrogen carbonate does not produce a pink coloration when the solution of the salt is treated with a small quantity of phenolphthalein (0.2 C.C. of a 0.05% solution) w. P. s.ANALYTICAL CHEMISTRY. ii. 153 The Use of Potassium Palmitate in Water Analysis. CARL J. BLACHER P. GRUNBERG and A%. KISSA (Chern. Zeit. 1913,3’7,56-58). -When potassium stearate is used in water analysis (compare Blacher and Jacoby A.1908 ii 897) certain side reactions occur which are objectionable. The authors consequently recommend the use of potass- ium palmitate and give the following directions for determining the temporary and permanent hardness of water. The carbonates are first titrated with N/lO-hydrochloric acid using dimethylaminoazobenzene as indicator the carbon dioxide being removed by a current of air. The slight excess of acid is then neutralised with N/lO-alcoholic potassium hydroxide using phenolphthalein as indicator and the total hardness is determined by titrating with N/lO-potassium palmitate until the liquid turns decidedly red. When the water contains salts of weak acids the neutral points of the two indicators are divergent and the number of C.C.of alcoholic potassium hydroxide used give a measure of t h e content of the water with respect to these weak acids. The estimations of sulphates and magnesium are carried out in a manner similar to that described for potassiuni stearate (Zoc. cit.). T. S. P. Q u a n t i t a t i v e S e p a r a t i o n of Calcium and Strontium. RAM~N LLORD Y GAMBOA (Anal. Pis. Quim. 1912 10 389-394).-1n the author’s experience the indirect method of estimation by precipitation of the oxalates conversion into carbonates and determination of carbonic anhydride yields more accurate results than either of the direct separations by means of the nitrates with ether-alcohol or by means of ammonium sulphate. G. D. L. Qualitative Separation of. Barium Strontium and Calcium. J.L. 11. VAN DER HORN VAN DEN Bos (Chern. WeekbZad 1912 9 1002-1003. Compare ibid. 5).-To detect barium strontium and calcium the mixed carbonates are dissolved in ddute acetic acid the solution boiled to expel carbon dioxide and diluted with water. Ammonium acetate is added any precipitate formed being filtered off and t8he barium precipitated quantitatively by addition of ammonium dichromate to the boiling solution. The cold filtrate is made slightly ammoniacal and the strontium chromate precipitated by addition of 96% alcohol. The presence of calcium in the filtrate can be detected by addition of ammonium oxalate. The method is rapid and accurate and can also be applied to the quantitative separation of the metals. A. J. W. Estimation of Lead in Tin.L. VANNIER (Ann. Fa&$ 1912 5 477-478).-For the estimation of small quantities of lead in tin it is recommended that exactly 1 gram of the metal be dissolved in nitrie acid and the metnstannic acid separated in the usual way. The filtrate from the metastannic acid is then diluted to 200 c.c. and 20 C.C. of this solution are treated with 1 C.C. of a 40% potassium iodide soliition. If less than 0.5% of lead is present in the metal the mixture will remain clear; 0.6% of lead will cause a precipitate of lead iodide t o separate within five minutes whilst 0.8% yields aii. 154 ABSTRACTS OF CHEMICAL PAPERS. large quantity of precipitate. by comparison with solutions containing known amounts of lead. The quantity of lead may be estimated w. P. s. Use of Meyer’s Reagent.UMBERTO PAZIENTI (Boll. chim. fawn. 1912 51 661-666).-The author confirms the statement of Tixier (BUZZ. sci. pharni. 1910 82)’ that the oxidation of phenolphthalin t o phenolphthalein (which is the basis of the action of this reagent) is shown by water containing very slight traces of copper (one part in one million) but the reaction is entirely prevented by the addition of 0.001 gram-mol. of hydrogen cyanide. The author suggests a possible mechanism for the reaction with copper salts which is apparently an example of catalysis involving the formation of intermediate substances. The Fensitiveness of the reagent towards copper salts depends on circumstances 0 Ol-O.OOl% of copper sulphate causes almost instantaneous oxidation of the phenolphtlialin without the intervention of hydrogen peroxide whilst when the solutions contain 0-000 1- 0*00001% the oxidation is very slow unless hydrogen peroxide is added The maximum dilution at which copper can be detected with fhe reagent (hydrogen peroxide being also added) is O.OOOOOl% and i t is thus much more sensitive than other tests for copper.Manganese cobalt lead iron platinum and various inorganic and organic com- pounds also affect the reagent which was originally suggested as a test for blood. Discussing its value for the last-named purpose the author is of opinion that it may be used to detect blood in urine if the latter is first ‘‘ defacated ” t o remove any substances which might interfere with it. R. V. S. A Case of Mercurial Poisoning and the Estimation of Mercury in Textile Materials.LORENZO L. LLOYD and WALTER M. GARDNER (J. Soc. Cheln. Id. 1912 31 1109-llll).-Cases of mercurial poisoning having occurred recen tlg amongst the operatives in a hat factory the authors h a w investigated the matter and record the results obtained. The source of the mercury was not far to seek since the great bulk of the rabbit and other fur constituting the raw material used in t h e manufacture of hats is treated with an acid solution of mercuric nitrate by the fur dealers. Although much of the mercury is removed in the processes which the furs undergo considerable quantities remain in the finished product ; at the same time portions of the mercury compounds volatilise during the opera- tioris and the vapours may be inhaled by the workers.A h a t which had been in use for about twelve months was found t o contain O*OOlS% of mercury. For the detection of mercury in textile materials a portion of the latter is treated with dilute aqua yegia a slight excess of zinc dust is added and the mixture is submitted to distillation with superheated steam at a temperature of 160’ ; the volatilised mercury is collected on a piece of copper gauze placed in the condenser. The gauze is then dried and heated in a tube which is drawn out to a capillary the mercury globules collecting in the latter being then identified by the iodine test. The quantity of mercury present may be estimated by extracting the material with dilut,e aqua regia renderingANALYTICAL CHEMISTRY. ii. 155 the extract slightly alkaline by the addition of sodiiim hydroxide precipitating the mercury as sulphide and then adding acetic acid.The mercury sulphide is collected on a filter washed with water and nitric acid and dissolved in aqm regia. This solution is neutraliwd and treated with a solution containing 0.2 gram of potassium iodide 6 grams of sodium hydroxide and 2 grams of ammonium chloride per 100 c.c. the coloration obtained being compared with th3t produced by known amounts of mercury. A kaolin filter for collecting the mercury sulphide is described. w. P. s. Estimation of Manganese by the Bismuthate Method. HARRY F. V. LITTLE (Analyst 1912 37 554-557).-'I'he author records results which show that this method (compare A. 1902 ii 107) is trustworthy in the case of both small and large amounts of man- ganese.The theoretical factor should be employed for calculating the quantity of manganese present and the author prefers t o dilut>e the oxidised solution before titration with a n equal volume of 3% nitric acid. w. P. s. The E s t i m a t i o n of Total Manganese in Soils. Ross A. GORTNER and CLAYTON 0. ROST (J. I n d . Eng. Chem. 1912 4 522-524).-1t is found that the methads of Marshall (A. 1901 ii 350) and Walters (Chenz. New? 1901 84 239) as described by Washington and Hillebrand (The Chsrnicd Analysis of Rocks ; and Bull. 422 U.S. Geol. Survey) for the estimation of manganese are not applicable to Nebraska soils and the following modification is found to give ac;3urate results. The soils are fused with sodium carbonate the solution of the fused mass acidified with sulphuric acid and oxidised with sodium bisrnuthate thus converting the whole of the manganese into permaugrnic acid which is then estimated colorimetricallg by comptrisoo with a standard solution of permangmic acid prepared by the reduction of potawium permanganate with sulphurous acid and sribseq lient re-oxidation with bismuthate.F. M. G. M. Manganese and P h o s p h o r i c Acid Content of Honeys. ARTHUR GOTTFRIED (Pliarm. Zmtr.-h. 1912 53 1440-1443. Com- pare A. 191 t ii 823).-The author has determined the arnoiint of ash and the phosphoric acid aud mangauese contained therein of it n:imber of honeys and honey substitutes and tabulated the re.sultu. These prove that the composition of the ash of honey differs widely and this is particularly so as regards t h e amounts of manganese and phoaphhc acid. Whether these variations are due to the different origin of the honeys is a matter for future research.L. DE K. E s t i m a t i o n of Iron in Waters. EUGENE TASSILLY (BdZ. SOC. chini. 1913 [iv] 13 34-37. Compare Kosenheim and Cohn A. 1901 i 455; Oerum A. 1904 ii 4 4 9 ; Stokes and Cain A 1907 ii 581).-The author firids that on examining solutions of ferric salix t o Fhich potassium thiocyanate has been added by FBry's spectro- photometer (1) the absorption of light becomes constant for a definitei. 156 ABSTRACTS OF CHEMICAL PAPERS. quantity of iron when the salts are present in the proportion FeCl 11 (KCNS) ; (2) the maximum absorption takes place in the bluish-violet but the maximum sensitiveness is in the green and (3) in presence of great excess of the thiocyanate the absorption as measured by the instru- ment is proportional to the amount of iron in the coloured solution.'l'be estimation is made by heating 100 C.C. of the water with 20 C.C. of hydrochloric arid and 0.5 t o 1 gram of potassium chlnrate until chlorine is nn longer evolved. On cooling 20 C.C. of thiocyanate solution (1.7%) are added the volume is made up to 100 c.c. and t,he solution examined in the spectrophotometer the percentage of iron being determined by reference to a curve prepared from data obtained by the examination of iron solutions of known strength. If a precipitate forms this is dissolved in hydrochloric acid and added to the liquid which is then evaporated t o 100 C.C.if necessary. T. A. H. Estimation of T r a c e s of Iron in C a n e and Beet Sugar Factory and Refinery P r o d u c t s . JOHN J. EASTICK JAMES P. OGILVIE and JAMES H. LINDFIELD (Internut. Xugar J. 1912 14 428-435).-The sulphide colorimetric method described by Winkler (A. 1903 ii 108) is recommended for the estimation of iron in sugar and sugar products. The process may be applied directly t o sugar solutions or t o the ash obtained from them. The standard iron solution used for comparison should be prepared from ferrous ~ u l phate and i t has been found that if instead of water alone a 50% sucrose solution is employed for the preparation of this solution the latter will keep almost indefinitely. w. P. s. Rapid Estimation of Chromium in Chrome Mordants.S. JAKUBOWSKI (Ftirb. Zeit. 19 12 23 415-41 6).-The est'imation of chromium can be rapidly and conveniently effected by first oxidising i t to chromic acid treating with potassium iodide and subsequently titrating with sodium tbiosulphate in acid solution. The following oxidising agents can be employed hydrogen or sodium peroxides or sodium percarbonate in alkaline solution. F. M. G. M. Estimation of Stannous Chloride and of Chlorates by m e a n s of Metbylene-blue. FREDERICK W. ATACK (J. Soc Dyers 1913 29 9-lO).-The process is based on the fact that in presence of a sufficiency of free hydrochloric acid stannous chloride has a quantitative reducing action on methylene-blue. About 1.4 gram of the salt are dissolved up to 250 C.C. in dilute hydrocbloric acid (1 l) and 25 C.C. are then titrated with N/50- methylene-blue (about 4 grams per litre) until the blue colour persists This solution is checked as follows About 0.7 gram of the pure metal is disholved in LO C.C.of dilute hydrochloric acid (1 1 ) and made up with air-free water to 250 c.c. 25 C.C. are withdrawn 25 C.C. of hydrochloric acid are added and titrated in a current of carbon dioxide with the methylene-blue solution. The result is not affected by the presence of antimony.ANALYTICAL CHEMISTRY. ii. 157 Chlorates may be estimated indirectly by this method by adding excess of stannous chloride and warming the solution in a current of carbon dioxide. When cold an equal volume of hydrochloric acid is added and the excess of stannous chloride titrated as directed.L. DE I(. A Volumetric Method for the Estimation of Thorium in the Presence of Other Rare Earths. The Analysis of Monazite Sand. FLOYD J. METZGER and F. W. ZONS (J. Ind. Eng. Chem. 1912 4 493-494).-when a n excess of ammonium molybdate solution is added to a cold acetic acid solution of a thorium salt the thorium is precipitated quantitatively as moly bdate. Other rare earths such as cerium lanthanum neodymium praseodymium erbium yttrium and gadolinium give no precipitate under similar conditions. The ratio of thorium to molybdenum indicates t h a t the precipitate is a normal thorium molybdate. As indicator diphenylcarbazide (the solution of which must have been prepared at least two weeks previously) is employed being used outside ” on a white bile and a t the end of the titration furnishes a pink colour which lasts about fifteen seconds and requires some experience to identify.The analysis is carried out as follows About 1 gram of monazite sand is treated with 10-15 C.C. of concentrated sulphuric acid in a porcelain crucible and after several hours’ heating carefully trans- ferred to about 700 C.C. of cold water and left overnight; the solution is filtered the filtrate nearly neutralised with dilute ammonium hydroxide followed by the addition of 50 C.C. of a cold saturated solution of oxalic acid and again left overnight. The mixed oxalates are collected washed with dilute oxalie acid transferred to a beaker and boiled with 20-25 C.C. of a concentrated solution of potassium hydroxide diluted the precipitate of rare earth hydroxides collected washed redissolved in hot dilute nitric acid and evaporated to dryness several times with small quantities of water to remove free nitric acid.The dry residue is treated with 20 C.C. of glacial acetic acid 300 C.C. of water and 1 gram of sodium acetate and when completely in solution titrated with standard ammonium molybdate solution. F. M. G. M. Analysis of Bismuth Subnitrate. MAURICE FRAN~OIS (J. Phawn. CItinz. 1912 [vii] 6 536-542; Ann. Falsrx 1912 5 569-573).-To determine whether a sample of bismuth subnitrate contains an admixture of oxide i t is recommended that the results of analysis should be calculated into percentages of water bismuth oxide and nitrogen pentoxide. For the pure substance the ratio of the per- centage amounts of nitrogen pentoxide to bismuth oxide (Ei203) should be 1 to 4.296.The authors find that commercial bismuth subnitrate frequently contains less water than the quantity mentioned in the French Codex namely 5.8%. w. P. s. New Apparatus for the Examination of Mine Air. LEONARD A. LEVY (J. SOC. Chem. Ind. 1912 31 115~-1155).-Forii. 158 ABSTRACTS OF CHEMICAL PAPERS. the combustion of small quantities OF methane in the estimation of this gas in air the author uses a silica capillary containing a platinum wire. The silica tube is about three inches long and has a diameter of 1 mm. whilst the platinurn wire is one inch in length and is stretched axially in the middle of the tatbe ; a spring a t one end of the platinum wire prevents the latt>er from touching the sides of the tube when it is hented.The wires supplying the electric current are fused into the ends of the silica tube and the platinum wire is heated t o a white incandescence during the passage of the gas through the apparatus. The gas is admitted through a capillary side-tube near one end of the platinum mire and a capillary side-tube near the other end is provided for the exit of the gas. Two portable forms of apparatus are described for the estimation of methane and carbon monoxide etc. respectively i n mine air. TV. P. s. The E s t i m a t i o n of Benzene in Goal Gas. ELLEN S. MCCARTHY ( J . Gasbaleuchtung 19 12 55 89 1-892).-A description of the method of estimating benzene in coal gas by means of the additive compound formed with ammoniacal nickel cyanide (compare A.1903 i 469). F. M. G. M. Estimation of Methyl Alcohol in Spirits. JOSEF HETPER (Zeitsch. Nahr. Genussm. 19 12 24 731-737).-1n the method proposed the quantity of methyl alcohol is estimated by oxidation with permanganate in phosphoric acid solution; 1 gram of methyl requires 187.5 C.C. of N/1-potassium permanganate solution and 1 gram of ethyl alcohol 87 cc. of this solution for complete oxidation. The spirit under examination is distilled and the dihtilate is either diluted or concentrated by further distillation until it has D 0.910 to 0.925; between these limits solutions of either methyl or ethyl alcol.101~ have the same density and the quantity of total alcohol present may be found by reference to tables. A weighed portion of about 1.5 c,c.of this alcoholic solution is then diluted to 200 c.c. and 10 C.C. are introduced into a flask containing 30 C.C. of N/2-per- manganate solution (containing 40 grams of crystallived phosphoric acid per litre) and 60 C.C. of water. The flask is then heated on a water-bath in a reflux apparatus for two hours. Afier cooling the excess of permanganate is titrated with oxalic acid solution and the amount of methyl alcohol calculated from the quant'ity of perman- gariate reduced. The method cannot be applied to spirits containing large quantities of furfuraldehyde or ethyl acetate. w. P. s. T h e Bromine and Iodometric Methods for the Volumetric E s t i m a t i o n of Gresol. C. M. PENCE (J. lnd. Eng. Chem. 1912 4 5 18-520).-A dtmription of experiments from which the author draws the conclusion that the usual bromine methods for the esti- mation of cresols depend on certain fixed conditions presupposing a previous knowlodge on the part of the operator which renders them undesirable. Tribromo-o- and tribromo-p-cresols cannot be formed in a n anaiogous manner to 2 4 6-tribromophenol but m-cresol can be estimated by conversion into tribrorno-m-cresol 0 - and p-Cresols formANALYTICAL CHEMISTRY.ii. 159 di-iodo-compounds and thiscan be made the basis of a method for their estimation but m-cresol does not combine quantitatively with iodine. F. M. G. M. The Behaviour of Blood-Sugar in Normal and Pathological Cases. I. The Technique of the Eatimation of Sugar in Blood. FR. KOLLY and FR. OPPERMANN (Biochem. Zeitsch.1913 48 50-63).-Details are given of the experimental methods for separation of the proteins for which the dialysed iron hydroxide method of Michrelis and Rona forms the basis and for estimation of sugar in the protein-free filtrate by Bertrand’s method. S. B. S. Analysis of Cane Molasses. Study of the Different Methods of Estimating Sucrose. C. FRIBOURG (Bull. Assoc. chim. Sucr. Dist. 19 12 30 3 12-327).-The following results were obtained by using different methods for the estimation of Bucrose in a sample of molasses Direct polarisation after clarification with basic lead acetate 35.90% ; with normal lead acetate and calcium hypochlorite 33.93%. Double polarisation with basic lead acetate 42.58% ; with normal lead acetate 41.86%. Fehling’s gravimetric method 41.44%. Double polarisation after treatment with carbamide and hydrochloric acid 41.52%; after treatment with sulphurous acid 41.68%.Direct polarisation after the reducing sugars had been destroyed by means of hydrogen peroxide 41 -65% ; double polarisation of this solution showed 41.57% whilst Behling’s method yielded 41.32%. The invertase method gave 41.36%. Excluding the results obtained on solutions clarified with basic lead acetate the average of the other figures was 41.54%. The difference between the amount of sucrose actually present and that found by the direct polarisation emphasisefl the necessity of employing the more trustworthy methods which are mentioned. w. P. s. Estimation of Sugar in “Baga~se” and in Sugar Cane. Estimation of Water in ‘‘ Bagasse.” HENRI PELLET (Bull.Assoc. Chirn. Sucr. Dist. 1912 30 305-312).-The total sugar may be estimated by treating a weighed portion of the substance with small quantities of calcium hydroxide and sodium carbonate and extracting it with successive quantities of hot water. The solution thus obtained is clarified with basic lead acetate and examined in the polarimeter. The small quantity of sugar which remains iu the “ bagasse ” after this extraction is estimated in the liquid which is recovered from the moist mass by pressure. An alternative method consists in heating the ‘‘ bagasse ” with water in a closed vessel and after cooling separating the solution by decantation and pressure; this solution is then clari6ed w i t h basic lead acetate and polarised. The method is suitable for the estimation of sugar in sugar cane provided that the latter is finely-divided previously. The moisture in ‘ I bagasse ” may be esti- mated by heating 50 grams of the sample in a wire-gauze basket t o a temperature of 110’ until no further loss in weight takes place.w* P. s.ii. 160 ABSTRACTS OF CHEMICAL PAPERS. Polarirnetric Estimation of Sugar in Beetroots using the Cold a n d Hot Extraction Methods of Pellet. HENRI PELLET (Bull. Assoc. chim. SUCT. Dist. 1912 30 328-333).-Results of experiments are recorded which show that exactly the same figures are obtained whether the beetroots are treated by the cold diffusion or by the hot digestion methods for extracting the sugar. W. P S. Determination of the Polarisation of Beetroot Sugar Pro- ducts by Double Polariaation. Comparison between the Carbamide-Hydrochloric Acid and Sulphurous Acid Methods. HENRI PELLET (Bull.Assoc. chim. Sucr. Dist. 1912 30 335-337).- The double polarisation method using for the direct polarisation a sugar solution containing carbamide and hydrochloric acid yields lower resiilts than is the case when the sugar solution is treated with sulphurous acid. This is due to the action of the hydrochloric acid on the sugar. The carbamide method yields about 0.25% less sugar than the sulphurous acid method in the case of beetroot juice containing 20% of sugar whilst with raw sugar the difference between the two methods amounts to 2.5% of sugar. A similar difference is obtained in the case of molasses and the carbamide method cannot therefore be considered as trustworthy. w.P. s. The Gelatinising Temperature of Starch Grains. MAX NYMAN (Zeitsch. Nahr. Genussrn. 1912 24 673-676).-Various starches were found to gelatinise a t slightly different temperatures when mixed with water and heated gradually for instance rye starch gelatinised at 57" barley starch a t 5 8 O and wheat starch a t 59". The gelatinising point was taken as being the temperature a t which the starch grains ceased to polarise light when examined under the micropolariscope. The larger starch grains gelatinised more quickly than the smaller. It was also found that the starches gelatinised a t different rates when maintained a t a temperature a few degrees below the actual gelatinising point. A t 53" rye starch is gelatinised completely in six minutes whilst wheat starch requires twenty-four minutes.This difference may afford some slight means of identifying these two starches in mixtures of the same as any ungelatinised grains remaining after about seven minutes' heating a t 53' would indicate the presence of wheat starch. w. P. s. N e w Method of E s t i m a t i n g Glycogen in the Liver. HENRI BIERRY arid (Mme.) Z. GATIN-GRUZEWSKA (Compt. rend. 19 12 155 1559-156 l).-A rapid method of estimating glycogen in liver. Twenty-five grams of the liver are crushed and heated to solution on a water-bath with 25 C.C. of 35% aqueous potassium hydroxide. Tbe solution is then heated in an autoclave a t 12bo for half an hour cooled and neutralised with hydrochloric acid. Five C.C. of hydro- chloric acid (D 1.18) are added the liquid made up to 100 c.c.and again heated in the autoclave a t 120' for half an hour. After cooling it is neutralised with sodium hydroxide the proteins precipitated by mercuric nitxate the solution made up to 300 c.c. filtered and the dextrose estimated in the filtrate by Bertrand's method. TheANALYTICAL CHEMISTRY. ii. 161 results so obtained were in all cases higher than those given by Pfluaer's method but the difference was shown not to be due t o the formvation of Z-xylose by hydrolysis of nucleo-proteins in the liver. W. G. The Estimation of Cellulose in W o o d and Spinning Fibres. CHARLES F. CROSS and EDWARD J. BEVAN (Zeitsch. Fcwb. Ind. 1912 11 237-238).-Polemical a further reply to Kanig and Huhn (A 1912 ii 1105).F. M G. M. F. L. SHANNON CJ. Ind. it'ng. CImz. 1912 4 526-52S).-The formic acid is isolated by steam distillation the volume of liquid reduced by evaporation (after neutralisation with sodium hydroxide) and the formic acid either reduced to formaldehyde with magnesium and dilute Eulphuric acid or converted into the lead salt which is readily identified by its crystallo- graphic habit. Detection of Formic Acid in Fruit Products. F. Ill. G. M. E s t i m a t i o n of Acetyl Groups. WILHELM NORMANN (Chem. Rev. Felt. Hum. Ind. 1912 19 205-206).--The following method for t h e estimation of acetyl groups can be completed in about two hours. Two grams of the accurately weighed fat or oil are acetylated by boiling with 4-6 C.C. of acetic anhydride during 0.5-1 hour and the excess of acetic anhydride expelled by heating in a stream of a neutral gas such as hydrogen or carbon dioxide.The acetyl groups are then eliminated by the action of standard alcoholic potassium hydroxide and the excess of alkali subsequently titrated with a standard solution of acid. F. M. G. M. The Fractional Precipitation of Mixtures of Fatty Acids. HANS KREIS and EMIL ROTH (Chem. Zeit. 1913 37 58).-An alcoholic solutiou of the mixture of fatty acids is precipitated by about one-tenth of the theoretical quantity of lead acetate and the acids obtained from the precipitate by boiling with hydrochloric acid. The melting point refractivity iodine value and molecular weight of the acids can then be determined. The results obtained with a number of oils are given and i t is shown V .consists mainly of erucic acid. mixture of acids by one frac- testing for earth-nut oil the T. S. P. Acid in Wines. PHILIPPE 11 1043-1045 ; BUZZ. ASSOC. that the first fraction from rape-seed oil Arachidic acid can be obtained from a tionation and this is made use of in details for which are to be given later. Estimation of Total Tartaric MALVEZIN (Bull. SOC. chim. 1912 [iv] Chim. Sucr. Dist. 1912 30 342-343).-Twenty-t~0 c.C. of the wine are distilled i n a conical flask until 'I C.C. only remain. The flask does not come directly into contact with the flame but is placed about 3 cm. above a thin metal plate which is heated directly. To the con- tents of the flask are then added 1 C.C. of a 10% solution of potassium bromide and 40 C.C.of a mixture of alcohol and ether in equal volumes i n order to favour the precipitation of the tartaric acid present eitherii. 162 ABSTRACTS OF CHEMICAL PAPERS. i n the free or combined state. The flask is then immersed for fifteen to twenty minutes in a freezing mixture made from eyual weights of water and ammonium nitrate. The precipitate is collected washed several times with the ether-alcohol mixture then dissolved in water and titrated with N/lO-sodium hydroxide in order to determine the amount of tartaric acid present. The volatile acids and the alcohol can be determined in the 20 C.C. of distillate obtained. T. S. P. Estimation of Citric Acid in the Presence of Certain Other Acids. L. GowrxG-ScoPEs (Analyst 1913 38 12-19).- The reagent used is prepared by pouring 68 C.C.of strong nitric acid on to 51 grams of mercuric nitrate and 51 grams of manganese nitrate. One hundred C.C. of water are then added and when all is dissolved the solution is made up t o 200 C.C. and filtered. A quantity of the substance containing not more than 0.04 gram of citric acid is carefully neutralised with N/lO-alkali using phenolphthalein as indicator. Ten C.C. of the reagent are added and the whole diluted to 200 c.c- The liquid is then boiled in a reflux apparatus for three hours and the mercurial precipitate is collected on a Gooch crucible washed with cold water dried in the water-oven for two hours and weighed. The weight divided by six equals citric acid. The following acids when present do not interfere tartaric succinic oxalic benzoic phosphoric sulphuric and acetic acids ; malic lactic and salicylic acids however cause the results to be less accurate.L. DE K. Eldimation of Salicylic Acid and Benzoic Acid in Fruit Juices Jams Lemonades etc. A. VAN RAALTE (Chem. Weekblad 19 12 9 1004-1005).-For the estimation of salicylic and benzoic acids and “saccharin” in the articles cited the author recommends boiling for five hours with dichloroethylene followed by titration with decinormal alkali and phenolphthalein. After separation from the dichloroethylene the neutralised liquid is examined for salicylic and benzoic acids. ‘‘ Saccharin ” can be extracted with ether from another portion of the aqueous liquid after addition of phosphoric acid. A. J. W. Nuclein Metabolism. ALFRED STEPHAN (Chem.Zentv. 191 2 ii 1583; from Apoth. Zeit. 1912 27 816-818).-A review of the subject. A method for estimating uric acid in blood as a copper urate is described. The method for estimating uric acid in urine recommended is a modification of Folin’s. W. D. H. A New Colorimetric Method for the Estimation of Uric Acid in the Blood. OTTO FULIN and W. DENIS (J. Biot. Chem. 191 3 13 469-476).-The phosphotungstic method yields positive evidence of the presence of uric acid in the blood. All previous evidence is regarded with suspicion. Quantitatively it gives accurate results. W. D. H.ANALYTICAL CHEMISTRY. ii. 163 Comparison of the Hubl and Wys Methods for E s t i m a t i n g the Iodine Numbers of Fats. AUGUET ( A n 7 ~ . Etcls?f. 1912 5 459-475).-The Hubl method yields low results as compared with the Wys method when t h e reagent used in the former method is freshly prepared owing t o the absence of hydriodic acid This acid forms gradually in the alcoholic iodine solution and the solution should not be used until i t is at least twenty-five days old.The same result is attained by adding 3.5 grams of hydriodic acid t o each litre of the iodine solution ; the reagent itself should be prepared immediately before being required for use by mixing equal volumes of the iodine and mercuric chloride solutions. If these precautions be taken the iodine numbers obtained by the Hub1 method mill agree closely with those obtained by the Wys method. The results obtained by either method are not influenced by variations in temperature varjing from 10’ to 2 5 O and for most oils one hour’s contact is sufficient in the case of Hiibl’s reagent; a much shorter time suffices with Wys’ reagent.The difference in the results yielded by the two methods does not exceed 1% for oils having a n iodine number below 130. I n the case of linseed oil the absorption of iodine is only complete after eighteen hours’ coutact with Hiibl’s reagent or two hours with Wys’ reagent. w. P. s. Relation between the Saponification Iodine and Refracto- meter N u m b e r s of Fats and Oils. OTTO RICHTER (iMiZch. Zentr. 1913 42 7-12).-1t is shown t h a t there is a definite relation betweeu the saponification number and the refractive index of trigly- cerides of t,he stearic acid series ; from tributyrin to trimelissin the refractive index increases by 0.001 for each increase of 28.02 (C,H,) in the molecular weight.I n the case of unsaturated glycerides the refractive index increases by 0.0112 for every two atoms of iodine absorbed by the glyceride molecule. Formuh are given for calculating the refractive index the saponification number or the iodine number of a glyceride when ’the othir two constants have been estimated. w. P. S. Detection of Earthnut Oil in Olive Oil by the Franz-Adler Test. HEINRICH LUERS (Zeitsch. N a h ~ . Genussnz. 19 12 24 683-684). -Samples of olive oil which contain a large proportion of rnyristin yield a turbidity with the Franz-Adler test ( A . 19 12 ii 8 I5) indicating the presence of earthrlut oil. The turbidity is due however not to arachidic acid derived from the latter oil but t o the formation of a potassium hydrogen salt of myristic acid ( K0,,W,,02,C14H,,0,).The production and precipitation of this salt in the test niay be prevented by adding 3 drops of glacial acetic acid (in addition t o the prescribed A New Colorimetric Method for the Determination of Epinephrine (Adrenaline). OTTO FOLIN W. B. CANNON and w. UEN~S (J. Biol. Chem. 1913 13 477-484).-Adrenaline like uric acid gives a colour reaction with phosphotungdtic acid and the quantitative results are almost identical with those obtained by physiological (blood-pressure) methods. quantity of dilute acetic acid) to the saponified oil. w. P. s. W. D. H.ii. 164 ABSTRACTS OF CHEMICAL PAPERS. Detection of Histidine. KATSUJI INOUYE (Zeitsch physiol.Chem. 19 13 83 79-82).-Histidine in aqueous solution reacts with diazo- benzenesulphonic acid in presence of excess of sodium carbonate to give a dark red coloration which is definite in great dilution. Histidine reacts also when combined in the protein molecule. Tyrosine however gives a similar coloration (compare Ysuly A .,- 1904 i 1068). Benzoylhistidine still shows the coloration ; dibenzoyl tyrosine no longer gives it or does benxoylhistidine when fixed in the protein molecule. It is thus possible to distinguish between free and fixed histidine. It is necessary to allow the excess of benzoyl chloride with which the protein or its decomposition product is treated to decompose before adding the diazobenzenesulphonic acid. LBON GRIMBERT and M. LAUDET (Compt.Tend. 1912 155 974-976).-A rapid and moderately accurate method of estimating cholesterol phosphorus- containing lipoids fatty acids and neutral fats in a small sample of blood-serum. The serum (20 c.c.) is treated with excess of alcohol and after twelve hours’ contact it is extracted with a further quantity of alcohol. The combined extract is concentrated by distillation the residue treated with ether and filtered the filtrate on evaporation leaving a residue which contains the constituents to be estimated. The residue is saponified with N/5-alcoholic potassium hydroxide the alcohol re- moved the liquid acidified with nitric acid and extracted with ether the ethereal extract on evaporation giving the cholesterol and a mixture of fatty acids. I n this mixture the cholesterol is estimated by Kumagawa’s method (compare A 1908 ii 331) the acids being obtained by difference The aqueous layer is evaporated to dryness ’ and calcined the residue treated with nitric acid filtered and the phosphorus estimated in the filtrate as ammonium yhosphomoly bdate according to Villier’s method (compare A. 1893 ii 438). The weight of the precipitate divided by 2.3 gives the weight of phosphorus- containing lipoids expressed as lecithin distearate. W. G. Mett’s Method for Estimating Pepsin and the Optimal Conditions of Peptic Activity. JOHANNE CHRISTIANSEN (Biochem. Zeitsch. 19 12 46 257-287).-Satisfactory results were obtained by Mett’s method when a soft coagulum of egg-white was used. With weak acids the amount digested is nearly proportional to the time. Hydrochloric acid has a deleterious action on pepsin and on this account when higher concentrations of acid are used the amount digested is not proportional t o the time. Schutz’s law y2= kx where y = length cd column of egg-white digested x = the amount of pepsin does not hold on account of the diffusion and the injurious action of acid on the ferment. For concentrations of acid between 3/10 and 3 / 2 0 the relation between the amount digested and quantityof pepsin can be approximately expressed by the formula y2 45 = kx. The acidity for optimal activity of human pepsin is less than that of animal pepsins. S. B. S. E. F. A. EstimQtion of Lipoids in Blood-Serum.

ISSN:0368-1769    

DOI:10.1039/CA9130405146

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

i. 153 Organic Chemistry. Puriflcation of Saturated Hydrocarbons by means of Potass- ium Permanganate. NICOLAI M. KISHNER (J. Rum. Phys. Chem. SOC. 19 12 44 1748-1 753).-Saturated hydrocarbons when prepared by the reduction of their halogen derivatives are usually contaminated with unsaturated hydrocarbons and the same is the case with trimethyl- enic hydrocarbons prepared by Gustavson's method. The removal of these impurities is an easy matter when the saturated hydrocarbons are stable to concentrated sulphuric acid or to fuming nitric acid; but in some cases the unsaturated hydrocarbons are converted into saturated ones by these reagents and in certain others the carbon- atom skeleton undergoes isomerisation. The author has investigated the efficacy of potassium permnnganate as a means of purification in these exceptional instances.The results show that the complete removal of small admixtures of the unsaturated compounds in this way is very difficult and is accompanied by the loss of much of the saturated hydrocarbons. As the concentration of the unsaturated hydrocarbon in the mixture diminishes its rate of oxida- tion decreases until finally it may become less than that a t which the saturated compound oxidises ; thus a mixture containing 15 parts of menthane and 5 parts of menthene is converted into one containing 11.5 and 2.5 parts respectively by one oxidation these amounts becoming 7-2 and 0.8 and 3.7 and 0.3 after successive oxidations. Somewhat similar results are obtained with mixtures of menthane and limonene. T. H.P. Fractional Distillation of Coal. L6o VIGNON (Compt. rend. 1912 155 1514-1551'7).-The author has distilled various samples of coal at successive temperatures of 400° 600° 850° 1000° and 1200° and analysed the gaseous mixtures evolved at these tempera- tures. The results show (1) that the unsaturated hydrocarbons (acetylene ethylene etc.) almost all pass over below 600' and dis- appear entirely at higher temperatures ; (2) methane and its homologues are very abundant (60430% of total gas) up to 800° after which they decrease rapidly with rise in temperature; (3) from 800-1000° hydrogen predominates b u t in its turn diminishes above 1000°; (4) very high temperatures favour the formation of carbon monoxide. Rise in distillation temperature produces an increase in the total volume of gas evolved but a diminution in its calorific power.W. G. A New Method for Determining the Position of the Double Bond. JOH. JEGOROV (J. pr. Chem. 1912 [ii] 86 521-539).-The method consists in combining the unsaturated compound with nitrogen peroxide and heating the resulting additive compound with concen- trated hydrochloric acid whereby the molecule becomes roptured at the position originally occupied by the double linking with the forma- VOL. CIV. rni. 154 ABSTRACTS OF CHEMICAL PAPERS tion of two carboxylic acids R*CH:CHRI-+ NO*OeCHR*CHR1*N02 or NO,*CHR*CHR**O*NO -+ R*C02H + R1*C02H. The transformation of a nitrite into a carboxylic acid has been investigated in the case of amyl nitrite which under the influence of hydrochloric acid yields amyl alcohol and an ester,.presumably amyl vnlerate the valeric acid being formed by the oxidising action of the nitrite on the amyl alcohol. When heated with water a t 160-170° the light yellow oily additive compound of oleic acid and nitrogen peroxide yields pelargonic acid o-nitrononane azelaic acid and 8-nitrononoic acid. The nitro- compounds could not be isolated in a state of purity and therefore were identified by reducing them to the corresponding amino- compounds. 8-Aminononoic acid NH,*CH2* [CH2I7-CO2H was isolated in the form of its ptatinichloride from the above mixture by distillation in steam and reduction of the residual nitrononoic and azelaic acids with tin and hydrochloric acid. Nonylamine is a viscid liquid and forms a hydrochloride which becomes black when heated without showing a definite m.p.; the platinichloride 2CQHlQ*NH,,H,PtCI crystallises in golden-yellow needles. When heated with concentrated hydrochloric acid the additive compound of oleic acid and nitrogen peroxide yields pelargonic and azelaic acids together with hydroxylamine. From these results the conclusion is drawn that the additive com- pound consists of a mixture of two isomerides (I) and (II) which when heated with water undergo the transformations shown in the following scheme (I.) 2C,H17*CH(N0,)*CH(O*NO)*C7H,,*C02H -+ H20 + N20 + 2C,H17*CH(N02)*CO*C7Hl,*C02H --f C,H,,*NO2 + C7H1,(CO,H),. (11.) 2C,Hl7*CH(O*NO)*CH(NO2)*C7H1,*CO2H -+ H,O + N20 + CSH,~~CO~U~(N02)~C7Hl,~C02H -+ C,H,7*C02H + N0,*C,Hl,*C02H. The action of hydrochloric acid on 8-nitrononoic acid gives rise to azelaic acid N02*CH2*[ CH2I7*CO,H -+ In a similar manner nitrononane yields pelargonic acid.The above method has been applied to the determination of the position of the double linking in a number of unsaturated compounds. I n all cases the unsaturated compound was allowed to combine with nitrogen pepoxide in light petroleum solution at a low temperature and the resulting oily additive compounds were heated with concen- trated hydrochloric acid at 130-140'. isoOleic acid decom- poses into octoic and sebacic acids corresponding with the structure CH2Me*[CH,],*CH:CHfCHz]8*C0,H ; erucic acid into nonoic and brassylic acids. From the behaviour of the hexylene prepared from mannitol which yielded formic acetic butyric and valeric acids the author draws the conclusion t h a t the hydrocarbon consists of a mixture of two isomerides CHMeX HPra and CH2:CH*CH2Pra.HZO HO*N :C(OH)*[CH2]7*CO,H -+ NH,*OH + C7Hl,(CO,H)2. Undecenoic acid gave sebacic and formic acids.ORGANIC CHEMISTRY. i. 155 Methoxy- and ethoxy-undecenoic acids obtained by the action of alcoholic alkali hydroxides on the dibromide of undecenoic acid gave results in agreement with the structure OMe*CH2*[CH,I7*CH:CH*CO2H. The unsaturated acids from linseed oil were also examined and found to consist of a mixture of the two following compounds CH Et:CH*CH,*CH CH*CH,*CH:CH*[CHJ7*C0,H. C H,* [CH,],*CH:CH*CH,*UH:CH*[CH2]7*C02H. F. B. The Theory of the Asymmetric Carbon A t o m and Pasteur's Principle. ERNST MOHH (J.pr. Chern. 1912 [ii] 87 91-95).-A theoretical paper in which the author shows that contrary to his previous views (A. 1904 i l) a compound of the formula C(dR),(ZR) where dR and ZR represent structurally identical univalent groups of ennntiomorphous configuration does not contain an asymmetric carbon atom and is therefore incapable of existing in two enantiornorphous forms. F. B. The Melting Point of Ethylene Dibromide. EUGEN VON BIRQN (Zeitsch. physikal. Chem. 1913 81 590).-Moles (A. 1912 ii 533) states tbat ethylene dibromide has m. p. 9.9754 Biron has Ehown that when purified by repeated fractional crystallisation it has m. p. 10*012' and DY 2.1804 (J. Russ. Phys. Chern. Soc. 1908 40 1609). He points out that the work must be carried out in the absence of light.EDMUND 0. VON LIPPMANN (Chern. Zeit. 1913,37,1-2. Compare A 1912 i 824).-The author combats the statement attributed to Davidsohn (Mitt. Ges. Med. Naturwiss. 1912 12 102) that the Celts first submitted fermented liquors to distillation and that the knowledge of the process passed from them to other nations. CHARLES BASEERVILLE (J. Amer. Chem. Xoc. 1913 35 93-96).-Sabatier and Mailhe (A. 1910 i 294) have shown that several metallic oxides including t h a t of thorium exert a catalytic action on alcohols between 300' and 350O. I n the case of ethyl alcohol the action appears to consist almost entirely of dehydration with formation of ethylene but at a lower temperature the dehydration is said to be capable of limitation to the production of ether. Experiments are described in which alcohol vapour was passed over pure thorium oxide a t about 250" but although the conditions specified by Sabatier and Mailhe were carefully observed little or no ether was obtained.E. G. Esters and Amides of the Phosphoric Acids. IV. Reaction between Esters of Metaphosphoric Acid and Uni- and Multi- valent Alcohols. Synthesis of Glycero-mono- and -di- phosphoric Acid. Preparation of Pure Silver Metaphosphate. KURT LANGHELD F. OPPMANN and E. MEYER (Ber. 1912 45 3753-3760).-1n part polemical (compare Grun and Kade this vol. J. F. S. The History of Distillation a n d of Alcohol. D. F. T. Ethyl Ether by Catalysis. m 2i 156 ABSTRACTS OF CHEMICAL PAPERS. i 159). benzyl alcohol the following three products are formed When ethyl metaphosphate reacts with ethyl alcohol and PO(OEt),*O*C,H7 PO(OH),*0*C7H7 OEt*PO(O*C,H,)*OH. The mono- and tri-esters are obtained in molecular proportions. The same result is obtained with glycerol in which case the excess prevents the determination of the relative proportions of the esters.Barium glycerophosphate is obtained in stellar aggregates of small platelets containing a molecule of water which is slowly removed on drying in a vacuum. On exposure of the anhydrous substance &H,O is absorbed quickly and the second 4H,O only slowly. The solubility in water a t 220' is 8*4% and approaches that of the natural product. Bccrium glycerodiphosphate 2H,O crystallises well. To prepare pure silver metaphosphate ( AgPO,),,H,O sodium ammo- nium phosphate is converted into metaphosphate by cautious heat- ing in a vacuum at 320'.About half the product is soluble in water from which it is precipitated in crystalline form on the addition of alcohol. This product 2NaPO,,H,O reacts with silver nitrate. Silver metaphosphate crystallises in large ocbahedrn. The Ctlycerotriphosphoric Acid of Contardi. PAUL CARRB (Compt. rend. 1912,155,1520-1521").-A reply to Contardi (compare A. 1912 i 743) in which the author maintains that the esterification of 1 mol. of glycerol with 3 mols. of phosphoric acid gives glycero- diphosphoric acid C,H,(PO,H,),*OH glycerophosphoric acid and a di-eeter of the form P0,R2H about 50% of the phosphoric acid remain- ing unaltered and no glycerotriphosphoric acid being formed. H e further maintains his views already expressed (compare A .1904 i 133 215 ; 1905 i 184) that on heating an equimolecular mixture of glycerol and phosphoric acid in a vacuum the mixture is transformed quantitatively into the normal tri-ester. Crystalline Forms of Salts of Ethanedisulphonic Acid. I(. BLEICHER (Zeitsch. Kryst. Min. 1912 51 502-520).-Detailed crystallographic constants are given for the following salts of ethane- disulphonic acid Sodium (2H,O) monoclinic ; a b :c=0*7893 1 0.4624; ,B=9l034'. /3= 111'7'. 126O18'. 120'21'. a b c = 0.746'7 1 0.5563. Disodium ammonium Na,(NH,),(C2H,S,0,)3 monoclinic ; a b c = 1.5637 1 0.5906 ; @ = 101'17'. Lithium potassium ( lH,O) mono- clinic ; a b c = 1.2401 1 1.2753 ; @= 104'41'. Lithium ammonium monoclinic ; a b c = 0.7627 1 0.7799 ; @ = 96'46'. Barium rhombic ; Q b c = 0.7678 1 09062.Barium (H,O) rhombic ; a 6 c = 0.93'74 1 0.4051. Strontium (H,O) monoclinic; a 6 c = 0.5347 1 0.0641 ; p = 101'3'. a = 90°1' p = 101°56' y = 100O54'. E. F. A. W. G. Lithium (2H,O) monoclinic; a b c = 1.5717 1 2,5939 ; Potassium monoclinic; a b c = 1.2594 1 5816 ; @= Ammonium monoclinic; a b c=1.1647 1 0.6959; p= Potassium sodium (2H,O) rhombic ; Cadmium (2H,O) triclinic ; a b c = 1,7421 1 1.0515 ; Zinc (3H,O) triclinic ; a b c = * and Bull. Xoe. chim. 1913 [iv] 13 66-69,ORGANIC CHEMISTRY. i. 157 0.5718 1 0.7813 ; a= 94OO' p= 110'28' y = 90O30'. Magnesium (4H20) triclinic ; a b c = 0.6546 1 0.4066 ; a = 96'1 8' p= 102'9' y = 94O14'. Copper (4H20) triclinic ; a b c = 0.6527 1 0.4350 ; a = 95'1 5' p = 96"39' y = 94'32'.L. J. S. Phenomenon of Double Melting for Fats. ANDREAS SMITS and S. C. BOKHORST (Proc. K. Akad. Wetensch. Amsterdam 1912 15 681-683).-According to Guth (A. 1903 i 225) tristearin melts a t 71*5O but if allowed to solidify in a capillary tube it melts at 55O solidifies again and melts a second time at 71.5". I n view of the improbable explanation of these results the authors have made a further examination of the behaviour of the substance and find that the above phenomena are due to the existence of two crystalline modifications. Of these the metastable form appears most readily. If however the liquid is kept for some time at a temperature between the two melting points the stable form crystallises out although very When the metastable form is heated it melts a t 54*5' and when the temperature is then raised to 63' the stable form is deposited.The stable unary melting point is 70%'. It is probable that tho double melting phenomena observed for other fat@ are to be explained in the same way. slowly. H. M. D. Anomalies in t h e Consistency and Melting Points of Fats. ADOLF GRUN (Bey. 1912 45 3691-3701j.-It has already been observed that glycerides can exist in two modifications (Kast A. 1906 i 922; Griin and Schacht A. 1907 i 462). To this phenomenon is attributable the variation in the m. p. recorded for certain fafs with the age or method of preparation of the sample. The present investigation endeavours. to extend the present limited knowledge of this phenomenon.[With A. Cus~o~~s].-ay-Dilaurin obtained from uy-dichlorhydrin and potaseium laurate is a mixture of two modifications ; the produch of higher m. p. 57" acetyl derivative m. p. 34' or after one year 32O is obtained in better yield the lower the reaction temperature (1 40-150°) whilst the other modification m. p. 40° preponderates when the temperature of formation is somewhat higher ( 170-180') ; the latter modification very easily remains in a supercooled condition. Both forms on keeping finally attain a m. p. 45' which is also the temperature observed for a mixed m. p. It is probable that the two substances are structurally iden tical. When the two forms of ay-dilaurin are treated with laurpl chloride at loo' two modifications of trilanrin are obtained one m.p. 45' the other forming soft needles which melt in the hand. The former obtained from the less fusibltr dilaurin is identical with natural trilaurin; the latter obtained from the more fusible dilaurin re- sembles its parent substance in having in benzene a molecular weight only one-half that expected from the formula ; the less fusible di- and tri-laurins are of normal molecular weight. uy-Dibenzoin OBz*CH,*CH(OH)*CH,*OBz by warming with glycerol and sulphuric acid can be converted into a modificationi. 158 ABSTRACTS OF CEEMICAL PAPERS. which remains oily at the ordinary temperature ; the molecular weight of the substance in benzene solution is however approximately normal. ap-Dibenzoin obtained from anhydrous potassium benzoate and ap-dibromohydrin and aLo in n purer condition by the use of silver benzoate is also a viscous uncrystallisable oil.I n an addendum it is remarked that lack of recognition of the above peculiarities of glycerides may lead to considerable errors as for example the reported formation of ap-dilaurin from ay-dichlorohydrin (van Eldik Thieme A 1912 i 333). The Synthesis of Fats. DAVID HOLDE (Ber. 1912 45 3701-3702. Compare Kremann and Schoulz A. 1912 ii 1152).- The author draws attention to the manner in which the results of Kremann and Schoulz (Zoc. cit.) support his views ( A 1903 i 140) that the stearic and palmitic acids in olive oil must be present i n the form of '' mixed " glycerides and not as tripalmitin and tristearin. D. F. T. D. F. T. Diglyceride-phosphoric Acids. ADOLF GRUN and FRITZ KADE (Bey.1912 45 3358-3367).-When phosphoric oxide acts on distearin a t temperatures ahove looo or in the absenceof moisture blackening takes place. When the requisite amount of water is added esters of pyrophosphoric acid or primwy orthophosphoric acid esters are obtained. The former decompose into phosphoric acid and the ortho-acid esters which are transformed in turn into secondary and tertiary esters and finally into the st ible form pentadistearin phosphate. In addition the reaction product contains free phosphoric acid and di- stearin. The changes are expressed by the scheme PO(OR)(OH)*O*PO(OH) -+ PO(OR)(OH) -+ PO(OR),(OH) -+ PO( OR) -+ P(OR),. ap-Distearin pyrophosphate C3H,(O~CO*C17H3,),*0.P,H,0 is a colourless crystalline fatty substance m.p. about 65' ; primary ap-distearin orthophosphate forms colourless somewhat lustrous matted crystals m. p. 71O. The secondary ester yields soft crystals m. p. about 67"; i t forms a waxy,.pde yellow silver salt with silver acetate and a potussium salt separating in colourless platelets. The tertiary ester is very similar to the other esters but the solution is neutral. Pentadistearin phosphate P[O* C H5( O*CO*C17H35)2]5 forms colourless brittle crystals m. p. 70°. All the compounds described are very ill-defined. E. F. A. Alleged S y n t h e s i s of Lecithins. ADOLF GRUN and FRITZ KADE (Ber. 1912 45 3367-3376).-To effect the synthesis of lecithins it is proposed to allow the components of choline to act in turn on diglyceride-phosphoric acid. Ethylene glycol and phosphoric oxide acting on distearin produce almost quantitatively distearin ethylene- glycol orthophosphate C,H,( 0*CO*C17H3s)2*0*P0(OH)~O*C2H4*OH. When ethylene chlorohydrin is used the reaction takes place in two directions the glycol ester as well as the P-chloroethyl ester C,H,(O~CO~C17H3,),~O* PO( OH) O*C,H,CJ,ORQANIC CHEMISTRY.i. 159 being formed. This compound reacts with trimethylamine forming tho trimethylammonium salt C,H,( O*CO*C17H,,),*O*PO(O* C,H,Cl)*O*NHMe and on more energetic action of excess of trimethylamine this under- goes rearrangement to lecithin hydrochloride C,H,( O*CO*C17H35)2*O*PO( 0. C,H,*NMe,Cl)*OK. The final product obtained was a mixture of both compounds together with an intermediate product. The P-chloroethyl ester from a@-distearinphosphoric acid forms colour- less crystals which sinter at 60° m.p. 65-66'; the isomeric ay-distearin compound is very similar. The ethyleneglycol ester of aP-distearinpho8phoric acid has m. p. 65-70' and is a typically fatty substance. The trimethyZamrnoniuna salt forms tough crystals which sinter at 60° m. p. 69'. The synthetic lecithin hydrochloride (ap-distearincholinephosphoric acid ester) product is a soft waxy compound which sinters at 60' to a clear viscid oil which becomes mobile at 64-65O and opaque at 74'. E. F. A. It reacts faintly acid. Preparation of Mixed UP-Diglycerides. ADOLF G R ~ N and B. SCHREYER (Ber. 1912 45 3420-3426).-Glycerol-a-monochloro- hydrin is converted by the action of myristoyl chloride into the ester CH,Cl*CH( OH). CH 0- CO C1,H27 which reacts with stearyl chloride to form myristostearochlorohydrin CH,Cl*CH(O*CO- CI7Ha8)* OH,( 0.CO-C 3H27). On treatment with silver nitrite the chlorine atom is replaced by bydroxyl and a-myristo-P-stearin obtained. a-Myristo-y-chlorohydrin is a yellow mobile oil; it is converted by silver nitrite into a-monomyristin m. p. 68'. p-Myristo-ay-dicldorohydrin forms colourless transpareot glass-like crystals m. p. 20'. The P-monomyristin obtained from it gives colour- less lustrous crystalline plates m. p. 69'. a-h?yristo-@-stearo-y-chlorohyd&n forms colourless crystals m. p. 31'. a-Myristo-P-stearin crystallises in slender platelets m. p. 58'. E. F. A. Alcoholysis and the Composition of Cocoanut Oil. GEORGE D. ELSDON (Analyst 1913 38 8-ll).-Coco~tnut oil when boiled in a reflux apparatus with absolute methyl alcohol containing 2% of hydrogen chloride for about twenty hours deposits on cooling a large quantity of methyl esters ; the remainder may be obtained by diluting the alcoholic solution with water and agitating with ether When the mixture of the esters is submitted to distillation a t 14 mm.pressure seven fractions may be isolated (b. p. 63-76' 204-21 6"). From the results obtained on weighing refractionating and further identification of the fractions the author considers that the composition of the fatty acids and of cocoanut oil may be represented approximately 76-looo 100-128' 128-153' 153-182" 182-204",i. 160 ABSTRACTS OF CHEMICAL PAPERS by hexoic acid 2% octoic acid 9% decoic acid lo% lauric acid 45% myristic acid 20% palmitic acid 7% stearic acid 5% and oleic acid 2%.L. DE K. Preparation of Ethyl Acrylate. FREDERICK G. TROBRIDGE (Proc. Univ. Durham Phil. Soc. 1912 4 223-224).-Ethyl acrylate is obt,ained in 80% yield by the action of the zinc-copper couple on ethyl a@-dibromopropionate in ethereal solution. Action of Zinc on a Mixture of Pinacolin and Ethyl a-Bromopropionate. NICOLAI N. BUNGE (J. Buss. Phys. Chem. Xoc. 1912 44 1776-1788).-This incomplete investigation is published owing to the appearance of Umnova's paper (this vol. i 7) and is a continuation of work begun by Lazarkevitsch and proceeded with by Reformatski and Agafonov. The products of the action of zinc on a mixture of pinacolin (1 mol.) and ethyl bromopropionate (1 mol.) vary with the conditions of the reaction.If the latter takes place a t the ordinary temperature and the viscous mass obtained after tbree or four days is decomposed with water a yield of 30% of ethyl /3-hydroxy-apyy-tetramethylvalerate is obtained. A t 50-70° however this ester is accompanied by (1) a lactone C9H,,0 which may also be obtained by boiling either the ester or the corresponding acid for some hours with 20% sulphuric acid solution ; (2) ethyl propionylpropionate which yields diethyl ketone on hydrolysis. F. B. PHy droxy - a /3 y y t e tramethy Zua Zeric acid CMe,*CMe(OH)*CHMe*CO,H forms large colourless crystals (? rhombohedra) m. p. 109.5-1 10*5O and has the normal molecular weight in freezing acetic acid. I t s ethyl ester C,,H,,O is a colourless viscous liquid b.p. 117'/20 mm. 3 0.96034 ng 1.44039 and exhibits normal cryoscopic behaviour in benzene. The potassium barium calcium ( + H20) and silver salts were analvsed. The lactone CMe,*CH<CHo-o CHMe.70 Or CMe2<CMe,-o CHMe.70 forms large crystals m. p. 65-66' and eibibits the normal nidecular weight in freezing acetic acid; when boiled with water it yields n neutral solution and does not combine with it. T. H I?. ARRIGO MAZZUCCHELLI and OLGA GRECO D'ALCEO (Atti R. Accad. Lincei 1912 [v] 21 ii 620-626).-The paper deals withcomplex uranium salts. Additive products are practically not formed in the following cases mercuric cyanate carbamide or thiocarbamide with uranyl nitrate ; carbamide or hexamethy lenediamine with uranyl oxalate ; hexamethylenediamine aniline or pyridine with the complex sodium uranyl pyrophosphate malonate or succinate.Attempts to prepare complex salts from aminoacetic aspartic aminobenzoic and sulphanilic acids were uneuccessf ul. was prepared but i t is not a complex derivative. The aminobenxoate U0,(C7H,0,N),,4H20 was obtained and also the basic su@hatdate U0,*C6H,0,NS,H,0. The uranous salts also appear to have little tendency to form aminic Uranium Salts. The aspartate UO,(C,H,O,N) 3H,O,.ORGANIC CHEMISTRY. i. 161 complexes Diurano-oxalic acid gives ordinary salts with pyridine [ 2 U( C,O,),* C,O,( C H,N) ,] and with aniline [ 2U ( C204) 2 * C,O,( C,H7N),]. Indications mere obtained of the formation of a complex salt in t h e case of uranous aminoacetate. The basic succinate UO*C4H,0,,2H,O was prepared and also the analogous malonate UO*C,H204,6H,0.When a solution of sodium uranylmalonate with an excess of malonic acid is electrolytically reduced the anodic liquid being an acid solution of sodium malonate separated from it by a parchment dark green dichroic crystals of the complex salt U( C3H,0,),Na2,2H,0 are obtained on subsequent concentration of the cathodic liquid in a vacuum. A basic uranou8 phthalate UO:C,H40,,3H,0 and uranoult trkhloroucetatte UO;C20,C1,),,3H20 were also prepared. R. V. S. Molecular Rearrangements in the Camphor Series. XI. Derivatives of isoCamphoric Acid isoAminocamphonanic Acid and Its Decomposition Products. WILLIAM A. NOYES and LEONIDAS R. LITTLETON (J. Amer. Chern. Soc. 1913 35 75-81). -It has been shown in earlier papers (A 1895 i 295 ; 1909 i 133) that aminocamphonanic acid (aminolauronic acid) is decomposed by nitrous acid with formation of lauronolic acid laurolene and iso- campholactone.The present work was undertaken with the object of preparing isoaminocamphonanic acid and studying its behaviour with nitrous acid. see. -Methyl isocamphorate (a-methyl isocamp horate) C0,H*C,H,,*C02Me has m. p. 89*5-90' and [a]= -58.4' in 10% alcoholic solution (com- pare Noyes and Knight A 1911 i 111). The tert.-methyl ester prepared by boiling a solution of the dimethyl ester in methyl alcohol with sodium hydroxide was obtained as a very yiscous oil; it has [a] - 53.1' in 10% alcohol solution. The terms "secondary " and '* tertiary " are used here to indicate the carboxyl containing the methyl group.Methyl sec.-isocamphoramate CO,Me*C,H,,*CO*N H,,.m. p. 126-127O prepared from the set.-methyl ester by converting it into the chloride and treating the latter with ammonia crystallises in rectangular plates and has [a] -54.2' in 10% solution in methyl alcohol. When this ester is warmed with sodium hypobromite solution it yields methyl isoaminocamphonanate b. p. 239' (corr.) m. p. 230' (decornp.) which forms white crystals ; the hydrochlovide CO,Me*C,H,,*N H,,HCl,H,O has [aID - 32.03' in 10% solution in water and - 42.03' in 10% solution in alcohol. If this hydrochloride is warmed with solution of sodium hydroxide and subsequently acidified with hydrochloric acid the hydrochlo ide of isoaminocamphonanic acid ( ? H 2 - C H 2 > ~ ~ e * ~ ~ ~ ~ ~ ~ NH,*CH*CMe2 m.p. 320' (corr.) is obtained which is decomposed by nitrous acid with formation of cis-camphonolsctone together with small quantities of an unsaturated acid b. p. 150°/60 mm. (decornp.) and a saturated acid which decomposes at 160'. E. G.i. 162 ABSTRACTS OF CHEMICAL PAPERS New Methods of Preparation of Camphonenic (y-Lauro- nolic) Acid and the Relation of the Latter to Laurolenic (Lauronolic) Acid. JULIUS BREDT [and in part PAUL LEVY and S. LINK] (J. p. Chcm. 1913 [ii] 8'7 I-ll).-The first part of this paper is mainly a summary of the authors' views on the constitution and relationships of the lauronolic acids and allied compounds together with suggestions concerning their nomenclature (compare A. 1911 i 417). When submitted to slow distillation dehydrocamphoric acid (A.1902 i 374) loses carbon dioxide yielding y-lauronolic (camphonenic) acid (I). It is accompanied by isodehydrocamphoric anhydride from which it may be separated by distillation i n steam. When purified by the calcium salt C,,H,,O,Ca,H,O and repeatedly csystallised from dilute acetic acid it is obtained in feather-like crystals m. p. 155-156' (compare Noyes A. 1912 i 159). Dehydrocamphoric acid combines with hydrobromic acid yielding a mixture of two stereoisomeric hydrobromides (11) of which the cis-form has m. p. 168-170° and is reduced by zinc and acetic acid t o cis- camphoric acid whilst the cis-trans-modification has m. p. 232O and on reduction yields cis-trans-camphoric acid CH=C*CO,H CHBr CH*CO,H CH(OH)* CH I I I 1 ?Me 1 CMe I 1 CMe2 I C €3 ,*CMe* GO,€€ CH,-C'Me*CO2H CR,-CMe*CO,€€ (1.1 (11.) (111.) When boiled in aqueous solution the sodium salt of the cis-trans- hydrobromide yields as main product a h,ydq*oxy-acid (111) which is accompanied by y-lauronolic acid (10%)).Oxidation of y-lauronolic acid with nitric acid or of its calcium salt with potassium permanganate gives rise to camphoronic acid. F. B. A New Method of P r e p a r a t i o n of Laurolenic (Lauronolic) Acid a n d the Decomposition of Camphanic Acid in an Electric Reflux Heater under Diminished Pressure. JULIUS BREDT and AUGUST AMANN (J. pr. Chern. 1913 [iiJ 8'7 12-26).-Lauronolic acid which the authors now torrns leurolenic acid is obtained by boiling y-camphonanic acid (A. 1912 i 113) for a short time with aqueous sodium carbonate.It is accompanied by' camphonololactone and has also been prepared (1) by distillation of camphanic acid under diminished pressure in a specially constructed electrically heated apparatus a sketch of which is given and (2) by heating chlorocamphoric anhydride (A 1912 i 411) with aqueous sodium carbonate. The m. p. of the acid varies from 5.5-7' to 8*5-10° according to its method of preparation and [aID from 181.3' to 195.29 The calcium salt separates from its aqueous solution a t the ordinary temperature with 2H,O and not 3H,O as stated by Noyes and Burke (A 1912 i 159). Methods for t h e Preparation of N e u t r a l Solutions of Ammonium Citrate. JAMES M. BELL and CHARLES F. COWELL (J. Amer. Chem. Xoc. 1913 35 49-54).-The methods at present F.B.ORGANIC CHEMISTRY. i. 163 employed for the preparation of neutral solutions of ammonium citrate are not satisfactory and two new methods have therefore been devised. I n one of these methods the excess of ammonia is estimated by extracting tha solution with chloroform,.and titrating the chloroform with 0.1 N-hydrochloric acid in presence of methyl-red as indicator. I n the other method the rise of temperature due to the heat of neutralisation is observed as the citric acid solution is titrated with ammonia the end-point being at the break in the heating curve. Both these methods are considered to be simpler than that involving the determination of the conductivity of solutions a t constant temperature. KARL FRIES and H. MENUEL (Be?. 19 12 45 3408-341 1).-On heating valerolactone with phosphorus penta- sulphide thio- y-valerolactone CH&le<S -bo is obtained as a colourless oil of pleasant aromatic odour b.p. 94-95"/20 mm. It is readily hydrolysed by a1 kali hydroxides to y-mercaptovaleric acid which is reconverted into the thiolactone on treatment with mineral acids. A further product oE the action of the pentasulphide is dithio- y-valerolactone CHMe< an orange-coloured viscid oil of un- pleasant odour. Condensing agents such as sodium methoxide convert it very readily into trithio-di- y-valerolactone E. G. Thio- y-valerolact one. CH,*CH CH,*YH s-cs c H p p s - - >CHMe S-C=ZC*CH CHMe< which crybtallises in bunches of large red piisms m. p. 77". E. E. A. Maleindialdehyde. ALFRED WOHL and BRUNO MYLO (Ber.1912 45 1746-1 756)- Maleindialdehyde diethylacetal an intermediate product i n the preparation of tartardialdehyde (A. 1912 i 162) has been bydrolysed by means of dilute sulphuric acid and the maleindi- aldehyde has been characterised. The most striking property of this compound is its yellow colour which is more intense than that of diacetyl and may be accounted for by the grouping together of con- jugated double bonds and the conveying of the influence of one carbonyl group to the other by a n ethylenic linking. Oxidation by silver carbonate gives maleic and also fumaric acids and since the original acetal yields a tartardialdehyde acetal of the type of meso- tartaric acid ( i b i d ) i t is suggested that this is the real maleindi- aldehyde whereas that obtained by Marquis from nitrosuccinaldehyde monoacetin (A.1905 i 224) is fumardialdehyde especially as the nitrous acid which is formed at the same time has a great tendency to convert maleic into fumaric acid. For the preparation of maZeindialdeh$de C HO CH CH CHO 35 grams of the acetal are shaken with 150 C.C. of N/lO-sulphuric acid and the faintly yellow pungent smelling solution is exactly neutralised with barium hydroxide. After removing the barium sulphate by centrifugation the solution is evaporated at 40° in a vacuum with ai. 164 ABSTRACTS OF CHEMECAL PAPERS. fractionating column which however does not prevent the loss of some aldehyde since i t is volatile in steam and the residue is extracted with chloroform and dried. The extract is evaporated in the same way and the syrupy residue is maintained at 105-115'/9 mm.when the polymeric substances slowly decompose and the aldehyde distils over. The distillate is collected in a Claisen flask in a freezing mixture and redistilled from a bath already heated to 75' when the mobile yellow pungent-smelling aIdehyde boils at 56-59'/9*5 mm. It dissolves in water and organic solvents and probably forms hydrates and alcoholates since yellow aqueous or alcoholic solutions soon become colourlees. It is only slowly affected by oxygen or bromine water but it immediately reduces permanganate or ammoniacal silver oxide. At the ordinary temperature it very quickly changes t o a syrup with less intense colour and odour and it is then only slightly soluble in ether benzene or warm water.From the aqueous solution an amorphous solid separates out ; probably a syrupy and a solid polymeride exist. Derivatives of the dialdehyde have been prepared by hydrolysing the acetal exactly neutralising with sodium carbonate and precipi- tating with the free base in the cold. The diphenylhydraxone NHPh*N:CH.CH:CH*CH:NDNHPh forms unstable yellow quadratic leaflets from hot alcohol m. p. 198-199' ; Marquis's dihydrazone melts a t 236-237' (ibid.). It gives a reddish-violet compound on oxidation which is similar to but not identical with Marquis's " tetrazone " ; they are probably not tetrazones a t all. The dioxime C,H,O,N forms pure white needles from hot methyl alcohol which decompose with violence a t 150-155' ; Marquis's compound decom- poses at 220' (ibid.).The disemicarbaxone CI/,H,,0,N6 is only very slightly soluble and crystallises best from a large volume of boiling water in slender needles m. p. 246-247' (corr,). J. C. W. The Isomeric Changes of Dextrose Produced by Alkalis. Theory of Catalytic Action. LEONOR MICHAELIS and PETER RONA (Biochem. Zeitsch. 191 2 4'7 447-461).-The changes in dextrose (measured chiefly polarimetrically ) produced by alkalis (in presence of phosphates etc. added t o keep the hydrogen-ion concentration constant during the experiment) is directly proportional to the hydroxyl-ion concentration. The acid nature of dextrose was demonstrated and its dissociation constant was found to be 5*10-15. This was measured by ascertaining the changes in the hydroxyl-ion concentration of sodium hydroxide solutions (measured electrometrically) produced by the addition of dextrose.From these facts the hypothesis is put forward that the '' catalytic " action of the hydroxyl ions increases the number of sugar ions according to theory of mass action and it is the latter which spontsneously undergo isomeric change. Conversion of d-Glucose [Dextrose] into a Methylpentose. EMIL FISCHER and KARL ZACH (Ber. 1912 45 3761-3773).- Triacetglmethylglucoside bromohydrin (Fischer and Armstrong A. 1902 i 263) CH,Br*CH(OAc)*CH*CH(OAc)*CH(OAc)-CH(0Me) l--O--' 9 S. B. S.ORGANIC CHEMISTRY. i. 165 is converted on reduction with acetic acid and zinc dust into a tri- acetyl derivative which on alkaline hydrolysis yields P-methybd-iso- rhamnoside CH,* CH (OH).CH CH (OH) CH( OH) CH* OMe. This is H H O H H hydrolyed by acids to d-isorhamnose CH,. &&&-&c H. 0 H (annexed formula) which is iden tical with the isorhodeose described by b H 1 -O- H i)H/ VotoEek (A+ 191 1 i 354) and obtained by him from purgic acid. Since no asymmetric carbon atom is concerned in the series of reactions no Walden rearrangement is possible and the methylpentose has the same configuration as d-glucose. Accordingly the annexed formula of I-rhamnose (methyl-Z-mannose) which was hitherto uncertain is established. P-Methyl-d-isorhamnoside like /3- CH,-b-C-&-b-CH*OH methplglucoside is hydrolysed by emulsin whereas P-methylxyloside is not attacked. Renewed emphasis is laid on this remarkable difference in view of the similarity in structure of the three glucosides.~riacetyz-methyl-d-isorr'lamnoside crystallises in well-formed colour- less needles m. p. looc (corr.) [u] - 20.22'. P-Methyl-cl-isorhamnoside forms slender colourless needles m. p. 133' (corr.) [u]' - 55*3' which taste bitter. d-isoRhamnose separates in hard colourless crystals in a variety of forms m. p. 139-140' (corr.). The rotation changes from [u] + 73.3' to + 2 9 . 7 O in aqueous solution. d-iso Rhaninosephenylosazone crystallises in yell0 w needles m. p. 185' (corr.) to a dark red liquid (compare VotoGek Zoc. cit.) [u] - 95' in white light; it is the optical antipode of Z-rhamnosephenyl- osazone. d-isoRhamnonolactone has m. p. 15 1-152' (corr.) [u] changing from + 66-88' to + 5.35'. I--()-' -- OHi H 'G-1 H H 6H 6H E. F.A. Properties of Phytin. M. A. EGOROV (Bied. Zentr. 1912 42 66-67 ; from J. Exper. Landw. 1912 12 361).-The phosphoric acid of phytin which is precipitat-ed by acid molybdate solution is not pre- cipitated under ordinary conditions in ammonium citrate solution by magnesia mixture. When phytin is boiled with water for fourteen to sixteen hours it is completely decomposed with production of inositol and inorganic phosphoric acid compounds. The yield of phosphoric acid is about 100%. N. H. J. M. Formation of Humus and Combustible Minerals without the Intervention of Atmospheric Oxygen Micro-organisms Eigh Temperatures or Great Pressure. LOUIS C. MAILLARD (Compt. rend. 1912 155 1554-1556).-A theoretical discussion of work previously described (compare A. 1912 i 13 169). The author has now shown that oxidation does not intervene in any way ini. 166 ABSTRACTS OF CHEMlCAL PAPERS.the generation of carbon dioxide and the production of humic sub- stances by the interaction of sugars and amino-acids. He has further obtained a jet black substance rich in carbon and containing nitrogen which exhibits a remarkable resistance to reagents and he suggests that this reaction should be taken into account in framing theories as to the formation of combustible minerals. W. G. Some Unstable Nitrites Fixed by m e a n s of Organic Bases. 111. GINO SCAGLIARINI (Atti A?. Accad. Lincei 1912 [v] 21 ii 640-643).-The author describes stable compounds of the nitrites of mercury zinc and cadmium with hexamethylenetetramine. The substances were prepared by adding sodium nitrite to a solution of a salt of the metal in the presence of hexamethylenetetramine.The compound 2Hg(N02),,8H 20,3C,H1,N4 forms white crystals with a greenish lustre. The compound Zn(N02),,2H20,C H12N4 forms colourless prismatic crystals as does also the compound Cd(N02)2 2H20,C,H,2N4* R. V. S. Alloxan Anhydride and Its Methyl Derivatives. HEINRICH BILTZ (Ber. 1912 45 3659-3675).-By heating under reduced pressure it is found possible completely to dehydrate alloxan and its methyl and dimethyl derivatives ; the anhydrous substances have an intense yellow colour and can be sublimed unchanged in a vacuum. Alloxan anhydride C,H,O,N obtained by heating the monohydrate for an hour at 210-220' in a vacuum produced by a mercury pump forms yellow rhombic crystals (a b c = 0.9974 1 ; 1.6841) m.p. 256' (decorup.). A partial dehydration of the monohydrate is also effected by recrystallising from acetic acid.' Hethylalloxan anhydride obtained from the monohydrate by similar treatment to the previous but a t 160° separates from acetic acid in leafy crystals (rhornbic system a b c = 0.6766 1 P ) m. p. 154-1 56' (decomp.). Dimethylalloxan anhydride (compare Holleman A. 1897 i 599) could be obtained from the monohydrate by heating in a water-pump vacuum at 210-220'; it crystallises from benzyl cyanide in short yellow columns (rhombic system a b c = 0.6847 1 P ) . [With E. Top~.]-The above anhydrous compounds separated from alcohols containing a little hydrogen chloride in the form of alcobolates which are analogous t o the phenolates described earlier (Boehrinqer & Sohne D.R.P.1898 107720; 1899 113722). Alloxan ethyl NH-CO alcoholate CO<,,-co>C(OH) *OE t prisms ; alloxan methyl alcoholate prisms ; alloxan benxyl akoholate prisms. Methylalloxan ethyl alcoholate tablets. Dimethylalloxan ethyl alcoholate tetragonal prisms rn. p. 95' ; dimethylalloxan methyl alcoholate m. p. circa 90° hexagonal tablets ; dimethylalloxan benxyl alcoholate crystals m. p. 185-188'. All these alcoholates when heated eliminate the molecule of alcohol giving a residue which has approximately the m. p. of the pure anhydride. The following compounds were prepared by crystallisation from aORGANIC CHEMISTRY. i. 167 solution of the anhydride and a phenol with hydrogen chloride in acetic acid ; alloxart phenolate decomposing a t 240-245' ; alloxan p-cresolate decomposing at 228-230' (compare Boehringer & Sohne loc.cit.) ; climethylulloxan p-cresolate hexagonal prisms m. p. 105'. [With J. I(ARTTE.]-A~ aqueous solution of dimethylalloxan di- hydrate when satmrated with sulphur dioxide and evaporated in a vacuum desiccator deposits dimeth~2aEloxan sulphite colourless prisms which decompose at 75'. Methylalloxan sulphite obtained in an analogous uistnner crystallises in prisms with 4H,O. Alloxan sulphite forms rhombic leaflets decomposing near 184'. Alloxan anhydride condenses in alcoholic acetic acid solution with dimethylcarbamide producing 7 9-dimethyluric acid glycol (corn pare Biltz and Krebs A. 1910 i 526) but the product from dimethyl- alloxan anhydride and dime thylcarbamide was allocaff eine (compare Biltz and Krebs Zoc.cit. i 521). Working details are given of the methods found most suitable for the preparation of di- and tetra-methylalloxantin and their conversion into methyl- and dimethyl-alloxsns. D. F. T. The System Ammonium Thiocyanate-Thiocarbamide- Water. ANDREAS SMITS and A. KETTNER (Proc. K. Akud. Wetensch. Amsterdam 19 12 15 683-686).-The investigation of the melting- point diagram of the pseudo-binary system ammonium thiocyanate- thiocarbamide has given results which indicate the existence of a compound NH4CNS,4CS(NH2)2 whereas Atkins and Werner (T. 1912 101 1167) are of the opinion that the compound has the composition NH,CNS,SCS(NH,),. The evidence for the former is supported by the results of the determination of the solubility isotherms a t 25' and the examination of the co-existing solid phases by the residue method.The solubility curves afford a simple explanation of the method of preparation of thiocarbamide from ammonium thiocyanate recommended by Reynolds and Werner (T.? 1903 83 1) which up to the present has not been satisfactorily accounted for. H. M. D. Selective Catalysis of Dehydrogenation. NICOLAI D. ZELINSKI (Be?.. 19 12 46 3678-36S3).-The catalytic dehydrogenation of cyclohexane compounds by palladium or platinum at 300' and the inactivity of these metals towards cyclopentane compounds under the same conditions can be applied to the separation of cyclohexane and cyclopen tane hydrocarbons. [With (Frl.) A.HERZENSTEIN.]-After a mixture of equal volumes of methylcyclopentane and cyclohexane has been thrice submitted to the action of platinum black at 300° no further liberation of hydrogen occurs and the hydrogen collected amounts to more than 90% of the theoretical. After removal of the benzene from the resu1t)ant hydrocarbon mixture by treatment at the ordinary temperature with sulphuric acid (two volumes of acid D 1.84 mixed with one volume of fuming acid containing 7% of anhydride) the residual liquid was pure me thy lcyclopen tane.i. 168 ABSTRACTS OF CHEMlCAL PAPERS. cycloHeptane resembles cyczopentane (Zelinski A. 191 1 i 958) in resisting the above catalytic dehydrogenation. A specimen of naphtha b. p. 102-104O D18 0.7647 n18 i.4215 from Baku petroleum by the above treatment gave a liquid which could be separated by distillation into two fractions.The less volatile fraction b. p. 105-107' contained much toluene whilst the other fraction b. p. 104-1 059 after one more treatment with platinum black followed by the removal of any aromatic hydrocarbons by means of the special sulphuric acid mentioned above gave a hydrocarbon C7H14 b. p. 101-102*5°/747 mm. DT 0.7488 n20 1.4101 which is probably a cyclopentane or cyclobutane derivative [With w. D O B R O C H O T O V . ] - ~ ~ O ~ ~ ~ ~ specimen of naphtha b. p. 100-100*5' D18 0.766 n20'5 1.4210 when submitted t o the action of platinum black at 300° liberated much hydrogen and after the removal of toluene and redistillation had b. p. 100-101' D:* 0.7490 n18 1 *4142.The original hydrocarbon a '' heptanaphthene," which had been previously treated with a mixture of nitric and sulphuric acids had therefore yielded a cycloparaffin product very similar to that obtained from the above naphtha fraction (b. p. 102-104') which had not been first treated with nitric and sulphuric acids. D. F. T. Formation of Dimethylstyrene [p-Phenyl-A@-butylene] from Phenyldimethylethy! Alcohol LP-Phenylisobutyl Alcohol]. ALBIN HALLER and EDOUARD BAUER (Compt. rend. 1912 155 1581-1585).-By the action of sodamide on phenylacetonitrile (1 mol.) in ethereal solution followed by the addition of methyl iodide (1 mol.) a liquid b. p. 115-120°/19-20 mm. is obtained which on further treatment with sodamide and methyl iodide gives a-phenylisobutyro- nitrile (compare Wallach A 1900 i 229).This substance on hydrolysis with 85% sulphuric acid on a water-bath furnishes the corresponding amide which by reduction with sodium in absolute alcohol yields P-phenylisobutyl alcohol CPhMe,*CH2*OH b. p. 122-123'/20 mm. which gives a phenylurethane white needles m. p. 59-60'. During the reduction there is produced at the same time some P-phenyliso- butylamine b. p. 115-1 16O/20 mm. (compare Wallach Zoc. cit.) which forms a platinichloride insoluble in water. By acting on P-phenylisobutyl alcohol with thionyl chloride in slight excess at Oo a liquid is obtained separable into two fractions of which one is P-phenyl-Ap-butylene CPhMe:CHMe (compare Klages A. 1902 i 666 ; 1903 i 19) and the other a chloride C1,H,,Cl b. p. 104-105°/ 20 mm.the constitution of which has not yet been established. With silver acetate it gives an acetate which on saponification gives an alcohol b. p. 115-117°/15 mm. isomeric with the alcohol from which the chloride was derived. w. G. 2 4 6-Tribromo-1-iodo-3-nitrobenzene. C. LORING JACKSON and WEBSTER N. JONES (Amer. Chem. J. 1913 49 46-55).-2 4 6- Tribromo-3-nitroaniline (Kerner A 1876 i 210) has m. p. 101.5'. Remmers (A. lS74 696) assigned the m. p. 214-215'to this com- pound but it is now shown that his substance was probably 2 4 6- tribromo-3-nitroacetanilide. 2 4 6 - Tribromo - 3 - nitrodiacetanilideORGANIC CHEMISTRY. i. 169 (Remmers Zoc. cit.) has m. p. 168-169' and seems to be identical with the substance supposed by Wheeler (A. 1896 i 157) to be the monoacetanilide. 2 4 6-T~*ibromo-3-nitroacctanilide m.p. 208-209' forms white rhombic crystals. 2 4 ti-Tribromo-2 -iodo-3-nitrobenzsre C,HBr,T.*NO m. p. 144-145' obtained by the action of potassium iodide on the diazotisation product of 2 4 6-tribromo-3-nitroaniline crystallises in w bite rectangular plates. When this substauce is treated witah a solution of sodium ethoxide it is convertad into a dibromoiodonitrophenetole NO,* C6H13r,I* 0 Et m. p. 121' which forms long white rectangular prisms; other compounds are produced in this reaction one of which has m. p. 149'. E. G. The Nitration of the Chlorotoluenes. ARNOLD F. HOLLEMAN and J. P. WIBAUT (Proc. K. Akad. Wetensch. Amsterdam 1912 15 594-599).-The position assumed by a third substituent in a benzene ring depends on the relative velocities of substitution caused by the two subdtituents already present.The hydroxyl amino- halogen and methyl groups which cause ortho-para substitution are placed in the order of decreasing velocity. I n order to obtain further knowledge of the relative substitution velocity caused by different groups the author has re-investigated the nitration products of a-chlorotoluene (Goldschmidt and Honig A. 1886 1022). All four possible chloronitrotoluenes 2 3 2 4 2 5 2 6 were found to be present in the product although the 2 4-isomeride proved difficult of detection. For the estimation of the relative amounts of the isomerides in the nitration product Valeton's modifica- tion of the m.-p. method was used and indicated in a product obtained at 0' from 10 grams of chlorotoluene and 40 grams of nitric acid (D 1-52) 19.2 17.0 43.3 and 20.5% respectively in the above order.I n extending a similar investigation to the nitration of m-chloro- toluene 3 6- 3 5- 3 4- and 3 2-chloronitrotoluenes were prepared in a high state of purity and had XP. p. 21.9" 58-4' 24*2* and 25.4' respectively. Analysis of the reaction product indicated no appreciabh quantity of the 3 :5-isomeride and 58.9 38.3 and 8.8% of the remaining three. By a calculation involving the composition of the nitration products of toluene chloro benzene and p-chlorotoluene it is deduced that chlorine causes a velocity of substitution 1,491 times as great as that caused by the methyl radicie. The knowledge of this number allows the calculation of the proportion in which the various isomeric products should be formed in the nitration of 0- and m-chlorotoluenes and the theoretical proportions exhibit a gratifying concordance with the experimental I).F. T. ~ZQ Dihalogenoarylsulphonylacetonitriles R*SO,*CX,* CN and a Peculiar Reduction of these Halogen CompoundB. JULIUS THOQER and W. KXOSEBERG (L pr. Chem. 1913 [ii] 8'7 67-84. Compare A. 1905 i 336 870; 1908 i 633 798),-lt has been shown previously that aa-dibromoarylaulphonylacetonitriles may be YOL. CIV. i. Izi. 170 ABSTRACTS OF CHEMlCAL PAPERS. obtained readily by the action of bromine on the sodium salts of ary lsulphonyl -a-oximinoacetonitriles SO,R* C( NOH). CN in aqueous solution. At tempts to prepare the corresponding dichloro- and di-iodo-compounds in a similar manner were unsuccessful.The dichloro-compounds may however be obtained by the addition of bleaching powder to a glacial acetic acid solution of the corresponding arylsulphonylacetonitriles SO,R*CH,*CN. The following compounds were prepared in this manner aa-di- chlorobenxenesulphon~~acetonitrile SO,Ph*CCI,*CN lustrous prisms m. p. 57' ; aa-p-ti*ichlorobenzenesuZphonyEacetonitriEe white'needles m. p. 96-97'' ; aa-dichloro-p- bromobenaenesu~p~onylucetonitri~e stout needles m. p. 105-1 06' ; aa-dichloro-p-iodobenzenesulphonytacetonitrile flat prisms m. p. 1 11-.--112' ; aa-dichloro-p-toluenesulphonylacetonitrile broad lustrous needles m. p. 92' ; aa-dichloro-p-methoxybenzenes~l- phonylacetonitrile 111. p. 12 1' ; aa-dichloro- p-ethoxybernzenesulphonyl- acetonitrile m. p.95' ; aa-dichloro - + - cumenesulphonylac~tonitrile m. p. 103-1 04' and aa-dichlo~*o-a-nuphthalenesuZpl~onylucetonitrite m. p. 118'. The benzenesulphonyl derivative may also be prepared by directly chlorinating benzenesulphonylacetonitrile in glacial acetic acid solution. When dissolved in aqueous sodium hydroxide and the solution treated with a large excess of sodium hypochlorite benzenesulphonylaceto- nitrile yields phenyl dichloromethyl sulphone CHCI,*SO,Ph. aa- Dibromo-p-toluenesulphon ylace tonitrile prepared from p - toluene- sulphonylacetonitrile and bromine in glacial acetic acid solutioa crystallises in long white prisms m. p. 121' ; aa-dibromo-o-methoxy- benxenesulpl~onylacetonitrile forms small prisms m.p. 123' ; aa-di- bromo-p-ethoxybenaenesulphonylacetonitrile stout white needles m. p. 1 18' ; aa-dibronzo-JI-cumenesulphonylucetonitrile crystallises in prisms m. p. 123' ; aa-dibi*omo-a-napAthaEenesuZphon ylacetonitrile in pale yellow needles m. p. 146'. Attempts have been made to prepare compounds of the type SO,R*CO*CN (1) by hydrolysing the a-oximinoarylsulphonylaceto- nitriles with dilute acids; (2) by the action of silver oxide on the above dihalogen compounds and (3) by oxidising the arylsulphonyl- acetonitriles with potassium permanganate but so far these attempts have not met with success. When heated with sodium benzenesulphinate in alcoholic solution aa-dihalogenoarylsulphonylacetonitriles undergo a remarkable reduc- tion to arylsulphonylacetonitriles thus SO,R*CX,.CN + 2S0,PhNa + 2H20 = 2NaX + 2SO,Ph*OH + SO,R*CH,*CN. The action of iodine dissolved in aqueous potassium iodide on the sodium salt of a-oximinobenzenesulphonylacetonitrile leads to the formation of the corresponding potassium salt SO,Ph*C(CN):NOE which crystallises in lustrous golden-yellow leaflets.The authors also record unsuccessful attempts to prepare compounds of the type SO,R*C(CN):NO*ONa by the condensation of ethyl nitrate and arylsulphonylacetonitriles by means of sodium ethoxide in alcoholic solution ; in the case of p-chlorobenzenesulphonylacetonitrile the product of the reaction consisted of the sodium salt C,R,Cl*SO,*CHNa*CN. F. B.ORGANIC CHEMISTRY. i. 171 Spontaneous Formation of Iodonium Bases Containing Iodine in a Pentatomic Heterocyclic Nucleus.LUIGI MASCARELLI (Atti R. Accad. Limei 1912 [v] 21 ii 617-620).-When 2 2'-di- iodosodiphenyl 10*C6H4*C6H4* 10 or 2 2'-di-iododiphenyl tetrachloride IC12*C6H4*C6H4*ICI are kept in water for some months the aqueous solution yields diphenyleneiodonium iodide YBH4>I*I when treated with sulphur dioxide. I n the case of the tetrachloride the di-iodoso- derivative is probably first formed together with hydrogen chloride. By subsequent simultaneous oxidation and reduction of the di-iodoso- compound all the following substances may be prodriced C6H41*C6H,T 10,. C,H,* C,H4* 10 C H,I C,H,*I02 10*C,H,*C6H,~I0 and C6H41*C,H,*I0. By rearrangement of the compound C6H4 Io*c6E4* - c,H4*Io2 ( j H diphenyleneiodonium iodate ' 4>1*10 is produced and this by CAH* the action of sulphur dioxidue =is reduced to the iodide (compare Forster and Schaeppi T.1912 101 1359). R. V. S. wo'-Diarylated Aliphatic Hydrocarbons. WALTHER BORSCHE and J. WOLLEMANN (Ber. 1912 45 3713-3725. Compare A 1912 i %).-The method for the synthesis of arc-diphenyldecane has now been extended to the preparation of other members of the series with certain modifications in the case of the pentane heptane and nonahe. Adipyl chloride from adipic acid and phosphorus tricbloride con- denses with benzene to form a(-diphenylhexan-at-dione m. p. 107' (Etaix A. 1898 i 124) 6-benxoylvaleric acid COPh*[CH,],*CO,H being formed at the same time in white needles m. p. 70-7'2'. The diketone has been converted into the dioxime m. p. 222-223' (ibid.) which on reduction yields a~-diarnino-a[-diphenyZhexune NH,*CHPhfCH,],*CHPh-NH as a colourless oil b.p. 250-254"/16 mm. the carbamide of which ~,,,H2,O2N4 melts at 121' and the benxoyl derivative C33H3,P2N2 at 238'. The conversion of the diamine into Rupe and Burgin's at-di- phenyl-Aae-hexadiene (A. 1910 i 161) gives a poor result but the method. of von Braun and Deutsch (A 1912 i 687) provides a better way of obtaining the desired a[-diphenglhexane. In the same way suberyl chloride has beenconvertedinto the corre- sponding dioxime (Etaix Zoc. cit.) and this has been reduced and the phosphate of the diamine has been distilled. A good yield of a0-di- phenyl-aaq-octudiene CHPh:CH*[CH,],*CH :CHPh is thus obtained in colourless leaflets m. p 61-62" b. p. 210--220"/11 mm.; it gives a tctmbromide C20H22Br4,. m. p. 1964 and absorbs hydrogen in the presence of palladium yielding a0-diphenyloctane (compare Braun and Deutsch Zoc. cit.). A characteristic derivative of aK-diphenyldecane (Zoc. cit.) is the nitration product 2 4 2' 4'-tetranitro-a~-diphenyldecane it forms yellowish-white needles m. p. 63'. C10H20[C6H3(N02)212 ; % 2i 172 ABSTRACTS OF CHEMICAL PAPERS. The acid chlorides for the corresponding pen!ane heptane and nonane are difficult t o obtain and the diaminee would probably yield ring compounds. Hence the necessary ketones have been prepared by the reduction of available unsaturated ketones (compare A. 1912 i 194) and reduced to alcohols wbich on dehydration with zinc chloride give the olefines. The reduction of distyryl ketone t o di-fl- phenylethyl ketone is usually accompanied by by-products the nature of which seems t o depend on the condition of the palladium employed.The substance C31H3402 m. p. 126' (ibid,) has not since been encountered ; instead the ae&- tetraphenyldecane-8-dione C3,H3,02 m. p. 173-774O of Harries and Gollnit,z (A. 1904 i 427) and apparently its unsaturated ketone C3,H3,O a white powder m. p. 207-208" which dissolves with a purple colour in concentrated eulphuric acid have been isolated. The required di-P-phenylethyl ketone can be more conveniently prepared from phenylethyl methyl ketone by saturating its benzy lidene compound (Harries and Gollnitz Zoc. cit.) with hydrogen in presence of palladium. On reduction with sodium and alcohol ae-diphenylpentan- y-01 OH *CH(C H,*CH,Ph) is obtained as a very soluble crystalline mass m.p. 47-48' b. p. 21S0/1 1 mm. which on distillation with zinc chloride yields acdiphenyl-AP-pentene as a colourless oil b. p. 184-185"/10 mm. Reduction readily results in the ae-diphenylpentane of Braun and neutsch (A. 1912 i 435). The same series of reactions has also been carried out with phenyl 6-phenylbutyl ketone (A. 1912 i 194) which has been obtained in colourless needles m. p. 47'. a€-Diphenylpentarc- a-01 OH*CHPh*[CH,],*CH,Ph is a colourless oil b. p. 217'/12 mm. which gives a poor yield of ar-diphen yZ-Aa-pentene a colourless mobile liquid b. p. 186'/ll mm. which polymerises when heated. The ae-diphenylpentane forms a tetranit?.o-derivative C17Hl,9,N in slender yellow needles xn.p. 126'. aq-Diphenylheptan-y-one is best obtained by the reduction of ar]-diphen yZ-A'-hepten-y-one CHPh C H*CO*[ C H2l3* CH,Ph which is formed in colourless leaflets m. p. 25' b. p. 240'/12 mm. by the con- densation of benznldehyde wibh methyl-8-phenyl butyl ketone ( A. 191 1 i 880). I t s reduction product aq-diphenylheptcn- yo^ m. p. 42-43' b. p. 233'/11 mm. is very readily dehydrated and the heptene is also easily reduced to ay-diphenylheptane b. p. 207-208"/12 mm. In the same way ar-diphenylnonan-r-one (A. 1912 i 194) has been reduced t o at-diplmzplnonan- ~-01 a viscous colourless liquid b. p. 251.11 1 mm. which yields the al-diphe'henyl-A'-nonene as a highly refractive oil b. p. 231-233'/12 mm. Reduction of the latter to ai-diphenylnonane a colourless oil b.p. 235'1 12 mm. proceeds very readily. J. C. W. Pyrosulphates of Sodium and Potassium as Condensing Agents. ALLAN F. ODELL and CLEVE W. HINES (J. Amer. Chem. Soc. 1913 35 81-84).-The alkali pyrosulphates have been used as condensing agents by Bogojavlenski and Narbutt (A. 1905 i 854) in the preparation of certain esters. The salts are readily converted into the hydrogen sulphates by the addition of water and should,ORGANIC CHEMISTRY. i. 173 therefore be efficient agents for the abstraction of water in organic synthesis ; they are easily prepared and convenient to handle. The pyrosulphates have now been applied to the preparation of tri- phen ylbenzene benzy lideneaniline benzy lidenemaIonic acid phenyl- styrpl ketone and acetanilide and have given good results.They cannot be employed however to effect the condensation of phenols with other substances. E. G. Nitro-derivatives of m-Cresyl Oxide [m-Tolyl Ether]. ALPHONSE MAILHE (Compt. rend. 1912 155 1531-1526).-8 study of the nitration of m-tolyl ether prepared by the aid of thorium oxide (compare A. 1912 i 767). Nitration in acetic acid solution a t the ordinary temperature yields nitro- rn-tolyl ether C,H,Me*O* C,H,Me*NO b. p. 245-250°/50 mm. rn. p. 48' which on reduction with iron and acetic acid gives the corresponding umine giving a violet coloration with calcium chloride. If during the nitration the temperature rises to 8O-9OG dinitro-m-tolyl ether O(C6H,Me*N0,)2 prisms m. p. 112O is obtained in which the nitro-groups are probably para to the oxygen.By gradually adding tolyl ether to fuming nitric acid kept cold and then adding water a paste is obtained which after extraction of the above dinitro-compound is added to a mixture of sulphuric and nitric acids and yields 2 4 2' 4'-tetraniti*o-m-tolyl ether a white amorphous powder m. p. 203O which on boiling with concentrated aqueous potassium hydroxide yields dinitrodihydroxy-m- tolyl ether a black crystalline powder m. p. 300' (decomp.). If tho original tolyl ether is nitrated in sulphuric acid solution by the gradual addition of fuming nitric acid the temperature being gradually raised to 90' towards the end of the reaction 2 6 2' 6'- tetranitro-m-tolyl ethes. hexagonal plates m. p. 147' is obtained together with a large proportion of its isomeride.Attempts to carry the nitration further have as yet not been successful. O[C,H,M~(NO,),I W. G . Preparation and Oxidation of Styrolene Alcohol [ Phenyl- ethylene Glycol]. WM. LLOYD EVANS and Lou HELEN MORGAN (J. Amer. Chem. Soc. 19 13 35 54-68).-This investigation was undertaken with the object of determining the mechanism of the oxidation of phenylethylene glycol (styrolene alcohol) with different reagents and of establishing the conditions undel? which mandel- aldehyde might be isolated as an intermediate product. Zincke (Annulen 1883 216 303) has shown that on oxidising the glycol with chromic acid benzaldehyde formaldehyde and formic acid are pro- duced that with potassium permanganate a quantitative yield of benzaldehyde may be obtained and that with nitric acid benzoyl- carbinol and benzoylformic acid are formed.Phenylethylene glycol is best prepared by the hydrolysis of the corresponding diacetate (Zincke Zoc. cit.). On oxidation with potassium permanganate either alone or in presence of alkali hydroxide it yields benzoic acid but not phenylglyoxylic acid the reaction taking placei. 174 ABSTRACTS OF CHEMICAL PAPERS. in accordance with the equation (1) C,H,*CH(OH)*CH,*OH -+ C,H,*CHO + CH,*OH or (2) C,H,*CH(OH)*CH,*OH -+ C6H5*CH2*OH + :CH*OH. When the glycol is oxidised with potassium ferricyanide benzoic acid is the chief product but mandelic acid is not formed and the reaction proceeds according to equation (1) or (2). With silver oxide in presence of alkali hydroxide the oxidation takes place with formation of benzoylcarbinol as the first product of the reaction in one of the follow- ing ways (3) C,H,*CH(OH)*CH,*OH + C,H,*$*CH,*OH + H,O ; and C,H5$!*CH,*OH + H,O -+ C0H,-CO*CH2*OH + 2H ; or (4) C,H,*CH(OH)*CH,*OH -+ C,H,*CH(OH)*CH + H20 and .C,H,*CH(OH)*CH + H,O -+ C,H,*CH(OH)°CHO + 2H ; at 604 both reactions occur. If silver oxide is employed alone at 20° the reaction seems to proceed entirely in accordance with equation (3). The oxidation of phenylethylene glycol by bromine in presence of potassium carbonate yields benzoylcarbinol. Aqueous solutions of copper salts do not exert any marked action on the glycol even at looo E. G. I Preparation of Beneyl Mercaptan. JOHN A. SMYTHE (Proc. Univ. Durham Phil. Soc. 1912 4 220-222).-Benzyl mercaptan may be?prepared\ from benzyl sulphide by reduction with iron filings in acetic acid solution. When dissolved in glacial acetic acid and the solution saturated simultaneously with hydrogen chloride and sulphur dioxide it yields benzyl disulphide and trisulphide in equal amounts.F. B. Derivatives of Ethylene Dimercaptan S K*CH,*CH2*SH s-Dithiolethylene SH*CH:CH*SH and of Dithiolacetylene SH*CiC*SH. EMIL FROMM HANS BENZINGER and FRITZ SCHAFER ( Amalen 1 9 12 394 3 25-3 3 7 ) .-s- Diethylthioleth ylene SEt CH CH*SEt b. p. 170°/13 mm. is obtained by the slow addition of dichloroethylene t o ethyl mercaptan and potassium hydroxide in alcohol the mixture being finally heated on the water-bath The addition of dichloro- ethylene to benzyl mercaptan in boiling 7*50/; alcoholic potassium hydroxide yields s-dibenzylthioZethyleMe C,,H,,S m.p. 61° colourless needles which decomposes by heating into hydrogen sulphide toluene beneyl mercaptan and stilbene and forms a dibromide C,,H,,Br,~ m. p. 73-74' with bromine in carbon disulphide. By heating with alcoholic potassium hydroxide this di bromide yields dibenxylthiol- acetylene CH,Ph*S*CiC*S=CH,Ph m. p. 53* straw-yellow needles or flesh-coloured leaflets. s-Dibenzylthiolethane CH,Ph*S*CH,*CH,*S*CH,Ph m. p. 38O pre- pared from ethylene dibromide and sodium benzyl mercaptide is oxidised by cold nitric acid (D 1-34) to the disulphoxide C16H:1802S2 m. p. 198* white leaflets ; the disulphone C16H180482 pearly leaflets subliming at 304O is obtained by oxidising the disulphoxide by 5% potassium permanganate or the sulphide by chromic and acetic acids.ORGANIC CHEMISTRY.i. 175 s-Di-o-nitvophenylthiolethylene C14H1004N2S2 m. p. 2 15O golden- yellow leaflets prepared from dichloroethylene o-nitrophenyl mercaptan and alcoholic potassium hydroxide forms a dibromide m. p. 1 3 2 O citron-yellow prisms which IS converted into di-o-nitro- phenylthiolacetylene m. p. 2 2 5 O yellow needles by hot alcoholic potassium hydroxide. This acetylene derivative absorbs only one mol. of bromine in chloroform forming dibromodi-o-nitrophenylthiol- ethylene C,Br,(S*C,H?*NO,) y. p 209O yellow leaflets. Sodium o-nitrophenyl mercaptide and di-o-nitrophenylthiolethylene dibromide react in alcohol to form glyoxaltetra-o-nitrophenylmercaptaZ CH(S*C,H4*N0,),*CH(S*C,H,*N0,) yellow needles m.p. 1 7 8 O . s - Di - o - arninophenylthiolethylene C2H,(SoC6H,*NH2)a m. p. 67" colourless leaflets obtained by the reduction of the nitro-compound by alkaline sodium hyposulphite forms a dibenxoyl derivative m. p. 1 3 2 O diacetyl derivative m. p. 1 5 9 O and a sparingly soluble dibydro- chloride m. p. 201O; the last reacts with only one mol. of sodium nitrite during its diazotisation. s-Di-o-nitrophenylthiolthane C2H4(S*C,H4*N0,) m. p. 2 0 7 O yell0 w prisms prepared by treating moist o-nitrophenyl mercaptan and ethylene dibromide with hot alcoholic potassium hydroxide is oxidised to the disulphoxide C,,H,,O,N,S m. p. 1 4 5 O pale yellow needles by chromic and warm glacial acetic acids and to the disulphone m. p. 164O almost colourless prisms by chromic and boiling glacial acetic acids and yields s-di-o-arninophenylthiolethane m.p. 74' (dibensoyl derivative m. p. 153'; diacetyl derivative m. p. 194-195') by reduction with tin and hydrochloric acid. s-Di-p-nitrophenylthiolethylene m. p. 126O prepared like the ortho- isomeride forms a dibromide Cl,Hlo04N,Br2S m. p. 1 3 7 O yellow needles and yields by reduction t h e diamino-compound (diacetyl derivative m. p. 194') which can be readily tetrazotised. s-Di-p- nitrophenylthiolethane m. p. 1 3 4 O crystallises in yellow prisms. Di-2 4-dinitrophenyl disulphide S,[C,H,(NO,),] yellow needles exploding at 280° is obtained by heating alcoholic 2 4-dinitrochloro- benzene with aqueous sodium sulphide and sulphur. 2 4-Dinitrophenyl benzyl sulphide yields the t ~ ? p h o ~ i d e C14H1004N2Br2S2 C,H,(~O,),*S~*CH,Ph rn.p. 144O (decomp.) straw-yellow needles by oxidation with 30% hydrogen peroxide in glacial acetic acid and the sulphone m. p. 177" by oxidation with chromic and warm glacial acetic acids. 2 4-Dinitrophenyl methyl suZphide m. p. 1 2 6 O prepared from 2 4-dinitrophenyl mercaptan methyl iodide and methyl alcoholic sodium methoxide yields the sulphoxide m. p. 159O yellow leaflets and the sulphone m. p. 184O (decomp.) colourless needles by oxidation with hydrogen peroxide and chromic acid respectively. c. s. Decomposition of Benzyl Disulphide by Alkalis. EMIL FROMM and AQUILA FORSTER (Annalen 19 12 394 338-343).-In addition to the substances identified by Price and Twiss among the products of decomposition of benzyl disulphide by alkalis (T.1910 97,i. 1'76 ABSTRACTS OF CHEMICAL PAPERS. 11 75) the authors have detected thiobenzoic acid and dithiobenzoic acid. Benzyl dithiobenxoate Ph*CS,*CH,Ph m. p. 55' is prepared by heating the acid and benzyl chloride with alcohol and 10% sodium hydroxide. When the preceding decomposition is effected in the presence of benzyl chloride the authors could obtain only about 5% of the benzyl- mercaptal of benzaldehyde instead of SO% as stated by Price and Twiss (loc. cit.) and they suggest that the latters' benzyl chloride was highly contaminated with benzylidene chloride which reacts with the sodium benzyl mercaptide to form the benzylmercaptal. [With MAX KLIN~ER.]-T~~ substance m. p. 164O obtained by Fromm and Schmoldt by the dry distillation of benzoyl sulphide benzoyl disulphide or thiobenzoic acid and stated to be tolane tetra- sulphide (A* 1907 i 702) is now shown to be a mixture.By treat- ment with ammonium sulphide or with ether and petroleum it is separated into sulphur and tetraphenylthiophen m. p. 184'. The substance described as tolane disulphide (Zoc. cit.) IS probably also a mixture of sulphur and tetraphenylthiophen. c. s. Some Mercaptals and Mercaptols and their Derivatives. EMIL FROMM AQUILA FORSTER and BORIS VON SCHERSCHEWITZKI (Amnalen 19 12 394 343-349).-The benzylmercaptal of formal- dehyde CH,(S*CH,Ph) m. p. 55' obtained by saturating with hydrogen chloride a solution of benzyl mercaptan and excess of 40% formaldehyde in glacial acetic acid is oxidised to the sui'phoxide CH,(SO*CH,Pb) m.p. 189O by hydrogen peroxide and to the sulphone CH,(SO,*CH,Ph) m. p. 216' by acidified 5% potassium permanganate. The benxylmercaptal of acetaldehyde CHMe(S*CH,Ph) b. p. 200-205'/5 mm. is oxidised to the sulphone CHMe(SO,*CH,Ph) m. p. 176O by 5% potassium permanganate. The benxylmercaptole of acetone CMe,(S*CH,Ph) b. p. 195'/5 mm. yields the sulphoxide m. p. 105' and,sulphone m. p. 125' by oxidation as above. This sulphone and also aa-di benzylsulphone-ethane are produced when dibenzylsulphonernethane is heated with alcoholic methyl iodide and aqueous sodium hydroxide. When aa-dibenzylsulphonepropane is similarly treated benzylmethylsulphone is obtained owing to the intermediate formation of benzylaulphinic acid. The following sub- stances are also described the p-tolylmercaptal of formaldehyde and its sulphoxide m. p.4 5 O and sulphone m. p. 135' ; t h e p-tolylrnercaptolc of acetone m. p. 64-65' and its sulphoxide rn. p. 75-76' and s u l p h m. p. 147-148'; aa-di p-tolylsulphona-ethana m. p. 156' and aa-di-p-tolyl- suZphonepropane m. p. 189". c. s. Catalysis of Dehydrogenation of Hexahydrobenzoic [cyclo- Hexanecarboxylic] Acid. NICOLAI D. ZELINSKI and N. UKLONSKAJA (Ber. 191 2 45 367 7-3678).-A n extension of the process which proved successful with cyclohexane and its methyl derivative to simple derivatives which are not hydrocarbons (Zelinski A 19 11 i 958). When cyclohexanecarboxylic acid is added gradually to palladiumORGANIC CHEMISTRY. i. 177 black at 300° in an atmosphere of hydrogen at 20-25 mm.pressure the vapours which pass away on condensation give crystals of benzoic acid in a smaller quantity of unchanged liquid cyclohexanecarboxylic acid. If ethyl cyclohexanecarboxylate (b. p. 195-197O 1217 1.4424) is submitted twice to the above treatment the liquid product can be separated by distillation into two fractions the smaller one consisting of a mixture of ethyl benzoate and ethyl benzoate (nI8 1*5071) whilst the main fraction is of pure ethyl cyclohexanecarboxylate. The progress of the dehydrogenation can be conveniently followed by the change in the refractive index. As with cyclopentane and its methyl derivative no dehydrogenation was observed when methylcyclopentanecarboxylic acid was treated in a similar manner. D. F. T Study of Double Linkings. ANTONIO MADINAVEITIA and JOSE SUREDA BLANES (And.Fis. Quim. 191 2 10 381-389).-Under the influence of platinum black cinnamic acid in glacial acetic acid solution is fully hydrogenised to Zelinski's cycZohexylpropionic acid whilst palladium black and colloidal palladium determine reduction to phenyl- propionic acid. Octahydroeugenole prepared by the hydrogenation of eugenole with platinum black as catalyst has b. p. 125Oat 12 mm. and forms an oil soluble in acetic acid alcohol and ether and insoluble in water and light petroleum. I n the presence of palladium black eugenole is reduced to hydroeugenole. G. D. L. Some Pars-derivatives of Phenylacetic Acid. S. ROBSON (Proc. Univ. Durham Phil. Soc. 1912 4 225-227).-p-Bromophenyl- acetic acid m. p. 114-115' has been prepared from p-nitrophenyl- acetonitrile by reduction with stannous chloride followed by replace- ment of the amino-group by bromine by means of the diazo-reaction and finally hydrolysing the resulting p-bromophenglacetonitrile m.p. 112O with suiphuric acid ; on nitration it +Ids 4-bromo-3-nitro- phenylacetic acid (Bedson T. 1880 37 100). p-Chloro- and p-iodo-phenylacetic acids have been prepared in a similar manner. F. B. Walden's Inversion and Substitution Processes. 11. EMIL FISCHER (Annalen 1912 394 350-362. Compare A. 1911 i 418). -Mainly a reply to Biilmann (A.> 1912 i 420) and to Noyes and Potter (ibid. 786). Phenylpropiolic acid is reduced to cinnamic acid by zinc dust in alkaline as well as in acid solution (compare A. 1912 i 187) ; conse- quently the presence of the acid is not the cause of the presumably abnormal course of the reduction. 0.s. Behaviour Towards Light of Cinnamylideneacetonitrile of a-Phenylcinnamylideneacetic Acid and of the Two Cinn- amylideneacetic Acids. HANS STOBBE [and NICOLAUS BABBA- SCRINOV] (Bsr. 1912 45 3396-3408).-When the dark yellowi. 178 ABSTRACTS OF CHEMICAL PAPERS. a-phenylcinnamylideneacetonitrile CHPh CH*CH:CPh*CN is exposed to light in benzene or chloroform solution a resin is formed together with benzoic acid and a colourless dimeride C3,H2sN m. p. 197O. It thus behaves very similarly to cindamylidenemalonic acid (Rii ber A 1902 i 61 7) which is polymerised by light to diphenyltetramethyl- enediethenyldicarboxylic [diphenylcyclobutyldiacrylic] acid. The dimeride when cautiously oxidised by potassium permanganate in aqueous alkaline methylacetate solution is converted into benzoyl cyanide and a-truxillic acid C02H*CH<C,ph>CH*C02H. CHPh This establishes the dimeride as 1 3-diphenyltetramethylene-2 ; 4-diethenyl- P-phenyl-P-cyanide [ 1 3-diphenylcyclobutane-2 ; 4-diatroportitriZe] CHPh CN CPh CH*CH<CHPh>CH*CH CPh* CN.It combines with bromine to a colourless tetrabromide indicating the absence of a conjugated double bond system whereas phenylcinnamyl- idene acetic acid forms only D colourless dibromide. The polymerisa- tion of the cyanide is accompanied by bleaching the absorption field of the dimeride being displaced Eome 800 wave-lengths towards the ultra- violet. On heating at 200° the dimeride is depolymerised yielding simply unimolecular cyanide This behaviour which is shared by a-truxillic acid is not in accordance with that of other cycEobutane derivatives and throws some uncertainty on the four-ring formulae adopted.A second colourless dimeride m. p. 215O is formed during exposure t o light. This is also produced as a by-product of the action of bromine on the first dimeride. It does not unite with bromine and it is not 50 easily depolymerised ; the constitution has not been determined. a-Phenylcinnamylideneacetic acid whether used in the form of the acid its sodium salt or methyl ester is stable towards light in the absence of oxygen but in presence of air i t is oxidised to benzalde- hyde and benzoic acid. No polymerisation product is formed. The methyl ester is more readily oxidised than the acid whilst the sodium salt is still more resistant Similarly under no conditions could 11 polymeride be obtained from the isomeric cinnamylideneacetic acids. Some oxidation takes place also the aZlo-acid is converted into its isomeride. The dimeric acid C,,H,,O obtained by Riiber (Zoc.cit.) on heating the dimeride o€ cinnamylidenemalonic acid could not be depolymerised to cinnamylideneacetic acid. The sodium salt and methyl ester behave similarly to the acid; the ester is more easily oxidised under the influence of light; the salt is more stable than the acid. The different behaviour of the compounds studied is not due to any differences in the selective absorption of light by them. The dibromide CI7Hl3NBr2 from phenylcinnamylideneacetonitrile crystallises in colourless needles m.p. 1 18'. The tetrabromide C3,H2,N2Brq of the dimeride has m. p. 276'. Cinnamylidenernalonic acid forms a dibromide Cl2HloO4Br2 m. p. 180'. The tetrabromide of the dimeride has decomp. above 100'. Methyl allocinnamyZi&neacetate is an oil solidifying below - 80'. E. F. A.ORGANIC CHEMISTRY. i. 179 Some Pharmaceutical Incompatibilities of Salol [ Phenyl Stclicylate]. ITALO BELLUCCI (Atti R. Accad. Lilzcei 1912 [v] 21 ii 610-616. Compare Caille A. 1909 i 594).-In pharmaceutical practice it is not infrequently observed that two dry solid drugs yield a pasty or liquid mixture. This phenomenon is not due in all cases to the occurrence of a chemical reaction but results in some cases from the formation of an eutectic mixture of low m.p. I n the present paper the author gives tables and curves which exhibit the results of the thermal analysis of the binary mixtures of salol with the substances mentioned in the following list Eutectic. Eutectic. - Temp. % Salol. Temp. % Salol. ...... Chloral hydrate ... 17" 61 ......... Thymol ............ 13 66 ......... Camphor ............ 6 56 &Naphthol _*_I 34" 90 : 1 ............ Guaiacol 3 53 An tipyrine 30 Urethane 29 Menthol 28 46 ............ B-Bromocamphor . 21 64 In the system salol-menthol there is complete miscibility in the solid state the curve being Roozeboom's type 111. with a minimum at about 28' and 45% of salol. From the temperature given it follows that some of the above binary mixtures are pasty a t ordinary tempera- tures others liquid.R. V. s. Condensation of Cyclic Ketones with Ethyl Oxalate. ARTHUR KOTZ K. BLENDERMANN and J. MEPER (Bey. 1912 45 3702-3705. Compare A. 1906 88 668).-Active l-methylcyclohexan-3-one condenses in the cold with ethyl oxalate and sodium ethoxide and when the dry product is treated with methyl iodide and subsequently hydrolysed 1 4-dimethylcycEohexan-%one is obtained b. p. 51°/ 10 mm. Inactive I -methylcycZohexan-2-one condenses to form a methyl- cyclohexenotpyruvolactone C,H,,O m. p. 14 lo alcohol being eliminated. When this is treated with methyl iodide a dimethyl compound C10H1P08 m. *p 87' is formed which absorbs 4 atoms CH2/\CMe CH2"CMe of hydrogen and yields CH),)C-O and CH,/ \/ 42-0 l-methylcyclohexan-2-one c=c-co C=C-bO on hydrolysis.Since \ these compounds give no OMe reactions for ketones and since Claisen has shown that the formation of lactones is possible in such circumstances (A 1895 i 373) they may be represented by the annexed formuls. I t s oxime C,H,,ON has m. p. 97-98'. CH2 CH2 \ OH J. C. W. Melting Point of Ethyl Gallate. HENRY C. BIDDLE (J. Amer. Chem. Soc. 1913 35 96).-Biddle and Kelley (A. 1912 i 714) suggested that the peculiar behaviour of ethyl gallate on melting might be due to the existence of two crystalline forms It has now been found however that by continued purification the ester cani. 180 ABSTRACTS OF CHEMICAL PAPERS. be obtained in long colourless needles melting fairly sharply at 160'. E. G. Kojic Acid a New Organic Acid Formed by Aspergillus oryzae.T. YABUTA (J. Coil. Agyic. Imp. Univ. Tokyo 1912 5 51-58). - Kojic acid C,,H,(OH),(CO,H) obtained from finely powdered Aspergillus oryzae forms colourlese needles or prisms m. p. 152'. The acid gives a strong red colour with ferric chloride; it has no action on alkaline diazobenzenesulphonic acid on Millon's reagent or on Fehling's solution. The aqueous solution absorbs much bromine. Methoxyl and ethoxyl groups are not present. The copper salt C,,H,,O,Cu forms light green rhombic crystals. The ucetyl derivative C,2H,o04(OL4c) crystallises from alcohol in colourless needles m. p. 102'. The dibenxoyl derivative C,,Hlo04(OH),(O€3z)2 m. p. 1 3 7 O and the tetrabenxoy! derivative C,,H,o04(OBz) m. p. 135" were prepared. The acid also occurs in Aspergillus ulbus A.candiduu and A .nidulans but was not found in thirteen other varieties or in PeniciZliztm or Mucor. The production of the acid seems to depend on the food supplied to the Aspwgillus. It was found in Aspergillus grown on certain cereals and potatoes but not with leguminous seeds. Synthesis of P-Glucosidogallic Acid. EMIL FISCHER and HERMANN STRAUSS (Ber. 1912 45 3773-3779).-Ethyl gallate com- bines with acetobromoglucose forming ethyl tetra-acetyZglucosidojalZate which is completely hydrolysed by cold barium hydroxide solution t o glucosidogallic acid C,Hl10,*C,H2( OH),*CO,H. This crystallises in colourless interlaced needles m. p. 193' (decomp.) after sintering from 155' [a]$' - 22'. It is monobasic and is hydrolysed by emulsin into dextrose and gallic acid With ferric chloride a brownish-red colora- tion is produced indicating that the p-hydroxyl group of the gallic acid is attached to the sugar residue.It differs from the supposed gluco- sides of gallic acid described by Gibson (A. 1903 i 355) and by Feist (A 1912 i 566 888). Ethyl tetra-acetylglucosidogallate crystalliees in colourless needles m. p. 18@-181° (corr,) [a] - 10.6'. Some Reduction Products of Ellagic Acid. MAXIMILIAN NIERENSTEIN and PREDERIC W. RIXON (Annulem 1912,394 249-258). -The electrolytic reduction of ellagic acid in a divided cell with mercury cathode and nickel anode yields different products a t different temperatures. By reduction in 4N-sodium hydroxide at the ordinary temperature ellagic acid yields chiefly leucoellugic acid N. H. J. M. E. F. A.C,H(OH)29 C,H( OH) /CH( OH)*O\ - \O*CH (OH)/ rn. p. 294-296' (decomp.) small needles. This substance is colourless does not possess any tinctorial properties forms a hexa-acetyl derivative M. p. 272-275' (decomp.) and a hexabenzoyl derivative m.. p. 300-305' (decomp.) and is reconverted into ellagic acid by oxidation with hydrogen peroxide. By boiling with aqueous potassium hydroxide and carbon tetrachloride leucoellagic acid is converted into theORGANIC CHEMISTRY. i. 181 potassium salt long rhombohedra of theqdicarboxylic acid CO,H-C,(OH ),LCH(oH) *o~c,(o H )20 CO,H \O*CH(O H)/ m. p. 123-124' (decomp.) small needles. A solution of the dicarb- oxylic acid in ethyl acetate has been separated by strychnine into the two (impure) active acids and the meso-modification.The impure d-acid has m. p. 122-124' and La] + 19.9' ; the impure 1-acid has m. p. 127-131' and [a]: - 2*3' and the meso-acid has m. p. 143-146' (decomp.). The electrolytic reduction of ellagic acid in alkaline solution at 70" yields pentahydroxydiphenylmethylolide (A. 1908 i 548) whilst its reduction in concentrated sodium hydroxide at 110' yields New Basic Component of the Muscle of the Dogand Its Relation to Hexamethylornithine. DANKWART ACKERMANN (Zeitsch. Biol. 19 12 59 433-440).-Myokylzine a basic substance obtained from dog's muscle is probably I-hexamethylornithine. Both substances give precipitates 'with phosphotungstic a :id and with alcoholic mercuric chloride solution. The aurichEoride from myokynine contains 2H20 and is lsvorotatory t h a t from hexamethylornithilze m.p. 204-205O is anhydrous. Myo- kynine platilnichloride (2H,O) has m. p. 232-234' ; the isomeride (H20) has m. p. 232-233'. Hexamethylornithine is obtained from ornithine by means of methyl sulphate ; it is dextrorotatory. The Bromination of cycZoPentanone. MARCEL GODCHOT and F~LIX TABOURY (Conzpt. rend. l912,155,1522-1524).-When bromine (4 mols.) dissolved in carbon tetrachloride is added t o a solution of cyclopentanone (1 mol.) in the same solvent either with or without the presence of aluminium bromide the mixture being kept cold there is obtained on evaporating off the solvent a n abundant crop of crystals with more or less oil. The crystals are separated and on purification yield tetrabvomocyclopentanone C,H,OBr large plates m. p.99'. It is very soluble in ether ethyl acetate etc. and when left t o itself slowly loses hydrogen bromide and is converted into a yellow oil. This change takes place rapidly in solution in ethyl acetate and the product when purified is tdwomocyclopentenone C,H,0Br3 colourless prisms m. p. 57-58'. This substance on brominatlon in carbon tetra- chloride solution adds on two atoms of bromine giving pentabromo- cyclopentanone C,H,OBr,. m. p. 93". The oil obtained in the original bromination slowly loses hydrogen bromide and on boiling the produch with water and extracting with ether a compound is obtained m. p. 147" which analysis shows t o be either C,H30,Br or C6H5O2Br the amount of material t o hand not allowing ot definite distinction between the two formulae.The substance functions both as an alcohol and a ketone. P. JOSEPH TARBOURIECH (Compt. rend. 1913 156 75-77).-The dehydration of cycZohexanoldimethy1- carbinol gives rise to a hydrocarbon C9HI4 and two isomeric ketone# 2 3 4 2' 3' 4'-hexahydroxydiphenyl. c. 8. 'E. F. A. W. G. 2 2-Dimethylcycloheptanone.i. 182 ABSTRACTS OF CHEMICAL PAPERS. C,H,,O one of which has been:shown to be 1-acetyl-1-methylcyclohexane (compare A. 1910 i 557) and the other is now proved to be CH,*CH2*$?H2 2 2 ~ dimeth ylcycloheptanone Me,C<CO-CH,-cH~ the :CO group having been introduced into the hexatomic ring. By purification through its oxime i t is obtained as a colourless liquid b. p. 82O/ 18 mm. giving a carbanilino-oxime m. p. 94O and a fternicai*baxone m. p. 176O. On oxidation with weak alkaline permanganate i t yields a-keto-pp-dimethylpimelic acid C0,H*CO*CMe,*CH,*CH,*CH2*C02H m.p. 67O giving a semicarbazone m. p. 185' and an oxime m. p. 140-141' which on heating further decomposes losing carbon dioxide and water,'giving 6-cyano-66-dimcthyZpentoic acid CN*CMe,*[CH,],*CO,H m. p. 34-35' which on hydrolysis with alcoholic potassium hydroxide is converted into aa-dimethyladipic acid. Electrolysis of cycZoPentanone. MARCEL GODCHOT and F ~ L I X TABOURY (Bull. Xoc. chim. 1913 [iv] 13 12-17. Compare A. 191 2 i 34 552).-On electrolysis in alkaline solution cyclopentanone yields cyclopentylidenecyclopentanone (Wallach A. 1897 i 160) and two other products which appear to be tetracyclopentane derivatives. It is probable that the cyclopentylidenecyclopentanone is formed by the condensation of two mols.of cyclopentanone in presence of alkali and that the other two products are formed from the condensation product by electrolytic action the first being the corresponding pinacone and tbe second the corresponding pioacolin. These sup- posed tetracyclopentane derivatives have the following characters. The first m. p. 160-162O has the formula C20H3002 and is probably identical with the substance obtained by Meiber (A 1899 i 741). It probably bas the annexed constitu- QH,*CH CH,-CH tion which makes i t the pinacone cor- CH,*CH 2>c:c<c(o~-.(!j~ responding with cyclopentylidenecyclo- I pentanone. This substance probably 7H2*CH2>C c< C(OH)*FH2 loses 1 mol. of water giving rise to CH,*CK,- CH,-CH the second product C,oH@ b.p. 320°/25 mm. a yellow liquid which gives no typical carbonyl derivatives although it probably has the following constitution being formed in a manner analogous to the transformation of the pinacone of cyclopentanone into the correspond- ing pinacolin (Meiser loc. cit.) CH,-C(C5H,)>C<CO*C(C H )>CH2* W. G. FH2-CH CH,-CH T A. H. Terpenes and Ethereal Oils. CXII. Condensation Products of Cyclic Ketones and Acetone. OTTO WALLACH and WOLFGANG TON RECHENBERQ (Annalen 19 12 394 362-384).- Many years ago a substance C,,H,,O isomeric with pulegone was obtained by the condensation of acetone and methylcycZohexan-3-one but its constitution could not be dehitely settled (A. 1896 i 310; 1898 i 484). An extensive examination of similar condensations now leads to the generalisation that the acetone attacks the carbonyl group of cyclohexanones but a nuclear methylene group of C?/C~O-ORGANC CHEMISTRP.i. 183 pentanones ; thus equal molecular quantities of cyclopentanone and acetone are kept in alcoholic sodium ethoxide for some hours at O' and then for two t o three days a t the ordinary temperature whereby in addition to a little mesityl oxide propylidenecyclopenta~~-2-one C0-7H2 CH,*CH,' CMe,:C< b. p. 195-199' D20 0.9565 n2,0 1.4932 is obtained (sernicarbaxone m. p. 215-218'; oxime m. p. 77') by the reduction of which by hydrogen and colloidal palladium isopropyZcyclopentan-2-one b. p. 176*5-177.5' .D21 0.9000 n2,1 1.4419 (semicarbaxone m. p. 197" ; benxylidene derivative m. p. 79-80') is formed.I n a similar manner i-methytcyclopntan-3-one b. p. 144-144*5' D22 0.913 nD 1.4329 (semicurbaxone m. p. 185' ; benxylidene derivative m. p. 157' ; m-nitrobenxylidene derivative m. p. 174' ; anisylidene derivative m. p. 197-198' ; pipsror&yl/lidene derivative m. p. 166-167' ; cinnumylidene derivative m. p. 148' [compare A. 1904 i 752; 1908 i 424]) prepared from i-B-methyladipic acid condenses with acetone to form - - - - CH,*QHMe 1-naethyl-4-propylidenecyclopelztccn-3-one CMe,:C<Co-CH b. p. 203-205' D2l 0.9315 n$ 1.4846 (semicarbaxone m. p. 2fO'; oxirne m. p. 89'). The constitution of this compound is determined by its exalted molecular refraction and by the fact that 1-methyl-4-isopropyl- cyclopentan-3-one b. p. 186-1 87' D20 0.8850 n 1.4392 (scmicarbazone m.p. 179'; oxime m. p. 66') obtained from it by Paal's method yields by oxidation with chromic and dilute sulphuric acids a keto-acid CHMe,*CO*CH,*CHMe*CH,*CO,H (semicarbaxone m. p. 164' ; oxime m. p. 76-77') by the further oxidation of which i-P-methylglutaric acid is produced. cycloHexanone and acetone condense to form Al-cyclo~exenylacetons C,H,*CH,*COMe b. p. 203-204' D19 0 . 9 3 7 5 ~ ~ ~ 1.4736 (semicaybaxone m. p. 144-145'; oxim b. p. 135'/20 mm.) the constitution of which follows from its molecular refraction and from its reduction by Paal's method to cyclohexylacetone m. p. 171-172' (not 165-166' A 1907 i 6 16). cycloHexyltrimethyZcarbinoE C,Hll*CH,*CMe2*OH b. p. 208' D20 0.902 ng 1.4627 is prepared from cyclohexylacetone and magnesium methyl iodide in the usual manner.MethylcycZohexan-4-one and acetone yield 1 -methyl-A%yclohexenyZ- 4-acetone C,H8Me-CH,*COMe b. p. 216-217" DZ1 0,916 ng 1.4672 (semicaybaxone m. p. 122-123') by the reduction of which 1-methyl- cyclohexyl-4-acetone b. p. 214-215" D21 0.8930 mg 1 *4499 (semicarbaxone m. p. 166") is formed. The compound C10H160 obtained from active rnethylcyclohexan- 3-one and acetone (Zoc. cit.) is now proved to be ~-methyl-A2(orY'-cyclo- hmenyl-3-acetone C,H8Me*CH2*COMe or a mixture of both. By reduction by Paal's method it yields l-methylcyclohexyZ-3-acetone C,H~oMe-CH2*COMe b. p. 212-214' D21'5 0.8915 n:"" 1.4496 (samzcarbaxone m. p. 154O) which is converted by alkaline hypo- bromite into 1 -methylcyclohexyl-3-acetic acid and by magnesium methyl iodide ultimately into l-rnethylcyclohexyltri~thyZcarbirnoZ C,Hl,Me*CH,*CMe2*OH,i. 184 ABSTRACTS OF CHEMICAL PAPERS.b. p. ll?o/20 mm. (phenylurethane m. p. 126'). By the elimination of water the carbinol yields a hydrocavbon CllH20 b. p. 186*5-187.5' DZo 0.81 20 ng 1.4546. i-Methylcyclohexan-%one condenses with acetone in the same manner as the active substance yielding a compound C,,H,,O b. p. 2 14-2 17" D21 0 a9 18 n 1.4704 (semicurbaxone m. p. 150-151°). 1-Methylcyclohexan-2-one and acetone after keeping with alcoholic sodium ethoxide for four weeks yield mesityl oxide and l-methyl-Al- cyclohexenyl-2-acetone b. p. 216-217° D19 0.936 ng 1,4778 (semi- carbaxons m. p. 173-174') ; the latter yields by reduction by Paal's method l-metlqlcyclohexyI-2-acetone b.p. 2 12-2 14O D2l 0.9050 ng 1.4546 (semicurbaxone m. p. 179") from which l-methylcyclohexp?- 2-acetic acid (silver salt (3,H1,02Ag; amide m. p. 160-161') is obtained by oxidation by alkaline hypo bromite. c. s. Studies in the cycZoPentadiene Series. 11. 5-Nitro-2 3-di- benzoylcycEopentadiene. WILLIAM J. HALE and LAMBERT THORP (J. Amer. Chern. Soc. 1913 35 68-75).-1t has been shown by Hale (A 1912 i 566) that acetonylacetone condenses with nitromalon- aldehyde to form 5-nitro-2 3-diacetylcyclopentadiene. A similar condensation has now been effected with diphenacyl. When diphenacyl (1 mol.) is added to a solution of sodium nitro- malonaldehyde (1 mol.) and sodium hydroxide (2 mols.) and the mixture is left for eight to ten days a t 40' 5-nitro-2 3-di6enxoylcyclo- pentadiene N02*CH<CH:CBz m.p. 237-238' (decomp.) is obtained in a yield of 75% of that calculated from the amount of aldehyde used. The compound crystallises in yellow prisms; its sodium barium and silwer salts are described The oxime m. p. 155-156' (decomp.} and the and m. p. 264-265O form slender yellow needles. The phenyl- hydruxone crystallises in yellow needles; it is unstable and readily undergoes an intramolecular condensation. If 5-nitro-2 3-di benzoylcyclopentadiene is boiled with dilute nitric acid it undergoes oxidation with production of carbon dioxide oxalic acid and benzoic acid A similar result is obtained by means of an alkaline solution of potassium permanganate 1 mol. of the com- pound yielding carbon dioxide (3 mols.) oxalic acid (1 mol.) nitric acid (1 mol.) and benaoic acid (2 mols.).CH:C;Bz E. G. Thio-derivatives of Ketones. EMIL FROMM ( Annalen 19 12 394 290-309).-[ With FRITZ Ha~s.]-The substance previously described as duplobenzylidenethioacetone by Fromm and Holler (A. 1907 i 710) is now shown to be a mixture of stereoisomeric bases the duplobenzylidenethioacetonea~mines C2,H2,NS2 and its extraordinary additive compounds with acids are oimply salts of these bases; consequently the theories advanced by Fromm and Holler to explain the formation of these additive compounds are abandoned. The hydro- cldoride C20H2,NS2,HC1 has m. p. 238" the sulphate has m. p. 192' and the nitrate bas m. p. 211'. duplobenzylidenethioacetono hydrate and the two additive compounds The substance previously describedORGANIC CHEMISTRY.i. '185 with ammonia rn. p. 142' and 145" respectively are simply duplo- benz y lide nethioncetoneamine. The neutral by-product duplobenzylideneoxythioacetone m. p. 1864 obtained by Fromm and Holler in the preparation of their so-called duplobenzplidenethioacetone (loc. ca't.) becomes the main product when sodium sulphide is employed instead of ammonium sulphide. It is now shown to be duplobenzylideneacetone mlphide C,,H,,O,S. It forms a ddbmmo-derivative CpoH2~OzSBr2 m. p. 1 6 4 O rhombic leaflets with bromine in chloroform and is oxidised by 5% potassium permangitnate by fuming nitric acid or by 30% hydrogen peroxide in glacial acetic acid t o duplobenzylideneacetone sulphoxide C,,H,,O,S m. p. 308O prisms which forms a dibromo-derivative C,,H2,0,SBr2 m.p. 211' felted needles with bromine. By treating a not too concentrated solution- of styryl methyl ketone in alcohol with ammonium poly- sulphide dzlplobenzylidsneacetone disulphide C20H2202S2 m. p. 1 2 5 O is obtained. Since duplobenzylidenethioacetoneamine yields hydrogen sulphide ammonia and styryl methyl ketone-phenylhydrazone by treatment with phenylhydraxine at a temperature not exceeding 1 40-150° it probably has the formula NH[CMe(SH)*CH:CHPh] despite its insolubility in alkalis. Moreover since it yields duplobenzylidene- acetone disul phide by oxidation by hydrogen peroxide or by iodine the disulphide probably has the formula S,[c;Me(OH)*CH:UHPh]2. By moistening with a little alcohol and then shaking with dilute sodium hydroxide the disulphide is converted into the sulphide.The latter therefore is probably S[C Me(OH)*CH:CHPh] and the sulpboxide is SO[CMe(OH)*CH:CHYh],. The disulphide and the sulphide cannot be benzoylated or acetylated but both and also the sulpboxide yield styryl methyl ketone-phenylhydrazone by treatment with phenylhydrazine. [With EMIL ~IuBERT.]-~enzylidenecccetophenone hydrosulphide CHPh:CH*CPh(OH)-SH m. p. 1 0 7 O is obtained by the action a t 0' of hydrogen sulphide on an alcoholic solution of phenyl styryl ketone containing a little potassium hydroxide. It forms a S-benzoyl deriv- ative CHPh:CH*CPAi(OH)*SBz m. p. 1 2 5 O which is not oxidised to a disulphide by iodine. Dibenzylideneoccstop~~enone ddsulphide S,[CPh(OH)-CH:CHPh] m. p. 159' is obtained by oxidising the preceding hydrosulphide by iodine in alcohol-chloroform F;olution or by adding cold alcoholic phenyl styryl ketone to alcoholic sodium sulphide saturated with sulphur and with hydrogen sulphide.The amorphous a- and P-duplobenzylideneacetophenone sulphides m. p. 96' and 1 8 1 O respectively described by Fromm and Lambrecht (A. 1908 i 989) are not pure The pure Substances are crystalline have m. p. 109O and 186' respectively and have tbe formula C,oH,,OzS not C,oH2,0S. The views previously advanced t o explain their isomerism are withdrawn. The pure substances are obtained by the action of alcoholic ammonia on phenyl styryl ketone hydroaul- phide in chloroform an excess of ammonia producing the P-isomeride m. p. lSS' a little ammonia forming the a-isomeride m.p. 109'. This method of formation together with the fact that the two sulphides VOL. clv. i. 0i. 186 ABSTRACTS OF CHEMICAL PAPERS. yield hydrogen sulpbide and 1 3 5-triphenylpyrazoloue by boiling with phenylhydrazine in glacial acetic acid leads to the formula S[CPh(OH)*CH:CHPh] for the two isomerides. a-Duplobenzyli- deneacetophenone sulphide is converted into the P-isomeride not by iodine as stated by Promm and Lambrecht (loc. cit.) but by ammonia. The stereoisomerism of tbe two substances is probably similar to that of dioximes consequently cis- trans- and amphi-modifications P h Ph Ph Ph CHPh 6H6H PhH'C' PhZH b H 6 H 'C'HPh . . CH-c. S. c-- CH CH--~&-- CH .. cis. trans. CH-C. S . c-- CH amphi. should exist. This view of the stereoisomerism receives strong support by the discovery of the third modification required by the theory.a-Duplobenzylideneacetophenone sulphide m. p. 109" (sulphone m. p. 198' is obtained by passing hydrogen sulphide without cooling into an alcoholic solution of phenyl styryl ketone containing a little potaesiurn hydroxide. P-Duplobenzylideneacetophenone sulphide xu. p. 186" (sulphone m. p. 216') is prepared by saturating an alcoholic solution of yhenyl styryi ketone with ammonia and then with hydrogen sulphide. y- Duplobe!i~zylideneacetophenone sulphide m. p. 2 1 2 O (sulphow C30H2604S m. p. 276') is obtained by adding an alcoholic solution of phenyl s tyryl ketone to alcohol saturated with anhydrous sodium Stereoisomerism of Derivatives of Phenacyl Sulphide. EMIL FROMM and JULIUS FLASCHEN (Annalen 1912 394 310-324)- Pheuacyl sulphide i d obtained i n almost quantitative yield by Tafel and Mauritz's method (A.1891,302) when the solution is kept at 0' during the reaction. I n addition to the diphenylhydrazone described by these authors a yhenylhydmxone C,2H200N2S m. p. 126' yellow needles can be prepared. Phenacyl sulphide in glacial acetic acid is oxidised to diphenacyl rrulphoxide SO(CH,*COPh)? m. p. 98' and in benzene is oxidised by a faintly acidified solution ot potassium permanganate t o diphenacylsulphone m. p. 1 20° colourless prisms. The sulphone yields diphenacylsulphone dibenzylmcrcaptole 80,[CH,*CPh(S*C?H7)~] m. .p. llOo by treatment with an excess of benzyl mercaytan in glacial acetic acid satuiated with hjdrogen chloride and forms only a dimethyl derivative S02(CHBle-COPh)2 m.p. 178' with methyl iodide and sodium ethoxide in alcohol. In boiling glacial acetic acid phenacylsulphone and the calculated quantity of phenyl- hydrazine yield diphenacy7sulphonediphenyElzydrcczone SO,(CH,*CPh:N*NHYh),. This crystallises from glacial acetic acid in yellow needles m. p. 148O and from alcohol or from benzene and petroleum in pale yellow needles m. p. 160". This second modification which can also be obtained by P h P h PhCK bH6H P h H 6 . . sulphide and with sulphur. c. s.ORGANIC CHEMISTRY. i. 187 the interaction of diphenacylsulphone and phenylhydrazine in alcohol containing a little sodium hydroxide is converted into the first modifi- cation m. p. 16So by crystallisation from glacial acetic acid.A third isomeride m. p. 170° is obtained from diphenacylsulphone and phenyl- hydrazine in alcohol archydrodiphenacylsulphonephenylhydrazone m p. 1 8 7 O being also produced. Diphenacylsulphonephenylhydraxonc m. p. 193O yellow needles is prepared by crystallising the preceding anhydride from glacial acetic acid or by boiling equal molecular quanti- ties of diphenacylsulphone and phenylhydrazine in the same solvent. Reasons are given for regarding this phenylhydrazone as trans-diphen- acylsulphonephenylhydrazone and the anhydride as a derivative of the cb-isomeride ; the diphenylhydrazones m. p. l4s0 160° and 170' are regarded as having the trans- amphi- and cis-configurations respectively. C,,H,802N,S? Anhydrodiphenacylsulphonedioxirne - f! ph*CH>SO*CH,*CPh NOH N-0 m.p. 167" white needles prepared from diphenacylsulphone and hydroxylamine hydrochloride (2 mols.) in alcohol in the presence of sodium carbonate or acetate yields acetyldiphenacylsulphoneoxime C,,H,,O,NS m. p. 1 loo by boiling with acetic anhydride. cis-Diphenacyk sulphonedioxime m. p. 2 0 4 O (acetyl derivative m. p. 15S0) is obtained from diphenacylsul phone and an excess of hydroxylamine hydrochloride in boiling alcohol containing a drop of hydrochloric acid. trans- DiphenacylsuZphonedioxime m. p. 190' (acetyl derivative m. p. 146O) is obtained together with the monoxime m. p. 173' by heating diphen- acyl sulphone with hydroxylamine hydrochloride (2 mols.) and calcium carbonate (1 mol.) in alcohol through which carbon dioxide is being passed.cis-DiphenacyZsulphoneoxime C1,H,,O,NS m. p. 1 4 4 O is obtained from equal molecular quantities of diphenncyisulphone and hydroxyl- amine hydrochloride in the presence of sodium carbonate or acetate. trans-~~phenacy~su~phoneoxime m. p. 173" is obtained from equal molecular qiiantities of diphenacylmlphone and hydroxylamine hydro- chloride in boiling alcohol in the presence of calcium carbonate. The monoximes each yield the same acetyl derivative m. p. llOo as that obtained from an hydrodiphenacylsulphonedioxime. The cis-oxime m. p. 1 440J yields anhydrodiphenacylsulphonedioxime by further treat- ment with hydroxylamine hydrochloride and sodium carbonate and t h e cis-dioxime by treatment with hydroxylamine hydrochloride and calcium carbonate. The trans-oxime m.p. 173O yields only anhydro- di phenacy lsulphonedioxime by treatment with hyd roxylamine hydro- chloride and sodium carbonate or calcium carbonate. Since the anhydrodioxime is produced from each of the monoximes it is ce1 tainly derived from the amphi-dioxime. The configurations of the Transformations of Thujane. 11. NICOLAI M. KISBNER (J. Russ. Phys. Chem. Soc. 1912 44 1759-1762. Compare A. 1911 i 71 996).-Decomposition by means of aniline or alcoholic potassium hydroxide of the unstable bromide obtained by shaking thujane with other substances are not established with certainty c. s. 0 2i. 188 ABSTRACTS OF CHEMICAL PAPERS. fuming hydrobromic acid for a comparatively short time (two to three hours) yields a mixture of two isomeric hydrocarbons CI0Hl8 the one with the higher boiling point predominating when alkali is employed.The properties of various preparations of these hydrocarbons are as follows (1) b. p. 160-161.5°/753 mm. 0.8085 (or 0.8082) m 1.4490 [aID + 17-86" (or + 15.59') ; (2) b. p. 166-168'/754 mm. D 0.8159 (or 0*8188) rz 1.4538 [a] +6*13O (or +2%'). If the action of the hydrobromic acid on thujane is prolonged for fifteen hourp distillation of the bromide yielded with aniline gives hydrocarbons with the constants (1) b. p. 16O-16Zc/762 mm. DP 0.8093 n 1.4494 +3*67O; (2) b. p. 167~5-170'/761 mm. Dfo 0*8171 nn 1.4555 kl D + 2.4'. Both hydrocarbons contain the same carbon-atom nucleus since reduction of them by Sabatier's method leads to one and the same hydrocarbon C,oH20 b. p. 161-163'/753 mm. (or 759 mm.) DF 0.7904 (or 0.7902) nD 1.4319 (or 1.4336) [a] - 1.29' (or -1.21') T.H. P. A Special Case of Racemism. MAURIZIO PADOA and G. ROTONDI (Atti Iz. Accad. Lincei 1912 [v] 21 ii 626-631).-The paper deals with the thermal analysis of the system formed by the two modifica- tions (namely the stable m. p. 75O and the labile m. p. 45') of optically active bromocamphor (d- or I-). This presents a case not considered by Roozeboom i n his analysis of the criteria for the characterisation of inactive mixtures because each enantiomorph exists in two modifications. Mixtures containing more than about 58$ of d-bromocamphor or more than 58% of I-bromocamphor have an initial m. p. with separation of pure solvent. As the cooling is continued the composition mentioned is reached and the labile form then appears.At this point the whole mass solidifies and pure solvent separates along a curve shown until the inactive conglomerate is reached which possesses the lowest transformation point. Below the curve just mentioned and the m.-p. curve of the labile modification only con- glomerates of the two bromocamphors are stable. Fused mixtures which contain less than 58% of d-bromocamphor and less than 58% of Lbromocamphor crystallise in the labile form and when cooling is continued they are transformed into conglomerates. The labile forms have therefore a small area of stability bounded by the curve of the labile modification and the curve of the separation of conglomerates already mentioned. As regards the characterisation of the racemism the racemic com- pound exists between 44' and 50.5'; below that it is split into inactive conglomerates.This is analogous to the behaviour of sodium The Constituents of Essential Oils (The Constitution of Selinene). FRIEDRICH W. SEMMLER and FELIX RISSE (Bey. 1912 45 3725-3731. Compare this vol. i 66).-1n the former com- munication t h e sesquiterpene selinene was shown to give a dihydro- chloride from which a regenerated selinene with slightly higher rotation due perhaps t o a different arrangement of the unsaturated linkings could be obtained. I n order to elucidate the constitution of these isomerides they have been oxidised with ozone. ammonium racemate studied by van't Hoff. H. v. s.ORGANIC CHEMISTRY. i. 189 Natural q-(p)-selinene on oxidation gave a very small amount of an acid but chiefly an indifferent product which was purified by conversion into a disemicarbazone C1,H,,(N*NH*CO*NH2)2 m.p. 22S0 from which the saturated diketone C13H200 b. p. 178-1t3O0/11 mm. D2O 1.0566 n 1.49994 a,,+ 1 5 O was recovered by means of oxalic acid. The fact that two carbon atoms have been eliminated by this process whereas the acid resulting from the oxidation by hypobromite contains only one carbon atom less indicates the presence in selinene of one methylene group attached directly to the ring and another in a side-chain. Regenerated selinene ortho-(a)-selinene b. p. 128-1 3 2 y 1 mm. ]I2* 0.9190 n 1.50920 a,+ 61°36' gives much less of the diketone on treatment with ozone the chief product being the acid which has been characterised as methyl selinenediketornonocarboxylate C,,H2?0 b.p. 185-190°/11 mm. D20 1.0635 n 1.47889 ~,+4'24'. l!he formation of this acid is explained by assuming t h a t the elimination of hydrogen chloride from the dichloride has resulted in the dis- placement of a double bond into the ring. A consideration of other sesqui-terpenes leads to the adoption of the annexed formulae. MeC:CH H I € € Me C CH I{. IH $-(B)-Selinene. Ortho-(a)-selinene. I J. Ozone COMe 1 I .j/ Ozone CORle H h H Diketone. Diketcmonocarboxylic acid. J. c. w. Chemical Investigation of the Oil of Chenopodium. 11. E. I(. NELSON ( J . Amer. Chern. Xoc. 1913 35 84-90. Compare A. 1911 i 797).-It has been found that when the glycol anhydride formed by the molecular rearrangement of ascaridole is treated with dilute sulphuric acid ascaridole a-glycol is produced together with two other crystalline substances one of which termed ascaridole p-glycol CI0Hl8O3 crystallises with 1H20; the anhydrous substance has m.p. 103-105°; when this glycol is warmed with dilute sulphuric acid thymol is produced. The other substance termed the " erythrite," C,,H2,0 also crystallises with 1H,O and when anhydrous has m. p. 128-130°; it is decomposed by boiling dilute sulphuric acid with formation of a ketone with a strong menthone-like odour and ai. 190 ABSTRACTS OF CHEMICAL PAPERS. phenolic substance m. p. 80-81’; the esmicarbazone of the ketone has m. p. 182-184’. On oxidising the “erythrite” with alkaline potassium permanganate an acid Cl0Hl8O6 m. p. 19O-19lo is produced which forms rhombic prisms; when this acid is heated at 210° it is converted into its anhydride and on further heating yields ascaridic anhydride m.p. 70-71’. If the acid C,,H,,O is oxidised with potassium permanganate in presence of sulphuric acid i t yields P-metbylheptane-yt-dione and it is therefore probable that it is a modi- fication of aa-dihydroxy-a-methyl-a-hopropyladipic acid. The “ ery- thrite ” therefore probably has the structure The acid CIOHIROB obtaineh b y the oxidation of the a-glycol is converted by further oxidation into P-methylheptane-y[-dione. When the glycol anhydride is boiled with a saturated solution ot oxalic acid a small quantity of the phenolic substance m. p. 80-81’ is produced which is formed on boiling the u erythrite ” with dilute sulphuric acid and is also obtained by treating the a-glycol with strong dehydrating agents. On heating the glycol anhydride with benzoic anhydride a t 150° an ester of carvacrol is produced.From the results of this work it is considered that the a-glycol has /CH2- CH the constitution CMe obtained by its oxidation has the structure of as-cioeolic acid C02H*CMe=C H,*CH,*C(C,H7)*C0,H. E. G. Op- \C-C,H and that the acid \CH(OH)-CH(OH)/ Action of Gaseous Oxygen on Caoutchouc. STANLEY J. PEACHEY (J. SOC. Chem. Id. 1912,31 1103~-1104).-When purified caoutchouc in the form of a thin film is exposed to an atmosphere of oxygen a t a temperature of 85O oxidation commences after a few hours’ heating and then proceeds rapidly t o completion. Results of experiments with Ceylon caoutchouc show that under these conditions each CloHIf unit of the molecule combines with 4 atoms of oxygen.This result is not in agreement with that obtained by Herbst (Aa 1906 i 196) and it may be assumed that the reaction which takes place when caoutchouc in benzene solution is oxidised by air (as in Herbst’s experiments) differs from that which occurs when caoutchouc itself is oxidised by pure oxygen. The oxidation most probably results in the formation of additive products. w. P. s. The Nitrogenous Constituent of Para Caoutchouc and Its Bearing on the Nature of Synthetic Caoutchouc. CLAYTON BEADLE and HENRY P. STEVENS (J. Xoc. Chem. Ind. 1912 31 1099-1 101. Compare A. 1912 i 789).-lt is shown that the removal of insoluble (nitrogenous) constituents from csoutcho~ic results i n deterioration of the latter although it is open to question how far the quality of caoutchouc is improved by the presence of more than a certain proportion of iusoluble matter.In the vulcaniPation process the insoluble matter appears to play the part of a sulphur carrier.ORGANIC CHEMISTRY. i. 191 The authors have also made experiments on the influence of the resinous constituents on the vulcanising properties of caoutchouc and find that the removal of the resins results in a marked deteriora- tion of the quality of the caoutchouc. The absence of nitrogenous substances and resins in synthetic caoutchouc should make the latter inferior to natural rubber. w. P. s. Chemistry of Caoutchouc. VI. Theory of Vulcanisation. IV. DAVID SPENCER and C.A. WARD (Zeitsch. Chem. I n d . Kolloide 1912 1 1 274-280. Compare A. 1912 i 706).-Experiments have been made to ascertain whether the so-called " depolymerisation " of caoutchouc which is brought about by mechanical or thermal treat- ment is accompanied by a change in the rate at which it reacts with sulphur in the process of vulcanisation. For this purpose comparative measurements were made with two exactly similar mixtures of 100 parts of caoutchouc and 10 parts of sulphur. In the one case the caoutchouc was kneaded for thirty minutes at a moderate temperature the sulphur being then added and the mixbg eEected by a further kneading for ten minutes. In the second case the treatment was similar except that the caoutchouc was subjected to the mechanical treatment for ninety minutes at a much higher temperature.From the observations made on the rate of vulcanisation a t 135O i t appears that there is no appreciable difference between the two samples and the authors draw the conclusion that '' depo1ymerisati.m " has no influence whatever on the chemical result of the vulcanisation process. The conclusions arrived a t by Axelrod (Gummi Zeit. 1909 24 352) are therefore not confirmed by these experiments. H. M. D. The Action of Chloroacetyl Chloride on Ethyl Malonate ; Iminotetronic Acid. ERICH BENARY (Bey. 19 12 45 3682-3686). -As the substance described as the ester-amide of tetramic acid (Benary A. 191 1 i 672) is in reality ethyl iminotetron-a-carboxylate (Anschutz A. 1912 i 836) the compound C,H,,05 from which it is obtained by the action of ammonia is presumably ethyl isotetron- a-carboxylate; this view is supported by the action of organic bases which give compounds similar t o that produced by ammonia; these compounds are probably ketonic but do not yield phenylhydrazones (compare Wolff A.1900 i 582) ; thoy frequently yield salts however derived from the enolic structure. Ethy? phen;yliminotetron-a-carboxylate O*C( ?Hz-co>CH-CO,Et :NPh) ob- tained by the interaction of equivalent quantities bf ethyl isotetron- a-carboxylate and aniline crystallises in needles m. p. 116-1 17" ; it exhibits both acidic and basic properties. Ethyl phenylhydrazinotetron-a-carboxylate (already described) yields a wotassium salt. 1 Ethyl pipericlinoisoletron-a-carboxylcLle 9H2-- Co>C*CO,Et m p.107-108° from equal weights of piperidine and ethyl isotetron- 0. C(C,NH,,)i. 192 ABSTRACTS OF CHEMICAL PAPERS. a-carboxylate as might be expected from the structure has no acidic properties. When iminotetronic acid in benzene solution is treated with rather more than an equimolecular quantity of bromine bromoiminotetronic acid ?H2*c.(oH)>CBr needles m. p. 182O is obtained; i t gives a 0-C(. NH) red coloration with ferric chloride. On adding ice to the reaction mixture from iminotetronic acid and CH,-CO >C:NO,H is pre- nitric acid aci-nitroiminotetronic acid I O*C( :NH) cipitated leaflets m. p. 255-258' (decomp.); i t is a strongly acidic substance which gives a phenylhydrazonc yellow tablets m. p. 21 1-212O. The conclusion is drawn that the action of chloroacetyl chloride on ethyl sodiomalonate consists of two concurrent processes one of which produces unstable ethyl chloroacetylmalonate which undergoes spontaneous change into ethyl tetron-a-carboxylate whilst the other process involves the enolic form of ethyl sodiomalonate which reacts with the acid chloride producing ethyl isotetron-a-carboxylate. D.F. T. Hydroxymethylfurfuraldehyde. FRANCESCO ANGELICO and A. COPPOLA (G'uzzetta 1912 42 ii 583-589).-The authors confirm the formula for this substance given by Fenton and Gostling (T. 1889 75 423) and by the application of the Angeli-Rimini reaction they have prepared from it a-hydro.2.yrnethylfurccnhydr- oxamic acid C,H?O,N which crystallises in pink lustrous soapy scales m. p. 13So t h e free acid being prepared from the copper Falt (C,H,0,N),Cu,H20.When the acid is hydrolysed witlh 25% bulphuric acid it yields hydroxylamine and hydroxypyromucic acid (m. p. 165'). R. V. S. Constitution of Bergapten. HERMANN THOMS and E. BAETCKE (Ber. 1912 45 3705-3712).-Bergapten which Pomeranz showed to be a coumarin-couma:one derivative of phloroglucinol (A. 1892 71 ; 1893 342) was found to occur in certain fruits accompanied by an isomeride xanthotoxin (A. 1912 i 40) to which the formula (I) was assigned. Bergapten has now been converted into an amine and this into a quinone contairhg no methoxy-group from which the conclusion is drawn that the methoxy-group is pura to the unsubstituted carbon atom and that the substance has the constitution (11). OMe OMe 11. CH< CH/\CH:FH 1 1 0-\ /o-co \/ This is confirmed by the fact that xanthotoxin yields the same quinone.Aminobergupten C1,H70,*NR is obtained by the reduction of the nitro-derivative (Ponieranz Zoc. cit.) with tin and hydrochloric acid in slender pale yellowish-green needles m. p. 19So and yields an acetyl compound m. p. 208'. When oxidised with sadium dichromate theORGANIC CHEMISTRY. i. 193 methoxy-group is replaced and the golden-yellow quinone C1,H,O5 m. p. 248-250° is formed. Aminoxanthotoxin is prepared in the same way and is similar in appearance to its isomeride; it melts however at 236” is more easily acetylated yielding an acetyl compound m. p. 246-247O and is much less soluble in cold sulphuric acid but it yields the same quinone. The quinol C,,H,O,(OH) crystallises with 2H,O in light green needles which lose water at 11 Oo and yield a diacet?/Z compound m.p. 208-209O and a diphenylurethane derivative CllH,0,(O-CO*NPh2)2 M. p. 229-230O. J. C. TV. Action of Hydrogen Peroxide on Hydroxythionaphthen Hydroxythionaphthen Carboxylic Acid and (‘ Thioindigo.” MAURICE LANFRP (Compt. rend. 19 12 155 1 5 17-1 51 9. Compare A. 191 2 i 293).-Hydroxythiouaphthen in alkaline solution gives a blue precipitate on the addition of hydrogen peroxide leaving a brown liquid from which only gummy substances could be extracted. The blue precipitate on solution in water and addition of strong acid gives a red flocculent precipitate which resembles ‘‘ thioindigo ” in all its properties. The addition of hydrogen peroxide t o a boiling Aolution of hydroxyt hionaphtben in acetic acid gives a red precipitate of ‘‘ thioindigo,” which slowly dissolves and t h e solution becomes colourless.Extraction with ben- (\,C*OH I (1 ICH zene separates out 3-hydroxy-1-diox~thio~phthen (annexed constitution) m. p. 139O which in i t s chemical properties closely resembles the hydroxy- thiouaphthen from which i t is prepared. The effect of hydrogen peroxide on the sodium salt of hydroxy- thionaphthencarboxylic acid is to destroy its phenolic character with the formation of a small quantity of “thioindigo.” The major part of the salt is resinified. In the presence of hydrogen peroxide finely divided ‘‘ thioindigo ” slowly dissolves in acetic acid to a red solution which gradually becomes decolorised. The only products of extraction were gummy substances.w. a. \/‘<,’ so2 ‘‘ Bisphenylthiophenindigo ” [5 5‘- Diphenyl- - bisthio- phen-3-one]. PAUL FRIEDLAENDER and ST KIELBASINSKI (Bey. 191 2 45 3389-3396).-Although m-hydroxydiphenyl shows no tendency to pass over into an ortho-quinonoid compound the analogous 3-hydroxy-5-phenylthiopben behaves entirely differently readily forming ‘‘ bisphenyZthiophenin&igo,” The dye is prepared by the following series of operations. On heating ethyl cinnsmate with sulphur a disulphide thiobenzoylthio- (Baumann and Fromm A. 1897 i 191),is acetic acid S< formed. The ring is opened by sodium sulphide and by the action of chloroacetic acid a compound >CH. co-y=y.co- cH‘CPh*S S-CPh’ s-7” CPh:CH CO2H*CH2*S*CPh 1CH.S CO*S*CH,*CO,Hi.194 ABSTRACTS OF CHEMICAL PAPERS. is formed which when boiled with acetic anhydride is converted into On hydrolysis 4-hydr- acetoxyphenylthiophen S< CH-y*O*CO *CH CPh:CH oxy-2-phenylthiophen is obtained. This condenses with aromatic aldehydes or with isatin to dyes forms a quinoneoxime with nitrous acid and is converted by alkaline or acid oxidising agents into '( bisphenyl thiophenindigo." The disulphide crystallises in broad needles m. p. 156'. 4-Hydrox~-2-phenylthio;nhen separates in slender needles m. p. 78' ; the acetyl derivative forms broad colourless compact platelets In. p. 75". The quinone oxirne S< CPb=z=(?H prepared by interaction with C( :N*OH)'CO sodium nit,rite forms broad 'faint brownish-yellow needles m. p. 21 6'. On bromination a product CPh< CBr*(?o is obtained crystallising in brownish-yellow plates m.p. 134". It does not react simply with aniline on warming with sodium acetate slender red needles or ruby- red prisms of a brominated diphenylthiophenindigo are obtained. 4-Hydroxy-2-phenylthiophen reacts with piperonal hhe coadensation product crystallising in long yellow needles m. p. 196'. b' Bis- 5-phen yl-2 -thiophenindigo " [5 5'-diphen yt- A2,w-bisthiophen-3 -one] separates in brownish-red lustrous needles m. p. 280". '( 5 - Phun yl-2-thiop?ien-3-i?edoleindigo " [ 5-phen y l- 2-( 3'-indoxy1)-t hi o- phen-3-one1 produced on condensation with isatin crystallises in sealing wax-red needles m. p. 281'). [ 5-phenyl-2 - (2'-indoxyl)- thio- phen-3-oneJ EH 'cyC:C<g>C6H4 obtained on boiling isatin- CPh*S anilide with phenylhydroxythiophen in acetic anhydride crystallises in slender dark violet needles.S-CBr,' ' b 5 - Phenyl-2 - thiophen- 2 - i ~ d o Zeindigo " E. F. A. Methylation of Histidine Arginine and Lysine. I. R. ENUELAND and FRIEDRICH KUTSCHEE (Zeitsch.Biol. 1912,59,415-419). -On methylation of histidine monochloride with methyl sulphate and barium hydroxide puntamethyEhistidine is obtained. The aurichloride crystallises in large lustrous needles the chloride is an oil and the free base decomposes rapidly. Small quantities of the crystalline aurichloride of tetramethylhistidine are obtained at the same time. Under similar conditions arginine yields a tetramethyl derivative the aurichloride forms short stout needles m. p.173-175'. Three of the methyl groups are attached to nitrogen in the side-chain one only to nitrogen in the guanidine complex. Lysine yields a compound probably the ethyl ester of hexamthyl- Zysine which gives an aurichloride m. p. 208' corresponding with the formula C,,H,,O,N Au,Cl,. E. F. A . Strychnos Alkaloids. XVI. Dihydrobrucinoic Acid and isoBrucinolone. HERMANN LEUCHS and GEORQE PEIRCE (Ber. 19 18 43 341 2-3420).-Dihydrobrucinonic acid which contains an alcoholicORGANIC CHEMISTRY. i. 195 hydroxyl (compare A.. 1212 i 210) forms an acetyl derivative when acted on by acetic anhydride and sodium acetate. More vigorous action produces a neutral compound containing two further acetyl residues less a molecule of water. Dihydrobrucinonic acid does not react with nascent hydrogen or with hydroxylamine.It is broken down by sodium hydroxide into glycollic acid and isobrucinolone C,lH,20,N2. The latter forms an acetyl derivative and on treatment with concentrated hydrogen chloride gives isobrwinolone hydrate. At higher temperatures this is reconverted into isobrucinolone (compare Leuchs and Brewster A. 1912 i 210). With concentrated nitric acid a nitro-derivative C,,H,,O,N is obtained ; the change involves the formation of a quinone and the subsequent nitration of this. With sulphurous acid a paler reduction compound is obtained from the quinone. AcetyEdih?ldrobl.uci~~o~~c acid forms colourless four-sided prisms rn. p. 235-238'. The neutral product C,7H2,0,N or C29KS0010N2 crystallises in colourless chisel-shaped prisms m.p. 280-282' after becoming yellow at 260'. By the action of acetic anhydride on brucinonic acid a componnd iC13H1404N)z is obtained crystallising i n long matted lustrous needles m. p. 125-127O. Acetylisobrucinolone forms large colourless platelets m. p. 281-283' (decom p . ). isoBrucinolone hydrate separates in four-sided prisms which froth at 205-208' become solid again turn brown at 290° m. p. 310-315' (decom p. ). The hydrochloride forms four-sided platelets ; the sulphate consists of massive prisms which become brown at 235' decomp. 238'. Nitrobisapomethyldihydroisobrucinolone crystallises in flat orange- yellow needles which become brown at 250' and completely charred a t 340'. fl~trobisapomethylisobruc~no~one gives massive reddish-yellow prisms which become brown a t 240'.Niti.obisapomethylbrucinoEona crystitllises in small yellow octahedra dissolving in concentrated sul phuric acid with a yellow coloration and in concentrated sodium hydroxide with a violet coloration. E. F. A. Strychnos Alkaloids. XVII. Isolation of the Hydrate of a Fourth Strychninesulphonic Acid. HERMANN LEUCHS and JOHANNES WUTKE (Ber. 191 2 45 3686-369 I).-Analogous to the fourth brucinesulphonic acid (Leuchs and Geiger A. 1911 i 1018) a fourth strychninesulphonic acid (compare Leuchs and Schneider A. 1909 i 671) has been obtained as a very stable hydrate which retains the additional water very tenaciously. The solution of the reaction product obtained as described earlier (Leuchs and Schneider loc. cit.) after crystallisation of strychnine- sulphonic acids I and 11 and subsequent concentration under reduced pressure deposits a mixture of the acids I 11 and 111 with the above-mentioned hydrate which last can be separated in the freei.196 ABSTRACTS OF CHEMICAL PAPERY. state and also as a compound with strychninesulphonic acid 111; the total yield of hydrate in the two forms amounts to approximately 3%. Strychninesulphonic acid IV hydrate C21H2496N,S 2H,O stout prisms or rhombohedra m. p. 275" (decomp.) [aJ$ + 18*3O could not be dehydrated beyond C21H2406N2S even at 135" in a vacuum over phosphoric oxide. The double compound with strychninesulphonic acid 111 C H,205N2S,C21H2,06N2S slender prisms or needles m. p. 250" (decomp.) fa] + l U l o can also be obtained by mixing solutions of the hydrate and excess of the acid 111; in the absence of excess of strychninesuiphonic acid 111 the compound is resolved by hot water into its constituents.D. F. T. Synthesis of Haemopyrrole-b. OSKAR PILOTY and A. BLOMER (Bey. 1912 45 3749 -3753).-Etbyl acetylpyruvate condenses with aminobutanone or with aminoacetone to form pyrrole derivatives. I n the former case 4-acetyl-2 3-dimetbylpyrrole-5-carboxylic acid is obtained which on heating at 215" is converted into 4-cccetyl- When this is treated with 3 3-climethyZpyrrole CH=y*COMe NH<CMe CMe hydrazine and sodium etboxide 2 3-dimethyl-4-etbylpyrrole (hzemo- CH=YEt is formed. CMe CMe' pyrroIe-6) NH < With aminoacetone the product is 4-acetyE-3-methylpyrrole-5-carb- oxylic acid NH< C(CozR):F*C*Me. This has m.p. ZOOo. During the CH===CRle reaction an isomeric by-product m. p. 250" (decomp.) is also formed. less prismatic rods m. p. 204' (decomp.). platelets with sharp edges m. p. 137'. is identical with the natural compound. 4- Acetyl-2 3-dimethylp~rrole-5-cal.boxy~ic acid crystallises in colour- 4-dcetyl-2 3-dimetkylpyrrole separates in short colourless prismatic The synthetic haemopyrrole-b E. F. A. Cyclic Imines VII. Ahrens' So-called 7-Picoline. JULIUS VON BRAUN and A. SCHMATLOCH (Ber. 1913 43 3649-3653).-The method described by Ahrens f o r the separation of pure 4-methylpyridine (y-picoline) by precipitation with mercuric chloride (A. 1905 i 232) is found to yield a mixture instead of a pure product. Successive reduction and benzoylation of 4-metbylpyridine prepared by Ahrens' method produced a benzoyl derivative C6H,,NBz b.p. 189-1 90°/1'7 mm. which on distillation with phosphorus pentabromide (compare von Braun and Sobecki A. 1911 i 413) formed a product which could be separated into two fractions by distillation. The smaller and less volatile portion b. p. 150°/19 mm. DY 1.9305 was pro ba b 1 y apt-tri bromo-a- metll ylpentane and gave an unsaturated organo-magnesium compound which absorbed carbon dioxide with the formation of s-muthyZene-n-I~exoic acid C0,H*[CH,]3*CMe:CH b. p. 218-221" r?;O 0.9406 n 1.4442; the formation of this series of compounds is attributed to the presence of 3-methylpyridine in theORGANIC CHEMISTRY. i. 197 original base. The m.ore volatile fraction C6H12Br2 b. p. 1 15-120°/ 19 mm.DT 1,608 on treatment with potassium cyanide yielded a dinitrile C,H,,(CN) b. p. 171-174°/10 mm. which was hydrolysable apparently t o a mixture of p- and y-methylpimelic acids. Neither fraction therefore was of pure 4-methylpyridine. D. F. T. The Action of Hydroxylamine and Phenglhydrazine on Benzoyldehydracetic Acid. A Correction. JOH. SCEIOTTLE (Ber. 1912 45 3779. Compare A. 1912 i 915).-Reaction between free hy droxylarnine and benzoyldehydracetic acid was effected by mixing hydroxylamine sulphate with the theoretical quantity of alcoholic potassium hydroxide filtering the precipitated potassium sulphate and adding the phenyl-lactam of benzoyldehydracetic acid to the filtrate. E. F. A. Cyclic Imines. VI. Ring Homologues of Tetrahydro- quinoline. JULIUS VON BRAUN and B.BARTSCH (Ber. 1912 45 3376-3389).-The tendency t o form seven-membered rings such as hexamethyleneimine is very much increased when two of the carbon atoms are members of a beuzene nncleus ; thus o-&chlorobutylaniline on elimination of hydrogen chloride readily forms tetrahydrohomo- quinoli.fle CsH4<JgH-CH2 CH2*CHq>CH2. The constitution of the quinoline is established by the fact that when the ring is opened by the action of phosphorus pentachloride 6-chloro-o-benzoylarinobutylbenzene COPh*NH*C,H4=[CH,1,C1 is formed which is in turn convertible into the already known 6-0- benzoylaminophenylvaleric acid. Homotetrahydroquinoline resembles the isomeric %methyltetrahydro- quinoline and the lower ring homologues in its stability towards hydrolytic and reducing reagents and also towards oxidation; it is hardly altered by distillation with silver sulphate.The quinoline could not be prepared by other methods such as the distillation of 6-o-diaminobutyl benzene hydrochloride or by the inter- action of y-phenylpropylamine with formaldehyde. o-Amino-6-hydroxybutylbenzene NH2*C6H,*[CH2]4-OH prepared by the reduction of the ester NH,*C6H,*[CH2]~C0,Et by means of so'dium and alcohol is a viscid almost odourless oil b. p. 180-183'/12 mm. The dibenzogl compound crystallises in snow-white platelets which sinter a t 127' m. p. 130' ; the platinichloride forms dark red platelets which blacken at 1689 m. p. 175'; the picrate separates in green leaflets m. p. 179'. 0- ArrLino-6-chlorobzctgZbenxene was not obtained pure ; the platini- chloride crystallises in pale yellow platelets m.p. 182-183'. Tetrahydrohomoquinoline is an almost colourless oil b. p. 131-133'1 16 mm. 253-255'/760 mm. DF 1.0325 solidifying to colourlesv crystals m. p. 32'. The hydrochloride has m. p. 186'; the pale yellow granular crystals of the platinichloride blacken at 192' m. p. 194'; the picrate crystallises in yellowish-red needles m. p. 179'; the benzoyl derivative has m. p. 96" whilst the benzznesdphonyi com- pound haa m. p. 109'.i. 198 ABSTRACTS OF CEEMICAL PAPERS. The p2atinichloride of the dimeth?~l derivative C,,H,,NMe2PtC1 produced on long heating with methyl iodide hits m. p. 137O. When heated with phosphorus pentachloride a t 150° tetrahydro- homoquinoline yields 8 -chZoro - o - benzoyhnzinobutylbenzene which crystallises in lustrous silvery platelets m.p. 11 So. The corresponding iodide when decomposed with potassium cyanide yields 6-benxoyl- aminophenylvaleronitrile C,H:,-CO*NH*C H;[CH2],*CN m. p. 114’ from which the corresponding acid (A. 1907 i 524) is obtained on hydrolysis. 6 - o-Diaminobutylbenxene prepnred hy reducing the nitrile of o-benzoylaminophenyl butyric acid forms a colourless oil of strongly basic odour b. p. 17Z0/14 mm. o-y-Chloropropylbenxonitrile is a pale yellow oil volatile in steam b. p. 153’119 mm. is obtained m. p. 79”. The nitrile condenses with sodium phenoxide to o-y-plienoxypropyl- benzonitrile CN=C,H,*[CH,],*OPh a pale yellow oil b. p. 210°/ 23 mm. The corresponding o-y-phenoxypropylbenxoic acid has m. p. 120’. On hydrolysis o-y-chloropropylbenxoic acid CO,H*C,H; [ C€€,],* GI E.F. A. Thiazoles. REINHOLD VON WALTHER and H. ROCH (J. p. Chem. 19 13 [ii] 87 27-66).-Although the condensation of thiocarbamide with w-bromoacetopheuone and other halogeno-ketones of the tjype CHXR*COR may give rise t o either aminothiazoles (formula I1 below R’ and R” = H) or iminothiazolines (IV or V R’,R = H) the work of Traumann (A 1889 414) and others has shown that only amino- thiazoles are produced. s-Disubstituted thiocarbamides always yield iminothiazolines whilst the as-disubstituted derivatives give rise to aminothiazoles. With respect to the mechanism of the condensation the authors suggest that the first stage consists in the addition of the halogeno- ketone to the sulphur atom of the thiocarbamide and that the removal of hydrogen haloid and water from the intermediate compound thus produced is preceded by the formation of an internal salt derived from the enolic form the constitution of this salt being determined by the relative basicity of the amino-residues of the thiocarbamide ; thus in the condensation of as-disubstituted thiocarbamides NR’R”*CS*NH with o-bromoacetophenone the compound NRR’-C(NH2):SBr-CH2*COPh is first produced which is transformed successively into the enolic salt I and aminothiazole I1 if N H R R is more feebly basic than NH, NR’R”-C==N Ntt’R’*g-NH,-Y I + H,O + HBr. I.SBr*CH:CPh -+ 1 I. S.CH:hPh On the other hand if NHRR” is a stronger base than NH the com- pound 111 IS formed as an intermediate product which decomposesORGANIC CHEMISTRY.i. 199 into a secondary amine and thiocyanoacetophenone as shown in t h e following scheme N H R’ R”-;C; - N H -+ HBr+H,O + ‘IL’ d*CPh:CH*SBr NR‘R”- 6Ph:CH-S -+ YN H2° NHR’R” + OH*CPh:CH*SCN. An explanation is thus afforded of the behaviour of as-dimethylthio- carbamide which with w-bromoacetophenone does not form an amino- thiazole but undergoes decomposition into dimethylamine and thiocyanoacetophenone (Spica and Carrara A 1892 215). s-Disubstituted thiocarbamides NHR’*CO*NHR‘’ in which the amino-residues are of approximately equal basicity may give rise t o two isomeric iminothiazolines the formation of isomerides of this kind has been observed by Stenz (Diss. Dresden 1899) and Wunsche (ibid. 1901). When the basicity of one of the amino-groups is much greater than that of the other only one isomeride will be formed ; thus both 8-p-tolylbenzylthiocarbamide and 8-p-tolylmethylthiocarbamide condense with w-bromoacetophenone to form only one iminothiazoliie (formula V where R’ =p-C6H,Me and R = *CH,Ph or Me).The constitution of t h e iminothiazolines derived from s-disubstituted thiocarbamides is readily determined (1) by heating with carbon disulphide which leads to the removal of the imino-group as the corresponding thiocarbimide or (2) by hydrolysis with hydrochloric acid the imino-group in this case being removed in the form of a primary amine. With respect to the thiazoles derived from mono-substituted thio- carbamides the authors point out that no definite proof of their constitution has hitherto been brought forward.Although the work of Traumann (Zoc. cit.) appears to indicate that the thiazole obtained from methylthiocarbamide and w-bromoacetophenone is probably a 2-methylimino-4-phenylthiazoline the observations described in the present paper prove conclusively that the tbiazole derived from p-tolyl- thiocarbamide has the constitution of an aminothiazole. 2-p-T’oluidino-4-phenyZthiazole Eph”>C*NH*C,H4Me is obtained CH-S in the form of its hydrobromide slender needles m. p. 205’ (decornp.) by heating ptolylthiocarbamide with w-bromoacetophenone in alcoholic solution the free base being liberated from the hydrobromide by warming with pyridine. It crystallises in leaflets m. p. 1 2 3 O and forms a hydrochloride which melts and becomes green at 2 1 2 O a sulp?hate m.p. 152O an acetate m. p. 85O an3 thiocyanate m. p. 1 2 5 O all of which crystallise in colourless needles ; the platinichloride forms orange leaflets m. p. 230° the picmte yellow needles m. p. 185’. It reacts with phenylcarbimide in ethereal solution to form the carbamide. L - 8Ph*N>C*N(C,H4Me)*CO*NHPh crystallising in lustrous leaflets CH-Si. 200 ABSTRACTS OF CHEMICAL PAPERS. m. p. 196.5'. Towards both oxidising and reducing agents the thiazoIe is remarkably stable but is decomposed by hydrochloric acid at 225-250' into acetophenone p-toluidine and ammonia ; when heated with carbon disulphide a t 250° i t forms p-tolylthiocarbimide. The acetyl derivative C,,HIGON,S forms colourless prisms m. p. 124.5' ; the benxoyl derivative prepared by the pyridine method in benzene solution crystallises in hard prisms m.p. 207'. With the object of synthesising the above acyl derivatives the authors have endeavoured to condense w-brornoacetophenone with 8- and us-acetyl-p-tolylthiocarbamide and s-benzoyl-p-tolylthiocarbamide in alcoholic solution but find that no condensation occurs. It would thus appear that acylthiocarbamides are incapable of undergoing the t hiazole condensation. 2-p-Toluidino-4-phenylthiazole combines with 1-chloro-2 4 6-tri- nitrobenzene in hot alcoholic solution to form an unstGble additive compound C2,H160,N,SC1 which crystallises in red needles m. p. about 90° and is resolved by acids or alkalis into its components ; the additive compound with 1-chloro-2 4-dinitrobenzene forms stout dark red crystals m. p.about 60'. as-p-Tol~lbenzylthiocurba~ide C,H,Me-N(CH2Ph)*CS*NH,! obtained by heating N-benzyl-p-toluidine hydrochloride with ammonium thio- cyanate and water crystallises in colourless needles m. p. 155.5' and is converted by the action of o-bromoacetophenone in warm alcoholic solution into 2-p-tolylbenxyZamino-4-phanyZthiazole EPh-N CH-S >C*N(C,K,Me)*CH,Ph which forms large prisms m. p. 125' and yields a hydrochlode ft picrate m. p. 155" and a platir&hZoride m. p. 225' (decornp.). 2-p- Tolylimino-4-phen?/E-3-benx~Zthiacol!ine C,H,Me*N:~-~*CH,Ph prepared from s-p-tolylbenzylthiocarbamide and w-bromoacetophenone forms colourless needles m. p. 152' ; the hydrochloride,. plattnichloridrz m. p. 233" (decornp.) arid picrate KKI.p. 155" are described. That the compound has the above constitution and not that of the isomeric 2-benzylimino-4-phenyl-3-p-tolylthiazoline has been established by its behaviour towards carbon disulphide which a t 200' leads to the removal of the p-tolglimino-group as p-toly lthiocarbimide and the >N* C H,Pii formation of 2-thion-4-p7~enyl-3-benzyltltiaxoEine I which crystallises in pale yellow needles m. p. 101". When heated with benzyl chloride for eight hours at 175O 2-p-toluidino-4-phenylthiazole yields 2-p-tolylbenzyZa~n~no-4-ph~n~l- 5 -benxyithiaxole &CH,Ph)*S N~U*N(C,H,Me)*CB,Ph. This forms S*CH:CPh ' s-cs CH:CPh CPh-- A t needles m. p. 1 Zj'. and is accompanied by 2-p-toZuidino-4-phe.nyl- 6-benxylthiazole I I N>C*XH*C6H4Me which crystallises in CPh-- C(CH,,Ph)*S needles 111.p. 1'74',' an; yields a platinichloride M. p. 203' (decomp.) and a picrate m. p. 151'.ORUANIC CHEMISTRY. i. 901 That the introduction of the benzyl group has taken place in the thiazole ring aud not in the p-toluidino-residue has been proved in the case of the last-mentioned thiazole by the formation of an acetyl derivative C,,H,,ON,S m. p. 144O and also by the removal of the p-tolylimino-group as p-tolylthiocarbimide when the thiazole is heated with carbon disulohide. 1 2 - p- To2 ylinzino- 4-phenyl- 3-meth ylthiaxoline sph "Me>C:N*C,H,Me CH-S obtained in the form of its methiodide large needles m. p. about 200' (decomp.) by heating 2-p-toluidino-4-phenylthiazole with methyl iodide in methyl alcoholic 'solution crystallises in colourless leaflets m.p. 118'. It has also been prepared by the condensation of s-p-tolyl- methylthiocarbamide with o-bromoacetophenone ; the hydrochloride and picrate m. p. 158O are described. When heated with carbon disulphide i t yields ptolylthiocarbimide and 2-thion-4-phenyl-3-rnethyl- thiaxoline S-cH>CPh which crystallises in pale yellow needles m. p. 127O. CS*NNe ~ p-Tolyli~ino-4-phenyl-5 - benxp I - 3-n~etl~yZt/iiuxoline EPh-NMe C(CH,P h) *S >C:N*C,H,Me prepared by the action of methyl iodide on 2-p-tolylimino-4-phenyl-5- benzylthiazole forms colourless prisms m. p. 151° and yields a hydro- chloride and a methiodide crystallising in needles rn. p. about 250' (decomp.). It is resolved by carbon disulphide into $1-tolyl thiocarbimide >C*CH,Pb and 2 -thion-4-phenyl- 5 - banzyl- 3 -met/& ylthiaaoline which forms silvery lustrous leaflets 1x1.p. 116'. 5-Brorno- 2 - p - toluidino-4-phenylthiasole obtained by brominatiog 2 - p - toluidino - 4 - phenylthiazole in benzene solution crystallises in colourless leaflets or needles which melt and decolnpose a t 134O yield- ing p-tolylthiocarbimide ; the hydrobromide m. p. 179" (decomp.) and ucetyl derivative m. p. 142.5' crystallise in colourless prisms. It is reduced by zinc and acetic acid t o the original thiazole. Attempts to prepare the bromothiazole by the condensation of p-tolylthiocarbamide with di-w-bromoacetophenone yielded a substance m. p. 142' (decomp.). When warmed with amyl nitrite i t 1 alcoholic solution 2-p-toluidino- 4-phenylthiazole yields the 5-nitroso-derivative YMe-CPh CS--S - - RPh-N >S*NH*CGH,Me. C( N 0) * S This separates in yellowish-brown leaflets m.p. 184' (decomp.) yields a hydrochloride red needles an ucetyl derivative lustrous dark red leaflets m. p. 1 6 3 O and is reduced by zinc and acetic acid in alcoholic solution to the corresponding amino-compound which however could not be isolated in a pure condition. On treatment with cold aqueous alkalis i t becomes brown probably owing to the formation of salts derived from the tautomeric form (see VI next page) ; when boiled with aqueous alkalis it undergoes com- VOL. CIV. i. Pi. 202 ABS'l'ltACTS OF CHEMICAL PAPERS plete decomposition yielding hydrogen sulphide p-tolyltbiocarbimide carbon dioxide t,hiocyanic acid benzoic acid ammonia and p-toluidine.The silvelr salt- c,6H1,0N,SAg prepared by treating an alcoholic solution of the nitroso-compound with the equivalent amounts of ammonia and silver nitrate separates as an indistinctly crystalline red precipitate which readily decomposes and explodes when rapidly heated. On treatment with benzoyl chloride a solution of the nitroso- compound in aqueous alkalis yields benzoyl-p-tolylcyanamide (Heller and Bauer A. 1902 i 444) benzoic and thiocyanic acids. This reaction which establishes the position of the nitroso-group i n the thiazole ring takes place according to the following scheme C,H,Me*NBz*C( :NH)*S*C( :NOH)*COPh -+ C6H4Me*NBz*CiN + HS-CiN + OH*COPh. 5-Bromo.2 -p-tolyEnitrosoanzino-4-~l~~n ylthiazo Ze 8 P h " > ~ * ~ ( ~ 7 ~ 7 ) - ~ ~ C Br-S prepared by warming 5-bromo-2-p-toluidino-4-phenylthiazole with amyl nitrite forms colourless needles m.p. 220". 3-p-Toluidino-4-phenyl thiazole corn bines with benzenediazonium chloride in alcoholic solution yielding 5-benzeneaxo-2-p-toluidino-4- phen ylthiaxole F'CPb>C*N:NPb which crystallises in orange-red needles m. p. 191" and forms an acetyl derivative red prisms m. p. 217O and a hydrochloride crystallising in dark violet-red needles having a greenish glance m. p. 184" (decornp.). 5-p-Nitrobenxeneaao-2-p-tolu~dino-4-p?~en~~~~~azoZe obtained in a similar manner from p-nitrobenzenediazonium chloride eryst allises in dark red needles m. p. 245" (decomp.); the hydrochloride reddish- violet needles and acetpl derivatives red needles both melt indefinitely at 250'.The authois have also studied the behaviour of the remaining aminothiazoles abd iminothiazolines described in this paper towards diazonium salts and find that the iminothiazolines in no circum- stances couple with the diazonium salts whilst the aminothiazoles in which the 5-position is unsubstituted readily combine yielding azo- compounds. The behaviour of 5-bromo-2-p-toluidino-4-phenplthiazole is however exceptional the action of benzenediazonium chloride leading to the removal of the bromine atom and the formation of the above-mentioned 5-benzeneazo-2-p-toluidino-4-phenylthiazole. The re- action towards diazonium salts thus furnishes a ready means of distinguishing whether the product obtained by the condensation of a monosubstituted thiocarbamide with w-bromoacetophenone and analogous halogeno- ketones is an aminothiazole or iminothiazoline. 2-p-Toluidino-4 5-dipl~enylthiaxole )$,:::>C*NH*C6H4Me pre- C,H,Me*NH*C--S C2&p,S,ORGANIC CHEMISTRY.i. 203 pared From desyl bromide and p-tolylthiocarbamide crys tallises in colourless needles m. p. 1789 and forms a hydrochloride. The condensation of w-bromoacetophenone and allylthiocarbamide yields 2-atZylamino-4-phenyZthiazoZe ~ ~ ~ ~ > C * N H * C H which has m. p. 7 3 O and couples with diazonium salts t o form red azo-comboun ds. - F. B. Decomposition of Alkylidenehydrazines. NICOLAI M. KISHNER (J. Buss. Phys. Chem. Soc. 1912 44 1754-1759).-MenthyZidene- hydraxine CH2<g2i:y$XX N-NH is a colourless liquid b. p. 144'/30 mm. 248-249O/769 mm.DF 0.9333 n 1.4940 [a] - 52.45'. When distilled under reduced pressure it leaves a viscous residue which on treatment with 10% sulphuric acid in the cold yields mentbone and Z-menthazine (compare A 1908 i 91). Pure menthylidenehydrazine yields no menthazine with cold 10% sulphuric acid the sole product being menthone which exhibits a low specific rotation owing to partial inversion. Distillation of the base with platinised porous tile yields hydrazine and Z-menthazine. Monthylidenehydrazine is slightly decomposed with evolution of nitrogen when distilled with fused potassium hydroxide whilst in presence of both platinised porous tile and fused alkali it is resolved into nitrogen and menthane. prepared from CHP+ $!H cMe%Me- C:N*NH,' isoThujyZideneli ydmzine isothujane and hydrazine hydrate is a faint yellow,biscous liquid b.p. 143-144'/17 mm. 152-153'/35 mm. Di0 0.9579 n 1.5328. Dis- tillation of the base in presence of potassium hydroxide spongy platinum or molecular silver yields (1) nitrogen (2) hydrazine (3) a mixture of the hydrocarbons CloH and C,,H, giving a cherry-red coloration with sulphuric acid and acetic anhydride and a green one with sulphuric acid and methyl alcohol and (4) isothujaxine which crystallises in golden-yellow needles m. p. 16 1-162'. When distilled with potassium hydroxide carvylidenehydrazine yields a hydrocarbon C10H16 b. p. 175- 176'/749 mm. (175-1 76O/ 757 mm.) DF 0.8361 (0.8349) n 1.4678 (1-4665) [.ID - 36.74' ( - 35*36O) which with hydrogen bromide gives the dipentene hydro- bromide Ci,Hlf,,2HBr m.p. 63' and with ethyl nitrite and hydro- chloric acid I-limonene P-nitrosochloride. '1 0H16:N!2:C10H16 T. H. P. Hydantoins. XX. Action of Thiocyanates on a-Amino- acids. TREAT B. JOHNSON (Amel.. Chem. J. 1913 49 68-69).-1t has been shown in earlier papers that by the action of thiocyanates on acyl derivatives of a-amino-acids acylthiohydantoins are produced. The author has now found that the salt used in certain experiments (A. 1912 i 53 316 390 807) which was supposed to be potassium thiocyanate was really the ammonium salt and the yields recorded were therefore obtained from the latter. The two salts show a remark- able difference in their behaviour with hippuric acid; the same com- P 2i. 204 B w r R A c r s OF CHEMICAL PAPERS. pound is formed in eihc:h case but with the potassium salt it is obtained as a n oily product which only slowly solidifies whilst when prepared from the ammonium salt i t solidifies at once on being poured into water..K. G. Tetraphengldi-iminotetrahydromiazthiole (3 5 - Diphenyl- imino-1 4-dipbenyltetrahydro-1 2 4-thiodiazole). EMIL FROMM 3 5-Diphenylimino-1 4-diphenyltetrahydro-1 2 4-thiodiazole is pro- bably a direct product of the oxidation of diphenylthiocarbamide and is not formed through the intermediate production of a n unstable dibulphide (compare Fromm and Heyder A 1909 i 903). It is best prepared by Hngers ttoff's method of oxidation by alcoholic bromine care being taken to work in the cold otherwise triphenylguanidine is obtained. The subhtance is converted into triphenylguanidine by con- centrated hydrochloric acid and is decomposed by boiling glacial acetic acid into acetanilide and 1-anilinobenzothiazole.By heating with aniline at 11 0' for several hours the diphenyliminodiphenyltetra- hydrothiodiazole is converted into the isomeric tri~~~~nylgua~~idobenxo- thiccxoEe NHPh*C(:NPh)*NPh*C<g>C,H m. p. 142' which is not desulphurised by lead oxide and an alkali and yields by the Schotten- Ba u m an n proce- s 2 -be n xo y lpheng Zaminobensot hiazole C,H,<f->C*NPh*COPh m. p. 156' which is also obtained from 2-anilinobenzothiazole benzoyl [with WILHELAl BL'L'TERICH] (dnrruhn 19 12 384 284-290).- chloride and aqueous sodium hydroxide. c. 5. Trinmthylparamide. HANS I~EYER and KARL STEINER (Ber.. 3512 45 3676-3677.Compare Mumm and Bergell A. 1912 i 1015).-Trimettiylparamide can be prepared in a pure condition by heating mettrylamine mellitate for two hours in a sealed tube at 200' and recry stallising the colourless product from chlorobenzene ; it is quantitatively hydrolysed t o mellitic acid on prolonged boiling with potassium hydroxide solution. D. F. T. Disulphide s with Neighbouring Double Linkings. Deriv- atives of Dithiobiurets and of Thiurets. EMIL FROMM [and RICHARD HEYDER ADOLF JTJEG and A~ARGRET ~ Y J R M ] (d?zna~en 1912 394 258-284).-Since only one example is known of the simultaneous production of an arylguanidoarylthiocarbamide and a diarylguanido- thiocarbamide by the decomposition of a n arylthiuret by a n aromatic amine (A. 1908 i 700) the action of different aromatic amines on a series of thiuret,s has bseri examined.It is found that as a rule the two products of the decomposition are formed when the arylthiuret and the aromatic amiae contain t,he same aromatic group. o-Anisyldithiobiuret C9H1,0N,S m. p. 153' yellowish-white needles obtained by heating equal weights of perthiocyanic acid and o-aniui- dine on the water-bath is converted by boiling hydrochloric acid and ferric chloride into o-anisylthiuret hydrochloride C,H,ON,S,,HCI m. p. 220' (hydrated) or 235' (anhydrous). The latter and o-anisidine inORGANIC CHEMISTRY. i. 205 boiling alcohol yield sulphur o-anisylguanido-o-anisylthiocarbamide OMe*06.H4*NH*CS*NH*C(:NH).NI-T.a,R,.01\e (the constitution of which is proved by its conversion into o-anisg~guanido-o-anisy~-~- benxy lt h iocar bamide OMe*C6H4*H C( S*C,K,)*NH*C( NH) *N H* C6H,*OMe m.p. 116' by boiling with benzyl chloride and an excess of aqueous alcoholic sodium hydroxide) and di-o-anisylguanidothiocarbam.ide which is isolated as the hydrochloride C(NH*C,H,*OMe), N*CS*NH,,HCl m. p. 205'. By boiling this hydrochloride with lead oxide and alcoholic sodium hydroxide di-o-anisy~dkyc6nodiamide CN*N:C( NH*C,B,* OMe) m. p. 16P white needles is obtained. I n a similar manner p-phene- tylthiuret hydrochloride and p-phenetidine in boiling alcohol yield di-p-phsnstylguanidothiocarbamide m. p. 142' (hydrochloride rn. p. 167") and p-p%nstylgunnido-p-phenetylthiocarbamide m. p. 172' of which the former is converted into di-p-phenettjldicyarcodinmide m. p.176' by lead oxide and alcoholic sodium hydroxide and the latter into p-phenetyl- guanido-p-phenetyl-$-benzylthiocarbamide m. p. 1 80° by benzyl chloride and alcoholic sodium hydroxide. p-Phenetylthiuret hydrochloride and aniline react to form phenylguanido-p-phenetylthiocarbamide m. p. 184O not 170' (A. 1907 i 982) and a small amount of plwtyl-p- phenstylguanidothiocalrbamide OE t *C,H,*NH* C( NHPh) N* CS*N H m. p. 137" the hydrochlorideof which C,,H,,ON,S,HCl,H,O has m. p. p-Phenetylguanidophenylthiocarbamide (Zoc. cit.) has m. p. 158" not 168' and forms a hydrochloride m. p. 168'. o- Tolylthiuret hydrochloride CSHPNSSP HC1,2H,O,- m. p. 1 75O obtained from o-tolyldi thiobiuret and boiling hydrochloric acid and ferric chloride reacts with o-toluidine in boiling alcohol to form tri-o-tolyl- diguanide hydrochlop.ide C23H2,N5HC1 m.p. 233' from which tyi-o- tolyldiguanide C(NH*C,H,Me),:N*C(:NH)*NH*C,H,Me m. p. 179' is liberated by ammonia. The by-product of the preceding reaction is di-o-tolylguanidothiocarba~,ide M. p. 172' or o-tolylguanido-o-tolylthio- carbamide C,,H,,N,S,EtOH m. p. 178' according to the dilution of the solution. o-'l'olylthiuret and aniline in boiling alcohol yield only phsnyZguccnl:do-o-tolylt~iocc~rbamide m. p. 135' (hydrochloride m. p. 183") and phenylthiuret and o-toluidine under similar conditions yield only phenyl-o-tolylguanidothiocarbamide m. p. 11 1' (hydrochloride m. p. 8 9'). Phen ylguanido-o-tolyl-+-benzylthiocaybamide C2,H2,N,S m. p. 124' crystallises in yellow octahedra. The following substances have been obtained by the interaction of arylthiuret hydrochlorides and phenylhydrazine in boiling alcohol (A.1907 i 982; 1908 i 700) and are converted into triazole derivatives by boiling aqueous alcoholic alkalis ; thus o-tolylthiuret hydrochloride and phenylhydrazine yield anilguanido-o-tolylthiocarb- amide or ani~-o-toly~yuanidothiocarbam~de ;?JHPh.NH* C( N H) *NH*CS*N H* C,H Me or 11 3 -1 14'. NHPh*NH*C(NR*C,H,Me$N.CS-NH m. p. "15i' [3 5(or 5 3-)- amino-o- toluidimo- 1 phsnpltriazole p H ~~ N======z ph<C( N K*C6H,Me) Ni. 206 ABSTRACTS OF CHEMICAL PAPERS. -- N P h < ~ C ~ ' N H ' C ' H 4 M e has m. p. 143'1 ; o-anisylthiuret and phenylhydrazrhe yield two substances which could not be obtained pure but have been converted into 5 -amino-3-o-anisidino* l-pAenyZtriaxoZe 0Me*c,H4*NH*C<N C ,NH,j and 3-amino-5-o-anisidino- 1 -phanyl- triazole one of which forms a sparingly soluble hydyochloride m.p. 22S0 and a picrate m. p. 250° red needles and the other an easily soluble hydrochloride and a picrate m. p. 169'; p-phenetyl- thiuret hydrochloride and phenylhydrazine (Fromm and Vetter A . 1907 i 982) yield anilguanido-p-phenetylthiocarbamide or anil-p- phenetylguanidothiocarbamide m. p. 1 70' not 1 SS' and aminophenyl- guanido-p-phenetylthiocarbamide or aminophenyl-p-phenetylguanido- thiocarbamide m. p. 168' white needles (not m. p. 236' white leaflets) the latter forming a benzylidene derivative m. p. 183'. The formation of 3-amino-5-thiol-l-phenyltriazole m. p. 234* and dianildithiobiuret m. p. 1 ?So from phenylhydrazine and phenyl- rnethylthiuret has already been recorded (A 1908 i 700).The former reacts with benzyl chloride and aqueous sodium hydroxide to form 3-amino-5-benzyZthioZ-~-phenyltriaxo2e m. p. 11 6' and with benzoyl chloride and aqueous sodium hydroxide to form 3-berazoylamino- 5-thiol-l-pheny2triaxole m. p. 267' from which 3-benxoylamino-5-benxyl- thiol-l-p~enyltriuzole m. p. 161' is obtained by means of benzyl chloride and aqueous sodium bydroxide. The action of benzoyl chloride and sodium carbonate on dianildithiobiuret or on 3-thiol- N-TPh C,,H,,ON,,HCl,H20 5-phenylhydrazino-1-phenyltriazole yields 3-thio2-5-benzoylphenylhydr- axino- 1 -phenyltriazole NH Ph*NBz C< NPh*E m. p. 218O which N-C *SH' yields the 3-benxylthiol derivative m.p. 171° by boiling with benzyl chloride and the calculated quantity of aqueous alcobolic sodium hydroxide and 3-benxylthio2-5-phenylhydraxino- I-phenyltriaxote m. p. 11S0 red needles when an excess of the alkali is employed. The substance m. p. 218'. obtained by the action of acetic anhydride on dianildi t hio bi uret (Zoc. cit. ) is 3-thiol-5 -met ylpheny Ihydraxino- 1 -phenyl- triaxole ; by treatment with benzyl chloride and an alkali it yields 3-benxy2thio2-5-acety2p~en~l~ydra~ino-~-phenyltriaxo~e m. p. 102' yellow leaflets. The constitution of the oxidation product m. p. 218' of 3-thiol-5-phenylhydrazino-1-phenj ltriazole as a benzeneazotriazole (loc. cit.) is proved as follows. I n the presence of an alkali the sub- stance is converted into 5-be?~zene~xo-3-thio~-2-benxoyl-l~hes~yltriccaole ._ . P h N 2 * C < ~ ~ ~ ~ z m. p. 167' red needles by benzoyl chloride and into 5 benxeneaxo-3-benzylthiol- 1 -phenyZtriaxole m. p. 11 6" reddish-yellow leaflets by benzyl chloride The latter is also produced when the former is treated with benzyl chloride and an alkali. The oxidation product can be acylated or alkylated but not,ORGANIC CHEMISTRY. i. 207 both simultaneously thus proving that the same hydrogen atom is concerned in each process and that the substance is tautomeric. The base C14H13N5S m. p. 1814 which is obtained together with the preceding aeo-compound by t be action of boiling hydrochloric acid on dianildithiobiuret (Zoc. cit.) forms in addition to the diacetyl and the dibenzylidene derivatives already described a dibenzoyl derivative m.p. 2 16" does not react with benzyl chloride in the presence of an alkali and requires 2 mols. of sodium nitrite for its diszotisation. Tbese facts are contrary to the formula previously ascribed to the base and are more in harmony with the constitution - s- ... Under the influence of hydrogen chloride substitrited dithiobiurets react with aldehydes or ketones to form aldurets or keturets (A 1893 i 575; 1906 i 656) which can be alkylated in consequence of the presence of the thiol groups ; thus o-tolyldithiobiuret and acetone yield o-toZyldimsthyZ-$-dithioketuret C H M e * N C ( S H ) * N < ~ ~ ~ ~ ~ ~ m. p. 236O which forms a benzyl derivative! m. p. 1 9 2 O and a dibsnxyl derivative m. p. 83' ; o-tolyldithiobiuret and benzaldehyde yield phenyl-o-tolyl-$-dithioalduret C,H4Me*s C ( S H ) * N < ~ ~ ~ ~ > N m.p. 207O yellow leaflets (dibeimzyl derivative m.. p.. 118') ; o-tolyldithio- biuret and 40% formaldehyde yield o-toZyl-~-cEzthaoaZduret C,H,Me*N :c(sH)*N<cH2->N C(YH N H~*c,H,-N C<~~)C:N.C,H,*NH,. m p. 197O yellow leaflets (dibenxyl derivative m. p. 80'). dithiobiuret does not react with acetophenone or benzophenone. o-Tolyl- c. s. Crystallographic Study of the Sodium Salt of isoHydroxy- tetrazole. ARISTIDE ROSATI (Atti R. Accad. Lincei 1912 [v] 21 ii 645-648).-The author has studied the salt CHON4Na,3H,O which was obtained by Palazzo (A. 1910 i 342). The salt loses its water at 120-130' and explodes at 240'. It occurs in two crystalline forms ( 1 ) pale straw-yellow tablets belonging to the pinacoidal class of the triclinic system ; ct b c = 1.2494 1 0.8521 a 130°6' p 114'47' y 79'34.5' ; (2) colourless tablets also belonging to the pinacoidal class of thatriclinic system ; ct b c = 0.6798 1 1.0834 a 54O53' /3 134O33.5' y 12 1'43'.R. V. S. Action of Chlorine on Ethyl Phenylazoacetoacetate. A New W a y to Prepare Derivatives of Formimido-chloride. CARL BULOW arid PETER NEBER (Ber. 1912 45 3732-3744).- Elimination of the carbethoxyl group takes place when ethyl phenyl- azoacetoacetate is hydrolgsed by sodium hydroxide (Richter and Miinzer A 1884 1342) or brominated (Hecking Dim 1910). The action of chlorine however results in the removal of the acetyl group and the formation of the dichlorophenylhydrazone of ethyl mono- chloroglyoxylate When this substance is completely reduced,i. 208 ABSTRACTS OF CHEMICAL PAPERS.2 4-dichloroaniline is formed and the compound may also be synthesised from this base. The remaining chlorine atom must necessarily be attached t o the a-carbon atom of t4he side-chain and it is very reactive. It may be replaced by an amino-group more prolonged action of ammonia replacing in addition the ester group. A method is given for the preparation of ethyl phenylazoaceto- acetate. Chlorination may be effected in glacial acetic acid by chlorine or sulphuryl chloride but the best results are obtained by chlorine in chloroform. The 2 4-dicT~lorophenyMy~ruzone of ethyl a-chloroglyoxylate C6H,C1,*NH*N:CC1*C0,Et crystallises in brilliant needles m.p. 98'. When treated with alcoholic potash hydrogen cbloride is eliminated and a product C,,H,O,N,CI is obtained in beautiful yellow needles m. p. 1 9 6 O . Its constitu- tion is probably represented by the annexed formula. The 2 4-dichlorophcn~yZhydrnzone of ethyl a-amino- ylyoxylate C,,H,,O,N,C1 which is immediately formed when alcoholic ammonia is added to the i imido-chloride crystallises in l o ~ g flat needles C0,Et from dilute ethyl acetate m. p. 9 9 O and is readily soluble in mineral acids but does not form a diazonium salt. More proloaged action of ammonia results in the formation of the amids CGH3Cl,*NH*K':C(NH ,)-CO*NH in long grey needles m. p. 170". Ethyl 2 4-Richlo~obenxenecczoacetoacotate C6H,C12~*N2*CKAc*C02Et may be prepared in 8 sitrdar manner by condensing the diazotised dichloroaniline with ethyl acetoacetate.It crystallises in yellow needles m p. 127O and gives the above a-chloro-compound with chlorine. When condensed with hydrazioe hydrate it gives 4-o-p-dichloro6enzenecczo-5-hydrolry-3-tnr,thyZpyr~zole C,,H,0,N2Cl in orange-yellow needles m. p. 207O which cannot be precipitated by water from piperidine in which the substance is very soluble. Simi 1 ar 1 y p hen y I h y d r azine y ie Id s 4-o- p-d ichlorobenzeneaxo-5 - hydrox y- 1 -phcnyl-3-methyZpyraxole C,,H,,0N,C12 in brick-red needles m. p. 1 9 5 O which concentrated nitric acid cou verts into 2 4-dichlorophenyl- diazonium chloride and 4-nitro-1-benzene-3-methylpyrazolone (compare A. 1910 i 902). The Racemisation of Proteins and their Derivatives Resulting from Tautomeric Change.I. HENRY D. DAKIN (J. Btol. Chem. 1912 13 357-362).-There is an analogy ''-TH and peptide CRH*CO' between the bydantoin NH< c1 /\ N=N "()-\d J. C. W. groupings in both of which the -CH*CO- iroup can exhibit keto- enolic tautomerism and hence racemisation (compare Dakin A 1910 i 590). I n the peptide complex the terminal amino-acid containing a free carboxyl group cannot however undergo this change. Such tautoweric change apparently takes place when a protein is digested at low temperatures with dilute alkali (compare Kossel and Weiss A 1909 i 54.2; 1910 i 791).ORGANIC CHEMISTRY. i. 209 The optical rotatory power of gelatin falls to a minimum when it is digested with dilute alEali. On subsequent hydrolysis with acids in- active leucine aspartic acid arginine histidine and phenylalanine are obtained whereas proline glutamic acid and lysine are obtained in the optically active forms together with part of the alanine.The conclusion is drawn that none of the carboxyl groups in the substances which were obtained inactive are free i n gelatin. On the other hand glutamic acid lysine and alanine may have some of their carboxyl groups free that is they may occupy terminal positions in the peptide chains. An alternative is that these amino-acids -are rapidly liberated in the free state by the hydrolytic action of the alkali and .SO escape racemisation. E. F. A. The Refractive Indices of Solutions of Certain Proteins. VIII. Globin T. BRAILSFORD ROBERTSON (J. Bid. Chew&. 1913 13 455-462).-Globin was prepared from ox-corpuscles by three different modificstions of Schulz’s method. The value of a for the purest prepara- tion dissolved in decinormal potassium hydroxide or hydrochloric acid is 0.00169 +_ 0.00005.W. D. H. The Preparation and Properties of a Compound Protein; Globin Caseinate. T. BRAILSFORD ROBERTSON (J. Biol. Chem. 191 3 13 499-506).-Globin caseinate may be prepared by mixing two parts of globin with one of casein each in a faintly alknline solution. It displays properties intermediate between those of the two component proteins the acid function of globin being enhanced by union with casein and the basic function of casein by union with globin. The compound is not decomposed by dilute acetic acid in the cold but it is by boiling dilute acetic acid or by pepsin and acetic acid.The change in t h e refractive index of decinormal potassium hydroxide due to the introduction of 1% of globin caseinate is 0.00162 +_ 0.00005. The refractivity of a compound protein is an additive function of the refractivities of its components. W. D. H. Constitution of the Blood and Bile Pigments. I. HANS FISCHER and ERICH BARTHOLONAUS (Zeitsch. physiol. Chem. 19 13 83 50-71).-The formation of tri- and tetra-substituted pyrroles on the decomposition of haemin is explained on the hypothesis that t h e pyrrole nuclei are united by a CH radicle in the 2-positions. Such 2- and 3-methylene derivatives have been synthesised by Colacicchi (A. 19 12 i 491). Bis-(5-acetyl-2 .Q-dimethylpprryl)methane in which the methplene group is in the 3-position resists the reducing action of hydrogen iodide and acetic acid d u r i q two hours. To some extent the a-acetyl residue is eliminated and bis-( 3 4-dimethylpyrryl-3 $)methane NH<CH=CMe MeC=CH>NHy is formed.This compound has many OF the properties of hemibilirubin; it gives the aldehyde re- action ig unstable shows the. urobilin bands and the fluorescence reaction with zinc acetate. CMe FCH,-Q CMe It forms a pzcpate and an a-azo-dyei. 210 ABSTRACTS OF CHEMICAL PAPERY. When t h e action of the reducing agent is prolonged for fourteen to sixteen hours 2 3 4-trimethylpyrrole admixed with some 2 4-di- methylpyrrole is obtained. Bis-(3-acetyl-2 4-dimethylpyrry1)methane (Colacicchi loc. cit.) is readily reduced to pyrrole derivatives by acetic acid and hydrogen iodide.The mixture of pyrrole picrates was not separated. Trialkylated pyrroles condense with formaldehyde in presence of alkali. The products are regarded as methylene derivatives although CMe y*CH,-OH the possibility of an alcohol structure NH< is not CMe:CMe overlooked. Tetramethylpyrrole was obtained on reducing the condensation product from 2 4 5-trimethylpyrrole ; phyllopyrrole from the con- densation product of cryptopyrrole. 2 3 5-Trimethylpyrrole-4-propionic acid CMe:$!*CH,*CH,*CO,H NH<CNe:CHe ? was not obtained on reducing the amorphous condensation product of formaldehyde with phonopyrrolecarboxylic acid but i t is readily formed on metbylation of phonopyrrolecarboxylic acid. Tetramethyl- pyrrole is obtained a t the same time.- - ,CMe 7 -CH,-$J =CMe NH* C M e 'CMe*NH >C;CO,Et ob- The pyrrole CO,Et*Cc tained by the action of formaldehyde on 3-carbethoxy-2 4-dimethyl- pyrrole when boiled with acetic acid gives an intense green solution showing a characteristic band in the red similar to that of the copper salt of hemibilirubin. Bis-5-acetyl-2 4-dimethylpyrrglethane >NH CMe- --C-CHMe-C ==CMe NH<C(COMe) CMe Meb-C( COMe) produced from 5-acetyl-2 4-dimethylpyrrole by the action of acet- aldehyde is decomposed by acetic acid and hydrogen iodide into 3 4-dimethylpyrrole. The formation of cryptopyrrole could not be determined. All the foregoing pyrrole derivatives are decomposed by sodium met h oxide forming tetrame t h ylpyrrole. Tripyrrole is absolutely stable towards acetic acid and hydrogen iodide in the sense that no volatile bases are formed.Big-( 2 4-dimethylpyrryl-3 3')methane crystallises in tiny pyramids and prisms m. p. 139-140'; the pimate forms yellowish-brown needles m. p. 125-126O. 2 3 5-Trimethylpyrrole-4-propionic acid forms a picrate m. p. 126-127'. E. F. A. Bilirubin and Haernin. WILLIAM KUSTER [and P. DEIHLE] (Zeitsch. physiol. Chem. 191 2 82 4G3-483).-Sodium amalgam does not necessarily reduce vinyl groups which remain unattacked during the conversion of hsemin into the leuco-compound or of bilirubin into hemibilirubin. The complex giving rise to methylethylmaleinimide an oxidation is contained already in bilirubin. One of the two complexesORGANIC CHEMISTRY. i. 211 in hsernin which gives haematic acid on oxidation loses carbon dioxide during conversion into bilirubin and so gives rise to the imide when oxidised.On esterification with methyl alcohol and hydrochloric acid bilirubin behaves differently from hsmin. A dimethyl derivative is obtained in wbich one methyl replaces hydrogen and the other is due to the addition of methyl alcohol. The formulae given by Piloty (A. 1912 i 923) and by H. Fischer and Rose (A. 1912 i 575) for bilirubic acid etc. are discussed and a complete structural formula for haemin is suggested. Piire mesoporphyrin yields methylethylmaleinimide on oxidation. Bilirubin forms a silver salt containing 4 atoms of silver when flesh preparations are used ; older preparations react with 2 atoms only of silver. The salts have a metallic lustre and the silver is not replaceable by barium. Bilirubin regenerated from the zinc salt di3solves in sodium hydrogen carbonate. This a&-form is more soluble in chloroform than the normal.Birnethylbilirubin Ca4H4007N4 is a blackish-green powder. E. F. A. The Action of Yeast on Yeast-nucleic Acid. SAMUEL AMBERG and WALTER JONES (J. Bid. Chem. 1913 13 441 -446).- Yeast has no action on thymus-nucleic acid but it causes the dis- appearance of yeast-nucleic acid. If compressed yeast is used adenine and guanine appear ; if yeast powder is employed adenine and guanosine are found. W. D. H. Nuclemes. 111. PHCEBUS A. LEVENE and F. R. LA FORGE (J. Biol. Chew. 1913 13 507-51O).-The pyrimidine ribostdev are more resistant towards the hydrolytic action of mineral acids than are the purine ribosides.Their behaviour to enzymes runs parallel to this. The differences towards acids can be removed by reducing the pyrimidine base iu the riboside to the corresponding dihydro- pyrimidine. No tissue enzyme has however yet been discovered which hydrolyses either t,he original or the dihydro-derivative. W. D. H. Influence of the Reaction of the Medium on the Action of Ptyalin. WILHELM E. RINGER and H. VAN TRIOT (Zeitsch. physiol. Chem. 1912 82 484-501).-'L'he action of ptyalin on starch is studied in presence of varying amount,s of sodium hydroxide and phosphoric acid and the amount of reducing sugar formed contrasted with the hydrogen-ion concentration of the liquids as determined by the conductivity method. At 37" the optimum activity is observed in a solution having p = 6.0.When citrate is substituted for phosphate the position of the optimum varies with the concentration of the citrate; it is observed in more nearly neutral solutions with citrate than is the case with phosphate. In presence of sodium acetate and acetic acid the optimum is a t pH=6.0. The presence of both phosphate and acetate reduces the amount of starch hydrolysis ; citrate has still more influence. The enzyme itself is not damaged during the duration of the experiment. When these are prolonged for five times as long the position of the optimum is not materially altered. E. F. A.i. 212 ABSTRACTS OF CHEMICAL PAPERS. Temperatures of Destruction of Emulsin in Ethyl Alcohol of Various Strengths. MILE BOUHQUELOT and MARC BRIDEL (J.Pharm. Chim. 1913 [vii) 7 27-31).-A solution of emulsin in water was diluted with alcohol or alcohol and water to produce alcoholic liquids of various strengths containing the same quantity of emulsin. Portions of these liquids were then heated to various temperatures and afterwards tested for activity on salicin. It was found that the temperature atL which emulsin begins to become inactive under these conditions varies from 60' to 40' for liquids containing from 10 to 50% of alcohol and remains constant at 45' to 40' for liquids containing 60 to 95% of alcohol. Total destruction of activity occurs at temperatures ranging from 70' t o 55'. Different figures are obtained when the preparations are made by macerating emulsin in the alcoholic liquids. T. A. H. Rennin. I. Properties of the Ferment when Prepared by Different Methods. 11. Acceleration of the Action of Rennin by Phosphoric Acid. 111. The Variation in the Length of Time Required to Curdle Different Specimens of Milk. A. ZINMERMANN (J. Ind. Eng. Chem. 1912 4 506-508).-The distinctive properties of rennin when prepared by the following different methods are described (1) precipitated by sodium chloride (2) precipitated by sodium sulphate (3) rennin in scales (granulm rennin) and (4) commercial rennin. Phosphoric acid (0 075%) when added to milk increases the activity of the rennin a property possessed in a less degree by lactic hydro- chloric and oxalic acids. The length of time required to curdle by the Fame specimen of rennin appears to be influenced by the length of time the milk has been kept; the staler the milk the more rapid the action of the rennin ; this would appear to be a bacterial effect yet i t is found that a mixture of rennin aud milk kept several hours a t 40' will not curdle whereas if the milk alone be subjected to this treatment the addition of the same rennin causes rapid curdling. The preparation of standardised rennin the permanency of rennin solutions and of pepsin are also discussed. F. M. G. M. Antagonism between Citrates and Calcium Salts in Milk Curdling by Rennet. J. R. KATZ (Proc. K. Akad. Wetensch. Amsterdam? 191 2 15 434-445).-Whilst Jr/1 25- and N/25-solutions of citric acid delay the curdling of milk more than two hours the action is much weakened when substitution occurs at one of the active groups of the citric acid and stops altogether when two or three of the groups are made inactive. When substitution occurs at the alcohol group the curdling is delayed three and a-half and nine and a-half hours respectively by N/125- and N/%5-solutions. Similar results were obtained by tribasic acids not containing an alcohol group. When substitution occurs a t one carboxyl group in citric acid a delay in curdling milk of one and a-quarter hours mitb N/125- and of six and a-half hours with N/25-solutions takes place. Results similarPHYSIOLOGICAL CHEMISTRY. i. 213 to these were again obtained by employing dibasic acids with one or more alcohol groups. The results show that when one active group is taken from citric acid the characteristic action of the acid is reduced to about 6% of its original value and t h a t when two groups are substituted to about 1%. N. H. J. M. Syntheaiaing Action between Galactose and Ethyl Alcohol under the Influence of Kephir. ENILE BOURQUELOT and HENRI H~MBSEY Comnpt. rend. 1912 155 1552-1554).-/j-Ethyl galactcside is slowly Pyntbesised in small quantities in the presence of kephir from an alcoholic solution of galactose. The authors suggest that the synthesising agent in this case and also in that of emulsin obtained from almonds (compare A. 1912 i 946) is really the lactase present in these two substances. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9130400153

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 165 General and Physical Chemistry. Refractive Index of Metals. P. A. Ross (Jahrb. Min. 1912 ii Ref. 314-316 ; from Physical Review 1911 33 549-556).- Prisms of the metals with a refracting angle of 15*311 were deposited on glass by means of the cathode rays; and the refractive indices determined for red yellow and blue light by the methods of deviation interference Newton’s rings and immersion in liquids of known refractive index. The results obtained by the different methods show some variation but they are of the same order. The following are selected as examples (for sodium-light) copper 0*46-0.57 ; iron 1-85 ; lead 1-95 ; platinum 1-75-1.88 ; silver 0.28-0.34; zinc 2-11 ; magnesium 0.40 ; gold 0*58-0*65 ; bismuth 1-98; nickel 1.88; brass 0.66. Further Remarks on a Formula for the Index of Refraction of Binary Mixtures.ARRIGO MAZZUCCHELLI (Atti 8. Accad. Lincei 1912 [v] 21 ii 701-707).-The author sustains and develops his former criticism (A. 1911 ii 781) in view of the reply of Schwers (A. 1912 ii 1). L. J. S. R. V. S. Optical Constants of Certain Metals in t h e Ultra-Red. K. FORSTERLING and VSEVOLOD FR~EDEHICKSZ (Ann. Physik 1913 [iv] 40 201-232).-The optical constants of silver copper gold platinum and iridium have been calculated from observations on the influence of the metals on the polarisation of the light reflected from the polished metal surfaces. These observations were made with monochromatic light of wave-length varying from A = 1000 pp to 5000 yp,. According to the electro-magnetic theory if the dielectric constant may be neglected in comparison with the conductivity it is to be expected that the relations K = 1 and n = &T will hold good where K is the index of absorption n the refractive index CT the conduc- tivity and T the period of vibration of the incident light.It has already been shown that these relations are not satisfied in the case of ultra-violet and visible rays and the data now obtained lead to the same result for ultra-red radiation. The Spectra of Nebula and the Aualogies to be Drawn From Them. JEAN MEUNIER (Compt. rend. 1913 156 391-393. Compare A. 1912 ii 432; this vol. ii 24).-The greater part of the nebulz present continuous spectra but there are some which show a number of definite lines. The author considers that these lines all coincide with definite lines in the solar spectrum attributeti t o various elements namely hydrogen iron and titanium there being thus a marked analogy between the solar spectrum and that of the nebulz.Finally from Watts’ examination of the spectrum from the flame of a Bessemer converter he draws the conclusion that iron and titanium can exist in flames which are absolutely H. M. D. VOL. civ. ii 12ii. 166 ABSTRACTS OF CHEMICAL PAPERS. gaseous and developed under physical conditions comparable t o those existing at the surface of the sun and in the nucleus of the nebulz. W. G. Influence of Different Gases and of Variations in Gas Pressure and Current Strength on the Appearance of the First Ultra-violet Band Spectrum of Oxygen. WALTER STEUBING (Ann. Physik 1912 [iv] 39 1408-1430.Compare A. 1910 ii 913; 1911 ii 558).-In previous papers it has been shown that the so-called water-vapour bands in the ultra-violet region are probably due to oxygen. Further observations have now been made with different gases purified and dried with the utmost care. Some of these experiments were made with an arc burning between platinum electrodes at atmospheric pressure and others a t pressures of less than 1 cm. of mercury the current being also varied considerably in intensity. The gases examined were oxygen nitrogen air hydrogen and carbon dioxide. Both at high and low pressures the spectral observations indicate that the ultra-violet band spectrum in question is due to oxygen and not t o water vapour. Pure oxygen which has been dried for weeks in contact with phosphoric oxide shows the band very clearly although the conditions of the experiment preclude the possibility of interaction of the gas with traces of either hydrogen or hydro- carbons.I n comparative experiments with nitrogen and hydrogen the band was not in evidence. In air and carbon dioxide which both show the band quite clearly its intensity increases with pressure and temperature. H. M. D. Systems of Series in the Spectra of Zinc Cadmium and Mercury. JOITANNES STARK (Ann. Physik 1912 [iv] 39,1612-1616). -The views of Paschen (A. 1911 ii 833) relative to the existence of certain series in the mercury spectrum are adversely criticised. According to Paschen the lines h=2536 and h=4078 belong to the same combination series. This is not in agreement with the general behaviour of the two lines.The flame spectrum of mercury shows only the former and in the arc spectrum the relative intensities are very different. I n regard to the manner in which they are resolved by a magnetic field there is no similarity between them and the Doppler effect for the two lines in the canal-ray spectrum afford no evidence of a series relationship. On the other hand the behaviour of h=2536 and h=1848 is similar and it is probable that they belong to one and the same series. The conclusion that the zinc line x=2138 the cadmium line h=2288 and the mercury line ~=1848 are homologous is also inadmissible. It is contradictory t o the rule that the wave-length of homologous lines of elements belonging to the same periodic group increases with the atomic weight and in the author’s opinion the line ~ = 1 8 4 8 should be replaced by h=2536. The members of this group behave quite similarly in many ways.The nature of certain ultra-violet doublets in the zinc and cadmium spectra is also discussed. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 167 Absorption Spectra of Some Uraoyl Salts. ARR~GO~MAZZUC- CHELLI atid OLGA GRECO D’ALCEO ( i i t t i tz. Accad. Lincei 1912 [v] 21 ii 850-854; 1913 [v] 22 i 41-43).-1n a recent paper (this vol. i 160) the authors have shown that a number of uranyl and uranous salts do not form complexes with certain nitrogenous compounds. The present papers record the results of photographic measurement of the absorption bands of solutions of these salts both before and after the addition of the nitrogenous substances and the results confirm those obtained in the former paper by purely chemical methods.As a control similar measurements were made with sodium uranyl tartrate and pyridine; the reaction (of whatever nature) which occurs between these substances is indicated by the absorption spectra. Uranous chloride shows the same absorption spectrum alone and after addition of carbamide so that no additive compound is formed. The spectrum of ~~/20-uranous sulphate is figured and also the spectrum of the same solution after addition of glycine in the proportion of 24 mols. to 1 mol. of uranium salt; the only difference observable is a slight displacement of the maxima of the bands. The spectra of the two corresponding solutions of uranous chloride (which are also reproduced) do exhibit differences and in this case the existence of an additive compound has been shown t o be probable by chemical means.R. V. S. Spectrographic Studies in the Triphenylmethane Group. RICHARD MEYER and OTTO FISCHER (Bsr. 1913 46 70-84).-The hypothesis that only such quinonoid substances of the triphenyl- methane group as contain an auxochrome group in the para-position to the methane carbon atom can possess the properties of a dye (Meyer and Fischer A. 1911 i 723; von Baeyer A. 1907 i 757) is not in accord with further experiment. Fuchsone CPh2:C,H4:0 in alcoholic solution gives an absorption spectrum (bands with maxima a t 380 and 260 pp) resembling that of the salts of phenolphthalein and a hot alcoholic solution of benz- aurin gives a similar curve (maxima 440 and 275 pp) ; the deepening in the colour of the benzaurin solution on warming is attributed to a change into the quinonoid structure OH*C,H,*CPh:C,H,:O and from the similarity of the absorption of this and fuchsone it is evident that the para-hydroxyl group is not essential to selective absorption.This is confirmed by a comparison of fuchsonimonium chloride CPh,:C,H,:NH,Cl (obtained by warming fuchsonimonium carbinol hydrochloride OH*~Ph,*C,H,*NH,,HCl in alcoholic solution) and Dobner’s violet NH,= C6*H4*CPh C6H4 :NH,CI each giving similar curves with three absorption bands (maxima a t 440 330 and 260 pp and a t 570 400 and 300 pp respectively); an alkaline solution of benzaurin gives a similar curve with maxima a t 550 375 and 290 pp.The elimination of a molecule of water is not necessary to the existence of colonr in a kriphenylmethane compound (compare von Baeyer Zoc. cit. ; p-hydroxytriphenylmethane di-p-hydroxytri- phenylmethane and p-diaminotriphenylmethane hydrochloride in 12-2ii. 168 A BS'l'ICACTS OF CHEMICAL PAPERS. alcoholic solution all exhibit an absorption band between 250 and 300 pp. The alkali salts of hydroxyphenyl- and hydroxydiphenyl-phthalide give only one-sided absorption resembling in this a colourless solu- tion of phenolphthalein containing excess of alkali ; it is possible therefore that these compounds exist in the solutions in the carbinol structure; this view is supported by the fact that the yellow solution of hydroxydiphenylphthalide is like pheno!phthalein decolorised by excess of alkali the colour re-appearing on warming.Phenolphthalein and hydroxydiphenylphthalide both dissolve in concentrated sulphuric acid to coloured solutions of which the absorp- tion curves run roughly parallel but that of the former contains an additional point of maximum absorption (maxima at 500 and 390 pp and a t 470 pp) ; the former curve is quite different from that of the alkali salt of phenolphthalein. Fluorane 0<2%>C<:f>O and dithiofluoran when dissolved in a mixture"of=acetic acid and alcohol give different types of absorption band the former having one point of maximum absorption (at 290 pp) and the latter three (at 515 360 and 300 PP). D. F. T. Spectrographic Studies in the Anthraquinone Group.RICHARD MEYER and OTTO FISCHER (Bey. 1913 46 85-92).-An investigation of the absorption spectra of the hydroxyanthra- quinones. The alkali salts of 1- and 2-hydroxyanthraquinone give curves which are quite different in character the former having one large band (maximum absorption at 500 pp) whilst the other has three bands (maxima a t 492 300 and 238 pp); a neutral solution of the alkali salt of alizarin (1 2-dihydroxyanthraquinone) gives a similar absorption curve to 2-hydroxyanthraquinone (maxima a t 527 330 and 260 pp) but an alkaline solution gives a quite different curve (absorption maxima a t 612 560 and 266 py). The alkali salts of 1 4-dihydroxyanthraquinone (quinizarin) and 1 5-dihpdroxyanthraquinone show similar absorption to l-hydroxy- anthraquhone giving maxima a t 565 and 500 pp respectively; the former substance in alkaline solution gives two bands with maxima a t 605 and 560 pp.2 6- and 2 7-Dihydroxyanthraquinones in alkaline solution exhibit four bands whilst 1 2 ,4-trihydroxyanthraquinone (pur- purin) whether in excess of alkali or not is similar to alizarin in excess of alkali. A neutral solution of the alkali salt of 1 2 S-trihydroxyanthra- quinone shows three decided bands (maxima a t 510,430 and 290 pp) with a much weaker one (at 620 pp) which develops more sharply on the addition of more alkali. The alkali salt of 5 6-dihydroxy- 1 4-naphthaquinone in absorption resembles the alkaline solution of alizarin.GENERAL AND PHYSICAL CHEMISTRY. ii. 169 A comparison of these results indicates that hydroxyl in the 2- 3- 6- or 7-position is more strongly auxochrome than in one of the other positions.The difference between the spectra of the alizarin and quinizarin salts in neutral and alkaline solution is probably due to the neutralisation of one hydroxyl or two according to the conditions. From a comparison of the above hydroxyanthraquinones with anthraquinone itself (Baly and Stewart T. 1906 89 511) all in sulphuric acid solution the conclusion is drawn that the intro- duction of hydroxyl in the 2- or 3-position influences the absorption spectrum more strongly than introduction in the 1-position. D. F. T. Optical Investigation of Diazo-compounds. JOHN C. CAIN (Ber. 1913 46 101-102).-The author draws attention to the simi- larity between the absorption curves of p-benzoquinonediazide ():/-\/p \=-/‘” and of a-naphthalenediazonium chloride on which Hantzsch and Lifschitz (A.1912 ii 1116) fail to comment. The similarity must indicate an analogy of structure CI*N ” /-\) which is best explained by the author’s diazonium \=/‘-5 formula for the latter substance (annexed formula) ; / \ from the general resemblance of the curves for the 1-/ above and other diazonium compounds (Zoc. cit.) the structure should be common to all. A consideration of the author’s diazonium formula would have foretold the fruitless character of certain experiments of Hantzsch and Lifschitz. D. F. T. Absorption of Light and Fluorescence of Aliphatic Acid Imides (Fluorescence Phenomena among Non-aromatic Compounds. I.) HEIWRICH LEY and W.FISCHER (Ber. 1913 46 327-335).-The authors have investigated the absorption spectra and fluorescence of imides of the general formula R<CO>NH since by suitable substitution in the group R the substances show considerable change in colour. Succinimide only shows absorption a t the boundary of the visible field whilst mogn~sium succinimide is still more transparent. Di- inethylmaleinimide shows distinct selective absorption. The intro- duction of bromine into the molecule of maleinimide has the effect of shifting the absorption towards the region of greater wave-length. The presence of an amino-group causes the absorption to shift towards the red end of the spectrum whilst on the addition of acid to solutions of amino-imides the absorption is moved towards the region of shorter wave-length.I n the case of amino-imides how- ever it is probably that salt-formation is accompanied by inter- molecular re-arrangement. Pluorescmce qf Imid~~.-Diphenylmaleic anhydride diphenyl- maleinimide chloroaminomaleinirnide and methylaminocitraconic COii. 170 ABSTRACTS OF CHEMICAL PAPERS. methylimide yield fluorescent solutions when dissolved in water alcohol ether or benzene and further the nature of the fluores- cence is found to be dependent on the particular solvent employed. Under the experimental conditions adopted no fluorescence was observed with dimethylmaleinimide. Since also ethyl 5-amino- 3-cyanofuran-2-carboxylate (Wislicenus A. 1908 i 965 ; Dieck- mann A. 1911 i 457) is fluorescent the authors itre led to the conclusion that the systems )I >Y and I >X can occasion fluorescence if an amino-group is also present. Chloroaminomaleinimide (compare Ciamician A 1890 24) was prepared by warming djchloromaleinimide with a concentrated alcoholic solution of ammonia during two hours at 70°.It had m. p. 219O. *c-C‘:x *CZC* .c-c X *C‘=c* MeC-CO NHMe* C-CO Meth ylarninocitmconmeth ylimide I I >NMc m. p. 140° was obtained by heating an alcoholic solution of methyloxalacetic ester with aqueous methylamine during three to four hours a t 70°. Diphenylmaleinimide was obtained in the form of its copper salt (C,,H,,02N),Cu when diphenylmaleic anhydride and copper acetate were warmed with 20% ammonia. When warmed with dilute acid the copper salt yielded the free imide.H. W. Stark’s Theory of Fluorescence. HANS VON LIEBIG (Zeitsch. fllelctrochem. 1913 19 117-122).-Polemical. The author criticises Stark’s statement (this vol. ii 2) “that fluorescence is not a con- stitutive property of the molecule but a property of the atom.” The author whilst admitting Stark‘s statement that fluorescence is due t o loosened valency electrons maintains in opposition to Stark that it is strictly scientific to consider the question of the relation between constitution and colour or fluorescence only so far as the visible spectrum is concerned and not over the whole spectrum. It is also shown that Stark’s statement based on Hartley’s work “ that the colour of benzene derivatives is due only to a shift of the ultra-violet absorption bands toward the red by substitution and condensation,” is not in accord with chemical facts.Stark’s experi- ments on the fluorescence of acetone diacetyl etc. are held to be untrustworthy on account of the fact that such substances undergo chemical change under the influence of ultra-violet light and that Lhe products of such changes or the changes themselves might easily occasion the fluorescence observed. The reasons offered by Stark to explain the non-observance of fluorescence with glycerol p-benzo- quinone anthraquinone and violuric acid are regarded as insuffi- cient to justify the statement that such substances are fluorescent. Finally it is shown that the action attributed to the loosened valency electrons and the chromophoric groups by Stark is directly opposed to the main point in Stark’s theory namely that con- stitution and fluorescence are entirely unconnected.J. F. s.GENERAL AND PHYSICAL CHEMISTRY. ii. 171 The Law of Elementary Photochemical Absorption. VICTOR HENRI and REN$ WURMSER (Compt. rend. 1913 156 230-233 Compare A. 1912 ii 882 883).-The examination of a number of photochemical reactions to see whether Grotthus's law of photo- chemical absorption that the photochemical susceptibility is pro- portional to the absorption holds good in all cases. For acetone and ethyl acetate the maximum decomposition corresponds with the region of maximum absorption. I n the case of acetaldhhyde the absorption curve presents a maximum at A = 2775 then diminishes to a minimum and finally increases steadily for the extreme ultra- violet rays whilst the decomposition is a maximum a t ~ = 2 7 7 5 and then diminishes showing no minimum and being very feeble in the extreme rays. In explanation of this the following law is enunciated.The photochemical susceptibility of a substance depends only on that part of the absorption spectrum which corre- sponds with the same molecular groupings as those on which the action is produced. W. G. Relation between the Velocity of a Photochemical Reaction and t h e Incident Radiant Energy. MARCEL BOLL (Compt. rend. 1913 156 138-140. Compare A 1912 ii 384 407 lll9).-The author has studied the rate of hydrolysis of tetrachloroplatinic acid when submitted to rays of different energy. The light from a mercury-vapour lamp was dispersed by two quartz prisms and certain of the resulting rays were used as a source of energy the amount reaching the acid solution being controlled by a screen consisting of a cell containing a dilute solution of caffeine the concentration and thickness of the layer being varied.The coefficient of absorption of caffeine as obtained from photometric measurements was in close agreement with the value calculated from these results on the hypothesis that the velocity coefficient of a chemical reaction is proportional to the incident radiant energy even if the reaction is bimolecular. W. G. Action of the Medium and Extreme Ultra-violet Rays on Acetaldehyde Acidification Polymerisation Resinification. DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 19 13 1 5 6 233-236).-A more detailed study of the photolysis of acetaldehyde (compare this vol.ii 90). Initial ultra-violet rays do not convert the aldehyde into acetic acid in the absence of oxygen. Under the influence of medium and extreme rays oxidation takes place even in the absence of oxygen a portion of the aldehyde being converted into acetic acid and the amount of acid produced is far greater when the aldehyde is in the form of vapour than when it is liquid. With rays (h(0'25p) polymerisation is rapid both para- and meta- acetaldehyde being formed. No resinification results from the action of initial ultra-violet rays and it is only slowly produced by the medium and extreme rays. The presence of water checks poly- merisation and resinification but favours acidification formic acid being formed in this case and in amount almost equal to that of the acetic acid.W. G.ii. 172 ABSTRACTS OF CHEMICAL PAPERS. Photo-electric Behaviour of Iron in the Active and Passive State. H. STANLEY ALLEN (Proc. Boy. Xoc. 1913 A 88,70-74).-The photo-electric activity of chemically active iron is found to be much greater than that of iron which has been rendered passive by the action of concentrated nitric acid or by anodic polarisation in a dilute sulphuric acid solution. It is considered that this observation affords support for the theory which attributes passivity t o the occurrence of a layer of gas a t the surface of the metal. H. M. D. Photo-electric Effect in Some Compounds. A. LL. HUGHES (Phil. Mag. 1913 [vi] 25 332).-It has been suggested by Wlllows (this vol.ii 4) that the photo-electric activity of moist zinc chloride may be connected with the fact that moist halogen salts of zinc emit large quantities of ions when heated to 300° whereas the dry salts are inactive. I n reply to this the author points out that the procedure adopted in the photo-electric experiments was such as to ensure that the effect is a direct result of ultra-violet illumination. H. M. D. Arc and Spark Lines (Uni- and Multi-valent Lines) in t h e Canal-Ray Spectra. JOHANNES STARK (Physikinl. Zeitsch. 19 13 14 102-109).-The conditions under which the so-called arc and spark lines of an element make their appearance indicate that the spark lines are due to carriers moving with much greater velocities than those possessed by the carriers which give rise t o the arc lines.Both kinds of lines are found in the canal-ray spectra and from observation of the canal-ray spectra of oxygen nitrogen chlorine iodine helium sulphur and aluminium it is found that the two groups of lines behave differently in regard to the Doppler effect. Photographs of the spectra show that in the case of the spark lines the maximum intensity of the displaced line is separated from the undisplaced line by an intervening region of minimum intensity whereas this region is not found in the case of the arc lines a t the dispersion which was employed in the production of the photo- graphs. The ratio of the intensity of the displaced line to that of the undisplaced line is moreover very much greater for spark lines than for arc lines. These facts seem to show that the difference in the two groups of lines is attributable to a difference in the magnitude of the electric charge carried by the ions.It is supposed that the carriers giving rise to the arc lines have a single positive charge whereas the spark lines are due t o carriers with two or more positive charges. H. M. D. Doppler Effect of Canal Rays. HEINRICH WILSAR (Ann Physik 191 '3 [iv] 39 1251-1312).-The canal-ray spectra of hydrogen oxygen and nitrogen have been examined and experi- ments made t o determine the dependence of the velocity of the particles on the discharge potential the magnitude of the Doppler effect and the electric charges of the carriers. Other observations have reference to the influence of a magnetic field on the Doppler effect the reflexion of the canal rays from a metal or glass surface and the nature of the reflected rays.ii.173 GENERAL AND PHYSICAL CHEMISTRY. The canal ray spectrum of hydrogen shows none of the lines belonging to the principal series and lines belonging to the many- lined spectrum exhibit no Zeeman effect. All the spark spectrum lines of oxygen which appear in the canal ray spectrum give rise to a Doppler effect of the same magni- tude and are presumably due to the same curve. On the other hand no Doppler effect is obtained with the series lines of oxygen. Certain nitrogen lines show the Doppler effect and since the magnitude of this varies from one line to another it is inferred that there are two or more carriers. The magnitude of the Doppler effect increases a t first with the discharge potential but not as might be expected in the ratio of the square root of the potential difference the effect attaining a maximum at an applied potential which varies with the nature of the gas.In the case of hydrogen tlie canal rays carry a single unit of charge but multiple charges are carried by the oxygen and nitrogen canal ray particles. The hydrogen canal rays are reflected to an appreciable extent a t both glass and metal surfaces and the reflected rays are found to behave quite similarly to the normal rays. The carriers which give rise to the displaced lines in the canal- ray spectrum originate in the cathode region where the rapid fall of potential occurs and travel through the surrounding gas a t practically constant speed.The luininous particles to which the undisplaced lines are due are accordingly unaffected by collision with the rapidly moving carriers in so far as the Doppler effect is concerned. The excitation of a gas by the canal-ray particles of a second gas appears to be of a mutual character as a general rule. I n the case of mercury however which is readily excited by the canal ray particles of other gases this relationship does not exist for the canal ~ a y particles of mercury are apparently incapable of exciting the luiiiinosity due to rapidly moving particles when they are allowed to pass through other gases. H. M. D. Gompar ison of the Spectra of Fluorescent Rontgen Radia- tions J . CROSBY CHAParhN (f!roc. Roy. floe. 1913 A 88 24-37. Compare A. 1912 ii 316 518).-Measurements have been made of the absorption in aluminium copper silver and platinum of the characteristic radiations which are emitted by elements belonging to the K and JT groups.The results indicate that any radiation characteristic of an element of group K and having a certain penetrating power in aluminium is absorbed by any other element t o just the same extent as the radiation from an element of group L which has the same penetrating power in aluminium. From experiments with bromine aiid bismuth which belong t o the two different groups it has been found that their radiations are equally transformed into corpuscular radiation and that the corpuscles ejected by the radiations have the same ionising and penetrating power. Other observations show that the radiations of bromine and bismuth are identical in type in regard to their ionising power in different substances.ii.174 ABSTRACTS OF CEEMICAL PAPERS. The fact that radiations from elements belonging to different groups are identical in nature shows that properties which are dependent on electronic structure are repeated in atoms of different elements containing different numbers of electrons. The observations may therefore be regarded as affording support for the theory that the corpuscles in the heavy atoms are arranged in bundles the distribution of the corpuscles in each bundle being similar to the distribution in the atom of some lighter element. There is no relation between the elements of different atomic weight which emit identical radiations and the grouping of the periodic system.H. M. D. Measurement of the Ionisation Potential in Different Gases. 3. FRANCK and G. HERTZ ( B e y . Deut. physikccl. Ges. 1913 15 3444).-The magnitude of the ionisation potential has been determined for a number of gases by a modification of Lenard’s method (Ama. Phys)k 1903 [iv] 8 149) an electrically heated wire being employed as the source of the electrons. In all cases the gases were carefully purified and the following values obtained helium 20-5; neon 16; argon 12; hydrogen 11; oxygen 9; and nitrogen 7.5 volts. The data are insufficient to decide the question as to the manner in which the energy required for ionisation depends on the dimensions of the gas molecules. The Occlusion of the Products [of Disintegration] of Radium.GIOVANNI COSTANZO (Compt. rend. 19 13 156 126-1 27).-A compari- son of the results of introducing disks of palladium rubber and brass of varying thickness into an atmosphere activated by barium chloride containing radium. The results show (1) that brae obeys Curie’s laws for .the induced radioactivity of metals (2) that pallad- ium occludes the products of disintegration of radium almost to the same degree as rubber when in thin sheets (3) that the thickness of the activated disks seems to have an influence on the occlusion (4) that with disks under like conditions the activity immediately after withdrawal from the sphere of activation is greater with palladium than with rubber. This radioactive occlusion could be used as a means of estimating radium in an activating atmosphere.The Valency of the Radio-elements. GEORG VON HEVESY (PhysikaE. Zeitsch. 1913 14 49-62*).-From t h e theory of the diffusion of a cation in presence of a great excess of its anion and assuming for the mobility of the cation a mean value of 55.7 from which none of the known cations widely depart it is deduced that the diffusion coefficient of the cation is expressed by 1-25/n (6111.2 day-I) where n is the valency. A series of measurements of the diffusion coefficients D of several of the radioactive cations in N/lOO-hydrogen chloride has been carried out by the Graham- Stephan method using the apparatus of Scheffer and from these the valency of the ion is deduced. The results are expressed in the following table H. M. D. W. G . * and Phil.Xag. 1913 [vil 25 390-414.ii. 175 GENERAL AND PHYSICAL CHEMISTRY. D (cm.2,day-1) Val- I D (cm.2,dy-1) Val- Cation. at 18". ency. i Cation. a t 18 . ency. Uraiiyl (U0,l) ......... 0.576 11 ' Radium-F ............... 0.760 11 (in water) Thorium ................. 0.329 I V Uranium-X ............... 0.400 IV Raclio-thorinin ......... 0.333 Iv Ioniuni .................... 0.327 I V Thorium-S 0.659 II Radium ................. 0,667 I1 Thorium-B (RnR,AcB) 1.21 I Kadiuin-D ............... 0.651 I1 I Thorium-C (RaC AcC) 0.625 11 Radium-E ............... 0.646 I1 ' Actiniutn-X ............ 0.664 11 For some of these the mobility (u in lo5 cm. sec.-1) has been directly determined. The value of u varies between the extremes of 54.0 for thorium4 and 68.8 for radium-F and the more exact value of the valency deduced by combining with u the value of D confirm those given above.Thorium-B which appears univalent has a value for u 55.4 which shows that it is not an alkali metal but is in the silver group and is probably between mercury (uni- valent) and thallium in properties. The known rule that the expulsion of an a-particle lowers the valency by two units is as the result of these measurements extended and supplemented by the further rule that the expulsion of a &particle acts in the opposite direction. After the emanation or zero group is reached the opposite takes place the change of valency with the expulsion of the positively charged a-particle always being in the direction of increasing the electro-positive character and of the fi-particle the electro-negative character.This is qLiite analogous to the reduction of a multivalent ion such as the ferric or stannic ion to the condition of lower valency ferrous or stannous by the loss of positive charges. The a- and @-changes have polar consequences for the residual atom. The Diffusion of Uranium. GEOR~ VON HEVESY and L. VON PUTNOKY (Physikal. Zeitsch. 1913 14 63-65*).-The diffusion of uranous and uranyl salts has been studied by chemical and radio- active methods as if there were any difference in the rates of diffusion of uranium I and uranium 11 it should be made manifest by a difference in the two methods of measurement. I n three ex- periments a one-fifth molar solution of uranyl nitrate in eight times molar nitric acid the same in water and a one-sixth molar uranous sulphate in water were diffused.The values of the diffusion coefficient D (cm.2 day-l) were respectively 0.442 0.576 and 0.480 and there was in no case any difference between the results by the chemical and radioactive methods. This proves that Liranium I and I1 diffuse at exactly the same rate and are extremely closely allied in chemical properties. To bring the uranium dis- integration scheme completely in accord with the rules as regards change of valency following a- and &ray changes (preceding abstract) it is only necessary to assume that uranium-X is the product of uranium I and is intermediate between i t and uranium I1 as shown Ur-I .-> Ur-X -.!+ Ur-I1 .-> 10 -& Ra. ............. F. S. (]TI.) (117.) (VI.) (IV.) (11.) F.S. * and Phil M f i g . 1913 [vi] 25 415-418.ii. 176 ABSTRACTS OF CHEMICAL PAPERS. The Radioactivity of Solutions of Uranium Salts. L. MICRIELS (Le Radium 19 12 9 432-4S4).-The ionisation produced by solutions of uranium salts of known concentration and density has been studied by means of an electroscope with amber insulation. These solutions lend themselves readily to the production of a-ray standards of greater uniformity than can be produced by films of solid uranium compounds. For a given volume and area of solution of given density the a-radiation is proportional to the uranium content. If the density of a number of solutions of uranium of different concentration is made the same by the addition of ferric chloride the activity is proportional to the concentration.This allows the content of uranium in a solution to be obtained by a radioactive method in the presence of other metals in the solution provided that no other radioactive material is present. F. S. Change in Activity of a Sample of Uranium Nitrate. M. LAROSA (Nuouo Cim. 1913 [vi]. 5 i 73-S2).-A sample of this salt was found to undergo changes in radioactivity (which are described in detail) under the influence of proximity t o an electric arc of slight heating or of variations in the humidity of the air with which it was in contact. The changes observed are to be attributed t o the hygroscopic nature of the substance and to the solubility of the emanation which it produces in the absorbed water. R. V. S. Behaviour of Uranium-X with Regard t o the Usual Methods of Electrochemical Separation.PAOLO ROSSI (Nuovo Cim. 19 13 [vi] 5 i 5-14).-The electrochemical separation of uranium-X and uranium is more difficult than is the case with the radium group This would seem in agreement with Lucas’s law according to which the radioactive elements transform themselves into electro- chemically more noble elements but in contradiction with this uranium-X is not more easily separable than uranium. When uranium solutions are electrolysed with increasing E.M.F. no uranium-X separates a t the cathode but it may be possible t o obtain deposits a t the anode which contain uranium-X and very little uranium if the solution contains traces of impurities and the deposition is probably due to these or to deposits arising from them by electrolysis.If substances are intentionally added to the solutions to produce anodic and cathodic deposits the former contain only uranium-X whilst the cathodic deposits are inactive or contain both uranium and uranium-X. The presence of uranium-X in the anodic deposits cannot be explained by the phenomenon of cataphoresis. It is more probably an adsorption phenomenon and this explanation is supported by the fact that precipitates and colloidal metals acquire activity due t o uranium-X when placed in contact with uranium solutions and the author also finds on calculating the relative amounts of uranium and uranium-X which should be adsorbed that the activity of the uranium would be masked by the much greater activity due t o the uranium-X present.R. V. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 177 Synthetic Observations on the Activity of Rain Water. JOSE Mmoz DEL CASTILLO and JosB BARRIO FERNANDEZ (Anccl. Fis. Quim. 1913 11 89-91).-Various specimens of rain-water were shown t o give in volts per litre-hour values ranging from -3'6 to 175-0. G. D. L. The Atmospheric Electricity and Radioactivity of the Atlantic and Pacific Oceans. I. Determination of the Emanation Content of Ocean Water. J. LAUB (Physikal. Zeits~h. 191 3 14 Sl-83).-A serieq of fifty measurements of the emanation content of the ocean water was undertaken on a voyage in the Atlantic Ocean from Montevideo through the Magellan Straits into the Pacific Ocean to Callao. The mean of all the results showed the content to be 0.1 Mache unit the mean for the Atlantic being 0.14 for the Magellan Straits 0.09 and for the Pacific 0.08.No dependence of the value on the place the neighbourhood of the coast or the temperature of the water was observed. F. S. Electrical Excitation in the Spraying of Liquids (Ballo- electricity). 11. CHRISTIAN CHRISTIANSEN (Ann. Physik 191 3 [iv] 40 233-248. Compare this vol. ii 297).-In continuation of the experiments on the electrical excitation which accompanies the spraying of liquids observations have been made on aqueous solutions of halogen substituted fatty acids amines amides esters hydroxybenzenes alkaloids and certain other substances. From the data obtained with mixed aqueous solutions it is found that solutions of two different electrolytes which change the ballo- electrical effect exhibited by a solution of a non-electrolyte to a given extent are also equivalent in respect of other non-electrolytes.I n a similar way solutions of noa-electrolytes which are equivalent in their action towards a particular electrolyte are also equivalent in respect of other electrolytes. The influence of the nature and the pressure of the surrounding gas on the electrical effect has also been examined. The effect increases in all cases with the pressure and for carbon dioxide air coal-gas and hydrogen i t increases as the density of the gas diminishes. HI. M. D. Improved Apparatus for Measuring the Conductivity of Electrolytes. EDWARD W. WASHBURN and 3 . E. BELL (J. Anzei.. Chem. Soc. 1913 35 177-184).-1n order to obtain an accurate method for determining the conductivity of aqueous solutions of strong electrolytes between 0.001N and 0~000001N a study has been made of the sources of error inherent in Kohlrausch's method when applied to such solutions.Apparatus has been devised by means of which great precision can be attained not only in the measure- ment of very large resistances but also of very small ones and which possesses the advantages of greater rapidity and convenience of manipulation. The chief modifications introduced into the usual apparatus are the substitution of a high frequency generator for the induction coil as a source of current and of special filmii. 178 ABSTRACTS OF CHEMICAL PAPERS. resistance units f o r the ordinary resistance box. These resistances are made by sealing platinum wires into the ends of a glass rod and connecting them by a film of platinum deposited on the glass.A tuned telephone is employed and an extended bridge wire all measurements being made a t the middle of the bridge. Experiments have been made with this apparatus which show that by its means the conductivity of any solution of an electrolyte from conductivity water itself up to a 6N-solution can be readily determined with a precision of O . O l % and that with care the pre- cision can be increased to 0.001% in most cases. The method should prove of considerable value for the exact analytical control of pure solutions of electrolytes. E. G . The Molecular Conductivity and Viscosity in Mixtures of Methyl Alcohol or Acetone with Benzene and Nitrobenzene.J. FISCHLER (Zeitsch. EleLb.ochem. 19 13 19 126-132).-The mole- cular conductivity and viscosity of solutions of potassium iodide and lithium bromide were measured in solutions of mixtures of methyl alcohol and benzene methyl alcohol and nitrobenzene acetone and benzene and acetone and nitrobenzene. The conductivity at infinite dilution was calculated from the results by the Eohlrausch extrapolation formula A =(hl 3d<- A 3 ~ 4 / ( 3 @ . . - 3 4 / Z J in which A and A are the molecular conductivities a t dilutions vi and v2. It is shown that with lithium bromide the value A is greater the larger the values of 2rl and 21 ; the same is observed for potassium iodide but not to so marked an extent. This irregularity is explained by the existence of complexes in the concentrated solutions which dissociate in the more dilute solutions.Walden (A. 1912 ii 23) showed that the product A 'I where 7 is the viscosity is a constant and equal about 0.700. For solutions of potassium iodide in mixtures met'hyl alcohol-nitrobenzene acetone-nitrobenzene the value 0.650 is obtained whilst the benzene mixtures give much lower values. With lithium bromide in methyl alcohol-nitrobenzene the value is low but in the 50% acetone-50% benzene mixture it falls to 0.0487. This is no doubt due to the complexity of lithium bromide in the solution (see Serkov A. 1909 ii 372; 1910 ii 177). The complexity of lithium bromide in the methyl alcohol and nitrobenzene mixtures is calculated by the Serkov formula and it is seen to be strongly complex.J. F. S. Aqueous Solutions of Ammonia Soaps. I. FRANZ GOLD- SCHMIDT and L ~ O N WEISSMANN (&itsch. Chenz. I n d . IidOide 19 13. 12 18-31. Compare A. 1912 ii 728).-The electrical conductivity and viscosity of solutions of an ammonia soap prepared from the fatty acids of palm oil has been examined in regard to the influence of concentration temperature and of the addition of ammonia and ammonium salts. The results are compared with those obtained in a previous investigation (Zoc. cit.) of the properties of solutions of a similarly prepared potassium soap. The relationship between the conductivity and concentration is represented by a straight line which cuts the concentration axiaGENERAL AND PHYSICAL CHEMISTRY. ii. 179 a t a point on the positive side of the origin.The molecular con- ductivity which is only about half as large as that of the potassium soap increases with the concentration and appears to approach asymptotically to a limiting constant value. The viscosity increases with the concentration a t a gradually increasing rate and the con- centrated solutions are characterised by viscosity values which are extremely sensitive to changes of temperature. The addition of ammonium chloride in small quantities increases the viscosity considerably and causes a diminution in the con- ductivity. Larger quantities give rise to the precipitation of acid soaps. On addition of successive quantities of ammonia the viscosity rises slightly a t first then falls and finally increases until the viscosity becomes much greater than that of the pure soap solution.The effect of an addition of ammonia on the conductivity is to increase it a t first but a maximum value is soon reached and further quantities result in a continuous fall in the conductivity. From observations made with solutioiis to which both ammonium chloride and ammonia were added it has been found that the increase in the viscosity produced by the addition of a given quantity of ammonium chloride is enormously magnified when ammonia is also present in the solution. For each concentration of ammonium chloride there is a particular ammonia concentration for which this effect has a maximum value. If this quantity of ammonia is exceeded the viscosity falls very rapidly. H. M. D. Electrochemistry of Non-aqueous Solutions.X. Schutzen- berger’s Etherobromide. VLADIMIR A. PLOTNIKOV ( J . Buss. Php Chem. Soc. 1912 44 1919-1929).-The author challenges Mclntosti’s statements (l’. 1905 87 784; A. 1911 i 256) that the electrical con- ductivity of Schutzenberger’s etherobromide (ettier tribrornide) (Annnle~ 1873 167 86) is due to the presence of hydrogen bromide developed in consequence of the gradual bromination of the ether and that in addition to the tribromide a dibromide also exists. As regards the first point seven separate series of observations of the conductivity give concordant results (A. 1907 ii 152) and the magnitude of the conductivity diminishes with lapse of time. Secondly measurements of the viscosity of the system ether-bromine give no indication of the existence of a dibromide of the empirical formula Et,OBr (compare Kurnakov and Anisirnov J .Buss. Phys. Chem. SOC. 1912 44 1005). Solutions of ether dibromide in chloroform and ethyl bromide exhibit conductivities of the same order of magnitude as those of aqueous salt solutions the specific conductivity increasing approxi- mately in proportion to the concentration. On electrolysis ether is liberated at the cathode and bromine in amount corresponding with the formation of the ion Br’ a t the anode. These results are in agreement with the hypothesis that the electrolytic conductivity of a solution is conditioned by the electrochemical relations of the solute with the solvent and not by any special property such as the dielectric constant of the solvent. Assuming the double formula for ether dibromide a represen-ii.180 ABSTRACTS OF CHEMICAL PAPERS. tation of its structure according to the co-ordination theory is suggested. T. H. P. The Apparent Potential Difference of Contact ofa Metal and Electrolytic Solutions. J. GUYOT (Compt. rend. 19 1 3 15 6 220-222).-The author has measured the potential difference between a gilded electrode and solutions of metallic chlorides with an unpolarisable electrode of mercury coated with calomel and secondly solutions of silver salts with a silver electrode. From his results he deduces the following law. There exists the same apparent potential difference between gold and equimolecu1a.r solu- tions of electrolytes containing a common ion and having an electrode corresponding with this ion.W. G. Theory of the Skinner-Case Electrolytic Thermo-element Sn( CrCJ,)Pt and on Other Hlements of Analogous Type. ROBERT KREMANN and FELIX Noss (Moncctsh. 1913 34 7-667).-'rhe E.M.F. of a cell composed of tin or tin amalgam and platinum or carbon in a dilute solution of chromic chloride increases with the temperature but the observations of Skinner (A. 1896 ii 3) did not agree with those of Case. Since the action of the cell depends on the reaction 2CrC1 + Sn SnC1 + 2CrCl this equilibrium has been studied a t the outset. The results show that the dissolution of the tin increases slowly from 22O to 42O faster from 42O to 62O and rapidly from 6 2 O to 80°. The constant K from the expression (c~cY,)~/ { (SnC1,) <CrCi,)z 1 increases with increasing dilution which is explained by assuming that it is only the gre& variety.of chromic chloride which takes part in the reaction (compare Olie's study of the equilibrium violet CrCl3Zgreen CrCl A.1906 ii 859). For the purpose of the further investigations it was necessary to know the dependence of the amount of tin in solution on the original concentration of the chromium chloride and on the temperature and therefore the factor SnCI,/ CrC1 + CrCl has been plotted against chromic chloride (constant temperature) and temperature (constant initial concen- tration). The stronger the solution the faster does this fa8ctor rise with temperature. Meaaurements of E.M.F. under different conditiond were made ; the E.M.F. of tlne system platinum or carbon as +pole and tin or tin amalgam as -pole in pure chromic chloride (5 niols.per 100) is independent of temperature and is about 1 volt but when the solution is saturated with tin the E.M.F. falls off enormously. The potential drop PtICrC1 is also strongly affected by changes in the solution from which the conclusion is drawn that the tervalent chromium ions are reduced at the anode a change which is very dependent on temperature. Hence when an exhausted cell that is one which is saturated with tin and chromous chloride is raised to a higher temperature more tin dissolves the reduction of Cr"'-ions t o Cr"-ions can proceed farther and a further current is obtained. When the element has been exhausted a t a high tern-GENERAL AND PHYSICAL CHEMISTRY. ii. 181 perature (93O) no further current is developed on cooling since a series of saturations is passed through but when heated afresh the current is renewed.The quantity of current measured by a copper voltameter is however small but it is about three times as much a t 9 6 O as at 1 8 O . It remains constant for some time then falls and later on rises again this change being accompanied by the precipitation of insoluble chromium sesquioxide. Other equilibria have been studied and the systems copper- chromic chloride-carbon tin-vanadic chloride-carbon and silver- chromic nitrate-carbon were found to show similar electrical effects although in the latter case the instability of chromous nitrate soon renders the silver passive and consequently the potential cliff erence between the electrodes smaller.J. C. W. The Influence of High Preseures on Faraday’s First Law. ERNST COHEN (Zeitsclb. Elektrochern. 191 3 19 132-133).-The amount of silver deposited in two coulombmeters one a t atmospheric pressure and the other a t pressures of 500 1000 and 1500 atmospheres was compared. I n most cases the weights are found to be identical; in one case there is a difference of 1 in 15,500. From the results the author draws the conclusion that the ionic charge does pot vary 1 in 17,000 on changing the pressure from one atmosphere t o 1500 atmospheres. J. F. S. Anodic Oxidation of Ammonia in an Acid Liquid in the Presence of Silver Salts. GINO ScilaLrAamr and A. CASALI ( A t t i h’. Accccdo Lincei 1912 [v] 21 ii 726-729 ; Gazzetta 1913 43 i 30-36).-When a solution of ammonium sulphate saturated with silver sulphate and contained in a porous pot is used as anodic liquid and a solution of sulphuric acid (10%) is taken as cathodic liquid on electrolysis some nitric acid is formed round the anode.From the authors’ experiments the production of the acid appears to be favoured by rise of temperature (about 3.5 grams of nitric acid per 100 grams ammonium sulphate a t 90° as compared with 0.13 grams at OO) but the amount of nitric acid formed is inversely proportional to the concentration of the ammonium sulphate. The production of nitric acid falls off as the experiment is continued probably owing to migration of the catalyst from the anodic com- partment. R. V. s. The Mechanism of the Chlorination of Benzene in the Electrolytic Cell. RALPH G.VAN NAME and CARLTON N. MARYOTT (Amw. J. Sci. 1913 [iv] 35 153-170. Compare Cohen Dawson and Crossland T. 1905 87 lO34).-The electrolysis of benzene in a solution of lithium chloride in glacial acetic acid gives chlorinated benzenes under favourable conditions to the extent of 50-70% yields. Both addition and substitution products are formed the latter predominating but there is nothing to show that the effects are not due to the secondary action of chlorine previously set free by the current and dissolved in the electrolyte. Benzene dissolved in the same solution is readily chlorinated by direct treatment VOL. CIV. ii. 13ii. 182 ABSTRACTS OF CHEMICAL PAPERS. with chlorine gas in the dark yielding additive and substitution compounds in proportions which vary with the conditions.The addition of benzene t o the acetic acid-lithium chloride solution during electrolysis raises the anode potential by an amount equal t o or greater than that produced by a similar amount of carbon tetrachloride. This indicates that benzene has little or no depolarising action towards chlorine a t least in this case and therefore that the chlorination of the benzene is not electrolytic in character. Phenol added under similar conditions produces a decided lowering of the anode potential substitution products being formed. The rate of chlorination of benzene when dissolved in the same iiiedium saturated with chlorine was measured at 1 0 * 2 O and then the rate under simultaneous electrolysis. I n the latter case there was no perceptible acceleration of the rate of chlorination under conditions where a 10% current yield should have been evident.Both additive and substitution products in the ratio of about 2 3 were formed this ratio increasing with the progress of the reaction. The reaction velocity calculated on the assumption that monochloro- benzene and benzene hexachl oride were the sole products showed ;t steady rise but the rate of chlorination of inonochlorobenze~ie as determined separately appeared t o be sufficient; to account for tlliis effect. From the above results it follows that tliere is no positive evideiice of strictly electrolytic that is anodic chlorination of benzene. T. S. P. Measurement of the Energy of the Ultra-violet Radiation Emitted by an Arc in Mercury Vapour under Different Gonditions.MARCEL BOLL (Conzpt. rend. 1913 156 313-315).- A study of the energy emitted by a mercury-vapour lamp under varying conditions of voltage and current strength. The results show that the energy for h=2536 emitted by the arc in mercury vapour is a parabolic function of the electrical power expended. A formula is given by means of which an approximate calculation can be made for the radiation from such a lamp under any con- ditions. W. G. Selective Absorption of Electromagnetic Waves. W. I~OMANOV (Ann. Physik 2913 fiv] 40 281-296).-The author hRs investigated the absorption of electromagnetic waves of wave-length ranging from about 40 to about 100 cm. in methyl ethyl iso- butyl and amyl alcohols. The curves which are obtained by plotting the absorption coefficient as a function of the wave- length exhibit distinct maxima and minima indicating that the absorption spectrum for long-waved electromagnetic waves is quite similar t o the spectrum obtained in the case of heat rays.E. M. D. The Additivity of Diamagnetism in Compounds. PAUL PASCAL (Cornpt. rend. 1913 156 323-325. Compare A. 1910 ii 100 179).-Tlie absolute values of the atomic coefficients of mag-GENERAL AND PHYSICAL CHEMISTRY. ii. 183 netisation of a number of non-metallic elements as calculated by difference from the coefficients of simple organic compounds con- taining them the coefficient f o r water being taken as - 7.2 x loe7 show a very close accord with the values obtained directly on the elements. In the case of a diamagnetic metal the coefficient similarly calculated by difference is not a constant value but diminishes with increase in molecular weight of the organo-metallic compound the values for a homologous series tending towards a limit figure which for the metals studied (tin and mercury) show a striking agreement with the values obtained by direct deter- mination.This method of difference thus affords means of deter- mining the coefficient of magnetisation of diamagnetic elements which it is difficult to prepare in the pure state but of which pure organo-derivatives can be prepared. TN. G. Relative Scale of Temperature for Solid Substances. HASY ALTERTHUM (Bey. Deut. physikd. Ges. 1913 15 25-33).-8 theoretical paper in which in reference to the Planck-Einsteiii formula for the energy content of a solid substance it is suggested that the temperature of a solid should be expressed on a scale determined by the condition that the energy content is directly proportional to the temperature.This scale will vary from one substance to another and even in the case of substances of high melting point the melting points on the relative scale will differ materially from those on the absolute scale. The author considers that Lindemann's formuh (Physikd. .Zeitsch. 1910 11 609) for the connexion between the melting point and the vibration fre- quency should be modified in such a way that the melting tem- peratures are expressed on the relative scale. The modified formula is applied to the dsta for silver aluminium; copper lead platinum and zinc. H. M.D. Speciflc Heat of Helium and Certain Diatomic Gases between 20° and - 180". KARL SCHEEL and WILHELM HEUSE (Sitxungsber. K. Bkad. Wiss. Berlin 1913,44-48).-The measurements were made by the method of continuous flow with the apparatus described in a previous paper (A 1912 ii 19). From the molecular heat a t constant pressure (C,) that a t constant volume (Cv) has been calculated. The following pairs of numbers represent respec- tively the values of C and k=C',/C, helium 1 8 O (4.993 1-660) - 180° (4.934 1.673) ; hydrogen 16O (6.860 1*407) - 76O (6.365 1*453) - 1 8 1 O (5.330 1.597) ; nitrogen ZOO (6.983 1*400) - 1 8 1 O (7.162 1.468) ; oxygen 20° (6.98 1*399) -'76O (6.86 1.416) - 181O (7.30 1.447) ; air 20° (6'965 1*401) - 76O (7.04 '1.401) - 1 8 1 O (7.23 1.450) ; carbon monoxide 1 8 O (7.006 1.398) - 180° (7.244 1'472).The above data are compared with the results of other observers and evidence adduced which indicates that the probable error attaching to Regnault's numbers is not less than about 1%. I n the case of all the diatomic gases examined it is found that the specific heat ratio increases very corisiderably when the temperature is lowered froin %Oo to -180O. J 3-2ii. 184 ABSTRACTS OF CHEMICAL PAPERS. Molecular heat values have also been calculated for the various gases on the assumption that they obey the simple gas laws. H. M. D. Influence of the Free Electrons on the Specific Heat of Metals and Alloys. OSKAR K~CHTEK (Ann. Yhysik 1912 [iv] 39 1590-1 608) .-The specific heats of complete series of bismuth-tin and bismuth-lead alloys have been determined with the object of ascertaining whether free electrons contribute in measurable amount to the heat capacity of metals.For both series of alloys the electric and thermal conductivities are much smaller than would be expected according t o the mixture rule and in both deries i t has been found that the deviations from the straight line relation- ship are such that the ratio of thermal to electric conductivity remains constant. According t o Drude’s theory the diminution in the electric and thermal conductivity observed in a binary alloy of this tlype is due to a decrease in the number of free electrons a.nd if these electrons are of any appreciable importance in coii- nexioii with tlie heat capacity of the alloys it should be possible t o cletect corresponding deviations from the mixture law in the specific lieat values.The meyureuients were made in a Buiisen ice calorinieter a d control experiments indicate that the accuracy attained in the specific heats amounts t o 0.01 to 0.02%. I n the case of the bismuth-tin alloys the observed specific heats are sliglitly greater than the calculated values if the mixtures close t o the tin end of the series are excepted. For the bismuth-lead series the differences between observed and calculated values are in the same direction but of much greater magnitude a maximum difference being exhibited by the alloy containing equal weights of the two metals. These experimental measurements afford therefore no evidence in support of the view that the free electrons ar0 responsible for a measurable fraction of the total heat capacity of the metallic alloys.This result is quite consistent with the theory of specific heat put forward by Richarz. H. M. D. [Law of Dulong and Petit.] FRANZ KICHARZ (Ann. Yhysik 1912 [ivj 39 1617-1624).-The author discusses the relation between Einstein’s theory and the views which he has put forward in reference to the law of Dulong and Petit. It is claimed that the essential difference is to be found in the special assumptions made by Einstein. as to tlie inecliaiiisiii by which energy transfer takes place between the atoms. These assumptions lead to the conclusion that the atomic lieat csiinot be greater than the normal value. Since this is not in agreement with experiment it would appear that these assumptions must be modified and it is suggested that the electrons responsible for tlie conductivity are also involved in the process of energy transfer.In addition to this it would appear to be necessary in those cases where the normal value of the atomic heat is exceeded to assume that these electrons are responsible for a portion of the absorbed heat energy. The fact that theQENERAL AND PHYSICAL CHEMISTRY. ii. 185 strongly electro-positive alkali metals have abnormally high specific heats at moderate temperatures is regarded as distinctly f avourable to this view. A further factor which may influence the atomic heat is the formation of atomic complexes. This will reduce the degree of freedom of the vibrating atoms and lead to a diminution in the heat capacity.This may give rise to a variation of the specific heat with the temperature which is quite independent of that indicated by Einstein’s theory. &MILE H. AMAGAT (Ann. Chin,. Phys. 1913 fviiil 28 5-48j.-A rbsumt5 of work already published in A. 1909 ii 549; 1911 ii 1061 and 1912 ii 428. H. M. D. Internal Pressure in Fluids. T. A. H. Melting Curves of Stable and Metastable Crystalline Sub- stances. FRIEDRICH KORBVR (Zeituch. physikal. Chem. 191 3 82 45-55).-From considerations of the Z-function of the thermo- dynamic potential it was shown by Tammann (Gottzhger 1\.’achv. math.-phvs. Kl. 1911 353) that the melting curves of the stable and metastable forms of a substance would probably not cut one another. The present paper gives an account of the determination of the melting curves of the two forms of acetamide phthalide ethyl aminocrotonate chloroacetic acid and sodium thiosulphate.These were determined a t pressures from 1 to 2875 atmospheres and although it is the opinion of the author that the pressure applied was not high enough to finally settle the question yet the results point to the conclusion that the two curves do not cut one another. J. F. S. Latent Heats of Vaporisation and Maximum Prelseures. ANATOLE LEDUC (Compt. rend. 1913 156 225-227).-Combining Clapeyron’s formula for the latent heat of vaporisation with his own formula for the specific volume of the saturated vapour (compare A. 1912 ii 831) and taking previously recorded values for the maximum pressures and specific heats of water ether and benzene the author has calculated the latent heat of vaporisation of these substances a t temperatures above their boiling points.His calculated results being a t variance particularly in the case of ether and benzene with the experimental values recorded by other workers the author suggests the advisability of redeterminipg the values of the maximum pressures on the pure substances the tem- peratures being converted to the thermodynamic scale. W. G. Constancy of the Boiling Point of Sulphur. WALTHER MEIssNER (Ann. Phpsik 1912 [iv] 39 1230-1242).-1n utilising the boiling point of sulphur as a thermometric fixed point the mercury or resistance thermometer is usually surrounded by a protecting cylindrical or conical sheath of some material such as glass asbestos iron or aluminium.With the object of determining the influence if any of the nature of the protecting sheath com- parative measurements have been made with sheaths of differentii. 186 ABSTRACTS OF CHEMICAL PAPERS. materials. These indicate that aluminium or other good reflectors cannot be satisfactorily employed in the standardisation of thermometers by means of the boilin point of sulphur for the amounting to as much as 0 * 2 O . If the aluminium sheath is blackened or lined on the inside with asbestos paper the depression caused by the reflection from the metal surface disappears and the normal boiling point is recorded. temperatures indicated are appreciab f y too low the difference H. M. D. The Vap mr-pressure Curve of Nitrogen Tetroxide. FRANZ Russ [with ERNST EBERWEIN] (Zeitsch.physikd. Chem. 1913 82 217-223).-The present paper is an account of experiments of the same nature as those of Scheffer and Treub (A. 1912 ii 132). The experimental pressures were obtained by use of a mercury mano- meter and despite what is said by Scheffer and Treub against the use of mercury for pressure determinations of this type they agree very well with those obtained by means of a glass manometer. The vapour pressures were determined from -80° to - 1 5 O and are compared with values of Guye and Drouginine (A. 1910 ii 1056) and found to differ more and more from these values as the tem- perature is reduced. The vapour pressure is controlled by a calculation of the heat of sublimation of nitrogen tetroxide by the Clausius formula the value 10,850 cal.being obtained. This agrees well with value of Berthelot and Ogier (Landdl Bornstein ‘‘ Ttrbellen”) and Ramsay (T. 1890 57 590). The pressure values are also calculated from the Nernst equation making use of the critical pressure 100 atmospheres as deduced by Scheffer and Treub (loc. cit.). The calculated and experimental values agreel fairly well. J. F. 8. Simple Demonstration of the Lowering of Vapour Pressure. WALTER W. REED (Chem. News 1913 107 64).-The lowering of the vapour pressure of a solvent by a solute a t ordinary temperature is readily demonstrated by using three similar thermometers two of which are treated as ‘( wet bulbs ” in hygrometry the wick in one case dipping into the pure solvent in the other case into the solution. It is found that the thermometer with the wick dipping into the solvent has a lower reading than that with the wick dipping into the solution and that both readings are lower than that indicated by the dry-bulb thermometer.The apparatus is available for organic solvents as well as for water. H. W. Variation of the Vapour Pressure of Aqueous Sulphuric Acid Solutions with the Temperature. CARL HACKER (Ann. Physik 191 2 [iv) 39 1338-2349).-According to the relationship known as von Babo’s Law the ratio between the vapour pressure of an aqueous solution ( p ) and that of pure water (p,J is inde- pendent of the temperature. This empirical result is however iliconsistent with the requirements of thermodynamics which leads to the relation d(logp f pW)/dT = A/RT2 where A represents the heat of dilution of the solution.I n view of this discrepancy the author has made measurements of the difference between the vapourGENERAL AND PHYSICAL CHEMIST’RY. ii. 18’7 pressure of water and a number of aqueous sulphuric acid solutions a t temperatures between 30° and 80°. The data show that the ratio (pw-ps)/pw is by no means constant but diminishes as the tem- perature rises I n the case of a solution containing 32.5904 of sulphuric acid the value of this ratio was found to fall from 0.277 at 3 1 - 3 O ko 0.252 a t 80.3O; for a solution containing 41’54% of acid the ratio fell from 0.460 a t 32’6O to 0.430 at 60.8O. By reference to Thomsen’s data for the heat of dilution of sulphuric acid solutions it is shown that the observed variation of (pzu - p8) /pw with the temperature is in fairly good agreement with that calculated from the above thermodynamic relation.In making this comparison it has been assumed that the heat of dilution of sulphuric acid solutions may be regarded as independent of the temperature. H. M‘. D. Thermochemical Investigations in the Alicyclic Series. WALTER A. ROTH and GUSTAF JIM ~ T L I N U (Ber. 1913 46,309-32’7. Compare T. 1912 101 457; A. 1910 ii 586; 1911 ii 1065 etc.). -The following molecular heats of combustion at constant pressure have been determined Methyl cyclopropane-1 1-dicarboxylate 827.7 Cal. ; cyclopropanecarboxylic acid 479.7 Cal. ; ethyl cyclo- butanecarboxylate 966-0 Cal. ; cyclobutanecarboxylic acid 641.6 Cal. ; dirnethylcyclobutanel 2-dicarboxylate 984.5 Cal.; methyl cyclopentane-1 2-dicarboxylate 1117.7 C’al. ; methyl a-tanacetone- dicarboxylate 1452.9 Cal. ; keto-a-tanacetonecarboxylic acid 1328.7 Cal. ; cis-methyl norpinafe 1288.8 Cal. ; methyl pinate 1441.6 Cal. ; methyl pinonate 1478.8 Cal. ; methyl spiwheptaiieclicarboxylate 1409.1 Cal. 8-pinolene or cyclofenchene 1471.1 Cal. ; cyclene 1469.1 Cal. ; thujane 1508.6 Cal. ; thujyl alcohol 1479.4 Cal. ; thujone 1431.9 Cal.; camphor 1412’7 Car. The following dis- sociation constants in aqueous solution at 25O were also determined c!/clopropanecarboxylic acid 0*0000136 ; keto-a-tanacetonecarboxylic acid 0.0000115 ; cyclobutanecarboxylic acid 0*0000173 ; pinonic acid 0.0000215. From a consideration of the above and other data the authors come to the conclusion that Stohmann’s rule according to which the molecular heats of combustion and dissociation constants run parallel holds very well for the simple polymethylene acids but not for the two keto-acids keto-a-tanacetonecarboxylic acid and pinonic acid.The relation between ring-form and energy-content as put forward by Stohmann-KIeber and Berfhelot is verified for the simpler compounds. The order of the energy-content is five-ring six-ring double linking three-ring four-ring. A seven-ring appears to have a somewhat greater energy-content than a six-ring. The influence of conjugation or non-con jugation semi-cyclic or endo-cyclic position of the double linking is discussed since these secondary influences make comparison very difficult.A marked non-symmetrical structure appears t o increase the energy-content. The results obtained with the one compound so far investigated appear to show that the spiro-cyclic arrangement of the carbonii. 188 ABSTRACTS OF CHEMICAL PAPERS. atoms is relativedy stable. A di- and tri-cyclic arrangement appears bo increase the energy content. For three- and four-rings which are attached either to or in a six-ring the energy-content is apparently the same as for the isolated rings. T. S. P. The Laws of Corresponding States. EMILE H. AMAGAT (Compt. rend. 191 3 156 271-277).-A theoretical discwsion of the above law which the author considers may hold good for normal substances deviations from the law being the result of secondary phenomena particularly those of polymerisation.This is borne out by the fact that of the organic compounds considered the alcohols which exhibit a tendency to polymerise show the widest deviation from the law. He further replies t o some criticisms of Mathias (CongrZs du .fi.oid 1912). W. G. The Elements of Energy. JACQUES DUCLAUX (Contpt. Tend 1913 156 142-144).-A theoretical discussion of the relationship between the element of energy as defined by Planck being the smallest amount of energy which can intervene in a radiation of wave-length A expressed by E = 19.6 x l O - 1 7 / ~ . and the element of energy from the Pictet-Trouton law the smallest amount of energy which can intervene in a chemical transformation or in a change of state a t a temperature I’ Taking the case of a dark body emitting rays entirely of wave-length ,lo at a tern- perature To the author finds the ratio is very close t o unity.=9-5 x 10-1V. w. G. The Molecular Association of Liquids. I. ALEXIUS J. BATSCHINSKI (Zeitsch. ph.ysiku2. Ch,em. 19 13 82 86-89).-Polemical. An answer to the criticism of Tyrer (A. 1912 ii 739) on the author’s calcu- lations of critical temperature (A. 1911 ii 189). J. F. S. The Molecular Association of Liquids. 11. ALEXIUS J. BAT- SCHTNSKI (Zeitsch. physikal. Chem. 1913 82 90-92).-The author has calculated the metacritical temperature and association factor by means of the formula deduced by him (A. 1902 ii 444) for propyl isopropyl butyl isobutyl amyl and ally1 alcohols and for formic propionic butyric and. isobutyric acids at a series of temperatures. He also calculates the metacritical density of water from the atomic critical volumes of hydrogen and oxygen and thus is able t o arrive a t the metacritical temperature for water.The result is the same as that previously obtained by him by the method quoted above. J. F. S. A Method for the Determination of the Density of Solid Substances. J. L. ANDREAE (Zeitsch. physikal. Chem. 191 3 82 109-114. See also A. 1911 ii 469).-A method is given for the determination of the density of solid substances which are either very soluble or lose water of crystallisation very easily. The deter- minations are effected in a dilatometer which consists of a bulb I IGENERAL AND PHYSICAL CHEMISTRY. ii. 189 of about 10 C.C. capacity which is connected by means ol a narrow tube b with a wider tube a?.The volume of the bulb is known as well as that of the tube b which is also graduated. The method consists in placing about 20 grams of the carefully dried crystals into d ; should these contain water of crystallisation the water content is first of all accurately determined. Then the whole is weighed the salt is then washed down into the bulb a and sufficient water is added to completely dissolve all the solid. The tube is then placed in an inclined position and heated until the liquid stands in the narrow tube. Then the whole is weighed again; thus the weights of crystals and water are known a.s well as the sum of the volumes a t a given temperature. I f then the solubility of the substance a t that temperature and the density of the mother liquor is known it is obvious that the volume of the mother liquor and consequently the volume of the crystals must be known.'Renee the density unaffected by efflorescence or absorbed air is known. The author has compared the values obtained by this method with the values obtained by other methods for substances which are not easily changed and comes t o the conclusion that by this method the density of a solid can be obtained with the same degree of accuracy as obtains in the case of gases. J . F. S. Normal and Abnormal Cases of Speciflc Volume of Binary Liquid Mixtures. H. 8. VAN KLOOSTER (J. Amar. Chem. Soc. 1913 35 145-150).-1t has been shown by Hyde (A. 1912 ii 1138) that when p-nitrotoluene is dissolved in car'bon disulphide the specific gravity of the solution is less than that of carbon disulphide itself although p-nitrotoluene has a higher specific gravity than carbon disulphide.Considerations based chiefly on Hubbard's work (A. 1910 ii 809) are now advanced which indicate that this phenomenon cannot be regarded as abnormal and reference is made to a really abnormal case that of chloroform and ether which was recorded by Guthrie (A. 1885 339). E. G. A Relation between the Atomic Volumes of the Elements and their Power of Forming Complex Compounds G. HIRSCH- FELDT HANSEN (Zeitsch. nnorg. Chern. 191 3 79,322-326).- Elements of small atomic volume have the greatest tendency to form stable complex groups. This principle is illustrated by an arrangement of the elements according to atomic volume. C. H. D.Viscosity and its Signiflcance for the Chemistry of Celluloid in Theory and Practice. 11. SCHWARZ (Zeitsch. Chem. Ind. KolEoide 1913 12 32-42).-An account is given of the application of viscometric methods in the investigation of nitrocellulose and the changes which it undergoes in solution. From measurements of the viscosity of solutions of nitrocellulose in camphor-alcohol ether- alcohol and in acetone i t is found that the viscosity increases very rapidly with increase in concentration and that the solutions exhibit the phenomena of ageing. The ageing is accompanied by a very considerable increase in the viscosity which is more pro-ii. 190 ABSTRACTS OF CHEMICAL PAPERS. nounced in the case of the more concentrated solutions. The influence of the nitration process including the washing and bleaching processes on the viscosity of nitrocellulose solutions is also examined and the question of the molecular weight of cellulose is discussed in reference to the viscosity data.H. M. D. Change of the Surface Tension of Mercury on the Addition of Metals. FRIEDRICH SCHMIDT (Ann. Physik 1912 [iv] 39 1108-1132).-The influence of small quantities of various metals on the surface tension of mercury has been examined. The surface tension data were obtained by a method involving the measurement of the dimensions of the wave forms which are set up in the jet of liquid which issues from a tube provided with an elliptically shaped aperture. For this purpose the mercury or amalgam jet was photographed and the required dimensions ohtained by measurement of the negatives by means of a micrometer microscope.I n addition the times required for the outflow of equal volumes of mercury and the amalgams were determined and from these data t,he ratio of the surface tensions can be calculated. The observations show that the metals examined can be divided into three groups. Even a t the highest concentrations investigated (about a:,) zinc cadmium thallium gold tin and lead produce very little change in the surface tension of the mercury. The alkaline earth metals and lithium increase the surface tension t o :t very considerable extent. Traces are sufficient to produce an appreciable increase and when the concentration of the added iiietal amounts to 0.003 to 0.006% the influence of the addition of rz furtlier quantity is relatively small.Sodium potassium rubidium and msium reduce the surface tension very markedly. Tn the case of the first three alkali metals the influence is very sniall a t the lowest concentrations ; larger quantities have a rela- tively very much greater effect but if the concentration of the alkali metal is still further increased the diminution of the surface tension becomes much less pronounced. The interval of concen- tration for which the influence of the alkali metal is greatest varies considerably from one member of the group t o another. In the case of msium the initial stage appears to be absent the smallest traces producing a lowering of the surf ace tension. From the observations it is evident that in general metals belonging to the same periodic group have a similar action on the surface tension of mercury.When the change in the surface tension is plotted as a function of the atomic weight of the added metal a periodic curve is obtained. I n the group containing the alkali metals and gold and in that which contains the alkaline earth metals lithium and thallium the surface tension of the amalgam is found t o increase with the melting point of the dissolved metal. Internal Friotion of Binary Systems. Characteristics of Deflnite Compounds. NIKOLAI S. KURNAKOV and S. F. SHEMT- SCHUSHNI (J. Russ. Phys. Chenz. A~OC. 1912 44 196&1991).-The H. M. D.ii. 181 GENERAL AND PHYSICAL CHEMISTRY. authors have investigated a t various temperatures the viscosities of the following binary systems which form definite compounds (thiocarbamides) and at the same time remain liquid and homo- geneous allylthiocarbimide and piperidine ; phenylthiocarbimide and diethylamine ; [with V.ZEJLIGER] allylthiocarbimide and methylaniline ; [with A. ARSENEV] ethylthiocarbimide and piperi- dine. The viscosity isotherms if these systems consist of two separate branches which are convex to the composition axis and intersect at an angle (increasing in acuteness as the temperature is lowered) in a maximum corresponding with equimolecular proportions of the components. A similar form is exhibited by the curves connecting the temperature-coefficient of viscosity with the composition. This “rational” type of curve represents an addition t o the three types given by Dunstan and Wilson (T.1907 91 83). The intk!rsectioii of the branches of the viscosity isotherms in a rational maximum is an example of the break in continuity indi- cated by Mendelgev on the basis of his views on the nature ot’ solntions. Assuming that the two branches of the viscosity isotherm belong t o one and the same curve the maximum points of diagrams of the rational type may be compared with singular or nodal points of curves of the third and higher orders. These points may be termed “Dalton points,” as they characterise phases con Lairring chemical compounds which are subject to the laws of’ constant and multiple proportions. Measurements of the viscosity of liquid systems represent on(’ of the most sensitive methods of investigating the formation of chemical compounds and of determining their purity.The system consisting of allylthiocarbimide and the tertiary base pyridine which form no substituted thiocarbamide gives a viscosity curve totally different from those described above the value of +; for LZ mixture of the constituents in equimolecular proportions being rather less than the arithmetic mean of the values for the pure components. T. H. P. Influence of Temperature on the Turbulent Flow. CL. SCHAEFER and G. FRANKENBERG (Phpz’kal. Zeitsch. 19 13 14 89-93. Compare Sorkau A. 1912 ii 900).-The conclusions drawn by Sorkau from his observations on the flow of liquids in the turbulent condition are criticised. The view that the influence of tempera- ture on the rate of flow in the first stage of turbulence is the same for all liquids is shown to be untenable a theoretical argument being advanced which indicates that the temperature-coefficient is dependent on the specific nature of the liquid.From the hydro- namic equations a formula is deduced for the temperature-coefficient which is in good agreement. with the experimental data. I n a similar manner it is also shown that the supposed lack of a temperature effect in the second and third stages of turbulence is inconsistent with the facts and that the actual temperature varia- tion may be expressed by formulce derived in the same way from hydrodynamic equations.ii. 1.92 ABSTRACTS OF CHEMICAT PAPERS. It is further shown that the observed temperature variation of the transition from the first to the second stage of turbulence is determined by the saine condition which has been shown by Reynolds to regulate the influence of temperature on the transition from the condition of steady flow to that of primary turbulent flow.H. M. D. Turbulence Viscosity. GUSTAV MIE (Phymkrsl. Zeiisclh. 191 3 14 93-95. Compare Sorkau A. 1912 ii 900 and preceding abstract) .-The irregular grouping of the experimental points on the diagram which is obtained by plotting the rate of flow as a function of the pressure is considered to be duel to the instability of the flow under the conditions which obtain in the second and third stages of tu.rbulence and not to mere accidental errors of observation. If this is the case the real influence of pressure 011 t h e rate of flow in the turbulent condition will not be obtained by simply drawing a mean curve through the experimental points 011 the diagram. The probable nature of the true curve is discussed in reference t o Sorkau’s data for et’hyl acetate chloroform and metone.H. M. D. Detsrrnination of the Degree of Dissociation of Molten Silver Chloride and Silver Bromide. GONTHPR SCEIULTZE (Zettsck. h’Z-ktrochem. 1913. 19 128-126).-The alithor shows t h a t when sodium glass is dipped into molten silver salts silver ions diffuse into the glass and sodium ions diffuse into the silver. Under constant conditions the quantity of silver which diffuses is propor- tional to the concentration of the silver ions for small concentra- tions. The relation between the quantity of silver diffusing and the concentration of the silver ions is obtained by introducing small quantities of sodium salts of the same anion and so reducing the silver ion concentration and then determining the amount of silver which has diffused.From two such experiments using small but different quantities of the sodium salt it is possible to calculate the factor which gives the desired relationship by means of the law of mass action. Consequently it is easy t o determine the degree of dissociation directly from the amount of diffused silver. From the experiments the values for silver chloride and silver bromide are found t o be AgCI = 1-17 x 10-3-1.35 x 10-3 at 461° AgBr=2*35 x 10-4 at 450O. These values agree well with those of Abegg obtained from measurements of the decomposition potential (A. 1900 ii 5). J.F. S. Method of Calculation of the Constant of Capillarity. The Etitvos-Ramsay Rule. The Coefficient of Compressibility of Liquids. PETRU BOGDAN (Zeitsch. ph?lsii%d. Chem 19 13 82 93-108).-A theoretical paper in which it is shown (1) that the molecular surface energy calculated from the values y = $grhp changes in a linear manner with temperature down to the critical point; (2) that in calculating the surface tension of liquids i t is unnecessary to subtract the orthobaric density of the vapoiir fromGENERAL AND PHYSICAL CHEMISTRY. ii. 193 the density of the liquid; (3) the coefficient of elasticity of a liquid is equal to the internal pressure and that the product of the internal pressure and the coefficient of compressibility of a liquid is equal t o unity; (4) that between the coefficient of elasticity the internal pressure and the vapour pressure of a liquid the relation- ship R = P + p holds.The Theory of Osmotic Pressure. JOHANNES J. VAN LAAR ( Z m t d . physikal. Chem.. 19 13 82 223 -224).-The author criticises the formulz derived for osmotic pressure of solutions by Stern (this vol. ii 28; see also A. 1595 ii 107; 1906 ii 526; 1908. ii 1018; Lewis A. 1908 ii 465). Diffusion through Rubber Membranes. WILLIAM J. GIES JACOB ROSENBLOOM WILLIAM H. WELKER GEORGE D. BEAL and GEORGE A. GEIGER (Biochent. Bull. 1912. 2 55-S6).-0n thct assumption that tile diffusion of a solute depends largely on the chemical affinity of the membrane and the materials on each side of it study was directed t o what occurs in membranes made of rubber in miation to substaiices soluble in ether.The experiments recorded deal with fats alkaloids lipoids proteins and pigments. W. D. H. J. F. s. J.F. S. General Characters of the Actions between Molecules. MAECEL BRILLOUIN (Ann. Chim. Pfhys. 1913 Lviii] 28 48-77).-A theoretical paper arid tlie first of a series in which the author proposes to consider the mechanical properties of matter regarded as composed of a large number of identical particles (molecules) which mzby be iaotrlipic or al;isotropic in equilibrium in motion due t o the action of a homogeneous medium having a mean uniform movement c;r undergoing translatory movement in any sense. I n this paper the conditions which govern the mutual mechanical action of molecules are discussed and the views advaiiced by Schroder by Sollas and by Barlow and Pope (T.1906 89 1723) are examined. The author considers that the forin of the neutral zone (in which mutual action between molecules is nil) and there- fore crystalline form may have a direct relationship to the consti- tution of the molecule in so far as this depends on valency but the molecular volumel is in addition to that dependent on the nature of the atoms. EMILE BAUD (Compt. rend. 1913 156 317-320. Compare A. 1912 ii 233 331).-Studying a mixture of acetic acid and cyclohexane the author. has determined the temperature of crystallisation of the acid in the solvent a t various concentrations mid has plotted a temperature-concentration curve. For conditioiis of partial miscibility the temperature at which crystallisation commences must be a minininni point on the above curve.W. G. T. A. H. The Partial Miscibility of Liquids. The Atomistic Theory of Polymorphism. GUSTAV TAMMANN (Zeitsch. physikal. Chem. 1913,82 17,”-200).-A theoretical papor inii. 194 ABSTRACTS OF CHEMICAL PAPERS. which the following points are discussed (1) Polymorphism and the molecular compoeition of the liquids. The conclusion is drawn in this connexion that in liquids which have a value for - d ( a d ) / d T less than 2.00 that is liquids which are associated more than one thermodynamic crystal group may separate whilst for liquids which have a value more than 2.00 only oner crystal group can separate. (2) The crystallisation of different crystal groups from associated liquids. (3) The characteristics of association in crystals.(4) The thermal characteristics of the forms of a thermodynamical crystal group. J. F. S. Jellies. RICHARD ZSIGNONDY and WILHELN BACHMANN (Zeitsch. Chem. h d . Kolloida 1913,*12 16-18. Compare A. 1912 ii 1149). --Polemical against von Weimarn (this vol.? ii 32). It is pointed out that the observations relating to the morphological structure of gelatinised soap solutions has not been put forward as evidence in support of the crystalline nature of jellies in general. It would appear that von Weimarn and the authors do not agree in respect of the question as to what properties determine whether or not a substance belopgs to the group of jellies. H. M. D. Reversible Coagulation Processes. SVEN O D ~ N aud E. OHLON (Zotsch.physikcal. Chem. 191 3. 82 78-85).-Colloidal solutions of silver and sulphur in 1% solutions were placed in a centrifugal machine and treated with a series of different concentrated solutions of electrolytes. In the case of tlie silver sqlution ammonium nitrate was used whilst with the sulphur solutions sodium chloride was employed. The addition of the electrolyte caused coagulation which was completed rapidly by centrifugalising. Then by more rapid centrifugalising the coagulating electrolyte was removed and the solution made up to its original volume with the pure solvent when the colloidal substance' again passed into solution. The solution was then examined by ultra-microscopic methods and the number and size of the particles determined. From these experi- ments the authors state that there is no change in the size of the particles even after many coagulations and re-solutions and that the individual particles maintain their identity in the coagulated inass.J. F. 8. Method for the Determination of the Size of Colloidal Particles. A. D u M m s K r E. ZABOTINSKJ and M. EVS~EV (Zeitsch. Chern. Ind. Koltoicls 1913 12 6-11).-0n the assumption that the colloidal particles are spherical in form it is shown that the radius of the spheres may be obtained from the formula in which 12 is the number of particles in volume u c the concentra- tion of the colloidal solution 6 the density of the solvent and d that of the solution. From the data for three colloidal solutions i t is found that the value of r given by this equation is from one atid a-half to three ?'= Y~V(S + c - d ) / 4 ~ / 1 8 ,GENERAL AND PHYSICAL CHEMISTRY ii.195 times as large as the value obtained from Stokes's eqttation for the rate Qf segregation of the particles Other formulz for the radius of the colloidal particles are deduced by combining Einstein's equation yl/ ylq= 1 / (1 - +) for the relation between the viscosities of the solution (7) and the solvent (q0) and the volume (4) occupied by the colloidal substance with Stokes's equation. These are applied in the calculation of the1 dimensions of the particles in colloidal solutions of arsenious sulphide which have been investigated a t Oo 20° and 50°. H. M. D. The Application of the Principles of Golloidal Chemistry to the Considerations of the Question of Specificity. WOLFGANG OSTWALD (Biochem.Zeitsch. 1913 48 225-229).- Michaelis and Davidsohn (this vol. i 121) have recently shown that the formation of specific agglutins and precipitins is largely independent of the hydrogen ion concentration and is t o a large extent independent of the electrical charge of the particles coii- cerned in the precipitate formation. They draw the conclusion from these results that the cause of precipitation is essentially of a chemical character and that the general principles of colloidal chemistry are not applicable t o these phenomena. To the latter statement the author takes exception on the ground chiefly that clectrical factors are not the only ones to be taken into account as the cause of precipitation from colloidal solutions.He quotes instances to show that adsorptive precipitation can be produced by two sitbstances both of which have the same kind of eIectrical charge (toxins and antitoxins) and furthermore certain concen- trated electolytes which can neutralise and discharge a colloid (gold sols) do not always produce precipitation. Other important factors which determine the precipitability of a colloid such as the surface tension a t the interfaces are not influenced solely by the electrical charges but other chemical and physical characters must be taken into account such as the grade of the dispersion and the degree of hydration of the colloid. S. B. S. Reciprocal Salt Pairs and Double Ternary Salt Mixtures. ERNST J~NECKE (Zeitsch. phyyst&d. Chem. 1913,82,1-34. See also A 1908 ii 808; 1909 ii 872; 1912 ii 150).-A theoretical mathe- matical paper.The relationship between weight % and molecules 76 curves for reciprocal salt pairs is discussed and a new method of representing the weight relationships introduced. The solid- liquid relationships of reciprocal salt pairs is discussed making use of the Z-function of the thermodynamic potential. The Z-function is defined by the equation 2 = E - TS + Pu where E is the internal energy S the entropy and T P and the absolute temperature pressure and volume. The reciprocal pairs are discussed for cases where one two three four five and more solid phases are present. Instances me cited of pairs which will probably show the properties theoretically deduced. The equilibrium of double ternary mixtures ( M ~ M f f M l l / ) (PS'lf) or (d4lMf') (S'S'~S'l) where ? f r i I f J f M / ~ ! l represent11. 196 ABSTRACTS OF CHEMICAL PAPERS.metals ,S”S’/S/// acid radicles are discussed for the cases where one two’ three four five six and more than six solid phases are present. J. F. S. The Partial Pressures of Ternary Mixtures. FRANS A. H. SCHREINEMAKERS (Zeitsch. physikal. Chem. 19 13 82 56-58).-A mathemat.ica1 paper in which from Duhem-Margules equation for binary solutions (A 1901 ii 227) the author deduces an expression for ternary mixtures which has the form iii which 7rl 7r2 and 7r3 are the partial pressures of the constituents in the gaseous phase and q y1 and (1 - z1 - yl) the quantities of the substances in the liquid. This equation is shown to be a special case of the Duheni-Margules equation.zldln + y l d l ~ z +- (1 - 21 - y l ) d l ~ s = 0 J. F. S. The Quadruple Point and Triple Gurves in Binary Systems FJ~ANS A. H. SCHRPINEMAKERS (Zaituch. yhysikal. Chem. 1913 8 2 59-70).-The author considers the relationships on the basis of the phase rule of liingry systems which can exist in four phases. The changes which occur when pressure temperature or concentra- tion is effected a t the quadruple point are discussed. The concln- sions arrived at are applied to the systems H,S-H,O (Scheffer A. 1911 ii 264 870) and iodine-chlorine (Stortenbeker A. 1889 102). J. F. S. The Equilibria in the System Barium Chloride Sodium Nit1 ate Barium Nitrate Sodium Chloride and Water. ANGELO COPPADORO (Atti R. Accad. Lzncei 1912 [v] 21 ii 84’L-850.Com- pare A. 1912 ii 441).-Of the four ternary systems comprised in this quaternary system that of sodium chloride barium chloride and water has been investigated at 30° by Schreineinakers and de Baat (Zmtsch. physikd CIietn. 1909 65 587). The other threo syst.ems and the quaternary system have now been investigated at the same temperature and the present paper gives the results of this work in a number of tables. R. V. S. Equilibria between Potassium Hydrogen Carbonate and Salts of Magnesium Nickel and Cobalt. T. NANTY ( A r m Chiin. Yhys. 1912 [viii] 27 5-89 ; 1913 [viii] 28 77-208).-Th~ results already recorded (*A. 1911 ii 103 282) for the action of potassium hydrogen carbonate on salts of magnesium are described in greater detail arid a mathematical discussion of the whole subject is given.It is then shown that the actioii of potassiuni hydrogen carboilate o n nickel salts is strictly analogous to its action on inagnesiurri salts both actions being reversible in the ordinary sense. ‘These results axe therefore at varknce with those observed by Engel (A. 1886 121). Cobalt salts behave differently no equilibrium being reached in this case. The conditions prescribed by various au’thors and especially Engel (Zoc. cit.) for the preparation of magnesium carbonate &1gCO3,3H,O and potassium hydrogen magnesium carbonate,GENERAL AND PHYSICAL CEEMISTRP. ii. 197 KHC03,MgC0,,4H,0 are examined and shown to be inaccurate and incomplete and experimental data supporting this conclusion are quoted.The conditions uiider which either or both salts may be formed are then determined by the use of Gibbs' graphic method for ternary mixtures and i t is shown that these conditions can be verified experimentally ; thus at temperatures 7-8O 1 5 O and 26-27O the composition of the precipitate is independent of the concentration of the magnesium salt and depends only on the con- centratiorr of the potassium hydrogen carbonate in the generating liquid. A t 7-8O 2.2% of the latter salt is the critical d u e anything below that giving magnesium carbonate and anything above it the double carbonate. At 1 5 O the critical value is about 4% and at 2,6-2SG about 6%. The only secondary reaction is the reversible decomposition of the double carbonate by water and to this is due the variation of the critical value with temperature.The second paper begins with a mathematical and experimental investigation of the conditions necessary for the formation of either carbonate and methods of calculating the composition of solutions which on admixture will give a precipitate of the required composi- tion are given with experimental verifications. The equilibrium conditions for the formation of the double carbonate and its decomposition by water are then investigated and shown to be identical for the :ame temperature under atmospheric pressure. The velocity of the reaction in either direction at the same temperature and pressure is proportional to the difference between the initial aud final concentration of potassium hydrogen carbonate in the solution; the velocity constant increases with the temperature.-4 similar but less detailed study has been made of the formation of nickel carbonate NiC0,,3H20 and of the double carbonate NiC03,KHG0,,4H,0 and the results are completely analogous to those obtained €or the corresponding magnesium salts. Cobalt salts on precipitation with potassium hydrogen carbonate give a basic carbonate CoC0,,Co0,5H20 and a double carbonate C'oCO,,KHCO,,4H2O the former amorphous the latter crystalline. No combination takes place between cobalt carbonate and potass- ium hydrogen carbonate and no equilibrium is reached in the action of water 011 the double carbonate referred to above. T. A. H. Displacement of the Primary Amylamines by Gaseous Ammonia. F ~ L I X BIDET (Compt. rend. 1913 156 315-31 7) - -4 study of the equilibrium pressures of amylamine hydrochloride and it7s iso-isomeride in the presence of gaseous ammonia a t different temperatures.The values for the straightrchain compound are considerably lower than those for the iso-compound at low tempera- tures but the values become practically equal a t 50°. The figures indicate the existence of several definite basic hydrochlorides the state of equilibrium being a function of the concent,ration of tho i j mmonia. w. G. VOL ctv. ii. 14ii. 198 ABSTRACTS OF CHEMICAL PAPERS Influence of Temperature on the Velocity of Chemical Reactions. 11. B. Scnv~cov (J. Rwss. P h p . Chem. Soc. 1912 44 Yhys. Part 516-519).-In a previous paper (this vol. ii l24) the author has suggested the characterisation of the influence of tem- perature on the velocity of chemical reactions by the logarithmic temperature-coefficient 7 expressed by (K,/ Kl)~~;~zgj+l where Ii and K2 are the respective velocity constant8 determined for the absolute temperature T and 112 and p is a constant.From this expression i t follows that constancy of 17 requires the fulfilment of tlhe condition dlogK/dlogT= constant'. Startling from the assumption that chemical reaction is a conse- quence of the reacting molecules impinging one on the other with a sufficient degree of violence the author now shows mathematically that in the case when molecules of only two kinds react dlogK/dlogT has the constant value 1.5. The assumptions made in arriviq a t this result are that the reaction shall be non-revers- ible and that i t shall take place either in it gaseous medium or in dilute solution.For reversible reactions constancy of the loga- rithmic teniperaturecoefficient is to be expected only when the velocity of the reverse reaction is virtually independent of the temperature. T. H. P. 1% P The Action of Carbonic Acid on Alkalis and Alkaline Earthe a s H Time Reaction. DANIEL VORLANDER and WALTER STRUBE (Ber. 1913 46 172-181).-When a solution of calcium hydroxide coloured red with phenolphthalein is rapidly mixed with an aqueous solution of carbon dioxide of slightly more than the equivalent strength there is no immediate disappearance of the red colour. The time necessary for decolorisation may vary from a few minutes to several days increasing with the dilution of the solutions.As the excess of carbon dioxide is increased the time diminishes but still remains of the order of several seconds when about four times the' equivalent of carbonic acid is used. If a precipitate forms it is deposited before decolorisation occurs. These results were shown not to be due to alkali being dissolved from the glass or to other such side-reactions. Similar results were obtained with solutions of barium arid sodium hydroxides but the times necessary for the disappearance of the red colour were very much less being generally of the order of a few seconds unless in the case of barium hydroxide the dilutions are very great. The authors consider that it is probable thab the above pheno- iiiena are due to the hydration of carbon dioxide to carbonic acid not being complete in aqueous solution and taking place only slowly during the neutralisation.No other weak acids such as hydrogen sulphide acetic acid etc. gave similar results. It is found that pure and well-washed calcium carbonate gives an alkaline reaction to wa.ter. The result,s show t,hat calcium hydroxide cxnnot be used for tho cstima tioii of t,lic frcc carbonic x i t i in water. Lowering the temperature increases the time. T. S. I',GENERAL AND PHYSICAL CHEMISTRY. ii. 199 The Slow Neutralisation of Carbonic Acid. ALFRED TRIEL (Ber. 1913 46 241-244).-Polemical against Vorliinder and Strube (preceding abstract). The author points out that according to experiments which are to be published later the hydroxides of tho alkaline earths are not suitable for studying the actual time- reaction with carbonic acid owing t o the gradual alteration in condition (" ageing ") which takes place of the carbonates formed. The author has previously observed the time reaction between carbonic acid and sodium hydroxide (Sitzber.Ges. IVLs. Murhwrg Nov. 1912) and given the same interpretation as Vorlander and Strube (compare also MacBain T. 1912 101 814). Kinetic Investigation of the Action of Carbon Monoxide on Solutions of Potassium Permanganate. GERHARD JUST and YRJO KAUKO (Zeitsch. physikal. Chem. 1913 82 71- 77).-The experiments described were carried out in exactly the same way as the previous experiments on the action of hydrogen on potassium permanganate (A 1911 ii 494). It is shown that in neutral solutions of potassium permanganate the rate of reaction is propor- tional to the concentration of the carbon monoxide.It was found necessary in order to get effective mixing of the gas and solution to rotate the reaction vessels 5000 times per minute. The concentra- tion variations were brought about by mixing the carbon monoxide with nitrogen. The reaction is shown to take place in the first place between one molecule of carbon monoxide and one molecule of potassium perrnanganate with the probable formation of an unstable quinquevalent manganese derivative. The influence of temperature was investigated and found to be such that an increase of loo doubled the velocity of readion. The reactions were also carried out with a series of hydrogen carbon monoxide mixtures from which i t is evident that both substances react normally without any influence on on0 another.The Velocity of the Reaction of Bromine and Aqueous Solutions of Monohydroxy-Aliphatic Alcohols. ELISABETR R ~ N A (Zeitsch. physikal. Chern. 19 13 82,225-248).-The velocity constants for the reactions between bromine and methyl propyI isopropyl butyl isobutyl arid tert.-butyl alcohols are determined by the iiiethod adopted by Bugarsky (A. 1910 ii 281) for ethyl alcohol. The reactions were carried out at 25O and with the exception of those with methyl and tert.-butyl alcohols all occurred in two stages the alcohol being first oxidised to aldehyde or ketone and this then to acid. ThO velocity constants were determined for both reactions as well as the total reaction constant.The constants increased with the molecular weights of the normal alcohol the value of thO first constmt increasing less than the constant for tho second reaction the amount of increase slowly increasing as the molecular weight increases. The iso-alcohol has in both cases larger velocity constants than the corresponding normal alcohol and the amount of increase between two consecutive iso-alcohols is much greater than that between the corresponding normal alcohols. T. S. P. J. F. S. J. F. S. 14-2ii. ZOO ABSTRACTS OF CHEMICAL PAPERS Gradual Hydrolysis. CARL L. WAGNER (Manatsh. 191 3 34 95-170).-'The hydrolysis of salts of weak bases with strong acids and of strong bases with weak acids can be conveniently studied by the increase in conductivity which is observed when the requisite dilution is reached. Kn some instances the increase is nQt sudden but proceeds a t a measurable speed and three explanations have been offered t o account for this phenomenon. I n the case of stannic chloride which is practically a uon-conduct.or Kovalevski (A.1900 ii 356) suggested that the scarcity of ions accounted for the sluggishness of the process. The hydrolysis of ferric chloride has bpen assumed to proceed through the stages FeC1 - FeCl,*OH - FeCl(OH) - Fe(OH) (coinpare Antony and Giglio A. 1896 ii 250; Goodwin A. 1897 ii 16; and Malfitano A. 1912 ii 337). A third explanation involves hydrate isomerism as exhibited by green and violet chromium chloride. It has tlieref ore been necessary to conclude that just this particular ionic reaction is measurably slow or t o assume purely theoretical ions or to construct co-ordinate coin- pounds for each case. It is remarkable however that in all the observed cases either the weak base o r the weak acid shows a great tendency to form a colloidal solution and the author therefore offers a simple explana- tion of the gradual increase in conductivity which is based on a conception of the changes in superficial magnitude of the colloid.As the result of hydrolysis the metallic hydroxide (or the acid) is liberated as a highly-dispersed phase on the enormous surface of which the liberated acid (or base) is a t first completely adsorbed. In the process o i time the particles become larger that is the surface of the dispersed phase rapidly diminishes and therefore the adsorbed acid or base is able to enter the continuous phase the solution.The theory is supported by experiments on the conductivity of ferric alum in various concentrations where contrary to the experi- ence of Goodwin yith ferric chloride (Zoc. cit.) the solutions get turbid deposit a precipitate finally become colourless and the con- ductivity does not reach a constant neither does it attain to the value for solutions of sulphuric acid and potassium sulphate con- taining the equivalent of -SO ions. The addition of protective colloids such as carefully washed agar-agar or better still gelatin retards the growth of the conductivity. It also prevents the pre- cipit,ate from settling in a dense form so that the acid is washed out by the solution to a greater extent and hydrolysis apparently proceeds farther. When the precipitate begins to form however the protective colloid is carried with it and is thus removed from further action.Goodwin found that ferric chloride solutions remained perfectly clear developed the brown colour of ferric hydroxide sols and attained a conductivity which agreed with the equivalent quantity of hydrochloric acid. This experience is confirmed and the csplaiiat ion offercd that the requisite diminution in the surface of t h e disperscd 1)liasc t'a,kcs place within the region of colloidalCIENERAL AND PHYSICAL CHEMISTRY. ii. 201 solution that is without the formation of macroscopic particles and therefore equilibrium is more quickly reached. The addition of gelatin again retards the growth of the conductivity to a great extent even when allowance is made for the smaller conductivity of hydrochloric acid in a gelatin solution. Th'e different behaviour of ferric alum is due to the intensive coagulating action of the bivalent *SO ions and the effect of these on a ferric chloride solution is extremely pronounced.The addition of 1/160,000 of an equivalent of potassium sulphate produces a noticeable difference in the conductivity curve (a possible test for traces of *SO ions) and more khan 1/2000 of an equivalent causes turbidity and precipitation. The final values are not as high as those for the pure solution plus the sulphate since the coagulating ions are adsorbed on the ferric hydroxide. This is shown by the fact that the addition of *SO ions to an already completely hydrolysed ferric chloride soliition causes coagulation and a fall in the total conduc- tivity.The influence of foreign electrolytes also explains some discrepan- cies which were observed with ferric acetate and aluminium acetate. When these solutions were prepared by double decomposition or by casual solution of the hydroxide the conductivities remained constant for a great length of €ime. A ferric acetate solution made from freshly precipitated hydroxide which had been completely extracted by conductivity water however showed the same gradual hydrolysis and rise in conductivity towards the value for acetic acid and the effect of potassium sulphate was the same as before. J. C". Saponiflcation in Stages.111. Hydrolysis of Acid Amides and Nitrilee. NICOLAS VON PESKOV and JULIUS MEYER (Zeitsclt. physikal. Chem. 1913 82 129-171. Compare A. 1907 i 463 S l 9 ; 1909 ii 391 803).-In the first part of the paper a general formula is deduced for the velocity constant of a reaction which takes place between two substances in four stages; thus the reaction RPlP2+ MN is considered to occur in the stages RP1P2 + MN = RPlM + NP2 RPlP2 + MN = RP2M + NP1 RPlM + MhT = RM + NP1 and RP2M + MN == RM + NP2 ; all four reactions are assumed to have different reaction velocities. The general formula is then simplified to make i t adaptable t o special cases. The simplified forms are the same as those deduced by Meyer from other considerations for the hydrolysis of the normal esters of dibasic acids.In the experimental part of the paper the hydrolysis of amides and nitriles of monobasic acids and of amiclee of dibasic acids are considered. The experiments were carried out with acetamide formamide propionamide butyramide isobutyramide valeramide and hexonamide ; acetonitrile and pro- pionitrile ; malonamide and succinamide. The amides or nitriles were mixed in weighed quantities with known amounts of hydro- chloric acid or sodium hydroxide in flasks which were kept a t 1 8 O or 2 5 O in a thermostat. A t measured intervals of time 10 C.C. of the reaction mixture were withdrawn and treated with an excessii. 202 ABSTRACTS OF CHEMICAL PAPERS. of sodium hypobromite and the quantity of nitrogen formed measured. It is shown that the amides of monobasic acids are hydrolgsed more rapidly by alkalis than by acid although here the difference is not so marked as in the case of esters of dibasic acids; in the latter case Meyer (Zoc.cit.) showed that the ratio between the two velocities was about 3500 whilst in the present case it is only about 6. The reaction in every case is strictly bimolecular and has a temperature-coefficient of about 2.6 for loo change of temperature. In the experiments with nitriles it was found that the reactions occurred too slowly with acids and consequently experiments were only made with alkalis. I n this case it was found that equally good reaction constants could be obtained by using the equations for either the two-step reaction (that is nitrile - amide - acid) or the one-step remtion (that is nitrile - acid).From this the authors draw the conclusion that the velocity of the first reaction is extremely great when compared with that of the second stage and consequently the second stage is the only one which conditions the measurement. The temperature-coefficient of these reactions lies in the region of 2.6 as in the case of the amides. Aii anomalous c‘as0 is presented by the hydrolysis of the amides of dibasic acids inasmuch as no reaction constant which is constant can be obtained. The values of k decrease very rapidly and after some time reach a figure which displays approximate constancy. This is explained by th0 authors as due to the fact that the first half of the reaction is abnormal whilst the second half is normal. It is also shown that both amido-groups are not hydrolysed a t the same rate.With acids the constant k is smaller than k2 whilst with alkalis k is smaller than k,. This is explained by the fact that there will be a repulsion between the negatively charged acid amide radicle NH,*CO*R*CO*O’ and the negatively charged OH’ group whilst. between the positively charged H’ ion and the acid ion there will be an attraction. J. F. S. The Dynamiceof the Change Acetochloroanilide -+ p-Ghloro- acetanilide in the Presence of Acids. ALBERT C. D. RIVETT (Zeitsch. yhysiha2. Chena. 1913 82 201-21 6).-The velocity of the change of acetochloroanilide into pchloroacetanilide in aqueous solution by hydrochloric acid of various concentrations is investigated. It is found to be a unimolecular reaction and the velocity increases with the coiicentration of the acid.The catalytic action is held to be due to the non-ioniseg acid alone. The relation- ship between the concentration of the acid and the velocity constant is expressed by the equation Ic = (1 - a)C(A + BaC) in which k is the velocity constant C is the concentration of the acid a the degree of ionisation of the acid and .4 and B two constants which have values 0.05 and 0.22 respectively. The temperature-coefficient of the reaction is found to be 3-27 for loo over the range 0-30°. This value agrees with the expression of Harcourt and Esson (A. 1912 ii 923) that the ratio k/T” is a constant; using the value m = 34 the value k / T34 x 1088 = 92 (approx.). The reaction was also (CGH,*NAcCl-+ C,H,Cl*NHAc)GENERAL AND PHYSICAL CHEMISTRY.ii. 203 carried out with solutions of acetic oxalic trichloroacetic and sulpliuric acids a t 60° since the reaction was too slow at lower temperatures. Constant values for k could not be obtained in any of these cases the reactions evidently proceeding in an abnormal manner. It is noticed that a purple coloration of the solution occurs after the reaction has been in progress for some time; 100 t o 200 minutes for sulphuric and trichloroacetic acids 300 minutes with oxalic acid and 3000 t o 4000 minutes with acetic acid. A t the end of the reaction a strong reducing agent is present in the solution. J. F. S. Velocity of Formation of Precipitates. KASIMIR J A B ~ Z Y N S K I (Zeitsch. phyZjSika2. Chem. 1913,82 115-121).-The author has studied the rate a t which precipitates are formed from dilute solutions. The method consists in mixing measured volumes of solutions of ammonium chloride and silver nitrate of known concentrations and observing the time required for the formation of a precipitate.The reactions are carried out in test-tubes which are covered with a paper mantle which has a square hole cut in it. This hole is partly covered with a narrow strip of black paper. The moment a t which a precipitate is judged to have been formed is that moment a t which the black strip becomes invisible. The reactions were all effected in absence of actinic light. Using a normal solution of silver nitrate and adding to it an equal volume of aminoniuni chloride of various concentration it is shown that the velocity diniinishes as the concentration of the ammonium chloride increases from 0.01N to 0*016N at which point i t reaches a minimum.Afterwards i t increases to an instantaneous precipi- tation as the concentration increases to normal. Similarly starting with 5 C.C. of 0.01 ammonium chloride and adding an equal volume of silver nitrate solution it is shown that the velocity decreases as the concentration of the silver nitrate increases from 0.01N t o 0*02N after which it increases t o an exceedingly high value as the concentration of the silver nitrate is increased t o 0.5A7. The addition of increasing sinall quantities of ammonia causes an increase in the velocity as the concentration of the ammonia increases up to 0.006L7\7 whilst on the other hand the addition of sodium thiosulphate causes a retardation of precipitation as the concentration of the sodium thiosulphate increases from 0*000012N to 0*0001201\'. The addition of alcohol decreases the velocity of precipitation.The velocity of precipitation increases 100% for an increase of loo in temperature. The velocity of precipitation of silver bromide is only about one-half that of silver chloride which the author is of the opinion points30 tlie fact that tlie velocity of precipitation is not conditioned by supersaturation. J. F. S. Influence of Temperature. CH. BOULANGER and GEORGES URBAIN (Cmpt. Tend. 1913 156 135-137. Compare this vol. ii 34).-A mathematical discussion of the rate of efflorescence of identical crystals a t different temperatures. Coupling this with laws previously deduced (Zoc.Theory of the Efflorescence of Saline Hydrates.ii. 204 ABSTRACTS OF CHEMICAL PAPERS. cit.) for the rate of efflorescence of crystals of different sizes and at different stages of efflorescence the authors have obtained an expres- sion by which it is possible to deduce the heat of hydrat,ion from the law governing the efflorescence a t two different temperatures. W. G. Velocity of Reaction and Catalysis. KURT H. MEYER LZeitsch. Elektrochem. 1913 19 76). -Polemical. An answer to Trautz (ibid. . . 1912 18 917) concerning the author's paper (A. 1911 i 350). J. F. S. Outline of a Theory of Homogeneous Catalysis. MARTIN A . ROSANOFF ( J . Amer. Chem. Soc. 1913 35 173-177).-Homogeneons catalysis is either direct or indirect.A direct catalyst is a sub- stance which influences the reaction by the formation of inter- mediate molecular complexes whilst an indirect catalyst is one which does not take any part in the reaction but influences its velocity by affecting the particular conditions (such as the association or dissociation of the reacting substances) on which the reactioii depends. A direct catalyst obeys the law of mass action but an indirect catalyst does not. An equation of catalysis has been deduced which is based on the assumption that the relative change of the velocity coefficient of a reaction is proportional to the change in the concentration of the indirect catalyst. It is shown that the number of indirect catalysts possible for a,ny given reaction is indefinitely large and that all negative catalysts belong to this class.According to this theory the velocity of chemical reactions is governed both by the law of mass action and a catalysis law. The equation expressing the effect of indirect catalysts has been found of great assistance in enabling the type of catalysis in any given reaction to be characterised and in thereby elucidating the mechanism of the reaction. Experimental evidence of this will be given in subsequent communications. Surface Combustion. WILLTAM A . BONE (Bor. 1913 46. 5-28). -An illustrated lecture on the catalytic influence exerted on gaseous combustion by hot surfaces delivered before the German Chemical Society. D. F. T. Catalytic Studies. 11. Barium Ion Catalysis. EYIL ABEL (Monatsh. 1913 34 171-191.Compare A. 1912 ii 927).-The addition of barium salts muses an acceleration in the oxidation of sodium thiosulphate by hydrogen peroxide. This catalytic action is not due to the mere influence of a neutral salt for alkali salts cause no acceleration neither is it due t o the liberation of hydrogen ions according to the equilibrium Ba" + K,O t BaO + 2H' for free acids have no effect and barium peroxide can hardly be expected to behave more powerfully than hydrogen peroxide. The author therefore suggests the possibility of changes in the valency of the barium ion and since the catalytic action is also observed in the oxidation of po6assium iodide with hydrogen peroxide and is therefore due t o the actio-i of the peroxide on the barium ion E. G.GENERAL AND PHYSICAL CHEMISTRY ii.205 the conclusion is drawn that quadrivalent barium ions are formed. Similar results have been obtained in preliminary experiments with calcium and strontium ions. J. C. W. Catalysis. XIII. Reaction of Ethyl Iodide with Sodium 3-Thio- 1 -phenylurazole. SIDNEY NIRDLINQER F. M. ROGERS and SOLOMON F. ACREE (Amer. CILem. J. 1913 49 116-127. Compare Acree A. 1912 ii 1047).-1n continuation of the quantitative study of the mechanism of the reactions of alkyl haloids with urazoles by determining the conductivity of urazole salts and the velocity of their reactions with alkyl haloids (Brunel and Acree A. 1910 i 520) an investigation has now been made of the sodium salt of 3-thio-1-phenylurazole. The velocity of the reaction of etliyl iodide anti sodium 3-thio-1- phenylurazole has been determined in solutions of concentrations from 0.3N t o 0.025N.The percentage ionisation of the sodium salt has been measured at the same concentrations by means of the conductivity method. By substituting the values obtained in the equation K = Kia+ K9,,(1 - a ) satisfactory constants have been found for Ki and K,. The r e s u h indicate that the velocity of the reaction is a function of the concentrations of both the urazole mid the non-ionised urazole salt. E. c:. The Periodic System and Atomic Weight. ALOIS BILECKI (Zeitsch. physikal. Chem. 191 3 82 249-252). -The author divides the elements into four groups which end respectively with helium argon xenon and an unknown element. The lengths of these groups are in the ratio of the squares of the uneven numbers.It is shown that if a series of chosen numbers from 21 to 125 are multiplied by the factor 1-86 the atomic weights of some 36 of the elements are obtained with fair approximation. There is also a series of elements the atomic weights of which are whole numbers and the author states that still a third series must exist the atomic weights of which will be found to be obtained by a combination of muitiples of the numbers 1 and 1-86. J. F. S. The Life and Work of Marcellin Berthelot. &MILE JUNG- FLEISCH (.BUZZ. SOC. chim. 1913 [iv] 13 i-cclx).-An obituary notice. T. A. H. Substitution of Grouo d Glass Stopper in Combination Barometer and Manometer. Ross ALLEN BAKER (J. Amer. Chm. SOC. 1913 35 199).-Rndulescii ( A . 1912 ii 37) has described a manometer in which a ground-glass stopper is substituted for the usual sealed end.The author points out that he has used a similar device on a combination barometer and manometer. The use of a mercury seal round the ground-glass stopper prevents the risk of leakage. The larger tube of capacity 10-15 c.c. which forms the mercury cup may be fused on to the main tube and is easily stoppered to prevent volatilisation of the mercury. E. G.ii. 206 ABSTRACTS OF CHEMICAL PAPERS. New Cover Glass Support. Ross ALLEN BAKER (J. Amer. Chem. Xoc.. 1913 35 200).-A convenient cover glass support can be made by fusing three pieces of glass rod together a t one end and after- wards bending them apart a t equal angles and downwards to any degree desired.E. G. A Simple Form of Gas Generator. FRANK SHEDDEN (J. Soc. Cldern. Iwd. 1913 32 3).-A cylindrical jar 48-50 cm. high and 18 cm. diameter and fitted with a stopcock a t the bottom contains an inner tube 10 cm. in diameter and narrowed a t the top to a neck about 6 cm. in diameter which is closed by a rubber stopper and glass stopcock. About 8-10 cm. from the bottom the inner tube is constricted to a diameter of 1-2 cm. The inner tube rests on a glass triangle arranged so as to allow free circulation and is held in place by a wooden cover which may if necessary be weighted with a leaden collar. When using powdery substances or fine-grained material a filter plate is placed on the constriction before charging. A generator of the above dimensions will hold 5 litres of liquid and several kilos.of solid. T. S. P. A New Reflux and Distillation Condenser. FRANZ MXCHEI (Zeitsch. alzgew. Chem. 1913,26 88).-The lower end of the oondenwr which is not in the water jacket is surrounded by a wider tube into the side of which is sealed a tube connecting it with and opening into that part of the condenser tube which is in the lower part of the water jacket. The vapour from the flask when the condenser is used as a reflux passes into the annular space between the two tubes and hence through the side-tube into the condenser from which i t flows back as liquid through the central tube into the flask. T. S. P. Two Lecture Experiments on the Diamond. WILHELM PRANDTL (Ber. 1913 46 216-217).-Moissan’s method of making diamonds may be modified as follows I n a cylindrical can of sheet metal 10 cm.in diameter by 12 cm. high is placed another cylinder open a t both ends of less diameter and the space between the two filled with dry powdered fluorspar. The inner cylinder is then filled with a mixture of 200 grams of iron thermit and 10-15 grams of powdered coke after which it is withdrawn so that the thermit mixture is surrounded at the sides by the fluor- spar but is in direct contact with the bottom of the sheet metal can. The can is fixed on an iron ring placed above a vessel con- taining mercury covered with a layer of 15-20 cm. of water and the thermit mixture fired. The liquid iron dissolves the carbon melts through the bottom of the can and is quenched in the water and mercury. The iron is then treated in the usual way to obtain the microscopic crystals of diamond which are accompanied by some doubly refracting hexagonal plates probably of carborundum. The combustion of a diamond in oxygen can be conveniently shown by heating it in a quartz test-tube fitted with a cork throughINORGANIC CHEMISTRY. ii. SO7 which pass inlet and exit tubes for the oxygen and products of combustion respectively. The combustion of the diamond is started by heating that part of the quartz tube on which the diamond rests with a blowpipe flame. Reaction between Calcium Eermanganrtte and Ethyl Alcohol F. ALEX. MCDERMOTT (J. Amer. C'hem. Soc. 1313 35 21 9) ,-The following is recommended as a lecture experiment for demonstrating the oxidation of alcohol to aldehyde. A few frag- ments of calcium perinanganate are dropped on a porous plate moistened with ethyl alcohol. The permanganate first scintillates and then glows for a few minutes and irritating fumes suggestive of formaldehyde acetaldehyde and acraldehyde are produced which if drawn through a warm ammoniacal solution of silver nitrate effect a marked reduction. isoAmyl alcohol reacts similarly but somewhat more slowly but methyl alcohol and acetone do not behave in this way. T. S. P. E.G. Lecture Experiments Showing the Formation of Binary Liquid Eutectics. NIHOLAI S. KURNAKOV and N. N. EFREMOV (J. Russ. Phys. Chorn. Soc. 1912 44 1992-2000).-Camphene and methylthiocarbimide readily form a liquid eutectic when mixed at the ordinary temperature the change taking place in a few seconds. Also owing to the appreciable vapour pressures of the two com- ponents if these are placed in separate vessels in a closed space the liquid eutectic makes its appearance in the vessel containing the camphene after the lapse of about twenty-four hours. The authors have investigated this system the specimen of camphene used having b. p. 158-158*5O m. p. 49.3O and [a]= + 57'4O. The eutectic mixture is found t o contain 73 mol. % of camphene and t o solidify a t - 8 O . The limits of existence of the liquid phase a t 1 5 O are represented by 140L and 76.5% of methyl- thiocarbimide. The system forms no solid solutions of marked concentration the two components separating in the pure state. Other systems forming liquid eutectics a t the ordinary tempera- ture are camphene-naphthalene ; camphene-benzene ; camphene- phenanthrene and methylthiocarbimide-naphthalene but in these cases this occurs only within much narrower concentration limits than with camphene-methylthiocarbimide. The following composi- tions (rnol. 7;) and solidifying points of the liquid eutectic were determined (1) 86 csmphene + 14 naphthalene + 7 . 5 O ; (2) 90.5 camphene + 9.5 phenanthrene + 1 3 ' 5 O ; (3) 65 methylthiocarbimide 4- 35 naphthalene + 4.0°. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9130405165

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. SO7 A New Hydrogen Table. LUDWIG VANINO and A. SCHINNER (Zeitsch. angew. Chem. 1913 26 55-56).-The authors have con-ii. 208 ABSTRACTS OF CHEMICAL PAPERS. structed a table showing the weight of 1 C.C. of hydrogen for each degree between the temperatures loo and 30° and for pressures of from 700 to 770 mrn. The weight of 1 C.C. of hydrogen a t Oo and 760 mm. is taken as 0.08995 mg Optical Investigation of Solidified Gasea. 11. Crystallo- graphic Properties of Hydrogen and Oxygen. WALTER WAHL (Proc. Roy. Suc. 1913 A 88 61-69. Compare h. 1912 ii l044).- The apparatus described previously has been modified so as to facilitate the investigation of the crystalline form of hydrogen and oxygen. I n spite of the low temperature of crystallisation the velocity with which hydrogen crystallises is very large. The growth- structures are isotropic and from the fact that the needle-shaped branches usually grow a t right angles to a crystal face of the fully developed crysta.1 it is inferred that the hydrogen crystals when fully developed belong to one of the forms of the regular system rich in crystal faces that is the trisoctJahedroii o r the hexoctrt- hedron.In the case of oxygen the liquid becomes very viscous before crystallisation sets in and the crystals which appear are badly developed and grow very slowly. I n order to obtain a homogeneous crystallised product the cooling must take place slowly and this condition is difficult of attainment. When the crystalline substance is further cooled i t is converted into a strongly doubly-refracting fine-grained mass of crystals and from this i t appears that oxygen is polymorphous.The transition from one form to the other takes place quite sharply but the temperature in question has not been determined. Since the physical constants of oxygen have been determined for the most part a t the boiling point of hydrogen these constants must refer to tdie second crystalline modification. It is however quite close to the melting point. H. M. D. Condensation of Water Vapour in Presence of Oxides of Nitrogen and of Hydrogen Peroxide. Evidence of the Forma- tion of Hydrogen Peroxide by Oxidation of Water Vapour. Action of Ultra-violet Sunlight on the Earth’s Atmosphere. WILLIE GIEBER (Ann. Physik 191 2 [iv] 39 1313-1337),-The condensation of water vapour from dust-free gases has been examined with the view of determining t*he nature of the nuclei which act as condensation centres. Ozonised oxygen which pre- liminary observations had shown to be free from condensation nuclei was found to remain inactive when nitrogen was mixed with it.The admission of a small quantity of nitrogen peroxide on the other hand gave rise to spontaneous condensation of the water vapour and subsequent expansion experiments showed that the nuclei formed persist for a considerable time. These observations indicate that Pringal’s statement (A. 1908 ii 798) that nitrogen is acted on by ozone in presence of water vapour cannot be accepted. I n reference t o the activity of the oxides of nitrogen i t has been supposed that nuclei are formed consisting of a higher oxide of unknown composition.Experiments with electrolytic oxygen andINORGANIC CHEMlSTKY. ii. 209 oxygen prepared from hydrogen peroxide indicate that the same blue-coloured cloud is formed in oxygen which is free from nitrogen. The search for tlie substance which is active under these circum- stances indicates that it is probably hydrogen peroxide. This is formed when ultra-violet light acts on moist oxygen as a result of tlie oxidatim of water vapour by the atomic oxygen which is supposed to be produced by the action of the short-waved rays oti t lic oxygen molecules. Thc formation of hydrogeii peroxide by ultra-violet suiilight is considered to be chiefly responsible for the atmospheric condensa- tion of water vapour alt!hough nuclei resulting from the action of a,tomic oxyge3 011 other constit,uents of the atmosphere such a s ainrxonia are probably responsible for some portion of the effect.H. M. D. The Preparation of Anhydrous Hydrofluoric Acid and the Isolation of Fluorine. FREDERICK D. CHATTAWAY (Chem News 191 3 107 37-39).-Historical. Chemical Reactions at Very Low Pressures. I. The clean-up of Oxygen in a Tungsten Lamp. IRVING LAX‘GI~IUIH (J. Arner. Chern. Soc. 1913 35 105-127).-0n heating a t i i n p t 8 ~ n wire in a vacuum a steady evolution of gas was observed. This was found to be due to water vapour given off by the glass of the bulb which on coming into contact with the hot wire produced hydrogen and oxidised the tungsten. It was found that in order to avoid the formation of the gas it was necessary t o heat the bulb a t 360@ for an hour or more after it had been exhausted and to absorb the water vapour by means of phosphoric oxide o r liquid air.By tliis means about 300 cubic mm. of water-vapour 20 cubic i r m . of carbon dioxide and 4 cubic mm. of nitrogen were withdrawn from a 40-watt lamp bulb. When a tungsten wire is heated in oxygen at a low pressure i t oxidises to l V 0 3 a t about 800° (ah.) but on raising the tempera- ture tcj 12130” (abs.) the oxide volatilises and leaves the metal clean and bright. At temperatures above 1200O (abs.) oxygen at pressures below 0.02 mm. acts on a tungsten wire at a rate which is proportional to the pressure of the oxygen and the surface of metal exposed and increases rapidly with the temperature. No fatigue effect can be observed.The velocity is not affected by varying the temperature of the bulb. Tlie nieclianism of the reaction is discussed. E. G. The Presence of Selenium in Hydrochloric Acid. ENJ~IQU K MOLES and s. PICA DE RUBIES ( A n d fli8. &?~im. 1913 11 73-77) -It is shown that selenium probably exists in some commercial acids in the form of the dichloride produced when seleniferous sulphuric acid is heated with salt. The presence of ferric chloride aids the f orination of the selenium dichloride although oxidising agents such as chlorates and nitrates do not have this effect. On diluting a seleniferons Iiydrochloric acid seleiiium is separated as a i l iii11)alp;tblc scarlet powder. c:. D. L.ii.210 ABSTRACTS OF CHEMICAL PAPERS. The " Chemically Active Modification " of Nitrogen. F. COMTE (Phvsikal. Zeitech. 1913 14 74-76. Compare Strutt A. 1912 ii 935).-Experiments are described which seem t o show that the after-luminosity effect which is observed when a Leyden jar discharge is passed through a discharge tube containing nitrogen is dependent on the presence of small quantities of oxygen. The apparatus used by the author was very similar to that employed by Strutt (Zoc. c i t . ) . With nitrogen containing 0.6% oxygen an intense orange-yellow after-luminosity was observed when the dry gas was passed through the discharge tube at a pressure of 0.5-1 inm. It is essential that the gas should be freed from water vapour for traces of this inhibit the phenomenon When the dry gas before entering the discharge tube was passed through a long tube containing copper gauze and reduced copper oxide heated a t 550° and then over phosphoric oxide the after-luminosity was found to disappear almost entirely when the gas had been passing through the apparatus for some time.When a small quantity of air was allowed to mix with the oxygen-free nitrogen the lumiiies- cent effect was again obtained. The observations indicate that there is a certain small proportion of admixed oxygen which gives the maximum after-luminosity effect. It is also shown that the passage of dry air through a discharge tube! is accompanied by a similar after-luminosity if the pressure in the1 tube is maintained at 6 to 10 mm. of mercury. Active Nitrogen.ERICH TIEDE (Bey. 191 3 46 3QO).-When pure nitrogen is used the active nitrogen of Strutt cannot be obtained. It is probable that the nitrogen used by Strutt con- tained oxygen the presence of which gave rise to the observed phenomena. The matter is being further investigated in order t o find the true explanation (compare also Comte preceding abstract). Catalytic Oxidation of Ammonia. 11. D. MENEGHINI (Guz- zettu 1913 43 i 81-90. Compare A. 1922 ii 344).-The experi- meluts have been continued for the purpose of comparing the efficacy of different catalysts. From the results (which are shown in tables and curves) it appears that the best catalysts are roasted pyrites chromic oxide and a mixture of oxides of the rare earths (Nd Pr La) ; Ve.,03 Mn02 and CeO are less active.Chemistry of the Formation of Nitric Oxide in the High Tension Arc. ADOLF KOENTG (Bey. 191 3 46 132-134).-The autbolr criticises adversely the coiiclusioiis which Fischer aud IIenc (this vol. ii 132) draw from their experiments. Since active nitrogen does not react with oxygen and ordinary nitrogen is not oxiclised by ozone i t is possible that both the nitrogen and ozone are made active before combining to form nitric oxide. Decomposition of Nitric Oxide. EMIL BRINER and BOUBNOFF (Compt. Fend. 1913 156 328-230. Compare A. 1909 ii 557; 1910 ii 707; 1912 ii 544 ).- A study of the clecornposition of tiitric oxide over wide H. M. D. T. S. P. R. V. S. T. S. P. Ghemical Reactions in Compressed Gases.INORGANIC CHEMISTRY. ii. 211 ranges of pressure (50 t o TOO atmos.) and teinilerature ( -SOo to 300O).Nitrogen iiitrous and nitric oxides and nitrogen trioxide and peroxide were found in the products of the reaction. The authors consider that two reactions take place simultaneously iiamely tlhe secoii d predominating the higher oxides of nitrogen beiiig produced by the secondary act?ion of the oxygen on the untrans- formed nitric oxide. At constant pressure rise of temperature accelerates the transformation and favours reaction (2) and the secondary formation of nitrogen peroxide. Increase in pressure accelerates the decomposition of t lie nitric oxide into more stable subetnnces. W. G . (1) 2NO = N + 0 and (2) 4 N 0 = 2N20 + O The Luminescence and Ionising Action of Inactive Gases Saturated with Phosphorus Vapour. HANS SCHMIDT (Phpikal.Zeitsch. 1913 14 120-123).-When a current of purified hydrogen carbon dioxide or nitrous oxide is passed through an emulsion of phosphorus in water or through a solution in benzaldehyde the luminosity and cloud formation which are observed in the early stages gradua.lly diminish in intensity and disappear when the oxygen has been completely removed from the apparatus. With a current of coal gas these effects vanish before the oxygen has been entirely displaced and in this respect coal gas behaves like small quantities of ethyl ether chloroform ethyl alcohol and other substances. On passing pure oxygen through the emulsion or solution the luminosity and cloud formation dis+ppear as the partial pressure of the oxygen rises in consequence of the removal of air.When the inactive gases charged with phosphorus vapour are passed into the chamber of an electroscope ionisation currents are obtained which are very much larger than the currents obtained when air similarly saturated with phosphorus vapour is pysed into the chamber. H. M. D. The Formation of Hypophosphoric Acid in Corne’s Reaction. FWTZ TAUCHERT (Zeitsch. anorg. Chem. 1913 79 350-354).-The action of yellow phosphorus on copper nitrate (Corne A. 1882 1264) has been investigated by Rosenheini and Pinsker (A. 1910 ii 708) who attributed the formation of hypophosphoric acid to the action of the copper ion and not of the nitrate ion. A comparison of other copper salts confirms this result copper sulphate chloride formate oxide and phosphate also giving hypophosphoric acid.When phosphorus acts on copper hypophosphate the quantity of hypophosphoric acid is also increased. The reactions occurring are (1) 5C’u(NO,) + P4 + 8H,O =2H,PO +- h3P + ~ C U + lOHNO,. The nitric acid then reacts with the copper phosphide and excess of phosphorus forming phosplioric and phosphorous acids and nitric osidc. Not more than 7?! of the phosphorus is ObtitiJletl as hypo- (2) 4Cu(NO,) + P + 6HzO = R4P20 +- C U ~ P ~ + CU + 8HNO3.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. phosphoric acid whilst as much as 2076 may be obtained from a hot solution of copper sulphate. The Synthesis of a Silicalcyenide and of a Felspar. J. EMERSON REYNOLDS (Proc. Roy. Soc. 19 13 A 88 37-48).-111 various papers (compare T. 1906 89 397; 1909 95 505 508 513 etc.) the author has given an account of organic compounds containing the silicocyanogeii group SIN in combination the existence of such compounds affording complete proof that silicon has a marked affinity for tervalent nitrogen.I n the mineral king- dom no definite compounds of silicon with nitrogen have been met with but the existence of the great group of “alumino-silicates ” affords clear evidence of the strong attraction of silicon f o r aluminium. The question therefore arises as t o whether some of the alumino-silicates may not be regarded as fully oxidised products of silicides of tervalent aluminium somewhat analogous t o SIN which have been formed a t high temperatures in the first instance below the oxidised crust of the earth. Such nuclear ” silicides should be obtained either by the complete deoxidatioii of the corresponding native silicates or by direct synthesis from tlie suitable elements.The first method has been found to be imprac- ticable but the second method has given satisfactory results. The compound of silicon and aluminium analogous to cyanogen would have the formula Si,Al the name suggested for it being silicalcyanogen. Attempts to prepare this compound by synthesis from the elements were not satisfactory combination t o any material extent not taking place when a liquid mixture in atomic proportions is heated to full redness for more than two hours. It is well known that carbon and nitrogen behave similarly but in the presence of a third element such as an alkali metal corn- bination takes place with the formation of a cyanide.A mixture of silicon (103 grams) aluminium (100 grams) and calcium (74 grams) that is in the proportion of Ca 2% 2A1 behaves in an analogous manner. The silicon and aluminium are fused together and then the calcium added in sinall portions a t a time the mass being stirred with a steel rod. After cooling a dark grey crystalline mass is obtained the brilliant crystalline faces of a fracture apparently belonging to octahedral forms. The substance is analysed by decomposing it in a current of dry chlorine and found to have the formula CaSi,Al that is i t is a calciuin silicalcyunide analogous to CaC2N2. It is readily attacked by hydrochloric acid slowly by boiling nitric acid and hardly a t all by hot sulphuric acid.Sodium and potassium hydroxides readily decompose it. It is only very slightly attacked by oxygen until the temperature of the oxyhydrogen flame is reached but if heated t o low redness in a stream of moist oxygen it is converted into a white mass having a composition agreeing with that of the mineral anorthite namely CaA1,Si208 with which mineral its physical properties are also in agreement. Experiments in which the alkali metals were used instead of calcium ave indications of tlie formation of a (sodium) silica2- c.y;tnicle But pure products coulrl not be obt8aiired. C. H. D. T. 8. P.INORGANIC CHEMISTRY. ii. 213 Tsoherrnak's Method for the Isolation of Silicic Acids. ENNIO BASCHIERI (Jahrb. Min. 1912 ii Ref. 323 ; from Proc.-verb. SOC. Tosdccna Sc;.Nut. 1910 19 84-87. Compare A. 1911 ii 50%).-The f ollbwing percentages of water were determined in the silicic acids isolated from apophyllite and datolite by the use of various acids of definite coltcentration. (The numbers given in parentheses are tlinse i t 1 which the transformation point had been passed.) Ht'l ( D 1.2). H,SO ( D 1 2 ) . HNO (D 15). hpphyllite ... 12.39 12.69 12'03j (10'01) 11-83 (10.63) Datolite . . ... (11'66) 13 6T 13.55 19-98 These results as well as those obtained with some other silicates are in close agreement with those obtained by other observers and the correspondence can scarcely be accidental. The method is t lierefore of value in indicating the constitution of silicates (com- pare Mugge A. 1908 ii 277). L. J. S. Tendency of Haloids and Phosphates of the Same Metal to Combine.11. Alkali Fluorides and Phosphates. MARIO AMADORI (Atti R. Accad. Lincsi 1912 [v] 21 ii 685-695. Compare A. 1913 ii 940).-The present paper deals with the systems formed by the fluoride and phosphates of potassium. The melting point of potassium fluoride was fouiid to be 856O. In the system KP-KPO there is evidence of the formation of tlic compound 2KF,KP03 at 7 0 3 O and of the forhiation af the oom- pound KF,KPO a t 880O. Mixtures containing from 0-20 mol. % of phosphate show a eutectic point corresponding with 742O and 20 mol. of KPO whilst those containing from 50-100 mol. % KPO have a eutectic at 604O (82 mol. % of KPO,). Mixtures with 0-45 mol. % of KPO show a slight pause a t 540° which probably corresponds with the transformation point of the compound 2KF,KPO,.The transformation point (450O) of the metaphosphate is observed in all the mixtures up t o 60 mol % of potassium fluoride. In the system KF-K4P2O7 there is a eutectic at 730° and 20 rnol. of K4P207. The transformation point (278O) of the pyrophosphate is shown by all mixtures down to 10 mol. % of The system KF-K,PO has a eutectic a t 766O (20 mol. % of K,P04) and there is a further development of heat in the solid mass a t 700° probably due to the decomposition of a compound. K4P207* R. V. S. Borates. The System :( N H,),0-B20,-H20 at 30". U. SBORGI (Atti R. Accad. Zincei 1912 [v] 21 ii 865-859).-The experiments were carried out by keeping mixtures of the three substances in a closed vessel in a thermostat a t 30° until equilibrium was reached.Of the eleven ammonium borates which have been described only one namely (NH4),0,5B20,,8H2O was obtained and in addition a new barate 2(NH,)i0,4B20,,5H20. A vertical axis bearing the pulley carries also a crank and the crank-rod is a A new form of stirrer and shaker is described. VOL. CIV. ii. 15ii. 214 ABS'IRACTS OF CHEMICAL PAPERS. rack wiiicli origages with a piiiiou borne on a second vertical axis. Tlie lower end of the second axis dips below the water of the thermostat and to i t the vessels to be shaken are attached sym- metrically. When the pulley is revblving the rack is moved to and fro so that axis of the pinion makes revolutioiis in opposite directions alternately ; this motion shakes the vessels and stirs the water of the thermostat at the same time.R. V. S. Silver Thioaluminates. Livio CAMBI ( A t t i If. ~ & x d . Lhcei 1912 [v] 21 ii 837-842).-The author has investigated the system Ag,S-Al,S by the method of thel'mal analysis. The thermal analysis was effected in graphite crucibles in a current of hydrogen sulphide and the composition of the mixtures was deduced by subsequent analysis. Mixtures containing more than 40 mol. % of Al& do not yield satisfactory results. Evidence was obtained of the existence of a compoum! 4Ag2S,5AI,S which iiiclts unclianged a t 1035O and probably aiiotlier compound deconi- posing a t 825O (which is very near a cutect,ic point) and containing 60-70 mof. % of AgzS. The compouiid 4Ag$,5A12S3 foritis 1~0ui0- gel ieou s flesh-col o 11 red biref ri ngcn t crys ta 1s.R. V. s. Hydracea of Calcium Oxide and thoir Molecular Cam- pounds. I. F. SELIVANOV (J. Buss. Phys. Ckem. Soc. 1913 44 I 79'1-1813).-Ths author has studied first the composition of hydrates of calcium oxide prepared by slaking lime obtained by lieatling marble or calcium nitrate or oxalatc o r by precipitating calcium chloride solution with sodium hydroxide and secondly the action on these hydrates of dry water vapour. The hydrates obtained by slaking specimens of calcium oxide of different origins all agree closely in composition with the formula Ca(OH) whilst the precipitated hydrate contains an appreciable excess of water. These hydrates absorb water vapour but hold i t only loosely change of temperature from 14.5-16O to 21° resulting in a loss of almost one-third of ths absorbed water.This absorbed water is largely lost in a desiccator containing heptahydrated zinc sulphate or hexahydrated calcium chloride' and is almost completely given up in presence of sulphuric acid or on heating at 60°; the last traces of the water are given up only with difficulty. Considerable differences in the proportion of absorbed water held by the hydrate are virtually without influence on the solubility in water. From the results of his experiments the author draws the conclu- sion that the amorphous hydrate of calcium oxide and water behave one to the other in the same way as two liquids exhibiting slight mutual solubilities a solution of the hydrate in water and one of water in the hydrate being formed when the two are shaken together.T. H. P. Solubility of the Nitrcttes of the Alkaline Earths in Mixtures of Alcohol and Water at 25'. JOH. PANS and R. SIEGLER (Zeitsch. physikal. Chem. 1913 82 35-44).-Mixtures ofI NO RG A N 1C C HEM1 SI'RY. ii. 215 alcohol and water of known coriipositioii are sliakeii with tlic various nitrates until equilibrium is attai tied and then analysed. Three types of solubility isotherinals are obtained (1) with barium nitrate which does not form conipouiids with either water or- alcohol a straight litie curve is obtained showing decreasing solubility with increasing alcohol concentration. (2) With stroll- tium nitrate which forms the conipound Sr(N0,),,4H20 with water but does not lorm a conipound wit'h alcoliol a curve wliicli i s divided into tywu branches is obtained owing t o the fact that t lie hydrated salt is stable in tlic dilute alcohol solutions whilst the anhydrous salt is stable in the concentrated alcohol solutions.(3) With cnlciiriii tiitrate which forms Ca(NC),,),,4€1,0 with water nnci Ca,(N0,,),.2C~H,*OH with alcohol a curve o f t hrcc branches i s ohtaiiicd. It is found that between the areas in wliich the hydratc a i d alcwholnte are &able there is a sinall irtetrlrstable regioii i r t whivli anhydrous calcium nitrate constitutes t'he solid phasp. The wlubility of the thee uitrates was aJso determined at 2 5 O iii methyl alcohol ethyl a.lcohol !)ropy1 al~.ohol isobut,yl alcohol a my1 alcohol acvtonc ether amd para~eta~ldeliydr. Barium nitrate i s found tr rlissolvc to 3 slight cxtcnf only i n a11 the solvents.St,roiitiuni nitratv is vcry sliglitly inorc solnhle whilst calcium nitratc i s v r i y solii h1.3 csr:r~pt iii the rases of ttlier mid paracetaldehydc in which it is i i o t niorc soluhlc t l ~ a r i t h e otlicr tiit,ra,tcs. .I F'. $. Action of Aqueoue Barium Hydroxide on Certain Kinds of Glass. CURT BUNGE (Zeitsch. anal. Chsni. 1913 52 15-17j.- lZii insoluble coating observed in a burette in which N/4-bariuiii hydroxide had been kept was fourid to consist of barium sulphate. Further investigation proved the sulphatc to be derived frorri the glass and evidently owing to the use of sodium sulphate in glass manufacture. L. DE K. The Solubility of Glucinum Sulphate in Water and Sul- phuric Acid. FRITZ WIRTH (Zeitsch.unorg. Ghem. 191 3 79,357-35'3. Compare Parsons A 1904 ii 658; 1905 ii 34; Levi-Malvano A. 1906 ii 165).-The solubility of glucinum sulphatc hexahydrate i ri water a t 25O is much less than that previously recorded being oiily 0.07857 mol. in 100 grams of solution. Sulphuric acid a t first only slightly lowers the solubility but beyond 12.51\; the hexahydratc passes into the tetrahydrate the solubility of which is much further diminished by sulphuric acid. As the solubility curve of aluinin- ium sulphate in sulphuric acid has an entirely different form this property may be used for the purification of glucinum salts. c. Er. D. Glucinum Chromates. N. A. ORLOV (ZeitscA. anmg. Clt,Jrn 19 1 3 79 365-367. Compare Bleyer and Moormann A. 1912 ii 762). -The following compounds have been obtained from glucinum sulphate and potassium chromate 9G1O,G1CrO4,16€&O and 2OH,O and 14G10,GlCr04,31H,0 ; from a solution of glucinum hydroxide in chromic acid and potassium chromate 12G10,G1Cr0,,16H20 ; and 15-2ii.216 ABSTRACTS OF CHEMICAL PAPERS. by precipitating a solution of glucinum hydroxide in chromic acid with alcohol 5GlO,GlCrO,,l4I-I,0. Glucinuin and aluminium chromates are gradually hydrolysed by water without the forma- tmn of any definite basic salt. The Thermal Dissociation of Amorphous Magnesite. 0. KALLAUNER (Chem. Zeit 19 13 37 182). - Amorphous magnesite begins to lose carbon dioxide a t 500° but the temperature a t which the evolntinii takes place almost inoiiientarily is 620-625O. C. H. D. T. 8. P. Action of Hydragen Peroxide on Alkaline Solutions of Lead Oxide v.ZOTJER (fiull. Soc. chi??z. 1913 [iv]. 13 61-66). --In this reaction lead peroxide is first formed which then reacts with some hydrogen peroxide giving rise to oxygen and sonie lead oxide so that the precipitate produced usually consists of botb oxides. With increasing quantities of hydrogen peroxide the quantity of lead peroxide rises to a maximum and then remains constant. For the quantity of hydrogen peroxide necessary to produce this maximum quantity of lead peroxide the reaction is expressed by the equation lOPbO + l@H,O = 10H20 + 4PbO2 + 6Pb0 + 30,. The amount of lead peroxide formed diminishes with rise of temperature slightly up to 30° considerably from 30° to 60° and very rapidly above 60°.About 90-95O lead peroxide is formed but disappears immediately due to the second phase of the reaction. Water has little influence on the reaction and considerable quantities must be introduced before differences greater than those clue to experimental error are noticeable. The quantity of lead peroxide formed diminishes as the ratio NaOH PbO increases and with sufficient sodium hydroxide the lead peroxide formed is immediately decomposed. Tendency of Haloids and Phosphates of the Same Metal t o Combine. 111. Fluoride Chloride and Phosphate of Lead. MARIO AnrAuoRI ( A t h R. Accad. Lincei 1912 [v] 21 ii 768-774. Compare this vol. ii 213).-Lead orthophosphate has m. p. 1006O and its cooling curve shows a transformation point a t 782O. Mixtures of lead orthophosphate and lead fluoride containing from 0 t o 10 mol.% of phosphate show a eutectic corresponding with 678O and 7.5 inol. % of phosphate. The curve also sholws a maximum at 1046O and 75 mol. % of phosphate and a t this temperature the compound of the same composition PbF2,3Pb,(P0,),r crystallises. The eutectic pause is not seen in mixtures containing more than 10 mol. % of phosphate. The curve of the compound PbF,,3Pb3(PO,) shows a transformation point a t 696O and it probably exists also in a third modificatioa. There is complete miscibility between the a-form of the compound and the a-form of the phosphate and there is extensive solubility in the solid state between the a-form of the compound and the fluoride. Retween the presuiried P-form of the compound and the &form of t.lie phosphate there is also probably complete miscibility whilst this T.A. H.INORaANlC CHEMISTRY. ii. 317 modification of the compound and the fluoride FrobabIy form a series of mixed crystals. The y-form of the compound is not miscible (or is miscible only to a very limited extent) with the P-form of the phosphate and it is not miscible with the fluoride. Owing to the volatility of the chloride the experiments with lead chloride and lead orthophosphate were mainly qualitative but it is probable that a compound is formed analogous to that above described; its m. p. lies above 1100O. The compound of fluoride and phosphate corresponds with calcium salts (apatite) occurring in nature and that between chloride and phosphate would correspond with pyromorphite. R.V. S. Double Salts of Thallous Chloride with Ferric Chloride and with Bismuth Chloride. G. SCARPA ( A t t i 3. Accad. Lincei 1912 [v] 21 ii 719-725).-The paper gives an account of tlie thermal analysis of the systems TlCl-FeCl and TlC1-BiCl,. I n the case of the former system the volatility of ferric chloride causes some experimental difficulties and it is necessary to determine the composition of the mixtures by actual analysis of the separated solid. For the same reason it is not possible to deal with mixtures caontaining more than 62 niol. % of ferric chloride. There is a eutectic corresponding with 266O a i d 26 11101. "/u of ferric chloride a d a maximum a t about 33 mol. % of ferric chloride and 290°. This indicates the formation of a coiripoutid 2T1C1,FeCI3 stable 011 fusion.Mixtures containing more ferric chloride show a eutectic point a t about 220° arid the initiation of crystallisatiori is very Iiigh; for instance tlie mixture with 62% of ferric chloride begiiis to crystallise a t 299O which is almost tlie tn- p. of ferric chloride. Lt is therefore legitimate to suppose that the curve woiiltl sliow another maximum above this point. I n the system TlCl-BiCl there is a eutectic corresponding with 360° and 12.5 mol. % of bismuth chloride and a maximum at 413O (25 mol. % of bismuth chloride). A pause occurs at 330° (about 40 mol. % of bismuth chloride) and a more evident pause at about 225O (52 mol. % of bismuth chloride). The curve then descends to a euhctic a t 150° (67 mol. % of bismuth chloride) and finally rises to the m.p. of this salt. Mixtures containing 0-25 mol. % of bismuth chloride show a pause at 360° which vanishes for the 25% mixture; this indicates the existence of the compound .3T1C1,BiCl3. Mixtures from 25% to 40% of bismuth chloride exhibit a slight pause a t 330° probably due t o the formation of a compound 2T1C1,BiC13 which decomposes on fusion. Mixtures containing 35-50 mol. % of bismuth chloride show a pause a t 234O which demonstrates the existence of a compound 3T1C1,2BiCl3 decomposing on fusion. Above 70% of BiCl the mixtures deposit Molecular Complexity of Metals in the Solid Phase. MAURIZIO PADOA and P. BOVINI ( A t t i R. Accad. Lincsi 19 12 [v]. 2 I ii 708-713).-From tlie diagram of the system copper- bislnuth which is known tIhe authors calculate the cryoscopic corlstallt uf 1 rtixed crystals.R. v. s.ii. 218 AHSTRACI‘S OF CHEMlCAL PAPERS. copper (874.5) in goosd agreement with the value obtained from the heat of fusion of copper (855). Mixtures of copper and silicon containing little silicon are simple solutions of the silicon in the copper and applying the above constant the authors calculate (from published data of this binary system) tlie molecular weight of silicon dissolved in liquid copper. The values obtained vary from 32.7 t o 24.5 indicating that in tliese circumstances silicon is ~nonatoinic. Ci; is probable that its state of aggregation is the same also ill solntion in solid copper. [With CARLO MAI~ANI.]--T~~ authors have also determined the ii~olecular complexity of cadiiiiuai in solutioii in solid iirt.1 1 1 the systenl S I ~ Ccl+ Bi hisnrutlt floes riot foi*in solid solutioiis wit11 either of tile utlier constituents whilst oatl~nizim gives ;L soli(1 solutiou wit11 tin. Analysis of the Crystals separating from Llie solution of cadniiuiti i n tin (bismuth being also present) shows that the solid solution has very nearly the same composition as the liquid sslutioii tlie partition coefficient being sensibly constaut and therefore the cadmium has the same degree of molecular complexity iii both that is i t is inonatomic also in the solid soliitioii. R. V. S. Electrical Conductivity of Alloys of Copper and Zinc. 191 2 44 1905-1 918).-Tnvestigation of the electrical resistance and of its temperature-coefficient for alloys oE copper and zinc gives results in general agreement with Shepherd’s conclusions based on the melting-point diagram and on the microstructure (A.1904 ii 662). The system forms (1) the solid solutions a 0-36 atom %; y 59-67 atom %; E 80-85.7 atom %; and 7 91-100 atom % of zinc; (2) the mixed crystals a+B 36-50; B+y 50-59; y + 6 67-80; and E + 7 85-7-91 atom % of zinc. The existence of the solid solution /3 within narrow limits is regarded as a sign of the existence of the definite compound ZnCu which is slightly dissociated at the ordinary temperature. The results also indicate the probable existence of the two compounds Zn,Cu and Zn,Cu (compare also Norsa A. 1912 ii 890). The Tensile Strength of the Copper-Zinc Alloys. J. M. LOHR (J. Physical Chem. 1913 17 1-25).-The brasseg examined covered the whole range of useful mixtures namely from 47.5% t o 100% of copper.The metals were melted under coal gas and poured from a plug hole in the bottom of the crucible in order to avoid dross. The pouring temperatures by thermocouple were from 50° t o 250° above the liquidus points. The mould consisted of a split Acheson graphite block arranged to cast a test-bar 6 in. long by 0.40 in. diameter with an S-shaped gate termed a “centrifugal sprew” and a very substantial riser the test-bar being slightly inclined so as to sweep forward and upward into the riser any floating zinc oxide. The mould was preheated by external gas hurners. With these precautions test-bars were usually obtained free from blow holes and dross. Any bar which showed signs under a lens of pipe formation or pinholing after fracture was rejected.Sfter casting the bars mere quickly removed from the mould NIKOLAI A. PUSCHIN and v. N. IIJASHSKI (.I. Rus~. p h ~ ~ . Chern,. S‘OC. T. H. P.INORGANlC CHIEM-ISTRY. ii. 219 and chilled in water from a temperature of 700-800° and were subjected to no other heat treatment before testing. Consequently they consisted of pure a-phase down to 66% of copper mixed a- and j3-crystals from 66% to 57% of copper pure j3-crystals from 57% to SO% and mixed 8- and y-crystals below 50%. Owing to the high temperature of quenching a- and y-mixtures were not present TIC^ iti tlte range of compositions studied pure y- as well as tlie 8 e and q-phases do not exist. The a-brasses have a tensile strength which is almost cotist:tiit at aLottt 33,000 lb.per sq. in. from 95% t o 66% of copper. Wllerl tho fl-phase appears tlie strengtli rises arid attains ;L r i i a x i i n ~ ~ ~ i i sl; 551L i i i tlie IJiire fl phase of about 71,000 ll). or wEieii calculated o i i tlie reduced area 200,000 lb. per sq. in. witli a 1 1 elongation of 14.8%. The strength falls oA’ rapidly when the 7-pliase appears the 47.57L copper alloy which appeared to contain about three= fourths B-crystals with one-fourth y-crystals giving 23,000 lb. only. The riiaximnni elongation of 36% was observed in the a phase a t 62% to 70% of copper the corresponding tensile strength being 36,000 111. Occasional specimens gave higher results ; for example in one case the elongation was 60”/ and in another tlie tletisilc strength 137,000 lb.per sq. in. It was noticed in casting that alloys between lOOyL and 80% of copper and between 65% and 47.5% of copper usually gave homo- geneous test-pieces whereas between SO ?; and 65 ?( of copper (maximum ductility) i t was difficult to obtain castings free from porosity. The best pouring temperature was from looo to 200° above the liquidus. Below this the metal was usually too viscous and above this it often contained black spots of porous material. R. J. C. Some Basic Copper Sulphates. GEORGE FOWLES (J. Xoc. Chem. I d . 1913 32 9).-The author points out that some of the resiilt,q published by Ermen (A. 1912 ii 453) have been obtained pre- vionsly by other investigators. T. S. P. Blue Gelatin Copper. WILDER D. BANCROFT and T.R. BRIGGS (J. Ind. Eng. Chem.. 1913 5 9-1 l).-One gmm of gelatin is dissolved in 325 C.C. of a 1% solution of cupric acetate and the solution electrolysed for five minutes between carefully cleaned and burnished electrodes of sheet copper using a current density of 0.15-0’45 amps. per sq. dcm. a t the cathode. The cathode becomes covered with a thin pale brown deposit possessing a peculiar slippery surface owing to the gelatin deposited with the copper. I f the cathode is washed and then immersed in a 5% solution of copper acetate containing no gelatin a series of remarkable colour changes takes place until the surface has acquired a magnificent deep blue coloration. The process of the formation of this blue colour is called “ development ” by the authors. Gelatin in concentrations varying from 0-25 to 0.66% miid bc present for development to occur.The copper acetate may be replaced by copper propionste or forniate (not so good) but not byii. 220 ABSTRACTS OF CHEMICAL PAPERS. the sulphate nitrate or chloride The most satisfactory tern- peratures lie between 20° and 40°; a t 50° or higher temperatures red or golden films are produced which will not develop but may be preserved by lacquering. The copper acetate or propionate solution should contain 1 or 2 parts of the crystallised salt to 100 parts of water; the limits of current density are given above. Anodes of nickel brass or platinum may be used. Experiments with various solutions showed that development takes place successfully only in solutions of copper acetate or propionate so that this phenomenon must be a function of the copper contained in the developing solutions.I f the developed electrode is placed in a solution of hydrazine hydrate the colour slowly disappears with evolution of nitrogen; i t may then be re-developed but not to such a good colonr as before in copper acetate solution. I f the deposited film is left undeveloped for several hours it completely loses its power of developing in copper acetate probably because o f oxidation. The deposited film of metal is probably an irreversible gel of colloidal copper and the process of development is an adsorption of hydrated copper oxide hy tlie surface of the colloid film. This hydrated copper oxide is present :LS a suspension i n very appreciable qii antities in the acetate or propionate soliit,ioiis.ALBERTO SCALA (Atti R. Accad. Lincei 1913 [v] 22 i 43-49) -When ordinary aluiriinium (Kal~lhu~ti) is kept i n contact with carefully prepared (listilled water at the ordinary i,emperature i t eventually shows signs ol' chemical actioti for the surface becomes black arid bubhles of gas appear. The time elapsing before this action is evident varies from months t o days iri different experiments but when once started it proceeds sorriewliat rapidly. Suspended in the water are then to be found alu niiniuni hydroxide and a chestnut-colouretl substance which is a compound containing aluminium iron and perhaps silicon. T. S. P. Action of Distilled Water on Impure Aluminium. During the reaction hydrogen is evolved.R.V. S. Alloys of Aluminium and Vanadium. NICOLAS CZAKO (Compt. rend. 1915 156 140-142. Compare Moissan A 1896 ii 608; Matignon and Monnet A. 1902 ii 326).-By fusing yanadic acid with aluminium in the necessary proportions the author has prepared alloys of aluminium and vanadium containing from 1 t o 80% of vanadium and has examined thep micrographi- cally. He has isolated crystals having the definite constitution A1,V and AlV and obtained indications of a compound AlV,. The hardness of the alloys increases with the vanadium content up t o SO% when it is from 6 to 7 after which it diminishes. The alloy containing 53% vanadium is full of cavities and in consequence w. G. The Crystallisation of Pure Aluminium Salts from Ssolu- tions containing Iron and the Artiflcial Preparation of Halotrichite. FRITZ W r R m (Zeitsch.angew. GAem. 191 3. 26. 81 - 83). -The aiit,hor has determined t,he soliibilities ai8 25@ of' difficult to examine micrographically.INOROA NIC CHEMISTRY. ii. 321 ferrous sulphate aluminium sulphate and of each of these salts in the presence of varying proportions o€ the other in order t o determine the region of the existence of the double salt halotrichite FeS0,,A1,(S04),,24H,0. The solubilities of the pure components are respectively 0.8124 mol. of aluminium sulphate and 1.503 rnols. of ferrous sulphate in 1000 grams of solution. The double salt exists over the region between the two solutions containing respectively 0'723 mol. of aluminium sulphate and 0.38 mol. of ferrous sulphate and 0.7045 mol.of alurtiiniam sulphate and 0,6827 rnol. of ferrous sulphate. It follows that from a solution containing equimolecular quantities of the two salts ferrous sulphate first crystallises and then the double salt. The preparation of the double salt is best carried out by shaking a solution saturated with respect t o the two components with the solid sulphates contained in a silk bag. Strongly supersaturated solutions are thus obtained frorn wliirh the double salt separates after a few hours. The solubility curve gives the conditions of relative concentrat,ioiis 11 rider which pure aluminium sulphate can be crystallised out froni a solution containing ferrous snlphate and experimeqts made by the author show that complete separation of aluminium from iron can thus be carried out.If the iron is in the ferric condition separation is impossible owing to the formation of mixed crystals; the iron must flrst be reduced to the ferrous state. A method is thus given which is applicable commercially for the preparation of piire d i ~ m i i i i i i ~ ~ i sulphate froin baiixite. T. S. P. The Solubility of Aluminium and Iron Sulphates in Sul- phuric Acid. FRITZ WIRTH (Zeitsch. anorg. Chem. 1913 79 :?60-364) .-The presence of sulphuric acid a t first increases the solubility of aluminium sulpliate in water but a further addition of acid produces an enormous depression. From 20N onwards there is again a slight increase without any change in the solid phase. This has already been observed with other sulphates. With con- centrated sulphuric acid aluminium sulphate forms the compound Al,(S04)3,H,S0,,3H,0 the mixture solidifying after a few hours.Ferrous sulphate is converted into the monohydrate by sulphuric acid of greater concentration than 12.5N a t 2 5 O . The solubility curve of ferrous sulphate in sulphuric acid is nearly parallel t o that of aluminium sulphate as f a r as 40% H,SO,. Perric sulphate is somewhat less soluble. C. H. D Ultramarine Compounds. 11. L. WUNDER (ZeitseA. anorg Chem. 1913 79 343-345. Compare this vol. ii 54).-When ultramarine red is heated out of contact with air it is converted into a blue product the loss of weight which occurs being due t o loss of water. The constitution is however changed as the new blue evolves hydrogen sulphide with acids whilst the red yields sulphur dioxide.It differs from commercial ultramarine blue in not being converted into viQlet by heating in chlorine (ond hydrogen chloride at l7O-25O0 and in not being reduced t o white by the action of phosphorus in carbon tetrachloride. Tn accordance withii. 282 ABSTRACTS OF CHEMICAL PAPERS. its higher proportion of silica the new blue is more stable towards acids and alum than ordinary ultramarine. The presence of the sodium is necessary for the blue colour complete replacement by mercury yielding a yellow product. The violet ultramarine yields a yellow silver derivative which again becomes violet when heated with lithiuiri chloride. The silver derivative of ultramariiie red is brown a i d is I'ree from sodiiiiu. Alkali haloids convert it into blue. The blue colour is considered to depeid on (I) the presence of ail alkali metal (2) the direct 11 tiion of a pwt of tlie sulphnr LvitJt metal (3) t,he presence of a part of t,he siilphur i n :L lower stale o f nxidatioii.Neither aliiiiiiniiuii xior silicic acid is esseiitisl as the Cornier may he replaced I)y boroii aiid tlie latter by s polytmric- acid. oro on-ultramariiie however fulfils tlie coritlitions iaeritionec t above ((*ompare Hoffmann A. 1908 i i 546). The colloidal theory nf the blue colonr is rejected. (1. H. 1) The Heusler Ferromagnetic Manganese Alloys. EDGAR WEDEKJND (Zeitsch,. nngew. Chew.. 1913 26 72).-Polemical. A reply to Heiisler (1,liis vol. ii 139) T,. DR K.< The Reactions which Accompany the Osmosis of Hydrogen through Iron. GEORGES CHARPY and S.BONNEROT (Compt. rend. 1913 156 394-396. Compare 9 1918 ii 336).-A studv of the change in iron and steel when submitted to the prolonged diffusion oi hydrogen through it a t 600-900°. Iron thus traversed for n long time by a current of hydrogen does not absorb any of the gas since the amount of hydrogen obtainable on heating the iron in a vacuum is generally slightly less after than before the osmosis. The physical properties of the metal are modified i t being softened by prolonged diffusion of the gas which exercises a reducing action removing such constituents as sulphur phosphorus and carbon in the form of their hydrides the desulphurisation being particularly rapid. I n an experiment on a steel tube 3.5 mm. thick containing 0.9% carbon a t 900° 2.3 C.C. of gas diffused through and was found to contain 4% of hydrocarbons.The iron thus undergoes n process of purification by the passage of the hydrogen and this may possibly explain certain of the anonialies in the metallurgy of iron and steel the hydrogen arising from the contact of water vajmur with the hot metal. W. G. The Transformations of Iron and Steel at High Tempera- tures. K ~ T A R ~ HONDA and HIROMU TAKAGI (Sci. Reports T8hoku Imp. Univ. 1912 1 207-217).-A series of specimens ranging from pure iron t o steel containing 1.50% of carbon have been examined in an electric furnace by a magnetometric method simultaneous observations of time temperature and magnetic deflection being made. The &a magnetic transformation extends over a sniall interval of temperature. The interval &a or y-a increases with increasiiig carbon in steels as measured magnetically whilst the thermalINORG AN IC C HEN I STKP.ii. 223 chaage is not recognisable. increase in the magnetic properties on cooling. The eutectoid point is marked by an C. H. D. The System Iron-Carbon. OTTO RUFF (Zeitsch. Eleklroc?wrr. 1913 19 133).-Polemical. An answer to Smits (this vol. ii 56). The author states that Sniits bases his calculations 0 1 1 experirnen18s which are onIy to be regardetl as prehinary. ,I. F. S. Complete Solubility of Chromium Hydroxide in Ammonia. MKLORAD Z. JOVITSCHZTSCK (Monatsh. 1913 34 225 - 242).- Chroniiuni may be precipitated wit11 midl qua~itities of 3ninioniuIii hydroxide as a light grey hydroxide which tlivsolvea i r i exce~s with ruby-red colour the solubility being in flueiicetl by salts of ammonium.From the solution substanc~es niay be ubtaiiied which contain hydroxyl groups ammonia and according to circumstaiices acid radicles. They are not t o be considered as derivatives of ilormal chromium hydroxide Cr2(OH),,4H,0 as for example (NH3),Cr,(OH),C1,4H,0 but rather as based on Colson’s hypo- thetical oxyhydroxide (A. 1908 ii 45) witit which the analyses and properties are most in accordance. The solution of chromium hydroxide may he effected in different; ways ,but the best consists in dissolving 1 gram of the substance in just sufficient mineral acid diluting to about 25 c.c. and adding the same volume of ammonia. A grey precipitate is iorMed which redissolves in the course of an hour or so. Tetrachronziu?nox:ide- (nTH,),:~r.0*NH3*Cr:S0 hexarnminodisulphute I 10H20 is precipitated (NH,), Cr*O* NH,*Cr SO,’ by alcohol from such a solution as a red oil which when freed from ammonium sulphate solidifies to a red mass.When dried over sulphuric acid it loses 4H,O but when left in contact with water. it gradually suffers hydrolysis and becomes paler the acid radicles being partly replaced by hydroxyl groups. It is stable in absolute alcohol but absorbs carbon dioxide when exposed to the air. The addition of alcohol to the solution made with nitric acid at first causes the precipitation of a pale pink a] timinochromium hydroxide. but later on tetruchrorndzcmozide- @H,),Cr*O*NH,*Cr( NO,) 3 2 NH Ir.e~lamminotrinitrute (NH Cr-,0.NH,.~,<N03 I ,1 OH,O separates as J a scarlet dense mass which is soluble in water but is speedily liydrolysed. The preparation of tetrachromiumoxidehexamminodi- chloride I t ,10H20 as a violet-red precipitate is even more difficult.It is soluble in water but only after some hours does silver nitrate form a precipitate. No change is observed when the ruby-red solutions are neutralised but when they are kept diarnrninochromium hvdroxide is precipitated as a violet-blue mass which absorbs carbon dioxide. J. C. W. (NH3)2Cr*O-Cr(NH3)2 ( nTH,)2Cr*O*CrC12 Cr (OH),(NH,),J OH@,ii. 224 ABSTRACTS OF CHEMICAL PAPERS. Diffueion of Molybdenum in the Goalfield of Liege. ARMAND JORISSEN (BUZZ. Xoc. chim. Beby. 1913 27 21-25. Compare A. 1897 ii 265).-The author has examined samples of soot and fine dust resulting from the combustion of coal from this district and has succeeded in isolating molybdenum in small quantities therefrom in tlie form of its sulphide and has further identified i t by the characteristic tests.A portion of the molybdenum is present in a form soluble in and estracted by water. w. G. Iso- and Hetero-Poly-salts. VII. Molybdic Acid Hydrates and Some Polymolybdates. ARTHUR RosENHEIhf and Josu.~ FELIX [with JACOB PINSKER] (i%itsch. anorg. Chena. 19 13 79 ‘292-304. Compare A. 1911 ii 116; Wempe this vol. ii 58).-0cto- rriolybdates are prepared by adding the ct;lcidatecl quantity of hydrochloric acid to normal niolybdates or by saturating solutions of the latter with rriolybdic acid dihydrate. The salts have the formula M’,Mo,O, the calcium and bariurii salts having 18H,O the sodium salt 17H,O the arnmoniuiti salt 16H,O :~iicl the potsssiurn salt 13€1,0.Sodium octarrio!ybtlate passes a t the ordinary terrtperature iiito a decaiiiolybdate Na,Mo,,O ,6H,O. The electrical conductivity of t,he aqueous solutioiis shows that the octarnolybdates coiitaiii ionisable hydrogeu. They ale therefore hydrogen tetramolybdates such as NaHMo,O, m d wlieu neu- tra.lised yield normal tetramolvbclates such as Na2Mo,0, tile electrical conductivity oi’ w1iic.h sliows t h a t J t,liey are elltirely similar to the met a t u ng sta t es . The tetraiviolybdates arc Ltius 12-iriolyl)tlic. acicl Iiyclrates M’,H,[H,( Mo,O,),; 1 and tEie octmiolybclstes :ire hydrogen salts w i t 11 the saint! complex anion M’,H7[H2(Mo207)Ci].Sodium tetramobqbdate Na,H,[H2(Mo,0,),] 21H,O f ornis micro- scopic yellow crystals. The potassium salt has 18H20 the barium salt 12H20 the guanidz*nium salt like the corresponding meta- tungstate is anhydrous. The cctamolybdates already known are formulated afresh i n accordance with this view of their constitution. Two series of decamolybdates exist one readily and the other sparingly soluble and either isomeric or polymeric. When a soluble salt is added t o hot water it dissolves immediately but if warmed with an insufficient quantity of water it passes into the sparingly soluble modification. The following salts have been prepared (soluble) (NH4)2Mo,0031 19H,O ; R2Mo,0031,15Hz0 ; Na2Mo,,03,,22H20 ; (sparingly soluble) (NH1),Mo,,03 ,3R00 ; K,Mo,,O3,,9H2O.T t has not been found practicable t o prepare tlie free acid. c. H. I,. Uranyl Iodates. PAUL ARTMANN (Zeitscl.. anorg. Chem. 191 3. 79. 327- -342).-Uranyl iodate has been described with 5H,O with H,O and anhydrous. It is now found that the precipitation of uranyl nitrate solution with sodium iodate yie1d.s a salt with H20 or 2H,O according to the conditlions. The monohydrate fornisINORGANIC CHEMISTRY. ii. 225 rhonihic prisms when precipihted from cold soluti6n or pyramids from hot solution. The two modifications have D1R 5.220 and D18 5.052 respectively. The first is converted into the second by boiling whilst the reverse tlransform ation occurs slowly at the ordinary temperature. The dihydrate has a lighter yellow colour and fnrins irregular aggregates.Umnyl ??otnssiunz iodate UO,K(IO,),,3H,O is a very sparingly soluble yellow powder and is obtained by precipitation with an excess of potassium iodate. It is hydrolysed by water and is convert,ed into uranyl iodate by an excess of uranyl nitjrat8e. Uranyl iodate does not give up its last mol. of water wheii heated. T t is assumed to have the constitution 0 tlie anliyctroas potassium salt being IO,.UO,.O*IO<~>IO*OK. C. H. D. Zirconium. 11. EDGAR WEDERIND (Annalm 1913 395 149-194. Compare A. 1910 ii 302).-pith HANS Ku~EL.]- The preparation of the metal by the reduction of the oxide by the Goldschrnidt process fails in the case of zirconium as also of other highly infusible metals. R.eduction of the oxide by magnesium also is unsatisfactory. The following process of reduction by calciuni however is convenient and gives good results.An intimate mixture of zirconium oxide and an excess of the finest calcium shavings is heated in an iron tube under a pressure of 0.1-0*5 mm. the heating being discontinued as soon as the reaction commences. When quite cold the contents of the tube are powdered and are treated successively with cold water acetic acid dilute hydrochloric acid and water (until the washings do not contain calcium chloride) all of these operations being per- formed in the absence of air. The residual powder is finally washed with acetone and dried at first at the ordinary temperature then in a high vacuum a t 250-300° and finally in a completely evacuated porcelain tube a t 800-1000°. At the last temperature which is f a r below the m.p. of zirconium the powder sinters t o lumps which exhibit the brilliancy of a mirror by polishing. The metal obtained in this manner contains 99.09% of zirconium. Ail attempt t o remove the small quantity of oxygen still present by heating again with calcium in a nickel tube resulted in the isolation of a less pure product. The yield of the powder is 97.5%; i t has DlS 5-98 the sintered modification having D11 6.280 and When pressed into rods and fused electrically in a vacuum (compare Weiss and Neumann A. 1910 ii 217) the powder is converted into globules D16 6-40 containing 98.5% of zirconium being therefore less pure than the globules obtained by Weiss and Neumann (loc. cit.). Titanium thorium iiraniuni vanadium and tantalum have also been prepadred by the calciuni iuethod.6.204.ii. 226 ABSTRACTS OF CHEMICAL PAPERS. The rn. p. of zirconium is given as about 2350O by Wedekind a d Bolton (A* 1910 ii 302). Estimations by Burgess's platinum method (A 1909 ii 41) give a mean value 1530° of the m. p. The latter value is probably more correct since zirconium cannot be employed for the manufacture of metal filament lamps. Weiss and Neumann (Zoc crt.) have described a zirconium hydride ZrH,. If this is a chemical individual i t is of great interest as being the first authentic example of a derivative of bivalent zirconium. The authors have aIso prepared this substaiice by heating zirconium powder in hydrogen a t 700° a11d 1.5 atmo- spheres and are of opinion that i t is a chemical individual of tlie formula ZrH,; its dissociation pressure a t temperatures up to 1100" has been measured.Evidence of the existence of a. volatile zirconium hydride has not been obtained. Tn contrast to t,itaniuni zirconiiim and nitrogeii do not react iiiuch a t tempera.tures below 100C)o but a t 1000-105U" a dride Zr,N T)lL 6.75 a microcrystalline tombac-coloured glisteiling powder is formed. The nitride is more stable than zmoniiini towards oxygen or chlorine dissolves readily only in hyd rofliroric acid a n d is stable to aqiieoits alkalis. Fused potassium hydroxide or sot1 i t 1 m mrbonate causes an incomplete evolution of the uitrogeii as a minoiiia. The nitride has no measurable dissociation In-essure at llc)Oo i t ~ i ( l jii t,lic compressed state is a conductor of electricit'y. Tlie riitridc whicli is also produced by heating zirconium i n ;i,iniiioiiia at 1000° partly loses its nitrogen by heating in hydrogen a( 1050°; a partial formation of the nitride is also observed when zirconium liydride is heated in nitrogen a t 1050O.[With S. JUDD L~w~s.]-According to the literature zirconiuiri lias been prepared in crystalline graphitic and amorphous modifi- cations. It has already been shown that '' crystalline zirconium " is an alurniniurn zirconide. The existence of Troost's graphitic zirconium prepared by heating iron and sodium zirconate is more than doubtful since a reduction of zirconium oxide by iron is impossible. The black amorphous zirconium prepared by Rerzelius by heating potassium zirconium fluoride and potassium lias also been prepared by the authors (a better result is attained by using sodium instead of potassium) and found not to be an individual substance.It has the characteristics of a gel and retains water inost pertinaciously. By treatment with acids i t is converted in to the hydrosol from which the gel is recovered by coagulation or by evaporation after dialysis. The la,tter contains more oxygen and an appreciable amount of nitrogen. It has Dl6 3-75 but the higher the temperature a t which the amorphous zirconium or its gel is dried the greater is the density until after drying a t about 1000° in a high vacuum it has D21 5.79. Compressed amorphous zirconium or its gel is a non- conductor of electricity a t low voltages but becomes a conductor after being heated a t 1000° in a vacuum. I n its chemical pro- perties amorphous zirconium or its gel behaves very like metallic zirconium.It burns brilliantly when gently heated is very stable Amorphous zirconium and its gel are very closely related.I NO RG A N J C C H EM 16TR Y . ii. 227 towards dilute acids and is slowly attacked by chloriiic. It inflames when heated with sulphur aiid yields a mixture of the oxide and sulphide ; with selenium a greyish-black selenide is produced Reasons are given for the belief that aruorphous zirconium is not a mixture of finely divided metal and the dioxide or of the metal and the monoxide. The authors are of opinion that amorphous zirconiulii is the colloiclal modification of the metal. By treatment with acids it yields the hydrosol.Tlie gel recovered from the latter by coagu- lation agrees in its properties with the amorphous zirconiuiii pre- pared directly by Berzelius’s nietliod. The two modifications of zirconium bear to one another the sairic relation as do ainorplioiis and crystalline silicon. [With J. T~~~~ow.]-Zircoliiu~ii dioxide has been reduced by i~iagnesiiini in hydrogen a t high temperatures whereby about one- third of the oxide escapes reduction. By a second a n d ;1 third repetitioii of the reduction the product becomes more aiid inore liyrophoric a lid unmanageable but in no case has the a~iiouiit o f zirconiir in corresponded wit11 ttliatl roquired by a zircoiiiuin oxide %rO tkc cxisterice o f wliicli lias 1,ecii assumed h y Winklcr a n d by I)cnriis atrd Speiiccr (.I.Artier. C I L ~ ~ L ~ o c . 1896 IS 651). C. f3. The Subhaloid Compounds of Some Elements. I. The So-called Bismuth Subiodide. L U J ~ I MARINO and R. BECARELLI ( A t t i B. Accccd. Lincei 1912 [v] 21 ii 695-701).-The authors have i iivestigated the system Bi-I by the inetliod of thermal analysis and find no indication of the existence of any compouiid of the two elements other than BiI,. The heating and subsequent cooling of the mixture of the two elements were effected in a sealed glass tube precautions being taken to exclude all traces of water. The eutectic of Bi and BiI lies a t 284O. When mixtures containing 5-43% of iodine are cooled two layers are formed of which the upper contains excess of Bi13 and the lower excess of Bi. At 340° the upper layer begins to deposit solid Bi13 and as an.invariant systeiti is thus. formed this crystallisation continues until all the upper has solidified ; during this process the upper layer contains 66*5‘% of BiI and the lower 7.73%. Mixtures with 43-64*63?& of iodinc deposit BiI until the temperature 340° is reached; two layers arc then formed as before. After the upper layer has. crystallised the temperature falls until the eutectic 284O is reached but there is a thermal effect a t 294O possibly due to a transformation product of bismuth. Mixtures containing more than 64.63% of iodine deposit Bi13 and show a eutectic a t 117O but mixtures with more than 90% of iodine could not be investigated owing to the breakage of the tubes in consequence of the pressure of the iodine vapour.R. V. S. History of Colloidal Gold. I. Gold Ruby Glass. ALFONSO CORNEJO (Zeitsch. Chem. Ind. Kotloide 1913 12 1-6).-The view that Kunckel (1679) was the original discoverer of ruby gold glass is erroneous for Libavius (1595) Neri (1614) Glauber (1648),ii. 228 ABSTRACTS OF CHEMICAL PAPERS. Cassius and Tachenius (1668) not only employed gold as a rolour- ing agent but gave exact directions for the preparation of ruby gold glass. H. M. D. Disintegration of Metals at High Temperatures. Coa- densation Nuclei from Hot Wires. ~ O S E P H H. T. ROBERTS (Phil. Muy. 1913 [vi] 25 270-296. Compare CroDkes A. 1912 ii 563).-The disintegration of the platinum metals 2 t high ten1 peratures has been investigated the formatioii of clouds in a Wilson expansion apparatus being employed as a delicate rneans of detecting the pi-esence of disintegrated particles in the gaseous atmosphere surrounding the electrically heated metal wires.As evidence of the superiority of this method of investigating the disintegratioii i t is stated that no loss of weight could be detected 011 heating H platinum wire for thirteen hours a t 650° whereas a dense cloud was obtained in the expansion apparatus when the wire was heated by the passage of the same current for two seconds. From observations in an atmosphere of hydrogen oxygen nitro- gen and air and in a vacuuni i t has been found that the dis- integration process is characterised by the emission of two sets of nuclei. The first set which are got rid of after continuous experi- ilienting depends on the presence of liydrogeii and other gases i i i the metal. The emission of the second set is conditioned by the presence of oxygen in the neighbourhood of the heated metal and also on the attainment of a certain definite temperature.I n regard $0 the first set of nuclei it has been fouhd that they are emitted at comparatively low temperatures the minimum tem- perature a t which they can be detected falling as the pressure of the surrounding gas is diminished. The power of emitting these nuclei is temporarily lost when emission has been taking place for scme time but is gradually regained when the metal is allowed to remain unheated. The emissive power is immediately regained when hydrogen is brought into contact with the metal whereas air oxygen and nitrogen do not produce this effect.If however the metal has been kept at a white heat in a vacuum for a long time hydrogen also fails t o restore the power of emitting the first type of nuclei. The fact that the nuclei diminish in size and disappear soon after their liberation indicates that these nuclei are not of the nature of solid particles and it is suggested that they may be either minute drops of water or traces of compound gases produced by the union of hydrogen with other occluded gases. The second set of nuclei are probably particles of an unstable oxide of the metal this view being in agreement with the fact that oxygen is necessary for their production that they begin to be formed at a fairly definite temperature are very persistent do not alter in size and are unaffected by light or by an electric field. At temperatures where the rate of loss of weight of platinum rhodium and iridium is immeasurably small in nitrogen hydrogen or a vacuum the rate is very considerable in oxygen. At a given temperature the rate of loss for platinum and rhodium is approxi- inat>ely proportional to the oxygen pressure stlid in the case ofMINE KALOGICAL CHEMISTRY. ii. 229 iridium i t increases much more rapidly than the pressure. From experiments with platinum in which the loss of weight of the metal was compared with the diminution in the quantity of oxygen in the surrounding gas it was found that in pure oxygen the ratio corresponded approximately with the formation of the oxide PtO,. I n air the ratio of oxygen absorbed t o platinum disintegrated was much smaller but this would be readily accounted for on the very probable view that the oxide PtO dissociates on cooling. Similar experiments with iridium gave numbers in close agreement with those required for the formation of the oxide Ir02. From these facts the author draws the conclusion that the dis- integration of platinum rhodium and iridium in air a t high temperatures 1*s conditioned entirely by the formation of volatile oxides of the formulae PtO Rho and Ir02. Palladium behaves quite differently from the above three metals and the disintegration in this case appears to be due to simple volatilisation of the metal. The fact that palladium does not yield nuclei of the second type is quite consistent with this view. The deposits which are obtained on the walls of the vessel con- taining the electrically heated metals have also been examined and these observations are consistent with the above views relative to the disintegration process. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9130405207

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemiatrg i. 213 Variations in the Irritability of the Reflex Arc. I. Varia- tions under Aephyxial Conditions with Blood-gas Estima- tions. E. L. PORTER (Amer. J. Physiol. 1913 31 323-244).-The experiments were made on the spinal cat subjected to asphyxia1 conditions. The records obtained offer no conclusive evidenae of increased reflex irritability under asphyxia but as the oxygen in the blood lessens and the carbon dioxide accumulates the flexion reflex dis- appears. This is the general result but the details differ according as the admixture of the two gases supplied varies. W. D. H. The Chemistry of P o r t a l Blood. I. A Portal Fistula. EFIM S. LONDON and N. A. DOBROVOLSKAJA (Zeitech . physiol. Chem. 191 2 82 415-416).-A description of the operative procedure in making a fistula €or the obtaining of blood from the portal vein.Results will follow later. W. D. H. Glycolysis. 111. PETER RONA and F. ARNHEIM (Biochem. Zeitsch. 1913 48 35-49. Compare A. 1911 ii 610).-The authors confirm the previous statement that sugar is not destroyed by lysed corpuscles. They now ahow that i f the corpuscles are previously lysed they can still destroy sugar provided that phosphate or carbonate ions are present in sufficient concentration. They further show that the glycolysia is much diminished if intact corpuscles are diluted with physiological saline alone ; if however carbonates or phosphates are added in sufficient concentration in a Ringer’s fluid when such a liquid is used to dilute the corpuscles the glycolysis is not Jess than that produced by the undiluted corpuscles.The comparative glycolytici. 214 ABSTRACTS OF CHEMICAL PAPERS. properties of white and red corpuscles was also investigated. The red corpuscles diluted with saline t o the volume of the original blood exerted nearly a s great a glycolytic effect as the original blood whereas the white corpuscles diluted to the same extent were almost inactive. Nevertheless if the white corpuscles are diluted with a liquid containing phosphates they exert a very marked glycolytic action. I n the experiments carried out no glycolytic power markedly superior to that of the red corpuscles could be demonstrated. S. €3. S. The Alkalinity of Pancreatic and Intestinal Juice in Living Dogs. FRIEDRICH AUERBACH and HANS PICK (Arb.hl. Gesundheitsamte 19 12 43. 155-186).-Both these juices are strongly alkaline in spite of t h e blood being nearly neutral in reaction; the alkalinity was determined in the juices obtained from fistulze in dogs by electrometric colorimetric and titrimetric met hods. It corresponds with that of a sodium hydroges carbonate solution rather than with one of sodium carbonate. It is probable that the juices contain free carbon dioxide. The H-ion concentration averages 0*5.10-8 mol./litre; the OH-ion concentration a t 18’ is about and a t 37” 5.10-6 mol./lit re. I n intestinal juice sodium chloride is more abundant than sodium hydrogen carbonate ; in pancreatic juice the reverse obtains. The alkalinity of the duodenal contents corresponds with that which is the optimum for peptolytic (not tryptic) activity.W. D. H. Effects of Nutrition with Maize. IV. Action of the Succus entericus of the Dog on Zein Gliadin Zeoses and Gliadoses. SILVESTRO BAGLTONI [with G. AMANTEA and L. MANINI] (Atti 12. Accad. Lincei 1912 [v] 21 ii 655-660. Compare A. 1911 i i 999).-Tbe Succus entericua of the dog has a weak digestive action on gliadin and an even weaker action on zein but i t has an almost equal digestive action on zeoses and gliadoses of peptic and tryptic origin. R. V. S. Are the Endogenous Purine Substances the Products of the Activity of the Djgestive Organs? FRANZ MARE; (P’iiger’s Archiu 1912 149 275-286).-Polemical against S i v h (A. 1912 ii 780 ; compare following abstract). W. I). H. The Source of Uric Acid in Man.11. FRANZ SMET~NKA (Pflilyer’s Aychiv 1912 149 287-317).-This also is a reply to SivBn’s criticism on the work of Mare5 (A. 1910 ii 973) and Smetknka (A. 1911 ii 218). The article IS mainly polemical but does contain some fresh experimental work and the main conclusions drawn are as follows. Intake of a purine-free diet causes an increase of purine excretion. This is due to nuclear catabolism occurring in and associated with the activity of the digestive glande. The increase lasts five to six hours after a meal; but when much protein is taken with the evening meal it may go on all night. The question whether variations in the protein intake produce variations in the purinePHYSIOLOGICAL CHEMISTRY. i. 215 output is not definitely answered. but less markedly.considered to remain unshaken. Diets rich in starch act similarly The original views of Mares on the question are W. D. H. Animal Calorimetry. VII. The Metabolism of a Dwarf. FRANCIS I i . MCCHUDDEN and GRAEAM LUSK (J. Biol. Chem. 1913 13 447-454).-A dwarf suffering from infantilism seventeen years old and weighing 21 kilos. had a basal metabolism of 775 calories per square metre of body surface in twenty-four hours; this is about the same as in a dog. The metabolism was increased by 6.6% after food and this again by 14.7% by reading illustrated periodicals in bed. The protein metabolism yielded the normal proportion of 15% of the total calories of heat-production. Nothing abnormal in metabolic processes was detected. W. D. H. The Part Played by Acid in Carbohydrate Metabolism.Acid Diabetes. HERBERT ELIAS (Biochem. Zeitsch. 19 13 45 120-1 43).- Relatively small amounts of acids administered to rabbits can cause glycogen in large quantities t o disappear from the liver; this dis- appearance results in hyperglyczemia and glycosuria in the animals The fact was established by the dibtinct positive resrilts obtained in a series of researches in animals with livers rich in glycogen whereas negative results were obtained from animals in which the livers were glycogen-free. The ~uprarenals take no part in this action as positive results were obtained when dyspnaea was avoided during chloral hydrate narcosis and after cutting the splanchnics. I n all cases furthermore the histological structure of the suprarenals remained intact.It was shown also by perfusion experiments through the isolated liver that adrenaline plays no part in the disappearance of the glycogen. The acid appears to act therefore directly on the liver itself. Perfusion experiments on the isolated liver of tortoises in- dicated that the glycogen separates from the liver cells for the most part unchanged when acid is added to the perfusion fluid. S. B. S. Has Heated Milk the Same Feeding Value a8 Raw Milk? EICHLOV (Bied. Zentr. 1913 42 56-58 ; from X i t t . deut. milchwirt. Ver. 191 2).-Blilk when heated loses the property of being coagulated by rennet and the soluble calcium salts become insoluble; both changes presumably decrease the feeding value of milk. Experiments i u which dogs (ten days old) were fed for several months with fresh milk and boiled milk respectively gave the follow- ing results.The bones of the dogs fed with boiled milk with oue exception contained less ash thap when fed with fresh milk ; the blood also contained less aah and only about half as much fibrin as the blood of the dogs which had fresh milk. When milk is heated for ninety minutes in boiling water ammonia and hydrogen sulphide are pro- duced in small amounts; the vapour from the heated milk also contained phosphorus. N. H. J. M.i. 216 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Standing or Lying on the Metabolism of Cattle. HENRY PRENTISS ARMSBY and J. AUGUST FRIES (Amer. J. Physiol. 1913 31 245-253).-Details are given of the increase of metabolism in cattle when they are in a standing as compared with the lying position.The increased emission of heat during t h e standing periods is accompanied with a correspondingly increased elimination of both carbon dioxide and water. W. D. H. Nitrogen Retention on Feeding with Urea. EDUARD GRAFE and K. TURBAN (Zedsch. physiol. Chem. 1913 83 25-44).-A full account is given of metabolic experiments in dogs and pigs which show that retention of nitrogen occurs when urea is added to a carbohydrate rich diet. Sometimes equilibrium was attained ; a small part of the nitrogen was excreted in the after period. W. D. H. Histochemistry of Spermatozoa. 111. HERMANN STEUDEL (Zeitach. plzysiol. Cherri. 19 13 83 72-78).-Dried defatted sperma- tozoa from herrings consists as to three-quarters of nucleic acid and oiie-quarter of clupeine.The two compounds are united through the free amino-groups of the arginyl groups of the protarnine. E. I?. A. The Biochemistry of the Female Genitalia. I. The Lipins (Lipoids) of the Ovary and Corpus Luteum of the Pregnant and Non-pregnant Cow. JACOB ROSENBLOOM (J. Bid. Chem. 191 3 13 511-5 12).-Data are presented showing the percentages of fat fatty acids cholesterol and lipoids in the ovary and corpus luteum of the cow. No increase in these occurs during pregnancy. W. D. H. The Sulphatide of the Brain. PHCEBUS A. LEVENE (J. Biol. Chem. 1913 13 463-464).-The lipoid of the brain (ox) which contains sulphur was isolated from the phosphatides; the method is not described. Elementary analyses are given which differ consider- ably from those of both Thudichum and W.Koch. W. D. H. The Influence of Quantity and Concentration of Poieons of the Digitalis Group on the Frog’s Heart. ARNOLD HOLYTE (Arch. expt. Path. ~ ‘ I L U L T ~ ~ L . 1912 70 435-438). -The experiments recorded show the importance of concentration as a factor. W. D. H. Systole and Diastole of the Heart Under the Influence of Djgitalin. ARNOLD HOLSTE (Arch. expt. Path. Yharm 1912 70 439-446).-1t is stated that digitalin applied internally t o the heart produces systolic standstill and to the exterior diastolic stand- still. This has been explained by sup,posing that the outer layers of the cardiac muscle respond differently to the drug from the internal layers. The present experiments show that the medium used is a factor. Fluids which contain blood or Albanese’s solution always produce stoppage in systole whereas if Ringer’s solution is employed as the medium the stoppage is diastolic.W. D. H.PHYSIOLOQZCAL CHEMISTRY. i. 217 Replacement of Urea in Artificial Solutions for the Isolated Heart of Selachians. R. BOMPIANI ( A t t i R. Accad. Lincei 1912 [v] 21 ii 667-672).-Solutions containing urea when adminis- tered by perfusion or otherwise increase the time of survival of isolated hearts. The author's experiments on isolated hearts of Torpedo ocellclta and Scylliurn show that no substance will quite replam urea in this respect but the derivatives of urea favour the survival more than other substances (methylcarbnmide survival 480 minute3 ; urea survival 600 minutes) but the action is less marked the more distantly the substances are related to urea.Neither glycerol acetone and urethane (although they are soluble in lipoids) nor the amino-acids glycine asparagine aspltrtic acid and its salts keep the isolated hearts alive. R. V. S. Toxicological Investigations on Bio-electric Currents. 111. Comparative Toxicological Specificity of t h e Chemical Altera- t i o n Current and Comparative Physiology and Toxicology of the Heart of Helix pomatia. C. LOVATT EVANS (Zeitsch. Biol. 1912 59 397-414). -Henze and Hermann have shown that skeletal and heart muscle of the frog responds specifically to poisons and that the electrical changes run parallel to such action. This thesis is supported by the present investigations on the snail's heart which is recommended as a convenient object for such work.I t s electrogram is very simple showing a pure diphasic effect which corresponds with the single peristaltic wave which travels over it. Carbon dioxide acts tonically on it. The heart of the snail is sensitive to potassium and very resistant to calcium ; muscarine has the usual eEect but this is not antagonised by atropine. Antiarin has no action but strophan- thin and saponin are active. W. D. H. Tolerance for Sugar in the Pig. ANTON J. CARLSON and F. 31. DRENNAN (J. Biol. Chem. 1913 13 465-468).-Minkowski stated that the removal of the pancreas in the pig did not result i n as severe diabetes as in other animals. I n the present experiments fa.ta1 diabetes did occur but it was of slow onset. The pig has alower tolerance for dextrose than any species so far studied; that is i t becomes glycosuric when quite small amounts of sugar are given by the mouth.Occurrence of Metals in the Human Liver. LEOPOLD VAN ITALLIE and J. J. VAN ECK (Pharm. Weekhlad 1912 49 1157-1163." Com- pare Lehmann A. 1896 ii 486).-An investigation of the corpses of persons of various ages indicates that arsenic is not a normal constituent of the human liver but that copper and zinc are always present the proportion of copper being greater during the f a t a l period than in later life. Otherwise age sex occupation and place of residence appear to have no influence on the proportion of copper and zinc. The values given by Lehmsnn for the amount of copper present are appreciably too low. * and Arch. Pharm..1913 251 50-55 A. J. W. VOL. CIV. i. 9i. 218 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Iodine on Autolysis. 31. KASCHIWABABA (Zeitsch. physiol. Ciiern. 19 12 82 425-438).-Contrary to the state- ments of Kepinov (A. 1912 ii 69) autolysis does not occur in a medium containing 0.5% of sodium hydroxide ; what does occur there is hydrolysis produced by the alkali ; this is only slightly increased by the presence of iodine. I n alkali-free mixtures iodine increases autolysis only in a slight degree. I n rabbits which had received an intravenous injection of Lugol’s solution autolysis of the liver is also slightly accelerated but even the fresh liver of such animals show an increase in non-coagulable nitrogen. W. D. H. The Catalytic Action of Iron Salts on the Autolysia of the Liver.LuiGr POLLINI (Biochenz. Zeitsch. 19 12 47 396-404)- Small and large quantities of ferric sulphate and ferric chloride increase the total nitrogen and the nitrogen of the rnonoamino-acids proteoses and purine substances in the autolysis products when calves’ liver is allowed to autolyse in the presence of these salts. Small quantities of iron citrate exert a weak inhibitory action whereas larger quantities exert an accelerating action ; still larger quantities inhibit the autolysis as regards total nitrogen and the nitrogen of amino-acids. The proteose nitrogen on the other hand continually in- creases with increasing amounts of the iron salt. Very small quantities of iron lactate accelerate the autolysis but progressingly larger quantities exert a progressive amount of inhibition. S.B. S. The Physiology of the Thyroid Glands. The Content of Phosphorus Nitrogen and Lipoids in the Organs of Thyroid- ectomised Animals. A. s. JUSCHTSCHENEO (Biochrn. Zeitsch. 1913 48 64-85).-The experiments were carried out with young dogs of which a certain number were submitted to thyroidectomy and an equal number from the same litter were used as controls. It was found that the organic and total phosphorus was diminished in the thyroidectomised animals in the brain heart and spleen whereas the inorganic phosphorus is increased. I n the liver the changes were similar but in the muscles the results were indefinite. In. the kidneys the amount of phosphorus in all forms and especially the inorganic was increased. The nitrogen in the majority of the organs of thyroid- ectomised animals was increased; this htatement does not apply horn- ever to the kidneys and the serum.In animals with hyperthyroidism the total and organic phosphorus in brain muscles and heart are diminished; in the liver kidneys spleen and serum on the other hand they are increased. In most organs the nitrogen content is diminished. In thyroidectomised animals the lipoids and all the fractions of the same are diminished in quantity in the brain liver and muscles whereas they are in increased amount in the serum. I n other organs the lipoid quantity is also less than in the normal. In hyperthyroidism t h e content of lipoid in the serum is diminished whereas no very definite results were obtained by the examination of other organs.The ratios of the nitrogen t o phosphorus in various fractions of the lipoids in thyroidectomised animals and in cases of hyperthyroidism were also investigated. Tbyroidectomy alsoPHYSIOLOGICAL CHEMISTRY. i. 219 causes increase in the content of the purine substances of the organs. Complete thyroidectomy causes at first an increase in the phosphorus nitrogen ratio in the urine followed by a diminution of this ratio ; the quantity of urea diminishes. The quantity of ammonia at first falls and then rises ; there is apparently an increase in amino- acids and purine bases; the creatinine on the other hand diminishes. S. B. S. Seasonal Variation in the Iodine Content of the Thyroid Gland. ATHERTON SEIDELL and FREDERIC FENGER (J. Bid. Chena.1913 13 517-526).-1n sheep ox and pig there is about three times as much iodine in the thyroid between June and November as between December and May. I n the sheep and ox (but not in the pig) the gland is larger during the latter months. Enzyme Synthesis. IT. Lactase of the Mammary Gland. HAROLD C. BRADLEY (J. Biol. Chem. 1913 13 431-440).-These experiments give no support at all to the theory of enzyme syntheses in tissues for lactase was never found in the mammary gland or in the milk. W. I). H. Muscle Chemistry. IV. The Extractive Nitrogen and the Free Amino-nitrogen Titratable by Formaldehyde in the Musculature of Different Animals. GIUSEPPE BUGLIA and A. COSTANTINO (Zeitsch. phpsiol. Chern. 1912 82 439-462. Compare A. 1912 ii 1077 lU78).-A large number of details of the dis- tribution of nitrogen in muscle in many animals are given and great variations are met with in both vertebrate and invertebrate animals ; bht no constant and characteristic features distinguish the muscula- turo of the various animal groups.W. D. H. W. D. H. Muscle Chemistry. V. Purine Bases of the Smooth Muscle of the Higher Animals. GIUSEPPE BUQLIA and A. COSTANTINO (Zeitsch. physiol. Chern. 1913 83 45-49).-The purine bases of the smooth muscle of the ox (retractor penis) consist of oxypurines; xanthine probably preformed exceeds hypoxanthine in amount which ie the opposite to that found in striated muscle. The Formation of Lactic Acid in the Antiseptic Autolysis of Organs. NICOLAUS SOBOLEV (Biocheni. Zeitsch. 19 12) 47 367-373).-1n estimating the lactic acid produced by autolgsis of the organs account mas taken of the amount of acid carried down by the coagulum when the autolysis product was heated the amount with drawn from the solution in this process being estimated by Mondschein's method.A t the ordinary temperature less lactic acid is formed on autolysis than at 40'. Most organs show a maximum production at this temperature after about thirty-three days after which the amount diminishes. The maximum production took place in the liver fol- lowed by the spleen heart muscles and kidneys in diminishing order. Enzyme Synthesis. 11. Diastase and Glycogen of Animal Tissues. HAROLD C. BRADLEY and E. KELLERSBERQER (J. Biol. Chern. 1913 13 419-424).-Tissues rich in diastase may or may not W. D. H. S.B. S. P 2i. 220 ABSTRACTS OF CHEMICAL PAPERS. contain glycogen and what is more significant from t h s point of view of the enzyme-synthesis theory tissues rich in glycogen may or may not contain diastase. W. D. H. Enzyme Synthesis. I. Lipase and Fat of Animal Tissues. HAROLD C. BRADLEY (J. Bid. Ciiem. 1913 13 407-418).-No broad correlation exists between the amounts of fat and lipase in tissues. Some of the tissues which actively produce fat may in fact contain relatively little lipase and tissues which are poor in fat may contain a good deal. The experiments afford no support to the theory of enzyme synthesis. W. D. H. The Influence of the Lipoids on the Action of Oxydases. HORACE M. VERNON (Biochem. Zeitsch. 19 12 47 374-395).-1f minced tissue is left for half an hour in varying strengths of solu.tions of a narcotic up to a certain concentration the narcotic is then washed out and the oxidising power of the tissue tested by a-naphthol and p-phenylenediamine i t will be found that the oxidising power is either uninfluenced or increased. I n higher concentrations the oxydase is injured. Concentrations twice or three times as large as those necessary to produce initial action destroy the oxydase completely ; thus for example acetone first in 4M-solution attacks the oxydase which is destroyed completely in 7M-solution. These limits were investi- gated in several cases. The concentrations of monohydroxy-alcohols which degrade the oxidative capacity SO% are about twenty times stronger than those necessary t o narcotise tadpoles whereas in the case of fatty esters and mettiylurethane they are twelve times stronger. I n poisons other than lipoid-soluble substances such as formalde- hyde the range of action is larger; thus 1330 times as much formaldehyde is necessary completely to destroy the oxydase as is necessary to produce the initial action. I n the case of the typical narcotic paracetaldehyde the relationship of these quantities is only 1.8 1.The range of action of ammonia is even greater than that of formaldehyde. Concentrations of narcotics which cause the initial effects are only a little greater than those necessary to haemolyse red blood-corpuscles. The author draws the conclusion that the action of the indophenol oxydase is dependent on the lipoid or perhaps the lipoid membrane which he considers holds together the tissue oxydase and the peroxydase which are thereby enabled to exert their joint action.S. B. S. The Ferments of the Purine Group ARTHUR SCHULZ (Biochem. Zeitech. 1913 48 86- 119).-In estimating uric acid in organs formaldehyde up to 2% was added to the solution after coagulating the proteins in the presence of sodium chloride and acetic acid. The effect of this addition is to render the uric acid more soluble. It was then estimated in the filtrate in the ordinary way by the Schmid-Kriiger method. For investigating the uricolytic ferment dried organ powders were generally employed. It was found that raaium emanations of an activity of 5-10 Mache units per c.c were without any recognisable influence on the uricolytic action ofPHYSIOLOCIICAL CHEMISTRY.i. 221 dogs’ liver or ox-kidneys. Radium emanations increase the activity of the uricolytic ferments of ox-spleen both as regards the formation of uric acid from added purine bases and from those produced by autolysis. The increased amount of uric acid formed varied under the condit,ions of the experiments from 10 to 20%. There was an increase in the case of autolysis in the activity of the proteolytic ferments as shown by the increase in the nitrogen OF the uncoagulable substances. This amount was however relatively less than the increased amount of uric acid formed. The uricolytic ferments of ox-kidneys are totally inhibited in action by fresh pulp of ox-spleen. Ox-kidney powder can inhibit the purine denmidaGes and the oxydases of the ox-spleen but not the autolytic uric acid formation by the same organ.The author did not succeed in producing anti- uricolytic ferments by immunisation of rabbits by organs containing uricolytic ferments. S. B. S. Creatine Creatinine and Monoamino-acids in Certain Fishes Mollusca and Crustacea. Y. OKUDA ( J . CoEE. Agric. Imp. Univ. Tokyo 19 12 5 25-3 1 ).-Seven varieties of fishes were found t o contain from 0.421 to 0.754% of creatine and 0.070 to 0.660% of creatinine. Mollusca contained only traces of these compounds and crustacea only traces if any at all. All the marine animals examined contained much more nitrogen as organic bases than in the form of monoamino-acids the amount of which is usually very small in fish but somewhat higher in lobsters and cuttle-fish.Most of the proteins are soluble in dilute alkali solution and a good deal is soluble in 10% sodium chloride. The Occurrence of Glycogen in Sea-Molluscs (Especially Cephalopods and Aplysize). EN IL STARKENSTEIN and S ARTIN IN HENZE (Zeitsch. physiol. Chem. 19 12 82 41 7-424).-Cephcr,Zopods and ApZysiae have been stated to be ftee from glycogen. This is not so; they contain abundance of it Glycogen is the same substance whether it is derived from vertebrates or,invertebrates. W. D.-H. Carbon Metabolism. The Labile and Stable Carbon of the Urine. ENRICO REALE (Riochem. Zeitsclt. 19 12 47 355-366).-The carbon of the urine was estimated by a met-oxidation process by oxidation with chromic acid and eulphuric acid for which a modifica- tion of the apparatus of Desgrez (which is figured in the text) was employed.It was found that only about half the carbon i n the urine exists in the form of urea. It mas also found that a part of the carbon is readily oxidised to carbon dioxide in the presence of hydrogen peroxide when manganese peroxide is used as a catalyst. This is designated by the author “labile carbon,’’ whereas the carbon which is not so oxidised is called “ stable carbon.” Full experimental details for the estimation OF carbon in these two forms are given. The Intensity of Urinary Acidity in Normal and Pa$tho- logical Conditions. LAWRENCE J. HENDERSON and WALTER W. PALMER (J BioE. Chem. 1913 13 393-405).-Normal urine ranges N. H. J. 31. S. B. S.i. 222 ABSTRACTS OF CHEMICAL PAPERS.from a concentration of ionised hydrogen of about 4.82 to 7.45 ; the mean value is 6.00. Pathological conditions occasionally cause a greater acidity but never unusual alkalinity. No attempt is made a t preseut to generalise except i n cases of cardio-renal disease where the high mean acidity may indicate a form of acidosis. W. D. H. The Origin and Destiny of Cholesterol in the Anirxial Organism. X. The Excretion of Cholesterol in Man when Fed on Various Diets. GEORGE W. ELLIS and JOHN A. GARDNER (Proc. Roy. SOC. 1912 B 86 13-18. See A 1912 ii 275 958).- I n man as in other animals the excretion of cholesterol in the faeces can he accounbed for by that taken in with the food provided the body- weight remains constant. If however a rapid loss of weight takes place as in illness the output of cholesterol exceeds the intake.Further work will be necessary before this view can be regarded as established. W. D. H. Influence of Alkaline Salts in the Elimination of Urinary Ammonia by Normal Dogs. HENRI LABB~ (Compt. rend. 1912 155 1620-1622. Compare A. 1911 ii 220).-With dogs in a state of nitrogenous equilibrium on a meat diet the simultaneous ingestion of ammonium salts and excess of sodium carbonate produces a slightly less elevated elimination of volatile basic nitrogen than when the ammonium salts are ingested alone. The difference is more marked with ammonium carbonate than with ammonium chloride. A large excess of sodium carbonate (about 2 grams per kilo. of body-weight) which provoked great thirst and marked polyuria did not cause all the basic volatile nitrogen to disappear.W. G. The Relationship between the Nitrogen of the Amino-acids and Total Nitrogen in Urine under Various Normal and Pathological Conditions. ERNESTO SIGNORELLI (Biochem. Zeitsch. 19 12 42 4S2-506).-'l'he experiments were carried out on dogs. The percentage of the amino-acid nitrogen (of the total nitrogen) varied in starvation between 1.09 and 1.30. It showed no very marked increase when oxidation was increased by the animals breathing pure oxygen. The value showed no marked differences when the proteins ingested by the animals were varied (caseinogen gelatin gluten and zein). The percentage was only slightly increased (1.57-2.51) when the hydrolysis products of these proteins were administered subcutaneously. When azoturia was produced by fever etc.the percen t a ge still remained normal. I n phosphorus poisoning when the functions of the liver were disturbed i t rose to 3.66. Two hypotheses are advanced to account for the approximate constancy of the percentage ( a ) that in all proteins there is a part which is not readily oxidked and (6) that in the enzyme reaction producing deamidisation there is an equilibrium point at which part of the substance remains unacted on. S. B S. The Fat Content of Normal and Pathological Urine. Kozo SAKAGUCHI (Biochem. Zeitsch. 19 13 48 1-34),-The methadPHYSlOLOGICAL CHEMISTRY. i. 223 employed for estimating fat was that of Kakiuchi (A 1910 ii 549). The amount excreted in a normal adult urine is 0.0085 gram in twenty-four hours which can be increased to 0.0341 gram after diets containing very large amounts of fat. Out of three cases of nephritis investigated in only one was the fat excretion regularly above normal.In diabetes tuberculosis of the lungs jaundice and cirrhosis of the liver the excretion was normal. KO extra excretion could be detected in cases of fractures of bones or re-section and in this respect the results of the author differ from those obtained by earlier investigators. 8. B. S. Urobilin. 111. and IV. G. FROMHOLDT and N. NERSESSOV (Chem. Zentr. 1912 ii 1678; from Zeitsch. expt. Path. Ther. 1912 11 400-407).-The administration of fresh bile leads to the appearance of urobilin in the urine but this does not occur when pure bilirubin or bile extracted with ether is given.A method of extracting urobilin from blood is described. After preliminary extraction with alcohol and filtration it is acidified and extracted with amyl alcohol in which solvent the pigment is detected spectroscopically. If urobilin is absent from the urine i t is also absent from the blood but when present in the urine it is usually present in the blood as well. IV. D. H. Blood Destruction Bile and Urobilin. The Formation of Bile Pigment in Blood. 111. THEODOR BRUGRCH and KARL RETZLAFF (Chern. Zentr. 19 12 ii 1678-1679 ; from Zeitsch. expt. Path. Ther. 19 12 11 508-525).-Estimations of urobilin in urine and faeces in various cases of liver disease lead to the conclusion that urobilinuria is the clinical expression for a series of substances related to blood and bile pigment.Hsematogenous or extra-hepatic urobilin- uria occurs after extravasation of blood in the tissues ; its other cause is usually hepatic insufficiency. If the bile enters the intestine its pigment is converted into urobilin and re-absorbed; the liver then manifests its insufficiency by being incapable of re-synthesising bile- pigment from the urobilin which therefore passes into the blood and urine. Urobilir in urine and fsces was estimated by making alkaline with ammonium carbonate and letting the mixture remain at 37’ €or two days. It was then extracted with light petroleum until Ehrlich’s reaction was negative then acidif~ed with tartaric acid and extracted with ether. A measured quantity of the ethereal solution was mixed with an ethereal solution of p-dimethylaminobenznldehyde and a few drops of hydrochloric acid in absolute alcohol and examined chromo- photometrically.W. D. H. The Protective and Curative Properties of Certain Food- stuffs against Polyneuritis Induced in Birds by a Giet of Polished Rice. EVELYN A. COOPER (J. Hgggiene 1913 12 436-462).-1n pigeons weighing 350 grams as much as 20 grams of raw beef are necessary daily to prevent polyneuritis; the anti- neuritic value of beef is therefore low. Heart muscle is better and sheep’s brain about twice as eacient as beef. Brain is specially efficient in preventing loss of body-weight which ensues when polishedi 224 ABSTRACTS OF CHEMICAL PAPERS. rice is given. Egg-yolk even if boiled is the most efficient of all the animal foods examined 3 grams daily is enough.Dried lentils and unhusked barley are about equal to egg-yolk. Yeast is the most efficient of all foods. The antineuritic and weight-maintaining action of the various foods differs. The weight-maintaining constituents are not protein fatty or lipoidal. W. D. H. Fish is very inefficient in both directions. Congenital Family Steatorrhoaa ARCHIBALD E. GARROD and W. H. HURTLEY (Quart. J . Med. 1913 6 242-258).-The details of a curious caw of an inborn metabolic error are recorded. The boy (aet. 8) has been subject since infancy to the passage of liquid fat from the bowel ; one cooling it solidifies; another brother who died in infancy had the same defect. Haalth was apparently unaffected ; the stools contained 25% of the fat in the food ; with a n intake of 177 grams of fat only 4% mas split; this figure rises when the intake is less but even then it is not absorbed.Sodium glycocholate and various pancreatic preparations increased fat-splitting but not the absorption ; indeed the latter aggravated the condition. W. D. H. The Mechanism of the Action of Silver Haloids. OSKAR GROS (Arch. expt. Path. Phnrm 1912 70 375-406).- Colloidal silver chloride and iodide intravenously injected in rabbits are strongly toxic and the chloride is more so even though the concentration of silver ions is the same in both cases. This is considered to be due t o the formation of a complex of the silver salt and the chlorides of the blood plasma which is more readily carried to the tissue cells. Sodium iodide which is non-toxic if given simultaneously increases the poisonous action of silver iodide.This is explained on similar lines. I n vitro both salts are hzemolytic and again the chloride is more effective but here sodium iodide does not increase the action of silver iodide. W. D. H. A Physiological Series of Cations. N. K. KOLTZOV (P’iiger’s A~chiv 1‘312 149 327-363).-The observations were made on the effect of salt solutions on the vitality and contractility of a marine infusorian (Zoothamlzium alternans). They follow in the main the work of Overton and others who have bestowed attention to osmotic phenomena and the rale of the plasmatic membrane of cells. If chlorides are employed throughout the cations are arranged in the following order K Rb Na Cs NH Li Sr Mg and Ca.Each member of the series lowers the surface tension of plasma-water less than the succeeding one and toxicity runs parallel with the adsorption of the cations. W. D. H. Temporary Fixation and Mode of Elimination of Manganese in the Rabbit. GABRIEL BERTRAND and FLORENTIN MEDIGRECEANU (%Compt. Tend. 1912 155 1556-1559).-Four rabbits received repeated subcutaneous injections of manganous sulphate in varying doses and the effect on their weight and length of life was noted.PHYSIOLOGICAL CHEMISTRY. i. 225 Even with minute doses there was a marked loss in weight and three injections of 5 mg. of manganese per kilo. of body-weight at intervals of twenty-four hours caused the death of the rabbit. The amount of manganese i n the various organs of the four rabbits aud of an uninjected rabbit was determined and the results show that manganese when subcutaneously injected is rapidly diffused throughout the body and all the tissues iucluding t,he nervous tissue become temporarily impregnated. It is readily eliminated through the liver bile and mucus of the alimentary canal and a small quantity is excreted in the urine.W. G. The Action of Certain S u b s t a n c e s of the Chloroform Group on the Vestibular Eye-Reflex. J. ROTRFELD (PJiiger’8 A r c h 19 13 149 435-446).-Nystegmus (vestibular eye-reflex) disappears under the influence of narcotics ; first vertical then rotatory and finally horizontal nystagmus. As anaesthesia passes off they reappear in the reverse order. The substances employed i n the research were chloroform ether chloral hydrate and paracetaldehgde.The diffeicnces in detail between these four substances are treated a t length. W. D. H. Tho Fixation of Digitoxin (Merck) in the Organism of the Rabbit after I n t r a v e n o u s Injection. Comparative Experi- ments with Strophantin-g. CAMILL LHOT~K VON LHOTA (Biochem. Zeitsch. 1913 48 144-154).-1f digitoxin is injected intravenously into rabbits it disappears almost immediately from the blood (as ascertained by tests on the frog’s heart) even when ten times the lethal dose is employed and the conditions of the animal are favourable. These conditions are that the heart should be active and the functions of the blood-vessels intact. If these are interfered with in any way (by narcosis etc.) digitoxin can be detected in the blood when only twice the lethal dose has been employed.After injection of ten lethal doses the digitoxin can be detected in all organs especially the heart and liver. The greater the length of the circulatory system the drug must travel from the point of injection to reach the heart the greater is the dose necessary t o produce the specific action This fact indicates that the drug is fixed by the vessels as well as the heart and was demonstrated by experiments on animals with crossed circulatory systems. The drug can also be detected chemically at the point of application. Intravenously injected strophantin-g only disappears immediat’ely froru. the blood in small quantities. S. B. S. T b e Fate of Prolirie in the Animal Body. HENRY D. DAKIN (J. Biol. Cherrz.1913 13 513-,516).-When proline is added t o blood and the mixture perfused through the surviving liver of a dog there is no increase in the formation of acetoacetic acid ; but in the glycosuric animal it causes a marked increase in the sugar output. The formation of dextrose from proline involves the disruption of the ring. Glutamic acid also yields sugar (Lusk) ; so also do arginine and ornithine. The close structural relationship of glutamic acid ornithine and proline is shown graphically. W. D. Hei. 226 ABSTRACTS OF CHEMICAL PAPERS. The Results of Poisoning with Adrenaline Histamine Pitu- itrin and Peptone in Relation to Anaphylaxis and the Vege- tative Nervous System. ALFRED FROHLICH and ERNST P. PICE (Arch. expt. Path. Pharm. 191 2 71 23-6 1 ).-The substances men- tioned in the title greatly lessen or abolish the excitability of the autonomic nervous system both to faradic stimuli and to drugs.The same occurs in '( peptone immunity " and i n anti-anapbylaxis. As both these phenomena soon disappear they are separable and reversible. The effect of the poisons is a selective one on the nerve endings. A considerable amount of the work recorded was performed on the uterus and it was then found that after the use of histamine adrenaline and pilocarpine had no effect and pituitrin very little. After treatment with tyramine pituitrin histamine and adrenaline act normally ; after treat- ment with pituitrin adrenaline acts normally ; after peptone pituitrin tyramine and adrenaline have no action. Barium chloride locally applied to the uterus causes contraction of the uterus after it has been rendered inexcitable by histamine tyramine or peptone.W. D. H. The Pharmacological Action of p-Hgdroxyphenylethyl- amine. A. BICKEL and MICH. PAVLOV (Biocherrz. Zeitsch. 1912 47 345-354).-This substance which can be isolated from ergot shows the following actions. When 1-2 C.C. of a 0.5% solution are injected into rabbits or dogs of medium size the arterial blood-pressure after a short-lasting fall rises remains high for two or three minutes and then sinks to normal. This is due to a contraction of the capillaries with rz consequent diminution of the amount of blood in the veins which mas detected by the measurement of the blood-flow in the venous system. As a further consequence there is a diminution of volume of organs which have a well-developed venous supply.This fact was demonstrated directly by the measurement of changes pro- duced in the kidneys after the injection of the drug and indirectly by the changes in the intestinal volume after injection of extracts of Secale cormuturn. S. E. S. Action of Scopolamine (Hyoscine). ARTHUR R. CUSHNY (Arch. expt. Path. Pharm. 1912 70 433-434).-A criticism on the work of Hug (A. 1912 ii 790) who finds like the author that I- and i-hyoscine differ in their action on nerves. The quantitative differences between the t w o workers are explained as due to differences in the methods used. W. D H. The Method of Action of Quinine. J. MOLDOVAN (Biochern. Zeitsch. 2912 47 421-446).-The action on Colipidia is to caucce a change in the state of the colloids of the protoplasm leading to a separation of droplets of lipoid character and producing a change in the osmotic relationship of the protoplasm to its surroundings ; after- wards the nucleus and motility of the cell are injured and finally death results.The cause of death is the stoppage of oxygen respira- tion. I n the case of trypanosomes the action is similar but the separa- tion of droplets is less marked owing to the smaller content of lipoids. Similar actions were also observed on plant cells. There is a con-PHYSIOLOGICAL CHEMISTRY i. 227 siderable difference of behaviour in the individual cells as regards the resistance to the action of quinine which depends on the energy of the oxygen respirations; older cells appear to be more resistant than young cells.The combined effect of two toxins on the cells is not the sum of the effect of each individual toxin but depends amongst other factors on the relative concmtrations of the two. I n rabbits and guinea-pigs the action of quinine is t o diminish the oxidative pro- cesses especially in the brain. This fact was demonstrated by various methods of intra vitam staining (according to the method of Ehrlich etc.). The quinine in influencing the oxidative process does not ef€ect the oxygen taken up but acts as an anticatalyst. In view of the first action of quinine on cells in causing the separation of the lipoids i t can act as a narcotic or local anathetic. To produce general narcosis however the required dose is so high that it acts deleteriously on t h e respiration and i t cannot therefore be used in practice for this purpose.s. B. s. Influence of the Constitution of Purine Derivatives on their Action with Respect to Arterial Pressure. ALEXANDRE DESGREZ and DORL~ANS (Compt. rend. 1913 156 93-94).-Whilst guanine on intravenous injection into a rabbit causes a diminution in the arterial blood pressure (compare A. 1912 ii 585) hypoxanthine xanthine and uric acid exert a hypertensive action. The increase in pressure whilst slight for hypoxauthine is greater for xanthine and still greater for uric acid. From this i t appears that the guanine owes its hypotensive action to the presence of the amino-group in its molecule. The action of these substances especially of uric acid is of interest in the patho- genesis of arthritic diseases in which Eouchard has shown that there is marked arterial hypertension. W. G. The Biological Action of Certain Protein Products Intro- duced Parmterally. ALFRED SCHITTENHELM and WOLFGANG WEICHARDT ((,'hem. Zentr. 1912 ii 1680 ; from Z&tsch. Tmmunitats- forsch. exper. T/her.8 1912 14 60%-630).-The simple and conjugated proteins introduced into the blood stream are relatively innocuous ; but the protein constituents of conjugated proteins (globin histone pro- tamine) cause great depression of blood pressure affect breathing and temperature and lead in quite small doses to death. This has been attributed to the high percentage of diamino-acids they contain but this cannot be the case because histone is poor in such acids and certain kyrines rich in them are not toxic. Such proteins when united to nucleic acid or to haemochromogen in t h e case of globin lose their toxicity. Toxic symptoms which occur when hsemolysis takes place in the blood stream may be due to the liberation of the poisonous globin (proteinogenous cachexia). W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9130400213

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

i. 228 ABSTRACTS OF CHEMICAL PAPERS. Cliemi stry of Vegetable Physiology and Agriculture. The Relation Generation Time of Concentration of Food-supply to the of Bacteria. W. J. PENFOLD and (Mrs.) DOROTHY NORRIS (J. Hygiene 19 13 12 527-531).-The generation time of B. tvvphosus in 1% peptone at 37’ is forty minutes. If the peptone solution is less than 0.2% in strength the generation time is inversely proportional to the concentration. The addition of 0.17% of dextrose to a medium containiDg only 0.1% of peptone lowers the generation time by 50%; with 1% peptone this effect is less marked. W. D. H. The Bactericidal Properties of Blood Serum. I. The Reaction Velocity of the Germicidal Action of Normal Rabbit Serum on the Bacillus coli commune and t h e Influence of Temperature Thereon.(Miss) HARRIETTE CHICK (J. Hygiene 1913 12 414-535).-The action in vitro of rabbit serum on B. coli consists of several phases the duration of which is inversely proportional to temperature. I t s germicidal action follows the logarithmic law and so falls into line with other cases of disinfection. Its temperature- coefficient is low (2.84 to 1.93). W. D. H. Chemical Action of Bacillus cloace (Jordan) on Citric and Malic Acids. JAMES ‘J’HOMPSON (Proc. Boy. SOC. 1912 B 86 1-1 2).-The respiratory coeacient for malic and citric acids was determined and found to be 1.63 and 2.35-3 2 respectively. I n the presence of oxygen B. cloaccz decomposes malic acid with the production of carbon dioxide acetic acid succinic acid a small quantity of fatty substance and traces of alcohol.It is suggested that the action probably goes on in two ways an oxidation of acid to carbon dioxide and acetic acid by atmospheric oxygen and an oxida- tion accompanied by reduction of a portion of the acid to succinic acid. The organism does not attack malic acid in the absence of oxygen. The products resulting from the decomposition of citric acid are the same as from malic acid. Under aerobic conditions the amount of acetic acid is greater whilst anaerobic conditions lead to a n increase in the production of acetic and formic acids. Acetylmethylcarbinol is not formed by the action of B. cloaca on malic or citric acids. H. B. H. The Degradation of Polypeptides by Bacteria. 11. The Action of the Non-liquefying Organisms TAKAOKI SASAKI (Biochem.Zeitsch,. 191 2 42. 462-471. Compare A. 1912 ii 669)- Organisms which are incapable of liquefying gelatin contain never- theless an erepsip-like ferment capable of hydrolysing glycyl-glycine and glgcyl-Z-tyrosine. Relatively large quantities of tyrosine could be isolated as a result of the action. This action was demonstratedVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 229 by typhus and various strains of paratyphus bacilli various bacilli of dysentery bacilli of mouse typhus chicken cholera aud Micrococcus tetrugenus. S. B. S . The Degradation of Polypeptides by Bacteria. 111. The Action of Liquefying Organisms. TAKAOKI SASAKI (Biochem. ZeitscA. 1912 47 472-4Sl).-Glycyl-glycine and glycyl-Z-tyrosine were hydrolysed (in Frankel’s solution) by the following strains.Bacilli of splenic fever Staphylococcus pyogenes U U T ~ Z I S citreus acd ulbus B. subti& B. proteuv vulgaris B. pyocyaneuv B. prodigiosus cholera ribrio and the vibrios of Metchnikov and Dunbar and the water vibrio. S. B. S. Production of Citric Acid from Glycerol by Fungi. CARL WEHMER (Chem. Zeit. 191Y 37 38-39. Compare A. 189Y ii 591 ; 1909 ii 602; 1910 ii 60 61).-When two species of Citromyces were grown in nutrient solution containing animonium nitrate potassium phorphate magnesium sulphate calcium carbonate and glycerol (3-20%) large quantities of citric acid were produced. I n the absence of calcium carbonate 110 such accumulation occurs and it is assumed that i n the absence of any neutralisable base any citric acid formed is destroyed immediately by the fungi.Similar growth takes place when the glycerol is replaced by sucrose lactose mannitol xylose or arabinose. Sucrose is inverted arid reducing substances are formed in cultures supplied with glycerol. The author discusses the mechanism of citric acid formation from glycerol and contests the view advanced by MazB that acid is only produced when there is a deficiency of nitrogen or that it is in any way due to a lack of iron or ziuc. Action of Hydrogen Ions Boric Acid Copper Manganese Zinc and Rubidium on the Metabolism of Aspergillus niger. H. J. WATEltnim (I’roc. K. Akud. Wetensch. Amstsrduna 1912 15 753-764).-1n investigating the culture conditions of Aspergillus niger it is not sufficient t o merely ascertain the dry weight produced as was done by Raulin and others.Spore formation €or instance produces differences in composition. It is therefore desirable t o determine the changes of the plastic equivalent or of the assimilation quotient. several times during development. Addition of 2.35 C.C. of N-sulphuric acid to 100 C.C. of culture solution and of 0:5% of boric acid has very slight effect on the plastic equivalent of the carbon. A high weight of mycelium is not alwajs a favourable indication. It was found that certain concentrations of copper suiphate zinc chloride and sulphate considerably increase the plastic equivalent of the carbon whilst the increase in the weight of mould is proportional to the retarded spore production. Very dilute zinc solutions have no effect ; copper salts in all dil iitions counteract spore formation.Minimal quantities of manganese do not alter the plastic equivalent of the carbon but only affect the rate of metabolism. The amounts of dry matter found by Bertrand should be considered as values indicating the velocity of the process. H. B. H.i. 230 ABSTRACTS OF CHEMICAL PAPERS. When potassium is replaced by rubidium spore formation is checked the weight of mould increased whilst the metabolism of the carbon remains the same. Influence of Zinc Magnesium Calcium Potassium. and Sodium Salts on the Growth of Aspergillus niger. J. BuRoni- SKI (Centr. Bakt. Pur. 1912 ii 36 54-66. Cornpara A. 1908 ii 124; 1911 ii 222 421 664; 1912 ii 377 861).-The fungus was grown in a medium consisting of ammonium sulphate or nitrate 1% sucrose 5% magnesium sulphate 0.25% monopotassium phosphate 0.4% traces of ferrous sulphate and distilled water.The addition of zinc sulphate in the proportion of 0-001-0.1% led to an increase in the respiratory coefficient (carbon dioxide crop) that of the control and treated cultures respectively being 1.8 and 2.4 at 30° and 2.8 and 3.5 at 20’. The addition of calcium sulphate to magnesium-free medium decreased the growth of the organism ; 0.25% magnesium sulphate to magnesium-free medium increased the crop very greatly whilst calcium and magnesium sulphates increased the growth still more. The presence of calcium salts prevents the accumulation of oxalatea in the cultures. Magnesium sulphate may be beneficially increased to 05% although fructification begins to be affected a t this concentration.Sodium salts proved to be without value but increasing amounts of potassium salts caused corresponding increases of growth. Magnesium and potassium salts therefore not only serve as nutrients but also exercise a stimulative action. H. B. H. Enzymatic Nature of Uric Acid and Hippuric Acid Ferment- ation. ALEXANDER Kossowrcz (Chem. &mtr. 1912 ii 1300 1482 ; from Zeitsch. Gahrungsphysiol 1 121-123 317-319. Compare this vol. i 146).-Filtered solutions from cultures of Aspergillus niger Mucor Boidin Phytophthora i?ifestans Isaria jarinosa and Botrytis bussiaua in which urea was present as only source of nitrogen liberated ammonia from uric and hippuric acid and from the latter benzoic acid as well. A filtrate from Ckadosporium herbarum only showed distinct production of ammonia in the case of uric acid.Similar results were obtained by means of the alcohol precipitates obtained from the filtrates from Aspergillus and Cladospmium. Referring to Shibata’s negative results with Aspergillus niger and uric acid it was found in similar experiments that AspergiZZus niger Mucor Boidin Phytophthora in festans Isaria farinosa Botrytis bassiana and Cludosporium herbarum all produce ammonia from uric acid and that all except Cladosporium decompose hippuric acid with production of ammonia and benzoic acid. The Rate of Fermentation aa Measured by Difference of Potential. M. C. POTTER (Proc. Univ. Durham Phil. SOC. 1912 4 230-231. Compare ibid. 1910 3).-It has been shown previously that during the fermentation of sugar by yeast an E.M.F. is developed. The author now finds that the measurement of the rate of fermentation by the development of the E.M.P. and by the evolution of carbon dioxide as in Slator’s method are in close agreement so that the electrical method provides a ready meam of determining the rate of fermentation X. H. J. M. N. H. J. M.VEGETABLE PHYSIOLOGY AND iuxwmcruREi;. i. 232 Experiments are also quoted showing that the carbon dioxide given off during fermentation carries an electric charge and t h a t the rate of fermentation is uninfluenced by the potential of the fermenting liquid. Fermentations with Yeast in the Absence of Sugar. IX. Fermentation of Keto-acids by Wine Yeasts. CARL NEUBERG and J. KERB (Bioch,em. Zeitsch. 19 12 4’7 405-412).-Wine yeasts of which a large number of German varieties were investigated exert the same action on pyruvic acid as the beer yeasts giving rise to acetaldehyde (which was isolated as its p-nitrophenylhydrazone) and carbon dioxide.These yeasts also attack oxalacetic acid and a-keto-1%- butyric acid. S. B. S. Fermentations with Yeast in the Absence of Sugar. X. The Fermentation of a-Ketobutyric Acid CARL NEUBERG and J. KERB (Bioehem. Zeitsch. 1913 4’7 413-420).-This acid is very readily attacked by various yeasts and yeast preparations. The actual course of fermentation is not yet ascertained in that propaldehyde could only be isolated in small quantity (about 4%). a-Ketoglutaric acid is also very readily attacked; phenylpyruvic acid is also fer- mented but not ay-diketovaleric acid.The Acidification of Musts by Yeasts during Alcoholic Fer- mentation. AUGUSTE FERNBACH (Cornpt. ~e92d. 19 13 156 77-79). A study of the influence of the original acidity of the medium on the production of acids during the fermentation by yeasts of a saccharine liquid. Even in varying conditions the results show that the aciditica- tion produced by the yeasts independently of their individual character is subject to the acidity of the medium in which they function low acidity in the medium favouring high acid production. Fixation of Elementary Nitrogen by Yeasts Monilia candida and Oidium lactis. ALEXANDER KOSSOWICZ (Bied. Zentr. 1913 42 68-69 ; from Zeitsch. Gahvungsphysiol l).-The results of experiments with (1 ) Xaccharonzyces Pastoriccnus 111 Hausen ; (2) Monilia candida ; (3) Suceharontyces menh-anuefuciem ; (4) Xt~ccl~uro- myces anomalus ; (5) Oidium lactis cultivated in solutions containing sucrose (5%) glucose (0*2%) and mannitol (0 2%) in addition to minerals showed in three months the following gains of nitrogen (1) 4.8 and 5.2 ; (2) 6.2 and 6-8; (3) 6.9 ; (4) 7.4 and (5) 4.8 and 5.8 mg.S. B. 8. W. G. The air in the flasks was freed from combined nitrogen. N. H. J. M. Mode of Action of Dilute Solutions of Electrolytes on Germination. HENRI MICHEELS (Bull. Acad. roy. Belg. 19 12 753-765. Compare A. 19 10 ii 883).-Germination experiments with wheat in electrolysed and non-electrolysed N/ 100-potassium chloride solutions through which chlorine was passed showed that chlorine was rendered more favourable by the cathode liquid and was poisonous in the non-electrolysed solution.i. 232 ABS'l'KAC'fS OF CHEMICAL PAPERY.In the case of potassium hydroxide (25 C.C. of a 0.1% solution added t o 500 C.C. of N/lOO-potassium chloride) a very injurious effect was observed in the non-electrolysed solution ; its toxicity was diminished in the anodic liquid but only in a slight degree. Copper sulphate (N/200) in anodic solution which is acid is more toxic than the cathodic solu?ion which is only slightly acid. The solution is toxic when not electrolysed. Compaxing N/lOO-potassium chloride witti electrolysed solutions in which the cathodic and anodic liquids received hydrochloric acid and potassium hydroxide respectively the best results mere obtained in the non-electrolysed solution and in the cathodic liquid notwithstanding the acidity whilst the disappearance of the acidity of the anodic liquid only slightly diminished its toxicity. The conclusion is drawn that anodic and cathodic liquids owe their characters in part t o the liberated cations and anions not passed to the chemical state.I n solutions of electrolytes the action of cations would not be exclusive but only preponderating. N. H. J. M. Effects of Manurial Salts on the Germination of Different Plants. ALBERT RUSCHE (J. Landw. 1912 60 305-365 ; from Dim Gottingen 191 2).-Potassiuni chloride does not act unfavourably on the germination of cereals peas rape and beet but is unfavourable in the case of clovers serradella lucerne and lupins especially white clover and serradella.Sodium chloride is more unfavourable than potassium chloride except with barley lupins serradella and rape. Magnesium and calcium chlorides generally have the same effect as potassium chloride but not in every case ; whilst ammonium chloride is injurious especially with clovers. Nitrates are generally mm0 favourable than chlorides ; ammonium nitrate however resembles the chloride. Potassium sulphate is generally favourable except with serradella ; sodium sulphate is similar in its effects whilst magnesium and calcium sulphates are also favourable. Of all the salts employed sodium and potassium carbonates are the most favourable. As regards the length of roots nitrates produced the shortest roots with cereals. The longest roots were obtained with sulphates and phosphates.I n the case of peas the longest roots were obtained when no manure was employed. With red clover the longest roots were produced under the influence of sulphates and carbonates the shortest with carbonates and chlorides. The full results relating to germination length and weight of roots and the development of the above-ground parts of the different plants are given in numerous tables N. H. J. M. Influence of Previous Conditions on the Value of the Respiratory Quotient of Green Leaves. L f o ~ MAQUENNE and EM. DEMOUSSY (Compt. rend. 1912 156 28-34).-'l'he authors have studied a riumber of abuormal cases where the respiratory quotient of leaves gathered in full sunlight was considerably lower than that of leaves which had been kept in the dark for several hours.They worked with leaves of sorrel stonecrop geranium rhubarb and XedumVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 233 acre and from their results they consider that the respiration of a plant is effected in two successive phases; the first leading to a produc- tion of fixed acids the result of an oxidation rendered incomplete owing to the slowness of penetration of the oxygen; the second to a combustion of these acids. It is necessary also t o take into account the solution of the carbon dioxide in the cell-sap and the temperature which has an in5uence both on the acidification and the absorption of carbon dioxide by the leaf. Working with an Aspidistya leaf and observing the variation of pressure using their manometric measuring apparatus (compare A.1912 ii 1201) they find that with leaves taken straight From the sunlight the pressure at first diminishes and then rises whilst with leaves kept in the dark for some hours before measuring the pressure rises immediately and continuously. W. G. Hydrolysis and Displacement by Water by Nitrogenous and Mineral Substances Contained in Leaves. GUSTAVE ANDRP (Compt. rend. 1912 155 1528-1531. Compare A 1912 ii 198).- Chestnut leaves show much the same loss of nitrogen phosphoric acid and potassium by exosmosis when steeped in water as do grains of wheat and haricot beans (compare A. 1912 ii 591). After 255 days stepping the leaves had lost 6*~'70/ of their nitrogen 74.14% of phos- phoric acid and 94.58% of potassium. Most of the loss occurred in the first few days and it was found to be more rapid the younger were the leaves.W. G. Does Potaseium Participate in the Building Up and Degrada- tion of Carbohydrates in Higher Plants 3 JULIUS STOKLASA and E. SENFT (Zeitsch. kandw. veys. Oesterr. 1912 15 711-736).-It is found that by the action of ultraviolet rays on nascent carbon dioxide and hydrogen in the presence of potassium hydroxide a photo- synthesis occurs with the formation of formaldehyde and that the latter subsequently condenses to furnish sugars ; the reduction of carbon dioxide in the cell does not take place in the absence of potassium hydrogen carbonate even in the presence of nascent hydrogen ; and formic acid (which is subsequently reduced) is also found to be one of the products of this reaction.E. M. G. M. Enzyme Synthesis. 111. Diastase and Starch of Plant Tissues. HAROLD C. BRADLEY and E. KELLERSBERGEH (J. Biol. Cham. 1913 13 425-430).-With some exceptions the results in this series are more favourable to the view of enzyme synthesis in the tissues for no tissues which contain starch are destitute of diastase although many tissues which contain diastase are free from starch. W. D. H. Occurrence of Arsenic in the Vegetable Kingdom. F. JADIN and A. ASTRUC (J. Pharm. Chim. 1912 [vii] 6 529-535).-The occurrence of arsenic in the vegetable kingdom appears to be general as the authors have detected its presence in some sixty-seven different kinds of vegetables fruits cereals plants parasitic plants fungi etc. VOL. CIV. i. ri. 234 ABSTRACTS OF CHEMICAL PAPERS.The quantity of arsenic found per 100 grams of substance varied from 0.008 mg. in dates to 0.266 mg. in radishes. Parasitic plants contained arsenic even although they were not in direct contact with the soil but there was no relation between the amounts of arsenic in the parasite and its support. Plants belonging to the same family do not in- variably contain similar quantities of arsenic but in the case of one and the same plant the portions containing chlorophyll contained more arsenic than tho parts not exposed t o light. It is pointed out that one of the sources of the arsenic found in animal organs lies in the vegetable substances consumed as food. w. P. s. Stimulative Action of Manganese and Copper Sulphates on Plants L. MONTEMARTINI (Bied. Zen&.1913 42 65; from #tax. spcr. agrar. ital. 191 1 41 564).-Manganese and copper sulphates absorbed from aqueous solutions stimulate respiration the effect varying with different plants. Vine plants are stimulated by 0.001% manganese sulphate whilst greater concentrations are injurious and are injured by 0.01% of copper sulphate. Garden beans and still more potatoes leaves are more resistant and more stimulated. N. H. J. M. Demonstration of Carotinoids in Plants. Separation in Crystalline Form. C. VAN WISSELINGH (Proc. K. Akad. Wetensch. Anzsterclam 1912,15 511-526).-The various methods employed in detecting the presence of carotinoids are described. Indications were obtained that several distinct carotinoids frequently occur in plants. N. H. J. M. Demonstration of Carotinoids in Plants.Behaviour of Carotinoids towards Reagents and Solvents. C. VAN WXSSELINGH (PYOC. K. Akad. Wetensch. Amsterdam 191 2 15 686-692).-1n presence of carotinoids a blue coloration is produced by strong sulphuric sulphurous and aitric acids bromine water and strong hydrochloric acid with a little phenol or thymol; iodine dissolved in potassium iodide solution or chloral hydrate gives a green coloration. Two new reagents were also employed concen- trated solutions of antimony trichloride and of zinc chloride both in 25% hydrochloric acid which colour crystals of caratinoids dark blue. Lists of flowers arid other parts of plants which were tested with the different reagents are given. N. H. J. N. Demonstration of Carotinoids in Plants.Leaf of Urtica dioica the Flower of Dendrobium thgrsiflorum and Hematococcus pluvialis. C. VON WISSELINGH (Proc. K. Akad. Wetensch. Amsterdam 1912 15 693-700).-The flower of Dew drobiurn thyrsifiorum contains two carotinoids one of which of a reddish-orange colour is not common in plants and perhaps belongs to the xanthophylls. The examination of Haernatococcus pluvialis indicated the presence of a greater number of carotinoids than have hitherto been detected (compare Zopf Biol. Cents.. 1895 15 417 ; H. C. Jacobson Folia Microbiol 1912 1 24). N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULI'URE. i. 235 Mannitol in the Sap of Asparagus. E. BUSOLT (J. Landu.. 1912 60 393-396).-The mannitol in the sap of asparagus is produced by fermentation and is not originally present.N. H. J. M. Presence of Stachyose in the Haricot and in the Seeds of Some Other Leguminoseae. GEORGES TAFRET (Corrzpt. rend. 1912 155 1526-1528).-The author has isolated stachyose in a crystalliue form by means of its strontium compound from the haricot bean and the seeds of certain other leguminoses namely lentils clover gnlega lupin and the soja bean. In all cases sucrose was present as well. The lupeose obtained as an uncrystallisable syrup from haricots and lupins by Schulze was therefore stachyose in an impure state. KO stachyose could be isolated from pea-seed3. W. G . Presence of Adenine and Aspartic Acid in Mulberry Leaves. Z. MIMUROTO (J. Goll. Agric. Z.mp Univ. Tok?/o 1912 5 63-65).-From 500 grams of air-dried mulberry leaves 1.2 gram of adenine (as picrate) and 0.3 gram of aspartic acid were obtained.N. H. J. M. Action of Stimulants on Rice. MANUEL ROCAS (Bied. Zentr. 1913 42 41-42; from Philippine Agric. Poorester 1912 1 89),- Previous investigations indicate that there are no poisons which cannot act as stimulants on plants ; that compounds of gold silver platinum mercury tungsten palladium copper nickel cobalt boron tin cadmium tellurium arsenic iodine a.nd fluorine are poisonous whilst chromium manganese bismuth sulphur and magnesium are only poisonous under certain conditions. The following concentrations of the various compounds were found to be favourable sodium borate 1/1000 ; manganese sulphate 1/1000; ferrous sulphate l / l O O O ; ferric chloride 1/5000 ; copper sulphate 1/2000 ; nickel sulphate 115000 ; cobalt nitrate 1/10,000 and zinc sulphate l/lOOO mol.solutions. Mercuric chloride in 1 /50,OOO mol. solutions inhibited growth whilst ferric chloride and copper siilphnte (1/1000) are injurious and sodium borate ( I /loo) somewhat injurious. The optimum results for rice are generally much higher than previous experiments have shown for other plants. The experiments were however not made with water-cultures but in soil. Presence of Nicotinic Acid in Rice Bran. UMETARO SUZUKI and S. MATSUNAGA ( J . Colt. Agric. Imp. Uniu. Tokyo 1912 5 69-61). -Nicotinic acid was obtained from rice bran freed from fat by extracting with 80-85% alcohol. The acid had not previously been found in any vegetable substance. The yield of picrdte amounted to about 1 gram from 1 kilo.of bran. The Substitution of Different Chemical Elements for Zinc in the Culture of Sterigmatocystis nigra. MAURICE JAVILLIER (Compt. Tend. 1912 155 1552-1552).-The author has N. H. J. M. N. H. J. M.i. 236 ABSTRACTS OF CHEMICAL PAPERS. replaced the zinc in the culture medium of Sterigmatocystis nigra by a wide range of other elements and with the exception of one namely cadmium they were all without influence on the crop. While the addition of zinc to the extent of 1 in 10,000,000 produces a crop 6.2 times as great as in its absence the same concentration of cadmium produces a crop only 2.6 times as great and cadmium has a marked injurious effect on the sporulation. W. G. Volatile Aliphatic Acids of Corn Silage. ARTHUR W. Dox and KAY E. NEIDIG (J.Amer. Chem. Soc. 1913 35 90-93).-With reference to the work of Hart and Willaman (Abstr. 1912 ii 1205) on the volatile fatty acids and alcohols in maize silage the authors draw attention to their own paper on the subject (Iowa Agric. Exp. Sta. Research Bull. 1912 7 32). The results are in fair agreement except with regard to formic acid and methyl alcohol; in the latter investigation only traces of formic acid mere found and methyl alcohol was absent whereas Hart and Wiliaman found 17% of formic acid in the volatile acids and 21% of methyl alcohol in the alcohols. Certain sources of error are pointed out in the methods employed by H a r t and Willaman and it is considered that these may account for the discrepancies. E. G. Action of Long-continued Exclusive Manuring on Plants and Soils.S. GRAF RosTwoRowsKr (J. Landw. 1912 60,371-392). -The results of experiments with potatoes showed that when there is a tendency to leaf curl it is desirable to employ potassium salts in moderation. As regards the effect of manures on the composition of potato ash it was found that the ashes of potatoes from plots manured with potassium and with potassium + phosphorus + nitrogen were almost identical in composition and there was also no difference between the ashes of potatoes from plots manured with nitrogen and the unmanured plot. The composition of the ash of potato leaves varied considerably with different manures; potash varied from 5% (unmanured) to 33% (potassium manure) and lime varied from 21% (potassium alone or with phosphorus and nitrogen) to 41% (unmanured).Application of sodium nitrate resulted in a high percentage of sodium in the leaf ash. Notwithstanding the long-continued application of potassium manures the potash in the ash of the tubers never reached 60%. Experiments were also made to ascertain the effect of the long- continued manuring on the soil. Chemical and Physical Nature of ‘‘ Roterden.” EDWIN BLANCK (J. Landw. 1912 60 397-400).-A reply to Hissink (A. 1912 ii 981 ; compare van der Leeden and Schneider Internat. Mitt. Bodenkunde 1912 2 81). ARCHIBALD A. HALL (Proc. Univ. Durham Phil. SOC. 1912 4 228-229).-The author gives an analysis of a clay subsoil underlying peat from Duval in the great swamp of Florida and points out that the composition of this clay on which N.H. J. M. N. H. J. M. Analysis of a Florida Clay.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 237 vegetation is now growing under conditions which approximate to those of the coal age is very similar to that of a typical uaderclay underlying coal. F. B. Osmosis in Soils. Soils Act as Semipermeable Mem- branes. C. J. LYNDE ( J . Physical Chem. 1912 16 759-765).- The movements of water in soil have been attributed to gravitation capillary action and heat. To these must now be added osmotic pressure. Osmotic cells of the Pfeffer type were prepared as follows Glass tubes 150 mm. x 11 mm. diameter were closed at one end with botton cloth and wire gauze. A layer of sterilised heavy clay subsoil was deposited in each tube and consolidated against the cloth by centrifugal action.The tubes were filled up with 10% sugar solution or 10% potassium sulphate solution and immersed in distilled water. I n each case water diffused into the cells osmotically through the clay. The rate of diffusion inwards was considerably greater a t 24.5' than at 22.5'. It is probable that the solution leak outwards through the clay mas considerable. I. R. J. C. Osmosis in Soils. Soils Act as Semipermeable Membranes. 11. C. J. LYNDE and F. W. BATES (J. Physical Chem. 1912 16 766-781. Compare preceding abstract).-Three pairs of osmotic cells were prepared with clay subsoil as already described the layers of sterilised clay being 54 mm. 36 mm. and 18 mm. thick respectively. The solution filling the cell was the aqueous extract of the clay forming the membrane in each case.The cells were closed by rubber stoppers carrying capillary tubes. The predetermined capillary rise of each solution was deducted from the total rise the remainder being the osmotic rise. The osmotic pressures obtained with the thickest layers ok clay were the highest but the concentrations OC the soil solutions were also highest in these cases. On the assumption that the osmotic pressures should be equal to these given by solutions of potassium chloride of equal electrical conductivity the osmotic efficiency of the membranes was calculated to be only 2.5% (54 mm. membrane) 1.4% (36 mm.) and 1.0% (18 mrn.) the efficiency being roughly proportional to the thickness of the membrane. An experiment with a membrane of clay 108 mm. thick gave still higher pressures. It is calculated that about 2 metres thickness of clay would be a perfect semipermeable membrane.I n all cases the osmotic rise a t 36.5' was somewhat higher than a t 16.7O. The soil used in the above experiments had the physical composition sand 10*6% silt 50-4% clay 36*3% organic matter a*$./,. A number of soils containing 44-61% of sand and only l2-16% of clay failed to show any decided osmotic properties. It is suggested that osmotic effects play an important part in agri- cultural operations particularly on heavy clay subsoils. Tillage drain- age manuring and mulching by favouring bacterial action increase the proportion of soluble matter in the soil and therefore the amount of moisture which is raised osmotically through the subsoil.The samei. 238 ABSTRACTS OF CHEMICAL PAPERS. effect may be brought about by the addition of mineral fertilisers and such substances as gypsum and salt which are not directly plant foods. There may be other substances whichare not plant foods but might be beneficial as fertilisers from the osmotic point of view. R. J. C. Importance of the Error of Analysis in Questions Relating to the Nitrogen Economy of Arable Soils. THEODOR PFEIFFER and EDWIN BLANCK (Landw. Yersuchs-Stat. 1912 78 367-374).-A final attempt was made to obtain a satisfactory nitrogen balance with the experimental soils at Breslau. Six plots (9 sq. metres each) were selected which had given similar amounts of crops during two years and from each plot five samples of soil were taken. Ten or twelve nitrogen estimations were made with each sample.The experimental error was found to be +_0*00086 which would correspond with 25.8 kilos. of nitrogen per hectare to a depth of 25 cm. if the weight of the soil is taken as 3,000,000 kilos. or 32.2 kilos. if the total weight of soil is taken as 3,750,000 kilos. As this number has to be multiplied by three it would only be possible to show a difference exceeding 77.4 or 96.6 kilos. of nitrogen per hectare. With fewer samples or analyses the error would of coIirse be greater. It must also be borne in mind that the nitrogen of crops is not all derived from the surface soil but from the subsoil as well. N. H. J. M. Estimation of the Value of Plant Foods in Soils and Manures so far as Dependent on Solubility. J. G. MASCHHAUPT and L.R. SINNIGE (Bied. Zmtr. 1913 42 16-20; from Verslug. Landbouwkum?. onderxoek. R?jkslandbouwproefstut. 19 12 No. 1 I).- Single extractions of different phosphates with a definite volume of water containing carbon dioxide will not show the relative values of the manures. Better results will be obtained when succeosive extracts are made and it is probable that a method of continuous extraction in which the dissolved substances are at onceremoved will give better results than intermittent extraction. Repeated extraction with fresh amounts of citric acid solution will probably indicate the relative values of phosphates. As however carbon dioxide is the chief solvent a t the disposal of soil and roots it is to be preferred to citric acid. Antagonism between Anions as Affecting Ammonification in Soils.CHARLES B. LIPMAN (Cerntr. Bakt. PUT. 1913 ii 36 38%- 394).-Experimen ts in soils on the lowering of the toxicity of salts by the addition of other salts as measured by the amount of ammonia produced. The first series which deals with the antagonism between the salts of “white alkltli,” sodium chloride and sulphate showed that addition of sodium chloride (0.2%) to the soil reduced the amount of ammonia from 54.46 to 30.73 mg. whilst the further addition of sodium sulphate (0.3%) increased the amount to 37.1 mg. less effect being produced by smaller or larger amounts of sulphate. I n an experiment with sodium chloride and carbonate the ammonia was reduced from 41.75 to 22.05 mg. by 0.2% of sodium chloride; sodium carbonate in amounhs of 0.2% and more increased the ammonia N.H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 1. 239 production the greatest amount being 70.7 mg. with 0.7% of sodium carbonate in addition to 0.2% of chloride. Further experiments are described in which sodium sulphate and carbonate were employed. The results show that antagonism is shown most strongly between sodium carbonate and sodium chloride ; next between sodium carbonate and sodium sulphate and least between sodium chloride and sodium sul phat e. When 0.3 or 0*4% of sodium carbonate is added to soil containing 0.9% of sodium sulphate there is an increased toxic effect; when however the amount of carbonate is increased to 0.5% the toxic effect of the sulphate is reduced and with 0.6% of carbonate it is still further reduced.N. H. J. M. Influence of Organic Substances on the Decomposition and [Manurial] Action of Nitrogenous Compounds. MAX GERLACH and ALFRED DENSCH (Bied. Zentr. 1913,42,21-30 ; from Mitt. Inst. Lacndw. Bromberg 1912 4 %g).-Pot experiments in which slightly humus loamy sand manured with sodium nitrate both alone and with dextrose and straw respectively ; with an ammonium salt alone and with dextrose; and with dextrose and straw re- spectively was kept for two montbs after which the amounts of total nitrogen and the nitrates and soluble organic nitrogen were estimated. The results showed that the total nitrogen changed very little and indicated that the nitrogen added as ammonium salt and as nitrate was converted into insoluble proteins.The same soil was then utilised for a series of vegetation experi- ments from April 1909 to August 1911 during which time oats mustard rye mustard and wheat were grown. Dextrose and straw was always unfavourable to oats but were beneficial to next plants (mustard). The fiual results relating to nitrogen did not show any greater increase when dextrose was added than without. Nitrogen applied as nitrate showed no loss whilst application as ammonium sulphate resulted both in loss and gain. Straw alone and in conjunction with nitrate had only a slight effect on the total nitrogen. The results indicate that ammonium salts and nitrates are con- verted into insoluble proteins in presence of undecomposed organic substances and that the insoluble nitrogen compounds readily decom- pose into substances which plants can utilise.N. H. J. M. Relation of Active Potash to Pot Experiments. GEORGE S. FRAPS (J. Ind. Eng. Chern. 1912 4 525-526).-An account of pot experiments with representative Texas soils from which the conclu- sions are drawn that (1) the percentage of crops deficient in potash decrease with the increase of active potash in the soil ; (2) the percentage of crops injured by potash increase with the active potash in the soil; (3) the effect of fertiliser potash on the weight of the crop decreases as the active potash content of the soil increases; (4) the percentage of potash in the crop increases as the active potash in the soil increases; (5) the total potash removed by the crop Fromi. 240 ABSTRACTS OF CHEMICAL PAPERS the soil increases as the active potash content of the soil increases. The term “active potash” is applied to that which is soluble in N15-nitric acid.F. M. G. 3%. Effect of Sugar on the Fertility of Soils. THEODOR PFEIFFER and EDWIN BLANCK (Landw. Versuchs-Xtat. 1912 ’78 375-388).- The results of plot experiments in which oats beet and oats were grown successively both without and with sugar and phosphoric acid and with both sugar and phosphoric acid showed that the application of sugar was slightly injurious the erst year and resulted in a slight increase the second year. I n the third year there was no appreciable difference due to sugar. No evidence of increased fixation of nitrogen was obtained. N. H. J. M. Calcium Cyanamide. C. J. MILO (Chem. Zentr. 1912 ii 1054-1055 ; from Med.Proefstat. Java-Suikerind. 191 2 427-527). -When calcium cyanamide is used as a manure the lime is readily taken up and held by the soil but the nitrogen is not held so well as in the case of ammonium sulphate. I n spite of this no nitrogen is lost if the cyanamide is applied in the dry season and the soil is not heavily watered immediately afterwards and none is lost by volatilisation if the manure is properly applied. The nitrogen is utilised mainly by bacterial agency but is also absorbed in other ways. Comparison of calcium cyanamide with ammonium sulphate as a manure has not yet given definite results. Dicyanodiamide is not poisonous to sugar-cane and although calcium cyanamide shows some toxic effects it appears to be rapidly converted into harmless cyanamide in the soil. T. A. H. Behaviour of Calcium Cyanamide when Stored a n d under the Influence of Soil and Colloids. G. HENSCHEL (Bied. Zentr. 1913 42 33-34; from Cent. Bakt. Par. 1912 ii 34 279).-Dry sterilised soil or colloids decompose cyanamide more quickly than when not sterilised. Under sterilised conditions urea and dicyanodiamide are formed but no ammonia. Experiments with different soils showed almost complete agreement between the intensity of the decomposition when sterilised and the production of ammonia when not sterilised; an exception however occurred in the case of a sandy soil containing much humus which showed a strong colloid but feeble bacterial action. When cyanamide is stored a good deal of urea may be produced under some conditions ; different preparations show however consider- able differences both in this and other respects. No loss of nitrogen was ever observed the lower percentages of nitrogen after storing being due to absorption of water and carbon dioxide. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9130400228

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

MINE KALOGICAL CHEMISTRY. M i n e r a l 0 gic a1 Chemistry. ii. 229 Asphalt Veins in Quartz-Porphyry near Eeidelberg WILHELM SALOMON (Zeitsch. lii-yst. Min. 19 13 5 1 634 ; from Ber. Oberrhein. Gaol. Vw. 1909 42 116-123).-A black asphalt with conchoidal fracture occurs with minute quartz crysials in crevices in the porphyry of Dossenheim. Analyses by Ebler gave C 77-8-79.8; H 7'7-89; N 0-2.7; S 2'2-2'8; ash 1.0%. Opti- cally active substances being absent there is no evidence of organic origin; and it is not improbable t h a t the material has been deposited by thermal waters. L. J. S . [Minerals from Sierra Mojada Coahuila Mexico.] FRANK R. VAN HORN (Arner. J. Sci. 1913 [ivl 35 23-30). -A description is given of 21 mineral species found i n the Veta Rica mine. The ores of silver lead and copper occur in a gangue of gypsum and barytes near the contact of Cretaceous limestone with rhyolite.The following analyses by N. A. Dubois are given I of argentite; 11 of proustite Ag. Cu. As. Sb. S. Total. Sp. gr. I. 86.18 0.70 - - 13.18 100.06 7'40 11. 64'65 0.70 15.25 trace 0.18 1C0.78 5.60 YOL. CIV. ii. rJ. J. s. 16ii. 230 ABS'I'RACTY OF CHEMICAL PAPERS. The Bauxite Question. FRAN TUCAN ((7pngr. -!in. 1913 65-68).-A discussion of previous papers (A. 1912 ii 357; this vol. ii 64 69).-Bauxite is a mixture of minerals and cannot be regarded as a definite aluminium hydroxide. A4dsorption com- binations of colloidal aluminium hydroxide and hydrated silica cannot always be distinguished by chemical and microscopical means from homogeneous materials. Some Minerals from Tuscany.ERNESTO MANASSE ( J d r b .l/i)t. 191 2 ii Ref. 343-346; from Mem. Soc. Toscanu Sci. Nat 1911 27 19 pp.).-Millerite a species not before recorded lroiii Tuscany occurs sparingly as fine needles with marcasite in a calcite vein intersecting black clay-slate in the antimony mine of Cetine cli Cotorniano. Turgite occurs in the Rio Marino mine a t Rosseto Elba as tliiii crusts and stalactites on linioiiite. It is fibrous steel-grey aiid lustrous and has previously been inistakeii for goetliite. Analyses I-TI1 (I fibrous-lamellar ; 11 iibrous-radiated ; III stalactitic). Formula H,Fe,O,. Goethite is found in an iron iiiiiie a t C a p d'Arco Elba as thin fibrous crusts on limonite. Analysis IV. k'oririiila HFeO I. 2'65 92.60 5-56 100'81 -_ 11.2'11 92.04 5 -68 99.73 4'34 111. 1'18 93 54 4 '95 99.67 - 11.. 3-21 87-10 10*11 100'42 4 '17 Zincif erous rliodochrosite (" zincorhodochrosite ") as imperfect crystals and rounded masses of a rose-red colour and vitreous lustre 011 the turgite (see above) from Rosseto Elba. Analysis V corre- sponding with 5076 MnC03 45% ZnCOg L. J. S. SiO,. Fc,O,. TI,O. 'l'otal. ep. pl-. GO?. FeO. MnO. %no. CttO. Q O . Total. Sib. gr. Y. 36.60 0-66 30.17 31.03 2-10 0.05 100-61 3-86 Jarosite occurs a t Capo d'Arco Elba as a thin encrustation on and as small nodules in limonite. It is brown with an adamantine lustre and under the microscope the minute rhombohedra1 crystals are transparent and gold-yellow. Analysis VI corresponds with 91.17% jarosite the remainder being admixed quartz and limonite.Jarosite [natrojarosite A. 1902 ii 6661 occurs also a t Capo Calamita Elba as a thin encrustation on limonitic ores. Analysis VII corresponds with 95.33% jarosite SO,. SO,. Fe,O,,. X20. Na,O. H,O. Total. VI. 2-16 28.71 48'68 7-52 1.77 [10*86] 100-00 7-11. 1.20 31-61 50*28 0.98 5.55 [10'38] 100-00 Aluiiogeii froiii Vigneria Elba is white when pure but fre- queiitly green from admixed inelanterite and ilileite ; it also eiicloses sitiall crystal3 of iron-pyrites. Aiialysis VIII corresponds wit11 88.37% of alunogen A12(SO& 1 6H20. Fibroferrite from Capo Calamita Elba is finely fibrous with yellowisli-green colour and silky lustre D 2.08-2.09. Analysis IX corresponds with Fe20(S0,),,10H,0. A t 98-looo 23.02% waterMINE RA LOO l C AL CH KMlS'l'RY.ii. 231 is expelled and a t 285O 35*60% with a gradual change in the optical characters. All the water is re-absorbed from a nioist atmosphere and it is therefore regarded as water of crystallisation. Fibroferrite also occurs at Vigneria and act Capo d'Arco in Elba Insol. in SO,. A1,0,. Fe,08. FeO. MgO. K20. Na,O. H,O. water. Total. VIII. 57-80 14.30 0.42 2-16 trace 0.45 0'21 44'31 0.24 99.89 IX. 32'03 - 30.58 1.50 - - - 36.40 - 10051 L. J. S. The StMsfurt Deposits. MICHAEL R~ZSA (Zeitsch. XlektrocJmn. 1913 19 109-115).-This paper is divided into two' parts the first of which is theoretical and shows that tlie nature of the Stassfurt deposits is iiot in accord witli the theory "that the area over wllicll the deposits were formed was separated froin the ocean by a bar,'' lmt rather that irregular floods took place and that t,hese with the evaporation periods are capable of explaining the peculiarities of the deposits.The layers of hard salt are held t o he the product of changed deposits. The second part of the paper gives a comparative table of the layers found in tlie Kieserite- Carnallite region and the hard salt region. The relative thicknesses of the various layers are indicated. Question of the Identity of Podolite and Dahllite. VLADIMIR TSCHIRVINSKI (Certty. &fin. 1913 97 - 102). - Podolite described as a new mineral by Tschirvinski (A 1907 ii 481) lias been suggested by Sclialler (A. 1910 ii 1076) t o be identical with clahllite. The following new analysis of a podolite concretion from the village of Krutoborodinzy govt.Podolia Russia agrees witli tlie formula previously given with the addition of a little water namely 3Ca,(PO,),,CaCO,,~H,O Water of Hygro- Undeteimiiied Organic crystal- scopic (hI,O Fe,O CaO. P,O,. CO I$'. SiO,. matter. lisatiou. water. alkalis etc.) 50*72 37 08 4-32 0.29 4.18 0.52 1.16 0.37 C1.361 Analyses of dahllite on the other hand lead to the formula 2C'~(PO,),,CaCO,,nH~O where q? = 4-1. The t w o minerals are tlieref ore regarded as being chemically distinct. I n physical charac- ters they however show little difference ; but here podolite approaches f rancolite and staff elite more nearly than dallllite. Mineralogy of the [Russian] Phosphorite Deposita. J . F. S. L. J. S. JAKOV SAMOTLOV (Jahrb. Min. 1912 ii Ref. 338-339; from Arb.Komm. ilfoskawsr Landw. Inat. Erforschung der Phosphom'de I 9 1 1 3 67 1-690) .-The f ollowiiig aiialysis is of an unweathered phospllatic nodule of Jurassic age from a boring a t Moscow corresponding with Ca?,(PO,) 46.96 CaF 3-74 CaCO 10.41 3fgC0 1.71% CaO. MgO. AI,O,. FezO::. &Iii,O,. K20. Na,O. Pz05. CO,. 1:. 39.08 0.82 1.70 1.67 trace 0.92 0.99 21.51 5 47 1.82 Loss Organic Total SiO,. FeS,. on ignition. matter. Insoluble. (less 0 for F). 0'47 2-52 3.91 0'61 19'43 100.16 16-2it. 232 ABSTRACTS OF CHEMICAL PAPERS. According to tlieir external appearance Russian phosphorites are divisible into two classes (1) Kodules with a dark lacquer-like surface eiCher polished or dull. These show an increasing amount of pliospliate from the interior to the exterior; for example a iiodule from die village Wopilowka govt.Pensa contained in tlie interior portion P,O 33-89 and insoluble material 18*22% and in the exterior portion P?Q5 26.81 and insoluble 4.55;. (2) Nodules with a lig2it-coloured grey earthy exterior due t o chemical alteration ; here in the exterior portion tlie phosphate is reduced in amount and tlie insoluble material increased. Occurrence of Scorodite in Rhodesia. A . E. V. ZEALLJLY (Smth African J. Sci. 191 1 8 133-1 34).-Compact o r crystnllised scorodite occurs together with mispickel limonite and quartz in several auriferous districts in Rhodesia. A mixed sample of aiiiorphous and finely crystallised green scorodite from Gwanda gave on analysis by J. B. Bull As.&>,. Pc,O,. H@.Total. 50.53 33.49 15 '98 100'00 L. J. S. L. J. 8. Uranium Minerals from Prov. Itasy Madagascar. ALFRED J,AVROIX (Bull. Soc. f r a q . Min. 2912 [ i . ~ . 19131 35 233-235).- The new species betafite ( A 1912 ii 567) has been found as fine crystals (octahedron with rliombic dodecahedron) a t some other localities in Madagascar. Analysis I by Pisani is of betafite D 3.75 from Ambalaliazo. The mineral is readily attacked by acids giving a yellow solution the iiraniuni being present as UO (not as UO as previously stated) C'b20> Ta20 ,. Ti()?. CiiO> Ttb02. U'; (Ce,La,Ui)203. A1&. Fe20;. MgO. CaO. PbO. HzO. Total. I . .;IW 1.00 l b ' 9 0.37 1.12 27.1; 1.00 1'50 0.50 trace 3.12 0.3s 1 2 . 3 !1'1%1 Euxenite occurring as crystals in association with betafite and green apatite in pegmatite a t Andibakely gave analysis 11 by l'isani ,.TiO? I'liCl2. U02. (Y,Er)20c;. Ce20;. (La,lji)zO;. AlzO,:. Fe203. CaO. n20. Total. 11. 33.00 3.70 :5 00 20'50 0.40 1.70 1'31 1-09 4.01 4.32 9'l.lO L. J. S. The Chemical Constitution of the Kaolinite I\bolecule. 11. JOSEPH W. MELLOR iind A. D. HOLDCROFT (7kUn8. E72g. Ceramic ,Sot. 1911-12 11 169-1i2 Compare A. 1911 ii 607).-The composition of a specinien of crystalliiie kaolitiite is as follows Loss 011 SiO,. TiO,. h1,0,. I~P~O,. MgO. CnO. K20. Na,O. ignition. 42 04 - 38% 0'14 0-01 0.38 0.18 0.13 15.94 The loss on ignition included H,O 14.44 and C 0.80%. The heating curve was determined and also the loss of water occurring a t different temperatures tlie results showing that there is no definite temperature of dehydration even with well-defined crystals.MINERALOGICAL CHEMISTRY.ii. 233 The kaolinite used was obtained from the coalfield of Glamorgan- shire and hzs been described by Butler ( M i t t . May. 16 No. 73). T. S. P. Mineralogy of Renfrewshire. ROBERT S. HOUSTON (Tmns. Paisleg Nat. SOC. 1913 1 1-88).-A review is given of the literature relating to the seventy-six species of minerals that have been found in Renfrewshke and several new analyses are given (compare A. 1909 ii 63). Cn. Fe. CuO. Fe,O,. CaO. MgO. Insol. Total. 95'61 0.56 1'02 0.80 0.58 0'28 1.20 100'06 11 olivine from Gleniffer; 111 ferrite from Gleniffer; IV-VI prehnite from Boylestone ; VII-IX analcite from Boylestone ; X analcite from Bardrain ; XI-XII thomsonite from Boylestone ; XIII-XV saponite from Boylestone ; XVI saponite from Kil- barchan ; XVII,.saponite from Bridge of Weir ; XVIII saponite (variety bowlingite) from Boylestone. Analyses are also given of impure samples of clialcocite iron-pyrites quartz wad and chalybite Analysis I is of native copper from Boylestone SiO,. Al,O,. F'e,O,. FeO. RlnO. CaO. MgO. 11. 43'31 15.46 6-72 5.54 - 17-82 8-87 111. 15-68 5-40 61.47 - trace 2-03 10.41 IV. 42-02 27.92 trace - - 23.82 1.23 VII. 54 42 23.02 - - - 0.95 0.26 IS. 54.22 23-42 trace - - 0.42 0.38 S. 55.31' 22.89 - - - 0.63 0'13 XI. 33.86 32.24 - - - 16-22 trace XII. 41-45 27'71 - trace - 18.61 0'51 XIII.* 33.96 16.14 8'00 8.93 - 7-10 7-49 X1V.f- 36.65 5-61 4'69 5-33 - 4-01 17.29 XV. 32.62 17'82 3-70 8-21 0.62 - 21 '26 XVI.85.02 22.82 4'16 3.55 - 1-22 23.99 XVII. 40.43 9-33 1'12 3-74 - 2-06 23.36 XVIII.: 29.71 22'01 1-60 15'41 traw 4'19 15'39 * Also GO 3'17. j- Also CO 3.15. : V. 40.22 24.64 4.22 - - 25.02 - VI. 42.25 27.40 trace - - 25'99 - VJII. 52-83 24'69 trace - - 0.33 - Origin of Moldavites and similar GEOR& P. MERRILL (Jahrb. illin. 1912 ii U.S. Nat. Mus. 1921 40 481-486).-A meteoric origin having been ascribed to the so-called tektites (a general term t o include moldavites billitonites and australites) the author has examined a series of obsidian pebbles from various localities in No'rth and South America and froin Iceland. These are of undoubted terrestrial origin and they show the sa.me peculiarities of surface markings as the typical tektites. The following analysis of ail obsidian pebble from Cali dep.Cauca Colombia is compared with published analyses of tektites from wliich i t does not appreciahly differ Qi02. TiO,. Al,O,,. l:e,O,. hCc0. C'aO. Na,O. K,O. H20. SO,. Total. $ 5 3 7 trace 14-36 0.22 0.29 nil 3-96 4.65 0-33 0-23 99.99 1,. r J . S. 1 Na,O. H,O. Total. Sp. gi.. 0.84 1-86 100'42 - 5-04 100.03 - - - 5-40 100'39 2.885 1-16 5.20 100-46 2.918 3.87 99.51 - 13.36 8-20 100.21 - 13.68 8'20 100.32 - 3.63 14'20 100'15 - 3-31 12-80 99.89 - 0.98 13'62 99.39 - - 12'92 8'60 99'43 2.165 23-49 8'40 100.85 2.252 2.55 20'44 99 72 2.224 2-41 13'91 10055 2'426 2.37 17.10 100.01 2.239 0.40 9.14 100'30 - 11.49 99.80 - - Plso CO trace. L. J. s. Sporadic Glasses. Ref. 351 ; from PTOC.ii. 234 ABSTRACTS OF CHEMICAI PAPERS. Cbloritoid (Ottrelite) from the Apuan Alps Tuscany.ERNESTO MANASSE (Jahvb. Min 1912 ii Hef. 329-330 ; from Mem. SOC. Toscnncc Sci. Nut. 1910 26 23 pp.)-The ottrelite of the ottrelite- schists of the Apuan Alps is proved on optical and chemical grounds to be identical with cliloritoid. Those analyses of ottrelite which show an excess of silica may be explained by the presence of admixed quartz. The optical characters are stated in detail and the following analyses are given of ottrelite from I Stazzema; 11 Camporaghena near Fivizzano ; 111 Corchia. These agree with tlie cliloritoid formula H,O (Fe,Mg)O,(Al,Fe),O,,SiO,. The ratios of Fe,O, A1,0 range frow 1 10.81 t o 1 23.99 aiid of MgO FeO frolu 1 3.85 to 1 7-31 YiO,. TiO,. A1,0,. Fe?O:,. VeO. hlnO. CaO. hlgO.H,O. Total. Sp. gr. I. 24-37 trace 37-03 5 36 21.91 0.52 0.16 4.32 7-16 100.83 5-44 11. 26-07 trace 37-01 2-97 24-76 trace 0.12 1-90 7’03 100 86 3‘51 111. 25.36 tmrr 33-99 2.54 23.06 trace 0.24 3.16 7-28 100.63 3.56 JJ. .J. S. Composition of Some Minerals of the Chloritoid Group. ERNESTO MANASBE (J~1/~rb. Min. 1912 ii Ref. 330-333 ; from.Proc.- verb. SOC. Toscana Sci. Nut. 191 1 20 29-42).-Previous analyses are quoted and discussed; tlie variations shown by tliem may be explained by the impurity of the materials analysed. The following new analyses are given of carefully selected material I Masonite from Natick Rliode Island. 11 Sismondine from Champ de Praz Aosta Piedmont. These two analyses agree closely with the formula H2R”R”’,Si0,. Associated with the sismondine is a chloritic mineral which gave analysis 111 corresponding with H,,Mg,,Fe,Al,Si,O,~,.IV Ottrelite from Ottrez Ardennes. Under the microscope this material is seen to contain a considerable amount of quartz together with small quantities of magnetite and ilmenite. Deducting 24.38% of admixed quartz the formula agrees with t h a t given above; corrected D 3.44. V Ottrelite from a quartz-phyllite on $It. Fenouillet near Hykres (Var) contains an excess of 7.65% silica as admixed quartz; corrected D 3.68. VI Venasquite from Vknasque Pyrenees contains 17.980, admixed quartz; corrected D 3‘56 SiO,. A1,0,. Fe,O,. FeO. MnO. I. 24.56 3 4 5 7 5-93 2 7 2 0 1-14 11. 25.36 42.58 0-72 18‘02 0.53 III.* 28’06 21’25 - 9’75 - IV. 42.93 29.60 0’86 15-43 3.75 \’.t 29.71 34.35 4’71 20‘33 1-41 \.I.37-87 31.12 3’25 20.48 0’62 * Also Na,O 0.55 ; K,O 0’30. CaO. NgO. H,O. Total. Sp. gr. - 0.36 6’64 100.40 3-54 G.18 5.96 7’50 100.85 3‘45 - 2‘12 5’48 100.17 3’25 1.16 1‘69 6-64 100.00 3.60 trnce 1’44 5-80 100*58 3’40 - 27‘46 11-78 99.15 - j- Also TiO trace. L. J. S. Minerals from Ambatofotsikely Madagascar. ALFRED LACROTX (Bzlrl. SOC. .franf. Min. 1912 [i.~. 19131 35 231-233).- The yegiiiatites a t this locality situated 217 kin. west of Miandrarivo coiit!ain abundance of ainpangabeite (,A . 191 2 ii 567) fine crystalsMT NERALOalCAL CHEMISTRY. ii. 23.5 of monazite (A. 1913 ii 69) and fragments of orthite. This orthite D 3.43 is rich in thoria; the following analysis by Pisani corresponds with the formula [(Si,Th)04],,(Al,Ce,La,Di,Fe),(Ca,Fe,H2)10 SiOp ThOy.A1203. Ce2O:j. (La,Di)zO:+ (Y,Er)20* Fe&+ Fe3. MttO. CaO. H,O. Total. 32.00 5.60 12.40 9.0s 7.3s 0.40 4-.-,0 I l . t i O 0 . x 13.iS 1.24 loo's:! L. J. S. Lavas from Central Madagascar. ALFRED LACROIX (Compl. ?-e.nd. 1913 156 175-180).-Twenty-seven detailed analyses by Hoiteau are given of rocks froin tlie volcanic districts of Aukaratrn. ~ i t d Itasy. They raiige froin rhyolite with 71.45% silica t o nq) heli ni te with 38.74%) silica. 1 J I S. Ilmenite from the Quarries of Potstone at Sasso di Chiesa (Val Malenco). I,. TV~AGISTRETTI ( A t l i 8. Accad. Lincei 1912 [v] 21 ii 761-7G7).-A crystallographic study of tliis mineral wliicli lias 1) 4.55 and tlie following composition [Witli A. MORESCHI] SiO,. TiO,. Fe,O,. Fro. MnO. A1,O::.MgO. Total. 0.65 4i.20 33-50 15.00 1'31 1.00 0.90 99-59 R. V. S. Meteorite of Gumoschnik Bulgaria. G. BONTSCHEW (Jahd. 1912 i i Ref. 354-355 ; from Periodl6eoko spisank? SoJia 1910 71 373-390).-A meteoric fall was observed on April 28th 1904 near the village of Gunioschnik i n the Trojan district. Five or six stones with a total weight of 5669 grams (the largest 3815 grams) were picked up. The material consists of olivine enstatite augite iron pyrrhotite cliromite and a fine-grained to compact mass of undetermined nature. Cliondrules of olivine and enstatite are set in a brecciated groundniass. The following analyses are o f I the magnetic portion; 11 the non-magnetic portion; and 111 the bulk analysis. The amount of nickel is unusually low Lost on Fr Xi. F e & .YiOz. Crz03. Fe203. FeO. MnO. CaO. MgO. igiid Total. v / 1. 117.141 2.13; 2.0% 29.310 0'1%1-I 11. - - - 45.9SO O * O W 2Pf+34 4*OF? O*IOO 2.41iO 24.470 - 100'OiS 111. i - b . ~ ~ i ~ o ~ G T 0.453 4 2 3 ~ 3 0'04s 1 7 . q ; ~ 3.20; 0.147 I .oiti isms 0.103 10om-1 L. J. S. Existence of Nahral Ozonised Waters and Probable Theories of the Phenomenon. The "Acqua Forte" of the Bagnore of Monte Amiata. RAFFAELE NASINI and C. PORLEZZA ( A t t i R. Accad. Lincei 1912 [v]~ 21 ii 740-750 803-811 ; Chem. Zeit. 1913 37 129.-'I'he authors have discovered two nrrtiiral waters wliicli contain ozone as a normal constitueiit aiid in such quantity as t o smell plainly of tlie gas. The acid waters of the Bagnore of Monte Ainiata are highly ozoiiised aiid those of the springs of the Baqnnli i n t,lic same region i n srn:tllcr t l e g ? ~ .Tlieii. 236 ABSTRACTS OF CHEMICAL PAPERS. data in the present paper refer to the former water. I n one litre of it a t 21*5O the following gases are dissolved :. carbon dioxide 543.72 c.c.; oxygen 1.26 c.c.; ozone 0.135 c.c.; the inert gases were not determined. The gases arising from the water a t the source have the following composition (per 100 c.c.) carbon dioxide 93.45 c.c.; oxygen and ozone 0.15 c.c.; residue unabsorbed 6.40 C.C. ; the ozone amounted to 0*00064 C.C. Dispersion experiments showed that the air above the well contained 1838 ions per c.c. whilst the number in the ordinary air of the locality did not exceed 1000 per C.C. From experiments with water in which known amounts of ozone had been dissolved i t was found that the odour is still perceptible when 0.037 C.C. of ozone is dissolved in one litre of water and the limit of sensibility of the iodide starch reaction is not reached a t 0.02 C.C. per litre. For this and other reasons the authors are sceptical concerning the few other alleged ozonised waters mentioned in the literature. As possible explanations the authors suggest the autoxidation of ferrous salts either alone or in conjunction with f erruginous micro-organisms. Tlie water con- tains 0.001565 gram of iron per litre probably in the form of ferrous hydrogen carbonate which is known to be an autoxidisable substance. Attention is drawn t o the possible therapeutic value of the waters. n. v. s.

ISSN:0368-1769    

DOI:10.1039/CA9130405229

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 236 ABSTRACTS OF CHEMICAL PAPERS. An alg tical C hernia t ry . Hempel Double Pipette Modified to Facilitate Filling. ALEXANDER CHARLES CUMMING (J. SOC. Chem. Ind. 1913 32 9).-A side-tube opening vertically is fitted to the second bulb from the burette and this enables the pipette to be filled as easily as a simple pipette. The pipette is first filled with an indifferent gas by passing i t through whilst the additional side-tube is closed with a cork. The reagent is then introduced through the side-tube and water is poured into the two last bulbs through the exit-tube from the last bulb t o form a water seal. The side-tube is then closed with a well-fitting rubber cork. Micro-chemical Reagents. WI~HELM LENZ (Zeitsch. anal. Chen~. 1913 52 90-99).-Directions are given for preparing absolutely pure reagents (acids ammonia alcohol pfatinum chloride ammonium uranyl acetate ammonium cobalt thiocyanate metallic tin and zinc) for use in micro-chemical testing.Glass utensils and slides should not be used. The reagents should be kept in flasks made of fused silica; the distilled water T. S. P. should be stored i n a preferably gilded silver flask. L. DE K. Apparatus for Electrolytic Estimations. FELIX CHANCEL (BUZZ. SOC. chim. 1913 [iv] 13 74-76).-The bottom of a tent*- tube 30 x 125 mm. made of thin Jena glass is pierced by aANALYTICAL CHEMISTRY. ii. 237 platinum-iridium wire 1 mm. in diameter and 50 mm. long of which 40 nun. are inside the tube and 10 mm. outside. This serves as an anode and is connected by a clip with a silver or copper wire bent twice at right angles and then brought parallel to the length of the tube and secured to the upper portion of the latter where when the apparatus is in use i t is connected to the positive pole of the ba~ttery.The cathode consists of a cylinder of platinum gauze 20 x 30 mm. hung inside the tube by a platinum wire 110 to 120 mni. long which is attached to a support in the usual way. I n use the tube is closed by a watch glass suitably pierced t o take the suspending wire. T. A. H. The Use of an Extract of Red Cabbage as an Indicator for the Measurement of the Hydrogen Ion Concentration. L. E. WALBUM (Biochem. Zeitsch. 19 13 48 291-296).-'1'tie alcoholic extract of red cabbage can be used as an indicator for concentrations between p = 2.0 and p = 4.5 within which limits results a4greeing closely with those by the electrometric method can be obtained.Good results are obtained even in the presence of relatively large amounts of proteins which are not affected by the presence of salts (even 4M-sodium chloride) toluene or chloroform. S. B. S. Estimation of Moisture. GEORGE N. HUNTLY and JOHN H. COSTE (J. SOC. Chem. Ind. 1913 32 62-67).-1n coasider~ng tho question of the estimation of moisture in commercial products the authors mention in some detail the various methods which are employed for the purpose. These methods are divided into three groups namely Utlact methods. 1. Water driven off by ignition condensed in part of the ignition tube and weighed directly. 2. Substance heated in a current of dry gas or in a vacuum water vapour collected in calcium chloride or sulpliuric acid and .weighed.3. Substance mixed with an excess of a volatile non-miscible liquid such as xylene distilled and the water measured under the hydro- carbon layer. 4. The substance is heated directly to 130° by a vapour (high pressure steam) jacket the steam given off condensed and measured. Gasometric me/hods. 5. The substance is mixed with calcium carbide ; acetylene measured. 6. The substance is mixed with magnesium methyl haloid in the presence of a suitable dry solvent; methane measured. 7. The substance is treated with sodium ; hydrogen measured. Indirect methods. 8. Estimation of the loss of weight by heating t o a definite or indefinite temperature (the usual method). 9. Prolonged exposure in a vacuum in the presence of sulphuric acid either at ordinary or a t a higher tem- perature. Most of the methods are trustworthy under particular conditions and when they are applied t o suitable substances Special attention is given to the last two methods mentioned and it is recommended that care should be taken t o have the temperature inside the ordinary drying oven as nearly as possible looo; for general work a few degrees higher will be found to be more satis- factory.I n the method where the substance is dried iii a vacuum,ii. 238 ABSTRACTS OF CHEMICAL PAPERS. the pressure should be as low as possible uid the exposed surface of the sulphuric acid large. When applied t o coals this method yields results which are invariably higher than those obtained by drying the coal in a water-oven.w. P. s. Estimation of Moisture in Organic Substances. F. H. CAMPBELL (J. SOC. Chem. Ind. 1913 32 67-'70j.-Tbe calcium carbide method is recommended for the estimation of moisture in such substances as coal coffee cocoa tea butter etc.; in the process employed by the author the amo~znt of acetylene evolved is estimated gravimetrically ;tiid an apparatus is described for this purpose. The results ohtnined agree closely with tliose found by ihying the substances iuitier reduced pressure over sulpliuric acid. Estimation of Moisture in Foods and Other Organic Substances. WILLIAM P. SKERTCHLY (J. SUC. Chem. Ind. 19 13 32 70).-Resixlts are recorded which show that many organic substances yield more moisture when dried under reduced pressure in the presence of sulphuric acid than when they are heated t o constant weight in the ordinary steam-oven.The difference was most marked in the case of farinaceous substances amounting in one instance (arrowroot starch) to 2%. It was also found that flours meals etc. increased in weight when heated for more than two hours a t looo. w . P. s. JOSEPH PIERAERTS (Bull. SOC. chim. 1913 [iv] 13 104-109; Bdb. Assoc. chim. Sucr. Dist. 1913 30 401-406).-When 1 C.C. of a 0.5% potassium chlorate solution is treated with 5 C.C. of a 2.5% aqueous aniline solution and 6 C.C. of concentrated hydrochloric acid a red coloration is obtained which changes in a few minutes to blue. The test is not t o be trusted when the potassium chlorate solution contains less than 0.1YA of the salt but 0.05% solutions yield a coloration when the aniline solution is prepared with 50% alcohol.The blue coloration may be extracted from the mixture by shaking with chloroform ether or amyl alcohol. The test is useless in the presence of iodates as these yield a similar coloration t o that obtained with clilorates. W. P. S. Disturbing Influence of Alcohol on Various Reactions. ERNST SALKOWSKI (Zeitscl,. p l p i o Z . Ghenz. 1913 83 164-165).- When half a volume of alcohol is added to a potassium iodide solution to which chloroform a few drops of sulphuric acid and a solution of nitrite are also added instead of the characteristic violet colour being formed in the chloroform layer after shaking an orange or reddish-yellow coloration is obtained.Methyl or amyl alcohol ethyl acetate and acetone have a similar disturbing influence. The cliaracteristic colour reaction of phenol with ferric chloride is also entirely altered by tlie presence of alcohol a dirty green or ycllow coloration heiiig oi)t,;tined instead of the characteristic lllne. w. P. s. Colour Reaction of Chlorates. E.F. A,AN A T,YTlCA L CHEMISTRY. ii. 939 Estimation of Hydriodic Acid in Tincture of Iodine. ANDHP LRCL~CRE (J. Pharm. Chim. 1913 [vii] 7 68-69).-ln general iodine is estimated in tincture of iodine by titration with sodium thiosulphate and then the liydriodic acid is determined by adding potassium iodate solution and titrating the iodine set free. It is pointed out that this last estimation is subject to two sources of error.I f the iodate solution used is not exactly neutral an excess of iodine is liberated. Further tlie amount of hydriodic acid is frequently calculated from the equation HIO + 5HI = GI -t- 3*H20 instead of from the relation KIO + 6HI = KT + 313,O i- G I which correctly represeuts what takes place. A New and Delicate Test for Oxygen. KARL BINDER and RUDOLF F. WEINLAND (Boy. 1913 46 255-259).-The authors bave previously shown that tlie deep retl soliltions formed wlieri ferric salts and catechol are mixed i 11 alkaline solution contain the salts of an acid I13[Fe(C&340.,),.~1 (conipare A 1912 i 184 445). They have now found that if ferrous sulpliate is used instead of ferric salts no colour is produced but that oxygen is very rapidly absorbed from tlie air giving tlie red colour.The formation df this red colour is an exceedingly delicate test for oxygen and the authors have devised a special apparatus in which the respsctivc? solutions can be prepared and mixed in an atmosphere of oxygeii- free hydrogen and then brought into contact with tlie gas which is to be tested for oxygen. The authors were able to detect oxygeij in the Tubingen coal gas and in carbon dioxide used in the esti- mation of nitrogen by Dumas’s method. The alkaline solution of ferrous sulphate and catechol can be used in the Heinpel pipette for the absorption of oxygen in gas analysis. For quantitative absorption it is necessary t o shake vigorously for five minutes. Estimation of Available Oxygen in Persalts and Washing Powders with Titanium Trichloride.LUDWIG MOSER and F. SEELING ( Z o i f s c h . (mat?. Chem. 19 13 52 7O-S5).-Perborates may be titrated by dissolving about 0.25 gram of the salt (or about 3 grams of washing powder) in water 25 C.C. of dilute sulphuric acid are added and while passing a current of carbon dioxide the liquid is titrated with standard titanium trichioride the end point being shown by the disappearance of the yellow pertitanic colour. Two mols. of titanium trichloride = 1 mol. of sodium perborate. I n the case of washing powders it is advisable t o add before titration some carbon tetrachloride to dissolve the separated fatty matter; or a definite volume of titanium trichloride may be added and the excess titrated ds usual by means of ferric chloride. Percarbonates may be tested similarly but as the direct titration is attended with loss of oxygen the solution should be delivered from a pipette which dips into a known volume of titanium tri- chloride in an atmosphere of carbon dioxide.The excess of titanium is then titrzteci with ferric chloride. Two mols. of titanium tri- chloride = i riiol. of potassin 1 1 1 lxrt*a t-l)otiat(>q Pc~~wlphntes ; ~ I Y > t reatrd likc i)ercaj*l,onat es. T. A. H. T. S. P. r,. DF I<.ii. 240 ABSTRACTS OF CHEMICAL PAPERS Apparatus for the Estimation of Sulphur in Steel and GEORG PREUSS (Choin. Zed. 19 13 37 82). -After the matrrial t o be tested has been placed in the flask A the cooler B is filled half way with cold water; this serves for the purpose of cooling and also for the absorption of hydrogen chloride.The cooler 23 is closed with the bent tube 11. Imme- diately after introducing the acid the cooler B is placed on the flask A in such a manner that the tube D dips into the beaker E contnining 40 C.C. of cadmium solution. An esczpe of hydrogen sulpliide during this momentary open- ing is not to be feared. On warming with a small flame the gases evolved pass through the serpentine tube G penetrate the water column in cooler 11 and then pass through the beaker B where every trace of hydrogen sulphide is absorbed. The sulphur may then be estimated either gravimetrically or volumetrically. Iron. L. DE K. A Source of Error in the Kjeldahl- Gunning Process. EM. CARPrAux (BUZZ. SOC. Chiw. Belg. 191 3 27 13-14).-The Gunning modification of K jeldahl’s process (heating with addition of potassium sulphate) does not work well in the case of several vegetable products (alkaloids for instance).The relation between potassium sulphate and free sulphuric acid towards the end of the operation is also a matter of importance because a loss of ammonia is to be feared when an insufficiency of free acid is present. When worlring as follows these sources of error disappear 1.5 grams of the sample (sesame cake for instance) are heated with 30 C.C. of sulphuric acid and after a while 15 grams of potassium sulpliate are added. To make sure of the complete conversion of the nitrogen into ammonia 1 gram of mercury and 1 gram of dry copper sulphate should also be added. The heating should not be continued longer than necessary so as t o prevent undue loss of Estimation of Ammoniacal Nitrogen by means of Form- aldehyde.GAILLOT (Ann. Chirn. anal. 1913 18 15-17).-When an ammonium salt is treated with formaldehyde the ammonia com- bines with the aldehyde to form hexamethylenetetramine and the acid radicle of the salt is set free; the amount of this free acid as estimated by titration is a measure of the ammonia present. For the estimation a weighed quantity of the ammonium salt is dissolved in water the solution neutralised an excess of neutral formaldehyde added and the resulting acidity of the mixture is titrated phenolphthalein being used as indicator. Estimation of Nitric Acid by Schloesing’s Method. MAURICE CANET (Bull. SOC. ohim. BeZg. 1913 27 10-ll).-This acid. L. DE K. W. P. S.ANALYTICAL CHEMISTRY.ii. 241 process based on the liberation of nitric oxide when a nitrate is boiled with hydrochloric acid and ferrous chloride does not always give a pure gas since the author finds that when treated with pure oxygen and then with alkaline pyrogallol it leaves an appre- ciable volume of unabsorbed gas. One of the sources of error must no doubt be attributed to the use of an indiarubber cork on the distilling flask which a t a high temperature does not completely prevent the entrance of atmo- spheric air. The error is somewhat counterbalanced but not removed when making a check experiment with a known amount of nitrate. If in the testing of nitrocellulose this is dissolved first in sulphuric acid the nitric oxide is contaminated with traces of carbon monoxide.L. DE K. The Reaction between Formaldehyde and Nitrous Acid. LUDWIG VANINO and A. SCRINNER (Zeitsch. anal. Chem. 1913 52 31-28).-About 0.25 gram of sodium nitrite is dissolved in water and boiled in a suitable apparatus until the air has been com- pletely expelled. A sufficiency of formaldehyde is then introduced followed by hydrochloric acid when carbon dioxide and nitrogen are evolved. The former is absorbed by aqueous potassium hydroxide and the latter is ihen measured with the usual pre- cautions. One ztom of citrogeii = 1 mol. of nitrous acid. L. DE K. Estimation of Nitric Oxide. KOERLER and M. MARQUEYROL (Bull. Soc. chim. 1913 [iv] 13 69-72).-The method described by Baudisch and Klinger (this vol. ii 74) is not applicable to mixtures containing in addition to nitric oxide nitrous oxide nitrogen carbon dioxide and carbon monoxide.I n such cases the authors absorb the nitrogen trioxide formed by means of ethylaniline. I n the residue carbon dioxide is estimated by means of potassium hydroxide and the excess of oxygen added is absorbed by alkaliiie pyrogallol; the rest of t.E.e analysis is carried out in the ordinary way. Ethylaniline dissolves a little more than its own volume of carbon dioxide a t 15O to 20° under atmospheric pressure so that when only one-sixth or one-seventh of the total pressure is due t o this gas the volume dissolved by tlie small amount of ethylaniline used is Pegligible. T. A. €I. Estimation of Phosphoric Acid Soluble in Citric Acid in Thomacs Slag. W. SIMMERMACHER (Chem.2%. 191 3 37 145-146. Compare A. 1907 ii 577; 1912 ii 992 993).-When ferric chloride is added to the citric acid solution of the phosphoric acid in order to prevent precipitation of silica the subsequent addition of the mixture of ammonium citrate solution and magnesia mixture must be made in small quantities a t a time otherwise ferric hydrox:de is precipitated and does not re-dissolve in the reagent. Ferrous chloride does not prevent the precipitation of the silica. The mixture of aininoniurn citrate soluti~n and mrtg- aesia mixture must be freshly made. w. P. P.Some Factors Influencing the Quantitative Estimation of Arsenic in Soils. J. E. G~EAVES (J. Amev. Chem. Soc. 1913 35 150-1 5 6) .-The methods which liave hitherto been recommended for the estimation of arsenic in soils are liable to give inaccurate results as tliey do not take into account the effect produced by the presence of iron.A study has now been made of the influence of iron on the estimation of arsenic by Marsh's method and of the effect of stannous chloride in overcoming the retention of arsenic by iron. The following method lras been found t o give the best results. To 10 grains of the soil are added 25 C.C. of concentrated nitric acid and the mixture is heated for tliirty minutes. Wliile still fairly hot 10 C.C. of concentrated sulpliuric acid are added ant1 tlie mixture is again heated for tliirty ininutes. The inixture is theii filtered and the soil waslied with liot wat,er; t,lie liltrate is c?vaporatecl t o dryiiess aiid Iieatecl iint,il free froiii nitrates.The residue is treated with dilute sulpliuric wid an(1 20 C.V. of 10% soliltion of stminom chloride and then slowly introducer1 iiit'o the illarsli apparatus. This niethod eiix1)lts very sinall qiiaiitities of arsenic- to bc estimated acciirately. E. G . Estimation of Arsenic In Urine and Blood. PRANZ LEHMANN (Arch. Pharrn. 1913 251 1-4).-A method described previouhly i n detail by the author and E. Rupp (A 1912 ii 866) may be used €or the estimation of arsenic in urine and in blood. In the case of urine 500 C.C. of the sample are treated with 2.5 grains of powdered potassium permanganate aiid evaporated almost to dry- ness a small quantity of solid paraffin being added to prevent frothing. This prelimimry treatment with permanganate is essen- tial in order to avoid loss of traces of arsenic during the evaporation. The estimation is then proceeded with as described.Blood (50 grams) is shaken for ten minutes with 2.5 grams of permanganate before the sulphuric acid and the main quant'ity of permanganate are added. w. P. s. The Separation of Arsenic and Tungsten. SIEQFRIEU HILPERT and THEODOR DIECKMANN (Ber. 1913 46 152-155)- Owing to the formation of very stable complexes between arsenic and tungstic acids precipitatior methods do not give a satisfactory separation. The authors make use of the distillation method for separating the arsenic using cuprous chloride as the reducing agent. To the mixture containing the complex of arsenic and tungsten (0.0646 graiii of arsenic and 0.1313 to 0-2626 grain of tungstic acid) 15 grains of cuprous chloride are added and 150 C.C.of hydrochloric acid (n = 1-16) and the distillation carried out until only a small residue is left. The distillation is again repeated with another 150 C.C. of liydrocliloric acid after wliicli 110 inme arsenic will pass over. It is found however that arsenic still reniaiiis in the residue altliough there is no definite molecular ratio between the arsenic and the tungsten. It is probable that it is adsorbed by the tungstic acid sifice if the residue is made alkaline with potassium hydroxide,ANALYTICAL CHEbllS‘kktY. ii. 243 heated cooled and theii again distilled twice with 160 C.C. of hydrochloric acid the remainder of the arsenic distils over and a quantitative separation is attained.The arsenic in the distillate is determined by titration with iodine. The quantity of tungstic acid should not exceed the ainount giveii above. T. S. I?. Estimation of Carbon and Carbon Dioxide. ACH. GHEGOIRE JAMES HENDBICK EM. CARPIAUX and E. GERMAIN (Ann. China. anal. 1913 18 1-8).-In the method proposed the substance containing carbon is ignited in a current of oxygen and the carbon dioxide (after the gases have been passed over copper oxide) is absorbed iu barium hydroxide solution. ‘The latter is contained in a Petteiikofer absorption tube am1 the resulting barium carbonate is then collected on a filter precautions being taken t o prevent absorption of carbon dioxide froin the atmosphere during the filtration. The barium carboiiate is next decoinposed i n ;I inoclifiecl Scheibler’s apparatus and the volume of the liberated carboil dioxide is measured. Particular attention is paid t o the volunie of carbon dioxide which dissolves in the nitric acid employed for the decomposition and a table is given showing the corrections tlo be applied on this acsoiint.For instance 10 C.C. of nitric acid I ) 1-20 at 1 6 O absorb 10.67 c.c. of carbon dioxide (calculated t o iioriiial temperature and pressure). MT. 1’. s. Portable Pettersson-Palmqvist Apparatus. K. P. ANDERSON (J. Amer. Chem. Soc. 1913 35 162-168).-A modification of tlie Yettersson-Palmqvist apparatus for estimating carbon dioxide in air is described which has the advantages of being more readily and conveniently manipulated than the original form and of being more easily portable.By mems of a coil of copper tubing sub- merged in the water in the glass cell the sample of air can be rapidly adjusted to the temperature of the apparatus. Carbon dioxide can be quickly and accurately estimated when present in quantities not exceeding 0.5% by volume. E. G. The Use of Phenolphthalein and of Rosolic Acid for the Estimation of Free Carbonic Acid in Water. HERMANN NOLL (Zeitsch. nngew. Chem. 1913 26 85-87).-Chiefly a reply to Tillmans and Heublein (A. 191 2 ii 685). Further experiments made by the author indicate that in the titration of the free carbonic acid in water the hydrogen carbonates behave differently towards phenolphthalein from what they do towards rosolic acid. With the latter inclicator a definite portion of the free carbonic acid is not ;I ccouiitecl for wliicll portion is always proportional t o tlie liytirogen carbonates present.Thus using a rosolic acid solution of the strength 1 1000 1 ing. of carbonic acid present as liytlrogeil carbonate masks tlie presence of 0.25 ing. of free carbonic acid whereas with a strength of 1 1500 0.15 mg. is masked. These results verify those of Tillmans and Heublein with respect to rosolic acid. T. S. P.ii. 244 ABSTRACTS OF CHEMICAL PAPERS. Microchemical Reaction for Carbonates in Rock Sections. W. IIEEGEK. (Cenlr. Min. 1913 44-51),-The reagent used consists of 2-3 C.C. i~-/lO-hydrocliloric acid t o which a few drops of potassium ferricyanide solution have been added. From the velocity of the reaction and tlie interisity of the blue coloration produced con- clusions can be drawn as to the presence of various carbonates- calcite dolomite ankerite etc.Only in very exceptional cases is calcite so free from iron that no colonr is obtained. This method has the advantage over other colouring methods in being applicable when the rock constituents are in a finely divided state. Qualitative Organic Analysis by means of Magnesium JOSE G I I ~ A L PEREIRA (Anal. Fis. Qu27n. 1913 11 6S-73).-When organic compounds are ignited with magnesium or better with magnalium carbon may be detected in the residue by treatment with aninioniacal cuprous chloride and acidification nitrogen by the generation of ammonia on warming with water and oxygeii by means of the feeble alkalinity of the magnesium oxide. The oxygen test is not trustworthy and magnalium gives better results tliari mngiiesiuni.G. D. L. L. J. S. Detection of Silicic Acid in Urine without Incineration. ERNST SALKOWSKI (Zsitsch. phgsiol. Chem. 1913 83 143-152).-The urine is partly evaporated and precipitated with alcohol. The sticky precipitate is stirred with alcohol brought on to a filter waslied with alcohol and dried after washing with ether. It is then shaken out of the filter stirred with dilute hydrochloric acid and finally returned t o the filter and the insoluble portion well washed. On incineration almost pure silicic acid is obtained. The daily urine con1 aim on tlie- average about 0.1 gram SiO,. E. F. A. Decomposition of Silicates. WALTHER HEMPEL (Zeitsch. maaE. Chern. 1913 52 86-90).-1f an electric oven is at disposal by means of which a temperature of 1360O can be obtained the best way €or rendering silicates soluble is t o heat 1 gram of the powdered sample with 3 grams of pure barium carbonate for ten minutes.The chief advantage of the process lies in the fact that the barium is readily removed from the resulting solution by means of sulphuric General Method for the Analysis of the Ashes of Body Fluids. W. MESTREZAT (.I Phccrm. Chirn. 1913 [vii] 7 G0-65).- A general method is described for the deteminations successively of phosphoric acid iron aluminium lime and magnesia on the same specimen of ash prepared from a body fluid. Estimations of sodium and potassium are best made on a second specimen of the ash. The method is particularly apphable $0 ash from the cerebro- spinal fluid.T. A. H. JULIUS F. SACHER (Zeitsch. anal. CAem. 1913 52 28-31).-To the solution of the sulphide is acid; also the platinum crucible does not suffer. L. DE K. Eraulation of Rariuni Sulphide.ANALYTICAL CHEMISTRY. ii. 245 added a definite number of C.C. of a solution of lead nitrate (16 grams per litre) a little acetic acid is added and the lead sulphide is filtered off and washed with cold water. The excess of lead is then titrated with ammonium molybdate (8.526 grams per litre; 1 c.c.=1 C.C. of the lead solution) using a 0.5% solution of tannin as external indicator 1 C.C. of lead solution=0~0081814 gram of Estimation of Magnesium Chloride in Water. EMIL BOSSHARD and W. BUHAWZOW (Zeitach. anyew. Chem. 1913,26,70-72). -A known volume of the sample is evaporated on the water-bath and the residue extracted with a mixture of equal volumes of absolute alcohol and ether which dissolves any magnesium (and calcium) chloride present.The filtrate is then diluted with water to a definite volume and in an aliquot part of this the chlorine is estimated volumetrically. In another part the calcium is estimated gravimetrically and after allowing for this the remaining chlorine Behaviour of Uric Acid towards Ammonia and Magnesium Salts and the Estimation of Magnesium in Urine. ERNST SALKOWSKI (Zeitsch. physiol. Chem. 1913 83 152-159).-When urine is precipitated by magnesia mixture and the precipitate filtered immediately there is no separation of uric acid. When the filtrate is left for a day or more in addition to a little ammonium magnesium phosphate there is a characteristic yellow separation.This substance contains uric acid ammonia and magnesia and represents perhaps a compound of the structure Various unsuccessful attempts to synthesise such a compound are described. The influence of these observations on the direct estimation of magnesium in urine without incinerating is investigated and proved to be without moment. Rapid Estimation of Zinc. KURT VOIGT (Zeitsch. angew. Chem. 1913 26 47-48. Compare Abstr. 1912 ii 298).-The author again proves by a number or" experiments that in the presence of sufficient ammonium chloride no insoluble zinc silicate is regenerated Influence of Lead on the Titration of Zinc with Ferro- cyanide. VICTOR LENHER and C. C.MELOCHE (J. Amer. Chem. SOC. 1913 35 134-138).-The most satisfactory volumetric method for estimating zinc in ores is the modified Wariag method. Conflicting statements have been made with reference t o the influence of lead on the titration with ferrocyanide and this question has therefore been investigated. The results show that when the titration is carried out in the usual way the presence of lead is immaterial. In estimating lead by the ferrocyanide method. an acetic acid solution should be used and mineral acids must not be present. barium sulphide. L. DE I(. is calculated to magnesium chloride. L. DE I-(. Mg(NH*)z(C,H,O,N,)z. E.F. A. on adding ammonia. L. DE I(. 1 7ii. 246 ABSTRACTS OF CHEMICAL PAPERS. In the estimation of zinc in ores in which lead and iron are the only heavy metals present in any considerable quantity such as the Wisconsin zinc ores the lead need not be removed before carrying out the ferrocyanide titration.The ore (0.5 gram) is dissolved in 10 C.C. of concentrated hydrochloric acid and a little nitric acid. After dilution the solution is treated with ammonia and afterwards filtered. The precipitate is dissolved in dilute hydrochloric acid and reprecipitated with ammonia. The filtrate is added to that from the earlier precipitation is acidified with hydro- chloric acid and after being concentrated by evaporation is ready to be titrated. The solution should be hot when titrated should have a volume of 200 c.c. and should contain 6-10 C.C. of con- centrated hydrochloric acid and 10 grams of ammonium chloride.The ferrocyanide solution should be of such strength that 1 C.C. is equivalent to 0.005 gram of zinc. Solution of uranium nitrate (5%) is the best indicator. E. G. Colorimetric Determination of Traces of Zinc. ANGEL DEL CAMPO CERDAN and Josk DE LA PUENTE (Anal. Pis. Quim. 1913,11 98-108).-The formation of a blue colour on the addition of aqueous ammonia and resorcinol to zinc solutions may be made the basis of a colorimetric method for the recognition of zinc down to 1 - 7 gram. For every 100 C.C. of liquid 2 C.C. of 0.92 ammonia and 2 C.C. of 5% resorcinol are added. The liquid is covered with paraffin to exclude oxygen and after twenty-four hours examined in the colorimeter. The maximum error observed was 6.6%. G. D. L. Detection and Colorimetric Eatimation of Lead Copper and Zinc i n Potable Water.LUDWIG W. WINKLER (Zeitsch. angew. Chsm. 1913 36 38-44).-In the usual colorimetric estimation of lead it is necessary to add to the sample and to the comparison fluid a certain amount of ammonium chloride otherwise the result will be deceptive. It is pointed out that in the presence of even traces of suspended ferric hydroxide the lead will pam into the deposit so that the water may appear lead-free. Instead of hydrogen sulphide water the author prefers a solution of sodium monmulphide; both acetic acid or ammoniacal liquids may be used. I f copper is also present the following process is recommended. The copper is estimated colorimetrically by means of ferrocyanide in the presence of potassium hydrogen carbonate potassium cyanide is added (which causes a green coloration) then an ammoniacal solution of ammonium chloride and finally sodium sulphide which will react with the lead only. The oxide obtained by the usual process is converted by way of a check into chloride and the chlorine is then titrated with silver in the usual manner after adding a little potassium hydrogen carbonate.Minute traces of zinc are judged from the turbidity caused by the reagents. A new process is given for the estimation of zinc. L. DE K.ANALYTICAL CHEMISTRY. ii. 247 Detection of Traces of Copper. WESLEY B. PRITZ A. OUILLAUDEU and JAMES R. WITEIROW (J. Arne,.. Chem. Soc. 1913 35 168-173).-1n the course of certain work on the electrolytic pre- cipitation of copper it was desired to ascertain the sensitiveness of the various reagents which are usually employed to determine whether the metal has been removed completely from the solution.It has been found that if the volume of the electrol@e is 100 c.c. and 1 gram of copper is originally present and other metals are absent the end-point can be detected by ammonium hydroxide within 0*105% by ammonium sulphide within 0.015% and by potassium ferrocyanide within 0.009%. The following method is recommended for detecting traces of copper in the solution after electrolytic precipitation has been effected. One C.C. of the sample is introduced into a glass tube 3-5 mm. in internal diameter 15 cm. long and with a capacity of nearly 3 C.C. The solution is rendered alkaline with ammonia acidified with glacial acetic acid and then treated with two drops of 2% potassium ferrocyanide solution.If more than 1 mg. of copper is present a pronounced red coloration is produced but if there is not more than 0.1 mg. of copper in 100 C.C. of the solution the colour is practically identical with that of a blank experiment made in a similar tube. E. G . Estimation of Copper with Sodium Hypophosphite. RICHARD WINDISCII (Zeitsch. anal.' Chem. 1913 52 l-lS).-The process previously recommended by Dallimore (A. 1909 ii 833) is intended more particularly for commercial copper sulphate. One hundred grams of the sample are dissolved in water 60 C.C. of dilute sulphuric acid (1 7) are added and the whole diluted to one litre; 50 C.C. are then heated to boiling in a deep porcelain dish with addition of 20 C.C.of commercially pure sodium hypo- phosphite (200 grams per litre). After fifteen minutes' action the precipitate consisting of metallic copper is collected washed first with hot water then with alcohol and finally converted by ignition into oxide. L. DE K. Estimation of Copper in Preserved Vegetables by means of the Spectrophotometer. E U G T ~ E TASSILLY (BuZl. SOC. chirtz 1913 [iv] 13 72-74).-The method depends on the complete extraction of the copper from the charred vegetables and its con- version into copper ferrocyanide which is then estimated by means of a spectraphotometer previously graduated by means of a similar copper ferrocyanide solution of known strength. From 10 to 15 grams of the product are ignited gently to produce a charred mass retaining the shape of the original. This is extracted a t 100° with 2 to 5 C.C.of sulphuric acid water added the solution filtered and the residue washed. The copper in the filtrate and washings is precipitated by sodium hyposulphite and the pre- cipitate washed and carefully ignited as usual. The residue is dissolved in 1 to 1.5 C.C. of sulphuric acid a few drops of nitric acid added and the excess of acid evaporated. The cupric sulphate 17-2ii. 248 ABSTRACTS OF CHEMICAL PAPERS. is dissolved in water 2 C.C. of potassium ferrocyanide solution (0.07 gram per c.c.) added and the liquid diluted to 100 C.C. and examined in the spectrophotometer using the portion 115-125 of the micrometer when the D-ray is a t 80°. The Mercury Cmtent in the Air Dust etc.of Places where Metallic Mercury is in Use. ARVID BLOMQUIST (Ber. Deut. pltarm. Ges. 1913 23 29-46).-The mercury vapour contained i n the air of rooms where mercury or its preparations are constantly being used is estimated by evolving chlorine and so converting the mercury into the chloride. Four thousand litres _of the air are then drawn through a series of absorbers two of which contain 100 C.C. of 5% hydrochloric acid containing 1% of stannous chloride ; the third contains 100 C.C. of 5% aqueous potassium hydroxide. The mercury is then estimated by means of a slight modification of Farup’s method (intended for urines). A large number of experiments are communicated showing the quantity of mercury found in the air and dust of laboratories and in the urine of the persons employed New Method for the Estimation of Mercury in Urine and in the Tissues.HANS BUCHTALA (Zeitsch. physiol. Chem. 191 3 83 249-303).-See this vol. i 318. Comparison of Farup’s and Schumacher-Jung’s Methods for the Egtimation of Mercury in Urine. WILEELI BECKERS (Arch. Pharm. 1913 25 1 4-?).-Farup’s method (collecting and weighing the mercury on a gilt asbestos filter after it has been reduced to the metallic state) yields results which agree closely with those obtained by the Schumacher-Jung method (A 1903 ii Application of Diphenylcarbazide as Indicator in the Titration of Iron with Dichromate. 0. L. BARNEBEY and S. R. WILSON (J. Amer. Chem. Soc. 1913 35 156-162).-Brandt (A. 1906 ii 309) has suggested the use of diphenylcarbazide as an indicator in the titration of iron.On applying this method concordant results could not be obtained and the present investi- gation was therefore undertaken. It has been found that the variation in the results is due to the indicator itself which is oxidised by the dichromate during the titration 3 mols. of diphenylcarbazide requiring 2 mols. of potassium dichromate for their oxidation. If a blank experiment is carried out to ascertain the reducing power of the indicator the method is rendered applicable to the estimation of iron in ores The end-point is excellent and small quantities of iron can be estimated as accurately as by the more common methods. E. G. T. A. H. there mostly fractions of a milligram. L. DE K. 44) and the methods are equally trustworthy. w. P.s. Estimation of Iron in Premnce of Organic Substances. EKNST SALKOWSKI (Zeitsch. physiol. Chem. 1913 83 159-164).-A critical study of the difficulties experienced in estimating iron inANALYTICAL CHEMISTRY. ii. 249 association with proteins or other organic substances. The iron is con- verted by fusion with a mixture of alkali nitrate and carbonate into oxide the fused mass dissolved in water and the iron oxide collected on an ash-free filter. It is advantageous to carry out the washing with a l0-15% solution of ammonium nitrate and finally to fill the filter with alcohol. A further difficulty is often experienced in removing all traces of iron oxide from the platinum dish. The method of estimation of iron as ferric phosphate is examined and found to be very unsatisfactory. Washing the ferric phosphate precipitate with ammonium acetate does not remove the difficulties E.F. A. The Separation of Iron and Manganese. F. H. CAMPBELL ( J . SOC. Chem. Ind. 1912 32 3-4).-Ths cold solution of iron and manganese salts preferably the sulphates is almost neutralised with ammonia and a mixture of equal volumes of a 25% potassium iodide solution and a saturated solution of potassium iodate then added. Ferric hydroxide is precipitated by the hydrolysis of the ferric salt the hydrolysis being made complete because of the removal of the acid formed by the mixture of iodide and iodate with liberation of iodine. After allowing the precipitate t o settle the liberated iodine is removed by a slight excess of 20% sodium thiosulphate solution.The precipitate is collected washed first with cold and finally with boiling water and the manganese deter- mined directly in the filtrate as pyrophosphate (compare Gooch and Austin A. 1899 ii 128). When metals such as calcium and magnesium are present the manganese should be separated as sulphide re-dissolved in acid and then precipitated as the phos- phate. Nickel cobalt and zinc do not interfere on account of the solubility of their phosphates in ammonia. So long as the conditions given above are observed the results for manganese are accurate one precipitation only being necessary. Hot solutions cannot be used since manganese is then precipitated with the iron. If the precipitate of ferric hydroxide is ignited and weighed the results f o r some unknown reason are high; the pre- cipitate should be dissolved the ferric salt reduced and then titrated with permanganate or dichromate.I n the tests carried out the mixtures contained 0.0287-0*2300 gram of iron and 0.0328-02628 gram of manganese. T. S. P. Analysis of Ferro-Zirconium. MAX WUNDER and B. JEANNERET (Zeitsch. anal. Chem. 1913 52 99-101).-A reply to the criticism of Weiss and Trautmann (A. 1912 ii 495). The authors uphold the accuracy of their process (ibid. ii 96) which is now used exclusively by many works chemists. L. DE K. The Direct Volumetric Estimation of Tin. HENRY J. B. RAWLINS (Chenz. News. 1913 107 53-55).-The anthor recommends the well-known titration with iodine or with ferric chloride in the assay of commercial tin. The titanium chloride process (estimation of excess of iron added) may also be used.The standard solutionsii. 250 ABSTRACTS OF CHEMICAL PAPERS. should be checked against a known weight of pure tin dissolved in hydrochloric acid in a current of carbon dioxide. The presence of antimony causes the results to be slightly in excess of the truth and in delicate assays it should be determined and allowed for. The author thinks the titration results are more trustworthy than a gravimetrlc assay based on an estimation of the impurities. L. DE I(. New Colorimetric Method for Titanium. VICTOR LENHER and W. G. CRAWFORD (J. Amer. Cbnc. Soc. 1913 35 138-145).- The most generally applicable method hitherto proposed for the estimation of small quantities of titanium is Weller’s colorimetric method (A 1883 381) in which hydrogen peroxide is employed.A study of the behaviour of a large number of organic compounds with titanium in concentrated sulphuric acid has shown that dis- tinctive colorations are produced by thymol phenol quinol salicylic acid and chromotropic acid. Of these thymol has proved to be the most satisfactory for detecting and estimating small amounts of the metal. The intensity of the coloration is a t least 25 times as great as that produced by the hydrogen peroxide method. The colour is not affected by diluting the solution with water until the strength of the sulphuric acid is reduced to 79*4% and beyond this point it fades in a regular manner. When the solution is heated the colour disappears but returns on cooling and is not per- manently discharged until the solution is heated to looo.The colour is bleached by fluorides or hydrofluoric acid. Chlorides phosphates and tin do not affect the intensity but tungstic acid reduces it in direct proportion to the amount of tungsten present. I n order to apply the test the substance containing titanium is fused with potassium hydrogen sulphate ; the product is dissolved in concentrated sulphuric acid an excess of thymol in sulphuric acid is added the solution diluted to a definite volume and the colour compared in a colorimeter with that given by a standard titanium solution. The method is simple and rapid and can be applied to smaller quantities of titanium than can be estimated by Weller’s method. E. G Use of Cupferron in Quantitative Analysis [of Titanium] ITALO BELLUCCI and L.GRASSI (Atti R. Accad. Lincei 1913 [v] 22 i 30-34. Compare Baudisch A. 1911. ii 939).-When an aqueous solution of cupferron is added to an acid solution of titanium chloride or titanium sulphate the canary-yellow salt (NOONPh-O),Ti is precipitated quantitatively. I f the precipitate is filtered off dried and ignited (TiO being formed) the process forms a very accurate and convenient means of estimating titanium. Very good results have also been obtained in the application of the method to the separation of titanium from aluminium. R. V. S. Estimation of Bismuth by Titration of the Hydrochloric Acid Solution of Bismuth Oxyiodide by Means of Alkalis. c. REtCHARD (PhW%%. Zmtr.-h. 1913 54 103-104).-The procesr3 isii. 251 ANALYTICAL CHEMISTRY.intended for the evaluation of bismuth oxynitrate. 0.4 Gram of the powder is dissolved in 10 C.C. of 25% hydrochloric acid 2 grams of potassium iodide are added and the liquid diluted t o 100 C.C. Twenty-five C.C. of the solution are then titrated with AT/ 2-sodium hydroxide until the yellow colour has disappeared. The difference between the alkali used and that required to neutralise the acid represents the bismuth; 2 mols. of sodium hydroxide=l mol. of bismuth oxide. L. DE K. The Reaction between Formaldehyde and Bismuth or Copper in the Presence of Strong Alkali. FRANZ HARTWAQNER (Zeitscl~ unal. Chem. 1913 52 17-20).-Bismuth chloride may be reduced to metal by heating with a large excess of both form- aldehyde and aqueous sodium hydroxide. I f only theoretical quantities are used or when the liquid is too much diluted the reduction is very imperfect Copper however is more readily reduced to metal.I n the presence of a large excess of alkali hydrogen is also evolved. The author also investigated the action of chloral hydrate and acetaldehyde on some metals. I n alkaline solution gold is com- pletely reduced and should it become colloidal it may be pre- cipitated by boiling with excess of dilute sulphuric acid. Acet- aldehyde also reduces gold in acid solutions. Copper salts are reduced to metal by chloral hydrate in presence of alkali; the metal however is very liable to oxidation; acetaldehyde causes no reduction but on boiling copper oxide separates. Bismuth chloride in the presence of alkali is reduced very slowly and incom- pletely by chloral hydrate but not by acetaldehyde. Silver salts are completely reduced in alkaline solutions both by chloral hydrate and acetaldehyde; here the latter is to be preferred in practice. L.DE K. Estimation of Tantalic Acid and Columbio Acid in Tantalites Columbites Yttrotantalites and Fergusonites and the Colorimetric Estimation of Columbium. E. MEIMBERa (Zeitsch. angew. Chem. 1913,26,83-85).-The principle of the method is as follows. The mineral is decomposed by fusion with potassium hydrogen sulphate. The fusion is digested with hydrochloric acid the residue of mineral acids neutralised with ammonia and then digested with ammonium sulphide a t a gentle heat for twenty-four hours. The residue is collected washed successively with hot water and boiling dilute hydrochloric acid and then dissolved in excess of hydrofluoric acid.The tantalum is then precipitated as potassium tantalum fluoride K,TaF by the addition of a con- centrated solution of potassium hydrogen fluoride the columbium remaining in solution. The filtrate from the precipitate is evaporated t o dryness digested with strong sulphuric acid boiled with water to remove the sulphuric acid dissolved in hydrofluoric acid and again precipitated with potassium hydrogen fluoride in order to remove any tantalum still remaining. This process is repeated until the tantalum is completely separated from theii. 252 ABSTRACTS OF CHEMICAL PAPERS. columbium. The potassium tantalum fluoride is then converted into the pentoxide and weighed as such.It generally contains some titanium which must be estimated colorimetrically. For the estimation of the columbium all the hydrofluoric acid filtrates are evaporated to dryness and then again taken down with strong sulphuric acid. The residue is treated successively with boiling water ammonia ammonium sulphide and very dilute hydrochloric acid and weighed as columbium pentoxide. Gallotannic acid has hitherto been used in testing colorimetrically for columbic acid but the colour is affected considerably by the presence of tantalum. The author makes use of the fact that the columbates especially the fluoride compounds are reduced by tin and hydrochloric acid to coloured products whereas the tantalates are not affected. The potassium tantalum fluoride which is to be tested for columbium is dissolved in dilute hydrochloric acid con- taining some hydrofluoric acid and the solution evaporated down until a copious precipitation of potassium tantalum fluoride has occurred.After cooling the crystals are collected and washed with cold dilute hydrofluoric acid. The columbium together with some tantalum is in the filtrate which is evaporated to dryness on the sand-bath. The residue is dissolved in concentrated hydro- chloric acid the solution placed in a colorimeter tube and reduced with tin. The reduction is complete in about fifteen minutes and the colour is then compared with that of a standard which must be freshly made for each determination. The solutions to be estimated as also the standard should not contain more than 0.1% of columbium.By this method 0*01-0*005% of columbium can readily be estimated. Delicate Colour Reactions of Gold Salts. JOHN EDWARD SAUL (Analyst 1903 38 54).-If a 0.1% solution of either of the following substances quinol pyrogallol gallotannic acid p-hydroxyphenylaminoacetic acid salts of phenylhydrazine 3 4-di- aminophenol (amidol) the monomethyl derivatives of m- and p- (metol) and o-aminophenol associated with quinol in (ortol) and m-phenylenediamine is added to ten volumes of a 0*002% solution of gold chloride a colloidal solution of gold is formed presenting a beautiful violet colour varying in intensity and shade with the reagent used. Gallotannic acid gradually produces a rose colour. The author recommends p-phenylenediamine as a suitable test for traces of gold. The coloration is a t first of a dark green and still shows with a 0.0001% solution.After some Estimation of Palladium and its Separation from Copper and Iron. MAX WUNDER and V. TRURINGER (Zeitsch. anal. Chem. 1913 52 101-104).-To the solution is added a 1% solution of dimethylglyoxime in dilute hydrochloric acid ; should ferric chloride be present a large excess should be added owing to reduction taking place. The precipitation of the palladium compound is favoured by gentle boiling and the precipitate is then converted into metal by ignition with the usual precautions. T. S. P. time the colour undergoes changes. L. DE K.ANALYTICAL CHEMISTRY. ii. 253 From the filtrate the copper is precipitated as thiocyanate by addition of sulphur dioxide and potassium thiocyanate and weighed as such.The filtrate contains the iron which is first pre- cipitated with ammonium sulphide and finally weighed as oxide. L. DE K. A Source of Error in the Determination of “Perman- ganate Absorbed ” by Drinking Waters by Schulze’s Method. LEO GRUNHUT (Zeitsch. anal. Chem. 1913 52 36-40).-This method (boiling with alkaline permanganate and kitrating the excess) is affected when the water itself contains manganese. This however may be remedied as follows To 120-150 C.C. of the sample is added 0*6-0*75 C.C. of 337; aqueous sodium hydroxide and after shaking a few times and waiting for a few minutes the precipitate which also contains the manganese is filtered off through a Gooch crucible and 100.5 C.C. of the clear filtrate are then boiled with permanganate as usual.L. DE K. A Method of Analysing Mixtures of Hydrogen and the Gaseous Saturated Hydrocarbons Hydrogen Methane Ethane and Propane. PAUL LEBEAU and A. DAMIENS (Compt. rend. 1913 156 144-147 ; 325-327).-‘t’aking advantage of the fact that of the four gases under consideration only hydrogen and methane have any appreciable vapour tension a t - 190° the authors first liquefied the gaseous mixture and then submitted it to fractional distillation by means of a mercury pump at -190O. The volatile portion contained the hydrogen and methane and was analysed eudiometrically the ethane and propane being pumped off a t higher temperatures. By an examination of more complex mixtures the authors have determined conditions of temperature favourable for a practical separation of other gaseous hydrocarbons from hydrogen.I n the second paper the mixture studied contained ethane propane and isobutane and it was found that by maintaining the mixture a t -127O and pumping off all the gas possible all the ethane and a portion of the propane were removed and could be analysed eudiometrically the residual liquid containing the remain- der of the propane and all the dsobutane being pumped off a t a higher temperature and similarly analysed. I n general by a study of the vapour tension of the hydrocarbons when liquefied it is possible by suitable choice of temperatures to separate mixtures into fractions containing only two of the hydrocarbons the fractions; then being analysed eudiometrically.W. G. Estimation of Glyceryl Acetate in Essential Oils. S. GODFREY HALL and ARTHUR J. HARVEY (J. Xoc. Chem. Ind. 1912 32 61-62).-The method depends on the separation of the glycerol and its estimation by the triacetin method. A quantity of not less than 10 grams of the essential oil is saponified by heating with alcoholic potassium hydroxide solution and the solution is then neutralised with hydrochloric acid. After the alcohol has beenii. 254 ABSTRACTS OF CHEMICAL PAPERS. removed by evaporation to dryness the residue is dissolved in a small quantity of water and the oily portion is separated by extraction with ether. The aqueous solution is then evaporated to a syrupy condition and the glycerol in i t is estimated in the usual way by the triacetin method.w. P. s. Detection of Pentoses in Urines containing Dextrose. ADOLF JOLLES (Zeitsch. anal. Chem. 1913 52,104-108).-To 100 C.C. of diabetic urine (containing up to 5% of dextrose) are added 4 grams of phenylhydrazine hydrochloride and 8 grams of sodium acetate (sugar-free urine is mixed with 1% of dextrose). The whole is heated for an hour in the boiling water-bath and then rapidly cooled. It is then removed from the filter into a beaker 15 C.C. of hot water are added and the whole heated for five minutes on a boiling water- bath. After filtering rapidly the liquid which contains the pentosazone is distilled with addition of 6 C.C. of fuming hydro- chloric acid and 6 C.C. are collected in a test-tube. Three C.C. of the distillate are then mixed with 5 C.C. of Bial’s reagent (1 gram of orcinol 500 C.C.of 30% hydrochloric acid 30 drops of officinal ferric chloride) and boiled for a short time. I n the presence of as little as 0.05% of pentoses a distinct green coloration is noticed. When testing urines with more than 5% of dextrose the amount The deposit is collected on a filter and well drained. of the reagents should be doubled. L . D E K. Estimation of Dextrose in Urine. K. K. JARVINEN (Zeitsch. anal. Clbem. 1913 5 2 14-15).-The dark colour obtained with diabetic urines on heating with alkaline bismuth solution (Almen- Nylander’s process) is matched by means of a series of tubes con- taining increasing quantities of dextrose added t o sugar-free urine. If much dextrose should be present in the sample it must be suitably diluted and the sugar-free urine likewise.L. DE K. Estimation of Reducing Sugars by Lehmann’s Method. L ~ O N GRIMBERT (J. €‘harm. chim. 1913 [vii] 7 10.5-109; Bull. 2hc. chim. 1913 [iv] 13 117-120. Compare A. 1898 ii 264 535; 1899 ii 529) .-Modifications of Lehmann’s method proposed by Riegler and Maquenne (Zoc. cit.) are open to the objection that the solution has to be filtered before the titration or that the titration has to be carried out in a relatively concentrated solution; further the time of boiling the sugar solution with the reagent varies in each method. Garnier’s modification of the method (A. 1899 ii 701) lengthens and coniplicates the process. The author recom- mends that after the sugar solution has been boiled for three minutes with a definite volume of Bertrand’s reagent (A.1907 ii 136) the whole solution should be diluted to 200 C.C. with boiled water filtered and the excess of copper in an aliquot portion of the filtrate titrated with thiosulphate solution after the addition of sulphuric acid and potassinm iodide. It is preferable t o add an excess of tbiosulphate solution and to titrate this with N/10-ANALYTICAL CHEMISTRY. ii. 255 iodine solution. in the same way. The copper sulphate solution used is standardised B. 0. FEINBERGI (Amel= Chern. J. 1913 49 87-116).-This investi- gation was undertaken with the object of determining the best methods for estimating various aldehydes. The following methods have been studied (1) the combination of aldehyde with alkali hydrogen sulphite; (2) the reaction with the normal sulphites; and (3) the precipitation of the aldehydes as hydrazones. These methods have been applied to formaldehyde benzaldehyde salicyl- aldehyde p-hydroxybenzaldehyde and vanillaldehyde and in all cases attempts have been made to establish conditions for the accurate estimation of the compounds. The compounds of the aldehydes with alkali hydrogen sulphite are resolved into their components by dilute acid or alkali hydroxide and the readiness with whibh this decomposition takes place is increased by the presence of a hydroxyl group in proximity to the aldehyde group.Formaldehyde can be estimated accurately by means of alkali hydrogen sulphite and vanillaldehyde and benz- aldehyde can be approximately estimated but the method does not give satisfactory results with salicylaldehyde p-hydroxybenz- aldehyde or anisaldehyde.It has been found that sodium sulphite does not combine with aldehydes with formation of sodium hydroxide as is generally supposed but that a reaction takes place on the addition of acid indicating that sodium hydrogen sulphite is first produced and unites with the aldehyde. Formaldehyde and benzaldehyde can be estimated fairly accurately by means of sodium sulphite and anisaldehyde can be estimated approximately but the method is inapplicable to salicylaldehyde p-hydroxybenzaldehyde and vanill- aldehyde. Precipitation with p-bromophenylhydrazine gives good results with anisaldehyde p-hydroxybenzaldehyde and vanillaldehyde but not with formaldehyde benzaldehyde or salicylaldehyde.p-NiCrophenylhydrazine has been found generaIly applicable and is very suitable for the estimation of vanillaldehyde and p-hydroxy- benzaldehyde whilst with benzaldehyde salicylaldehyde and anisaldehyde it yields results from 2 to 4% too low. w. P. s. Quantitative Study of Some Aldehyde Reactions. A bibliography of the subject is appended. E. G. Estimation of Formaldehyde. GAILLOT (Ann. China. unaZ. 1913,18,17-18).-A definite quantity of the formaldehyde solution under examination is neutralised treated with an excess of neutralised ammonium sulphate solution and the resulting acidity of the mixture is titrated (compare this vol. ii 240); this acidity is equivalent to the amount of formaldehyde present. WILTIELM FRESENIUS and LEO GR~~NHUT (Zeitsch. anal. Chem.1913 52 31-35).-A criticism of some of the processes employed. The following conclusions are W. P. S. Detection of Citric Acid in Wine.ii. 256 ABSTRACTS OF CHEMICAL PAPERS. arrived a t (1) The process given by Denigks (based on oxidation and treatment with a mercuric salt) cannot serve to prove the presence of added citric acid in wine. (2) The reaction of Moslinger as modified by Kries (based on precipitation of potassium hydrogen tartrate by addition of- alcohol and precipitating the filtrate after evaporating off the alcohol and largely diluting with water with acetic acid and lead acetate) is applicable and is fairly delicate. (3) The reaction of Schindler (based on the different solubilities of the barium salts of citric and malic acids and sub- sequent use of lead acetate) is only serviceable when large quantities of citric acid are present.L. DE K. Hardened (Hydrogenised) Oils and the Detection of Arachidic Acid. HAM KREIS and EMIL ROTH (Zeitsch. Nuhr. Genussm. 1913 25 81-85).-Sessme arachk and cottonseed oils still yield a coloration with Bellier’s resorcinol test after they have been “hardened” by treatment with hydrogen in the presence of a catalyst. Hydrogenised whale oil gives an orange colour with this test. The sesamol of sesame oil is not affected by the treatment and the hydrogenised oil gives the reaction described by Kreis (A. 1904 ii 75 790). Arachis oil either natural or hydrogeuised may be detected in admixtures with other oils by saponifying 20 grams of the oil under examination separating the solid fatty acids and dissolving them in 100 C.C.of alcohol; in the case of hydrogenised oils 200 C.C. of alcohol are required. The boiling solution is then treated with 1.5 grams of lead acetate dissolved in 50 C.C. of alcohol; the precipitated lead soap is collected after about twelve hours decomposed with hydrochloric acid and the liberated fatty acids crystallised three times from alcohol using successively quantities of 50 c.c. 25 c.c. and 12.5 C.C. of alcohol for these operations. Should the oil contain not less than 5% of arachis oil the fatty acids obtained after the third crystallisation will have in. p. above 70°. This process may be shortened by acidifying th saponified oil with 50% acetic acid and then adding the lead acetate solution without previously separating the fatty acids.w. P. s. Estimation of Caoutchouc in Vulcanised Rubber Materials. PAUL GOLDBERG (Chem. Zeit. 1913 37 85-86).-For the indirect method of estimating caoutchouc in which the mineral matter present in the material is estimated by ignition and the caoutchouc taken by difference the following process for estimating the ash is recom- mended as it prevents certain chemical changes taking place during the ignition between the constituents of the ash and the oxygen of the atmosphere. One gram of the sample previously extracted with acetone and dried at 50° is placed in a weighed porcelain boat which is inserted in a tube through which a current of nitrogen is passed. When all the air has been displaced from the tube the boat is heated until the caoutchouc melts and distils and a t the end of the operation the mineral matter remaining in the boat is weighed.When the added mineral matter consists ofANALYTICAL CHEMISTRY. ii. 257 calcium oxide magnesium oxide calcium carbonate litharge red lead lithopone zinc sulphide zinc oxide barium sulphate silicates etc. this method of incineration yields trustworthy results the error not exceeding 0.3% but when magnesium carbonate is present the carbon dioxide liberated must be absorbed and estimated. If the rubber material contains ‘‘ sulphur auratum,” the antimony trisulphide is estimated in the ash and calculated into penta- sulphide ; cinnabar if present is volatilised completely and must be estimated separately by the method described by Frank and Birkner (A.1910 ii 244) and its quantity added to the amount of ash found. w. P. s. The Prussian Blue Reaction. DANIEL TORLANDER (Ber. 1913 46 181-192).-The author finds that the reaction between ferric chloride and potassium f errocyanide is a time-reaction which is retarded by acid and salts; the extent of the retardation increases with the strength of the acid. In very dilute solutions such as often occur in analytical practice it is possible for no blue colour to be produced at all and only an indefinite green colour after a few hours; after twenty-four hours a few coagulated flocks of Prussian blue may be found. When a ferrous salt is used instead of ferric chloride the formation of ferrous ferrocyanide is an instantaneous reaction which is followed by oxidation to Prussian blue by means of the dissolved oxygen.The presence of dilute hydrochloric or sulphuric acid accelerates the formation of a blue colour as also does the use of excess of the ferrous salt. The test is so delicate that a millimol. of potassium ferrocyanide per litre can be detected. I n carrying out the test for cyanides (or nitrogen) it is best t o filter the solution after boiling with ferrous sulphate and sodium hydroxide. The filtrate should then be acidified with dilute hydro- chloric acid and 3-10 drops of fresh ferrous chloride or sulphate added. Ferrous salts react immediately with potassium ferricyanide which points to the fact that the slow reaction between ferric salts and potassium ferrocyanide is not due to the formation of a colloidal reaction product but depends on the condition of the ferric salt solutions.Examination with the ultramicroscope of the solutions of the various iron salts used leads the author to the conclusion that solutions of ferric salts may be considered as incomplete colloidal solutions in which the particles are scarcely visible in the ultra- microscope althoygh much greater than in disperse molecular solutions. Further experiments with colloidal ferric hydroxide solutions indicate that the colourless solutions obtained by acidifying the colloidal solution prepared from alcoholic ferric chloride and sodium ethoxide are not identical with the colourless solutions obtained from ferric salts and nitric acid. The latter are practically optically clear in the ultramicroscope whereas the former are seen to consist of colloidal solutions containing large submicrons. T.S. P.ii. 258 ABSTRACTS OF CHEMICAL PAPERS Rapid Estimation of Tannin Matters and Acidity in Tanning Liquors. RUDOLF VANI~EK (Zeitsch. angew. Chem. 1913 26 68-70).-The process is briefly as follows The acidity of 50 C.C. of the liquor is taken by means of N/lO-sodium hydroxide using phenolphthalein (or phenolphthalein test paper) as indicator before and after treatment with 50 C.C. of gelatin solution (6 per 1000). The difference in acidity (a - b ) is due to the acid principle of the tannin matter. I f a gravimetric analysis of a particular ‘‘ tannin ” has been made the titre of the soda solution may be found by dividing the number of grams found in 50 C.C. by (a- 6).Working with solutions of unknown strength the result of the titration (a- b ) has only got to be multiplied by the titre in order to find the total content in tanning matter. L. DE I(. Comparative Examination of Methods for the Estimation of Dyes. H. SALVATERRA (Monatsh. 1913 34 255-281).- Knecht’s reduction process with titanium chloride and the method elaborated by Pelet-Jolivet and Garuti (A. 1908 ii 441) for the estimation of pure dyes dyed silks and dye vats (waste vat liquors) have been compared the colouring matters examined being malachite-green crystal-violet magenta naphthol-yellow-S Martius- yellow crystal-ponceau-6B f ast-ponceau-B cotton-scarlet extra f asbscarlet-PX orangeG and orange-GRX. Both methods give satisfactory results when pure materials are to be estimated although Knecht’s process gives values which are too high with malachite-green and too low with orange-G.The trouble expe- rienced in preparing suitable type solutions is however a drawback to Pelet’s method. Only Knecht’s method gives good results for the titration of dyed silk and in the case of easily reduced dyes it may be applied directly. For the examination of waste vat liquors both methods are trustworthy whereas colorimetric comparisons with standard solutions are quite impossible. Experiments have been conducted in order to ascertain whether dyes are taken up by silk in molecular proportions but no such rule could be discovered. It can only be said that with an increase in the number of sulphonic groups the affinity of silk for the dye diminishes.J. C. W. Chemical Detection of Verona1 Poisoning. W. MACADIE (€‘harm. J. 1913,90 134).-The following methods were employed for the detection of veronal in a suspected case of poisoning by this substance. The stomach wash-out was acidified with hydrochloric acid shaken out several times with ether and the ethereal solutions were evaporated ; the residue obtained was then extracted with alcohol the solution evaporated to dryness the residue dissolved in a small quantity of dilute sodium carbonate solution filtered and the filtrate extracted with ether after the addition of hydro- chloric acid. On evaporating the ethereal solution a residue was obtained which was dissolved in a small quantity of alcohol; a portion of this solution was treated with alcoholic sodium hydroxideANALYTICAL CHEMISTRY.ii. 259 solution heated to remove the alcohol and the heating then con- tinued until the mixture fused. The fused mass when treated with sulphuric acid yielded carbon dioxide and an odour resembling that of a mixture of acetic and butyric acids (compare A 1911 ii 670). Another portion of the alcoholic solution was evaporated to dryness and the residue tested with Millon’s reagent in the presence of nitric acid; a gelatinous precipitate soluble in excess of nitric acid but not in an excess of the reagent was obtained. Verona1 was also separated from the urine of the patient; for this purpose the urine was treated with calcium chloride to precipitate uric acid and after the recipitate had been removed by filtration the filtrate was acidifiecf and shaken out with ether the residue of veronal obtained being identified by means of the tests mentioned.w. P. s. Rapid Estimation of Pyridine in the Presence of Ammonia in Gas Liquors. OTTO BAESSLER (J. Gasbeleuchtung 1912 55 905-906) .-The total ammonia and pyridine are first titrated together with standard sulphuric acid; the mixed vapours are then distilled through a warm solution of sodium hypobromite whereby the ammonia is oxidised to water and nitrogen; the pyridine is carried on into standard sulphuric acid the excess of which is subsequently titrated. F. M. G. M. Micro-chemical Tests for the Identification of Some of the Alkaloids. EARL B. PUTT (J. Ind. Eng. Chem. 1912 4 508-512).- An account of the preparation with micro-photographs of the characteristic crystals formed by alkaloids with certain reagents which affords a ready means for their identification.Alkaloids pro- ducing characteristic crystals with iodine are (1) morphine shining red plates ; (2) codeine clusters of yellow blade-like needles ; (3) dionine (ethyl-morphine) similar to codeine ; (4) atropine small red crystals whilst heroine apomorphine and narcotine furnish amorphous precipitates. Alkaloids producing characteristic crystals with palladous chloride are (1) morphine light brown clusters of sheaf-like crystals ; (2) codeine yields first a labile form which rapidly changes to clusters of needles. Alkaloids yielding characteristic crystals with platinic chloride are (1) cocaine ; (2) p-eucaine clusters of golden (flower) petal-like- crystals ; (3) nicotine resembles those obtained with cocaine but are only formed in neutral or faintly acid solution whereas the cocaine precipitate is insoluble in acids ; (4) antipyrine yellow branching feathery crystals ; (5) strychnine peculiar chisel-shaped clusters which rapidly separate into individual needles ; (6) heroine golden- yellow clusters of needle-like crystals which when fully formed disintegrate. F.M. G.M. (3) 8-Eucaine deep yellow characteristic crystals. Factors Affecting the Measurements of Absorption Bands. H. HARTRIDQE (Proc. Rog. Xoc. 1913 B 86 128-140).-1n estimatingii. 260 ABSTRACTS OF CHEMICAL PAPERS. the absolute value of the carbon monoxide saturation of hEmo- globin the spectroscopic method is complicated by the fact that each observer must obtain a calibration curve for himself because indi- vidual differences to the threshold values at different wave-lengths occur.These detract from the value also of accurate measurements of absorption bands. Other factors to be considered are the initial intensity of the light and contrast. Provided work is carried out under standard conditions accurate carbon monoxide estimations are obtainable. W. D. H. Behaviour of Copper Salts towards Ganassini’s .Reagent for Blood. DOMENICO GANASSINI (Boll. cliim. farm. 1912 51 815-81 8).-Possible confusion between traces of copper sa1t.s and traces of blood (compare Pazienti this vol. ii 154) can be avoided by adding to the blue liquid a small quantity of potassium cyanide; if copper is present the solution a t once becomes yellow. Blood does not give this reaction. If copper is absent the usual blood test is then performed by adding a drop of hydrogen peroxide to the same solution. I f copper is present a trace of potassium cyanide is added t o another portion of solution then the blue reagent and finally a drop of peroxide; the presence of blood will be indicated by a change of colour from blue to yellow. Schardinger’s Reaction for Cow’s Milk. W. RULLMAKN Compare A 1911 ii 667).- R. V. S. (Biochem. Zeitsch. 1913 48 155-156. A reply to Romer (A. 1912 ii 610). S. B. S. Nephelometry in the Study of Proteases and Nucleases. I. PHILIP ADOLF KOBER (J. Biol. Cliem. 1913 13 485-498).-At microchemical method for following the digestion of a soluble protein edestin based on the use of a nephelometer is given. This instru- ment can be easily made from a Duboscq colorirneter. Its readings follow a curve which can be expressed by a mathematical equation. W. D. H. The Nature of Peroxydase. WALTHER GRIMHER (Zeitsch. Nahr. Genus~m. 1913 25 85-88).-The author controverts the statement made by Hesse and Kooper (A. 1912 ii 1107) that the peroxydase reaction of milk is brought about by the catalytic action of iron salts such as ferrous lactate. He argues that milk does not contain iron compounds of this type and that the albumin solutions used in Hesse and Kooper’s experiments contained upwards of thirty times more iron than is found in milk. Further when these iron solutions are heated and then cooled they regain their power of giving the peroxydase reaction but such is not the case with milk when it is heated; protein solutions when mixed with ferrous lactate solution inhibit the activity of the latter owing to the formation of insoluble iron-protein compounds. The presence of chloroform or of mercuric chloride interferes with and may inhibit the peroxydase reaction of milk. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9130405236

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

i. 241 Organic Chemistry. Some Reactions of Sodamide in the Presence of Liquid Ammonia. Formation of Ethylene Hydrocarbons. E. CHABLAY (Compt. rend. 1913 156 327-330).-Sy the addition of alkyl iodides or chlorides to sodamide in liquid ammonia primary amines are not the only products as has been supposed (compare Lebeau A. 1905 i 401,512) but at the same time except in the case of the methyl haloids the corresponding olefine is formed in varying amounts. Starting from the ethyl haloids the yield OF olefine increzses on passing up the series and is always greater when using the chlorides than i f the iodides are employed; thus isobutyl iodide gives a yield of 62.4% of isobutglene whilst the chloride gives a yield of 83.6%. I n this reaction sodamide resembles alcoholic potassium hydroxide in its behaviour (compare Meunier and Desparmet A.1907 i 186). W. G. The Adsorption of Acetylene by Palladium Black. CARL PAAL and CHRISTIAN HOHENEGGER (Be?.. 1913 46 128-132).-In the previou.; investigation on the same subject (A 1910 i 807) the palladium black wa8 suspended in aqueous solutions of various substances. The authors have now investigated the adsorption of acetylene using either suspensions OF palladium black in pure water or else dry palladium black. The experiments in which 60% alcohol was used in place of pure water were also repeated. I n all cases the adsorption of the acetylene takes places slowly and the results given do not point to auy fixed ratio between the weight of palladium and the amount of gas adsorbed. It is probable that the acetylene is not completely adsorbed as such but undergoes partial polymerisation. When the dry palladium black is not completely free from oxygen formation of feeble sparks occurs immediately i t is brought into contact with the acetylene.T. S. P . Acetylene or Acetylidene Compounds. The ‘( Oxidation Rearrangement.” HEINRICE BILTZ (Ber. 1913 46 143-149).- Nef and his school assign t o the halogen substitution products of acetylene a n acetg lidene formula as for example CI,:C di-iodo- acetylidene. No definite proof of this constitution has been afforded and the facts observed are more in favour of the acetylene structure CIiCI. Di-iodoacetylene is very readily formed from acetylene by the action of hypoiodites and iodine t h e process involving simple siib3ti- tution of iodine for hydrogen.The reasons for the representation of dibromoacetylene as CBri CBr are discussed. E. F. A. Sodium Silver T h i o m l p h a t e and Acetylene-Silver Acetyl- ide. KSHITIBHUSHAN BHADURI (Zeitsch. ccnory. Chem,. 191 3 79 355-356).-Sodium thiosulphate is added to an ammoniacal solution VOL. CIV. i. si. 242 ABSTRACTS OF CaEMlCAL PAPERS. of silver nitrate and acetylene is passed through the clear solution. The yellow precipitate is collected washed wit,h water and alcohol and dried in air. It is stable in dry air but is decomposed by water yielding a brick-red product. The final products of decomposition are silver sulphide and sodium sulphate. The yellow compound is soluble in ammonia and is re-precipitated by acids again dissolving in an excess to form unstable solutions which evolve sulphur dioxide and acetylene. Analysis leads to the formulae 2Na2S20,,~Ag2S20,,18A g2C2,3iZc2H2 for the- yellow compound and 4Ag2S20,,7Na,S,0,,S6Ag2C2,13C2H2 for the red compound.C. H. D. The Production of Chlorine Substitution Products of Methane from Natural Gas. CHARLES BASKERVILLE and H-. S. R~EDERER (J. Ind. Eng. Chem. 1913 5 5-8).-The authors have investigated the conditions necessary for the chlorination of the methane present in natural gas especially those which mould lead t o the formation of carbon tetrachloride from which cbloroforrn could be obtained by reduction. The apparatus used was so dosigned that the gases could be constantly circulated through it the circuit always containing n heater for heating the gases and a condenser for con- densing out the products formed.In the first trials the circuit also contained an arc either between carbon or iron terminals but this was omitted later as i t was found that chlorination was not effected by the combustion taking place in the arc. It was ultimately found t h a t the primarily important condition for the chlorination is a source of light rich in the rays of the visible blue spectrum that ip the spectrum from the bluish-green through the visible violet. The ultraviolet part of the spectrum plays little part in the reaction. Apparently the necessary source of light may be obtained by a n arc between iron electrodes in the circuit and in some experiments a 20-25%. yield of a mixture of carbon tetrachloride and chloroform was obtained T.s. P. Primary Dinitro- Ni tro-ni trite and Dialdoxime Compounds of the Aliphatic Series. 11. Derivatives of the Heptane Series and Synthesis of Pimelaldehyde. JULIUS VON BRAUN and E. DANZIGER (Ber. 1913 46 103-110).-As has already been shown (von Braun and Sobecki A. 1911 i SSO) the action of silver nitrite on aliphatic compounds of the type I*[CH,&*I gives a mixture of dinitro nitro-nitrite and dinitrite derivatives the first two,of these being reducible to dialdovimes and amino-alcohols respectively. These changes have already been performed with n equal to 4 5 and 10 and are now extended to the heptamethylene chain. ay-Di-iodoheptaue was prepared from ae-dibromopentane by conver- sion of the latter into an organo-magnesium compound causing this to react with monochloromethyl ether (compare Dionneau A 1906 i 134) and hydrolysing the product with bydriodic acid.It was also obtained by the stages di brornopen tane diaminopentane dichloro- heptane and diphenoxyheptane the last of which again is converted int,o di-iodohnptnne by bydriodic acid. I n the conversion of dichloro-ORGAKIC CHEMISTRY. i. 243 heptane into diphenoxyheptane by sodium ethoxide a small quantity of a-phenoxy-c-methylene-n-hexane b. p. 145"/12 mm. was obtained as by -product. aq- Di-iodoheptane reacts vigorously with silver nitrite producing a mixture which can be separated at 10 mm. into three fractions b. p. 108-140" (mainly heptamethylene nitrite NO,-[C K,],*NO,) 140-1 60' (mainly 7-nitroheptyl nitrite) and 160-205" the last on refraction- ating yielding pale yellow aq-dinitroheptane b.p. 1 98-200°/ 10 mm. The second fraction when reduced with tin and hydrochloric acid yields q-hydroxyheptylamine a strong base b. p. 150-152°/10 mm. ; beiazoyll nitrobenzoyl and picrate derivatives are oily ; platinichloride solid m. p 15'7". ay-Dinitroheptane when treated with sodium ethoxide in alcoholic solution gives an immediate precipitation of the white sodium s-tlt the aqueous solution of which can be used for the preparation of the salts of the heavier metals for example the coppel. (green) barium and calcium salts; with bromine i t forms a n oily bromide (compare von Braun and Sobecki loc. cit.) and with a diszobenzene solution there is obtained yellow is h-red ay- bisphenylazo-aq-dinitroheptune N,Ph*CH(NO,)*[CH,],*CH(NO,)*N,Pb m.p. 139O. The reduction of a solution of the sodium salt of dinitroheptane by gradual addition to a solution of stannous chloride in hydrochloric acid gives pimelaldoxime OH*N:CH*[CH,],*CH:N*OH a pale yellow crystalline powder m. p. 150-151" from which on boiling with dilute sulphuric acid pimelaldehyde is not obtained as i t partly poly- merises to a viscous oil and partly becomes dehydrated to tetrahydro- benzaldehyde semicarbazone m. p. 2 11-212" (Wallacb A. 1906 i 563). PirnelaUehyde a pungent colourless oil of b. p. 110-112°/ 13 mm. Di0 0.9895 is obtainable by the action of nitrous fumes on a suspension of the dioxime in cooled water until no more nitrous oxide is liberated ; it readily reduces Fehling's solution and a n ammoniacal silver solution and gives a semicarbaxone m.p. 1 8 3 O ; the phenyl- hydrazone and p-nitrophenylhyd~azone are oily whilst the diphenyll- methanedimethyEdihydrazone C H 2 < 8 ~ 1 ~ ~ ~ ~ i ::>[ CH,] (s t ruc- ture not proved) is a yellow solid m. p. 96-97". The aldehyde resembles adipaldehyde in showing much less tendency to polymerise than do the other dialdehydes of this series. A preliminary investigation has shown that glutaraldoxime when heated with mineral acids gives pyridine probably by reason of the condensation of glutaraldehyde and hydroxylamine which are first formed. D. P. T. Synthesis of an Unsaturated Hydrocarbon. CORNELIS J ENKLAAR (Chey. It'eeeekblad 1913 10 60-63).-A note on the preparation of nnsaturated alcohols by the interaction of unsaturated aldehydes and unsaturated haloids in presence of zinc and ether and the conversion of such alcohols into unsaturated hydrocarbons by heating with potassium hydrogen sulpbate. On treatment with zinc filings or shavings and ether crotonaldehyde and ally1 iodide give a $ 2i 244 ABSTRACTS OF CHEMICAL PAPERS.good yield of ac-heptadiene-8-oZ CHMe:CH*CH(O€€)*CH,*CH :CH,. Its properties are still uninvestigated but heating with potassium hydrogen sulphate converts i t into a liquid. Repented fractionation finally over sodium at 755 mm. gives three frsctions b. p. 105-110°~ 110-112' a.nd 112'. On cooling to -76" these three fractions solidify. The first has m. p. - 35O t o - 32" the second - 23" to -2L' and the third - 15' to - 14.5'.One of these substances is believed t o be an ayeheptatriene and their constitutions are to be determined. It is anticipated that the method will prove of general application. A. J. W. History of Distillation and of Alcohol. EDMUND 0. VON LIPPMANN ( ZeitscA. ccrtgew. Chem. 19 13 26 46-47).-Polemical against Schelenz (this vol. i 2). T. s P. Action of Magnesium on a Mixture of Ethyl i s o v a l e r a t e and Allyl Bromide. G. MOSKALENICO (J. Buss. Phys. Chem. Xoc. 1912 44 1862-1865).-Decomposition by means of water of the product of the reaction of magnesium ethyl isovalerate and allyl bromide yields diaZZyZisobut?lZcus.6inoZ CHMe2-CH2.C(OH)(CH,*CH:CH,) which forms a colourless mobile liquid b. p. 92'/37 mm. DF 0.8616 1.45682 and exhibits the normal molecular weight in freezing benzene or boiling ether.T. H. P. Adipiopinacone. LOUIS MICHIELS (Bull. Soc. chim. Bdg. 191 3 27 25-26).-Adipopinacone OH*CMe;[CH,],*CMe,*OH m. p. 88-89' is obtained in the form of its hydrate containing 2H20 by the action of magnesium methyl bromide on ethyl adipate. The hydrate is obtained in large white crystals m. p. 56*5O which effloresce in air and completely lose their water of hydration when left in a vacuum desiccator. Rv the action of warm dilute .I sulphuric acid the pinacone is readily converted into tetrumethyz- CMe2*CH2*(?H2 a liquid with an ethereal hexamethylene oxide O<CMe;CH,.CH,' O Y 1 odour b. p. 156-157'/756 mm. W. G. Action of Magnesium on a Mixture of Allyl Bromide and Ethyl Levulinate. E. SCHTSCHERICA (J. Kuss.Phys. Chem. Xoc. 1912 44 1853-1858).-The interaction of magnesium allyl bromide (1 mol.) and ethyl 13evulnte (1 mol.) and subsequent decomposition of the product with water should yield the ester C,H,* CMe( OH)*CH,*C€€,. CO,E t but this reaction could nct be realised. No matter whether I rnol. or 3 mols. of allyl bromide were employed the resultant compound WRS always the y-glycol C,H,~CMe(OH)*CH,-CH,*C(C,H,),*OH which i s a faintly yellow syrupy slightly mobile liquid with a characteristic odour b. p. 157-159O/10 mm. DY 0.9545 ng 1.48712. When boiled with 20% sulphuric acid solution the glycol is converted into the corresponding oxide ~ ~ ~ ~ ~ ~ ~ ~ which is an almost colour-ORGANIC CHEMISTRY. i. 245 less liquid with a peculiar pleasant odour b.p. 1045 -105*5°/10 mm. DY 0.8905 nz 1.46915 and has the nornittl molecular weight in boiling ether. T. H. P. Synthesis of Lecithin. -Polemical. and Kade t h i s pol. i 158). ADOLF GRGN (Ber. 1913 46 125-127). A reply to Langheld (this vol. i 155; compare Grun E. F. A. Thionium Dibromides of Sulphides. VLADIMIR V. TSCHELINCEV (J. Russ. Phys. Chem. Soc. 1908 44 1885-1594).-The action of bromine on ethyl sulphide in carbon tetrachloride solution yields t h e thionium dibromide SEt2Br2 which forms yellow crystals and resembles oxonium compounds in its general characters and also as regards the nature of the solvents in which it dissolves readily or with difficulty. With acetic acid i t forms solid solutions but in freezing benzene it exhibits the molecular weight 199-21 1 the theoretical value being 250.By excess of water the dibromide is rapidly decolorised with develop- ment ol a considerable quantity of beat and the formation of a white emulsion. Concentrated ammonia solution decomposes the thionium di bromide much less energetically than the corresponding oxonium c~mpound heat being developed and an oily layer of the srilphide formed a t the surface of the liquid. Sodium hydkogen sulphite solution effects the decomposition rather more rapidly and concentrated potassium hydroxide solution much more rapidly than does water. Moist silver oxide converts these di bromides into the corresponding oxides for example SMe,:O which are appreciably more stable than t,he analogous oxonium compounds. The heat of formation of the diethyl dibromide from the alkyl sulphide and bromine is 14.15 Cal.per gram-mol. that of the diamyl dibromide being 12-91 Cal. Measurement of the amounts of heat evolved when the reaction proceeds in carbon tetrachloride solutions of various concentrations shows that the solvent is virtually without influence in this respect. As the heats of formation of the oxonium compounds corresponding with the above thionium compounds are 9.13 Gal. for OEt,:Br and 8.72 Cal. for O(C5HlJ2:Br2 it is to be expected that alkyl sulphides would displace the ethers from oxoniiirn compounds. Calorimetric investiga- tions show that when the oxonium compound is prepared in absence OF solvent such displacement does occur but does not proceed to com- pletion at any rate within the linii~s of time available for calorimetric measurements ; it appears probable that the bromine finally becomes distributed between the sulphide and the ether.When however a carbon tetrachloride solution of ethyl sulphide (1 mol.) is added to a solution of ether (1 mol.) and bromine (1 mol.) in the same solvent 13.76 Cal. are developed; as this amount is somewhat less than the theoretical quantity 14-15 Cal. for complete displacement of the ether from the oxonium compound by ethyl sulphide i t may be that here too the bromine is distributed between the sulphide and the ether. T. H Pti. 246 ABSTRACTS OF CHEMICAL PAPERS. Catalytic Acceleration of the Esterification of Organic Acid by means of Glucinum Compounds. OTTO HAusER and A. KLOTZ (Chem. Zeit. 1913 37 146).-Experiments on the solubility of gluciuum acetate in various organic solvents have led the authors to the discovery that the rate of esterification of organic acids and alcohols can be considerably increased by the addition of glucinum acetate or hydroxide to the bailing mixture. The catalytic action of glucinum compounds is still more pronounced when the mixed vapours of the acid and alcohol are passed over the oxide heated at 310'.The authors claim that better yields are obtained by this process than by that of Sabdtier (actually 70% and over) that there is no loss of catalyst since the glucinum oxide after use can be regenerated by simple ignition and that tertiary alcohols and acids of high molecular weight can be esterified in this manner. The following new esters have been prepared tert.-butyl n-ocloate b.p. 241'; tert.-arnyl n-heptoate b. p. 137" and tert.-amyl n-octoate b. p. 229'. H. W. Mechanism of the Action of Bromine on Chlorides of Fatty Acids. ARTHUR MICHAEL and ERWIN SCHARF (Uer. 1913 46 135-1 38).-M7hen butyryl chloride saturated with hydrogen bromide a t 0'' i8 heated in sealed tubes at loo' double decomposition takes place with the formation of butyryl bromide and hydrogen chloride. It is probable therefore that the formation of hydrogen chloride by the action of bromine on acyl chlorides is not due to the decomposition of a bromine additive product formed from the enolic modification of the chloride but is brought about by the direct action of the chloride with hydrogen bromide produced during the reaction.This is not i n agreement with Lapworth's (T. 1904 85 30) interpretation of the change. Proof is further given that by the action of bromine on butyryl chloride in sunlight some quantity of the p-derivative as well as the a-derivative is formed. Hydrogen chloride and bromide iu equnl proportions are liberated on opening the tube. When the contents were converted into the ethyl ester and hydrolysed with barium hydr- oxide considerable quantities of crotonic acid derived from the p-ester were obtained. E. F. A. Aliphatic Nitro-compounds. XIII. Preparation of a-Nitro-a- methylbutyric Acid. WILHELM STEINKOPF (Ber. 1913,46,9S-100). -An unfinished attempt to prepare a terbiary uitrocarboxglic acid containing a n asymmetric carbon atom. [With HARRY GRUNUPP and LEO Hua.1-A mixture of butanoneoxime with anhydrous hydrogen cyanide is kept i n a closed fl.tsk for four to eight daya at the ordinary temperature and the excess of acid then removed in a vacuum ; crystals of a-hydroxylamino-a-methylbutyro- nitrile OH*NH*CMeEtl-CN m.p. 61.5' are obtained. When this substance is oxidised by the cautious addition of a n acidified solution of potassium permanganate a blue oil (probably a-nitroso-a-methyl- butyronitrile) is fir& formed but disappears later with the production of ~ - n i t ? . o - a - n z e l h y ~ b u t y ? . o ~ ~ ~ ~ ~ ~ ~ e NO,-CMeEt.CN a n almost colourless oil b. p. S7-8S0/17 mm. Attempts t o hydrolyse this to the corre-OHGAN 1C C H EM ISTKY. i. 247 sponding acid or to convert it into a n imino-ester hydrochloride were unsucces~ful.D. F. r r . Action of Alkali S u l p h i t e s on the E t h y l e n i c Acids. J. BOUGAULT and MOUCHEL-LA-FOSSE (Compt. rend. 1913 156 396-398).-1t being known that on adding benzoylacrylic acid to a solution of normal or sodium hydrogen sulphite combination instantly takes place giving the sodium salt of a saturated sulphonic acid (compare Bougault Ann. Chim. Phys. 1908 [viii] 15 299) the authors have compared the activity of different types of ethylenic acids in this reaction. h large number of ethylenic acids combine in this way with sodium hydrogen sulphite giving acids of the type CH2R*CH(S03Na)R' which are very soluble in water and on heating with aqueous sodium' hydroxide t o 160° regenerate the original un- saturated acid.The more energetic is the acid and the more eiectro- negative groups i t contains the more rapid is the fixation of the sodium hydrogen sulphite. Acids such as cyclogeranic undecenoic and oleic acids and i n general those with long straight chains do not combine with the sodium hydrogen sulphite evan after prolonged heating. The reaction can be employed to estimate the amount of unsaturated acid in a mixture of saturated and unsaturated acids and also lermits of the separation of the saturated acid in a pure state. w. G. The Salts of Rare Earths with Hydroxycarboxylic Acids. I. The Glycollatea of the Rare Earths. GUSTAV JANTSCH and A. GRUNKRAUT (Zeitsch. anorg. Chern. 1913 79 305-321).-The internally complex salts of rare earths with hydroxycar boxylic acids might be expected to differ more widely in solubility than the normal salts and therafore to be suitable for the purpose of separation.It is found that the glycollates of the cerium group are anhydroup and crystallise in crusts whilst those of the yttrium group crystallise in needles with 2H,O. The yttrium salt is the least soluble then follow the lanthanum cerium and praseodymium salts which are almost equal and theu in order the neodymium samarium and gadolinium salts. The solutions exhibit the normal reactions but conductivity determinations show that complexes are present. Lanthanum hydroxide dissolves in a warm solution of glycollic acid the solution a t first remaining clear but a t a definite temperature depending only on the concentration the complex salt separates as a precipitate La(C2H,03),.The praseodymium neodymium and samarium salts behave iu the same manner. Gadolinium glycollate Gd(C,H303),,2 H,O crpstallises without first forming a n unstable solution whilst the yttrium salt behaves like those mentioned above. The fractionation of the earths from xenotime previously freed from cerium has been carried out by adding a solution of sodium glycollate to the hot solution of the mixed nitrates. After each addition in order to overcome the unstable condition the mixture is stirred vigorously for two hours at SO-90'. I t is then filtered and the filtrstr; is treated in similar manner. Successive fricctians shorn a1. 248 ABSTRACTS OF CHEMICAL PAPERS. progressive increase in the atomic weight whilst the spectra show a concentration of neodymium and praseodymium in the last fractions.C. H. D. Succinic Semialdehyde [P-Aldehydopropionic Acid]. EDMOXD E. BLAISE and E. CARRIBRE (Compt. rend. 1913 156 239-241).- A reply to Harries (A. 1912 i 827) in which the authors uphold the views already expressed by CarriBre (A. 1912 i 410) that /3-aldehydo- propionic acid changes spontaneously into a polymeride which is ter- molecular and that the bimolecular compound m. p. 147' of Harries (Zoc. cit.) is the compound obtained by the elimination of 1H,O from two molecules of the aldehyde. W. G. General Method for the Preparation of the Ammonium Salts of Organic Acids. EDWARD H. KEISER and L. BECMASTER (Amer. Chem. J. 1913 49 84-86).-On account of the hydrolytic action of water on the ammonium salts of organic acids comparahively few of them have hitherto been prepared and in the case of most dibasic acids only the ammouium hydrogen salts have been obtained.It has now been found that normal salts can be readily prepared by pass- ing dry ammonia into a solution of the organic acid in ether or alcohol or a mixture of the two. The salts are insoluble and separate in the form of white precipitates. Ammonium maleate fumarate nzesaconate citrmonate malonate and phlhalate are described. E. G. Sebacates and Cacodylates of the Rare Earths. C. F. WHITTEMORE and CHARLES JAMES ( J . Amer. Chem. Soc. 1913 35 127-132; Chem. News 1913 107 75-77).-1n an earlier paper (A. 1912 ii 690) it was shown that yttrium can be separated quantitatively from the alkali metals by precipitation with ammonium sebacate.It has now been found that lanthanum and cerium can also be separated from the alkali metals in this way. The following salts are described lanthanum sebacate [C,H,,(C02),]3La2,2H20 ; praseodymium sebacute leeodymium sebacate [C,H,,(CO,) ],Nd2,3H20 ; samariuna sehucate ~C8H,6(C0,)2],Sa2,4H20 ; yttrium sabacate [CSH1~(CO2)218P31292H20 ; [CSH16(C02)213Yr2~ 4H20* On fractionally precipitating a solution containing chiefly the chlorides of yttrium dysprosium and holmium with sodium cacodylate i t was found t h a t yttrium tended t o accumulate in the early fractions and holmium and dysprosium in the later fractions. On boiling a mixture of hydroxides consisting mainly of those of neodymium samarium and gadolinium with cacodylic acid and fractionally crystal- lising the cacodylates from hot water neodymium collected in the more soluble fractions whilst nearly all the terbium and dysprosium remained in the least soluble portions.The following salts have been prepared praseodymium cacodylute (AsMe202),Pr2 1 6H20 ; yttrium cacodylute (AsMe,O,),Yr 1 8H,O ; thu Zium cacodylate ( AsMe20,),Tmg,I 6H,O.ORGANIC CHEMISTRY. i. 249 Neodymium and samarium cacodylates have been described previously (A. 1912 i 233). The rare earth cacodylates readily form double salts with other salts such as the chlorides nitrates and sulphates. The following are described ; lanthanum chloride cacody late 2La(AsMe202),,LaCls 18H,O ; cerium chloride cacodylate 2Ce( AsMe,02),,CeC1 18H,O ; cerium sulphate cucodylate ; and neodymium chloride cacod9 lute 2Nd(AsMe202),,NdCI 18 H20.E. G. The Action of p-Bromophenylhydraeine on Glycurono- lactone. GUIDO GOLDSCHMIEDT and ERNST ZERNER (Bar. 1913 46 113-115).-1n reply to Jolles (this vol. i 9) the authors maintain their previous statement (this vol i 9) that even with purified p-bromopheny lhydrazine the test for glycuronic acid is so uncertain as to be of little practical value. D. F. T. Behaviour of Chloraloxime Towards Water and Alkalis. F. CAELQ PALAZZO and V. EGIDI (Guzxetta 1913 43 i 57-69. Compare Palazzo A. 1912 i 9 4 6 ; Palazzo and Fazio 191i i 421)-When Meyer's chloraloxime is kept for some days with ten times its weight of water a n acid solution is obtained from which can be isolated a product having the composition of oximinoacetic acid ; it has however an indefinite m.p. and is to be regarded as a mixtdre of two stereoisomerides. It differs from the oximinoacetic acid ru p. 1 3 8 O already known in yielding a red coloration with ferric chloride When Meyer's chloraloxime is distil led several liquid fractions b p. 65-85"/20-25 mm. are obtained and also a portion b. p. 85'/20 rum. which solidifies and has DI p. 56". Even if carefully freed from the liquid form the solid substance yields when treated with water a product similar to that given by the original mixture. By the action of h ydroxylamine hydrochloride on bromal hydrate bromuloxime is obtained in acicular crystals m. p. 115'; it has the composition and molecular weight required by the formula CBr3*CH:NOH.Oximinoacebic acid forms two copper salts namely a blue salt and a dark gsmn salt of the probable composition &02->Cu. [OH*N:CH*CO2],Cu,2H20 CH:NO R. V. S. Inosite-phosphoric Acid. ANTON RICHARD ROSE (Biochem. Bull. 1912 2 21-49).-A useful review with bibliography on the subject . W. D. H. Syntheses of Alkylgalactosides by means of Emulsin P-Propylgalac toside and P-Beneyl Galactoside. EMILE BOUR- QUELOT HENRI H~RISSEY and MARC BBIDEL (Compt. rend. 1913 156 330-332).-The two galactosides have been prepared from galactose and the corresponding alcohols under the influence of emulsin by the method previously described (A 1913 i 946).i. 250 ABSTRACTS OF CHEMICAL PAPERS. /3- Propglgalactoside m. p. 105-106° (corr.) [a]. - 8*86O crystallises in long white ceedles having a slightly bitter taste.It is not hygro- scopic but is very soluble in alcohol and water and gives a slight reduction with Fehling’s solution. P-Benx?,Zgalactoside m. p. 100-3 Ole [aID 25*05O crystallises in long white needles having a disagreeable bitter taste. It is not bygroscopic and gives but traces of reduction with Fehling’s solution. Both of these gnlactosides are readily hydrolysed by emulsin in aqueous solution. W. G. Photochemical Synthesis of Carbohydrates. WALT HE^ LOB (Biochem. Zeitsch. 1913 48 257-25S).-A reply to Stoklasa Sebor and Zdobnickg (this vol. i 18). S. B. S. CelluloEe. C. PIEST (Zeitsch. angew. Chcrn. 1913 26 24-30).- The viscosity of a solution of a cellulose nitrate decreases with time and generally a deposit settles on the bottom of the vessel containing the solution.Experiments have been made which show that the decrease in the viscosity is not due to the separation of this depobit from the solution. It has been stated previously that a diminution in the viscosity of a solution of cellulose nitrate is probably clue to the presence of nitrates of ox-j-celluloses. It is bhown now t h a t if a viscous solution of a cellulose nitrate be mixed with a less viscous solution of a nitrate of a highly bleached cotton wool the viscosity of the mixture is considerably less than the calculated value although j € two solutions of the same cellulo~e nitrate but of different concentrations (and therefore different viscosities) be mixed the mixture has a viscosity which is very close to the calculated value.Cellulose when treated with oxidising agents is known to yield oxycelluloseP the part soluble in sodium hydroxide solution being termed P-oxycellulose whilst the insoluble portion is called a-oxy- cellulose. The’ results of numerous trials based on deter minations of the ‘‘ copper value ” and viscosity of a standard solution in a cupram- monium solution by Ost’s method (compare A. 1911 i 838) show that a-oxycsllulose when carefully freed from the degradation products grouped under the name P-oxycellulose is chemically identical with normal cellulose and differs from i t only in that the fibres are much shorter and finer owing to the attack of the oxidising agent. It is also shown that the products of the action of acids on cellulose (“hydrocellulose”) or of a hot 30% solution of sodium hydroxide (6‘ alkalised cellulose ” ; compare Ost and Katayama A.1912 i 680) contain a portion insoluble in sodium bydroxide solutious which is unattacked cellulose. W. H. G. Preparation of Higher Aliphatic Chlorinated Aminee. JULIUS VON BRAUN and H. DEUTSCR ( B e y . 1923 46 228-231. Compare von Braun and Miiller A 1907 i 28).-The bis-imidochlorides of the type CPhCI:N*[CH,],*N:CPhC1 obtained by the action of phosphorus pentachloride on the corresponding dibenzoylated diamine when distilled undergo decomposition mainly into benzoaitrrle and theORGl AN IC CHEMISTRY. i. 2.51 dichloride but t o a slight extent a product Cl*[CH,],*N:CPhCl in which only one of the phenyl radicles has been eliminated is obtained (compare von Braun and Dmziger A.1912 i 597). As the latter class of substance on hydrolysis would give rise t o chlorosmines the method might prove valuable if the yield of the second class of product could be increased. It is now found that a t very low pressures the desired decomposition a t one end of the chain is greatly favoured. at-Di-iodohexane reacts with potassium cyanide giving suberoni trile CN*[CH2],*CN b. p. 176-17S0/11 mm. which by successive reduction (by sodium and alcohol) and benzoylation is converted into ~f3-dibenxoyl- diamino-octane N H Bz *[ CH,],.NHBz. When the last s51 bstance is carefully fused with a bimolecular proportion of phosphorus penta- chloride and the resultant mixture warmed under a pressure of 0.1 mm. there distils into the 'receiver which is cooled by liquid air a mixture of benzonitrile af3-dichloro-octane and 0-chlorobmzo-octyl- amide COPh*NH*[CH,],*Cl colourless leaflets m.p. 65O the last of which is most conveniently purified by means of its compound with calcium chloride. 6-Chlorobenzo-octylamide is hydrolysed by hydrochloric acid at 1 50° with the formation of 6-chloro-octylarnine ; hydrochloride hygroscopic ; platinichloride m. p. 193-1 94' (decom p.) sparingly ~oluble. The base on treating its hydrochloride with alkali easily undergoes intramolecular change t o a base U,H,,N with an odour resembling pyridine ; yellow platinichloride m. p. 197'. I n a n analogous manner by the distillation of dibenzoyldiamino- heptane and of dibenzoyldiaminododecane with phosphorus penta- chloride under a pressure of 0.1 mu. r l - c h l o r o b e n z o h e ~ t y ~ ~ ~ m ~ ~ e C1*[CH,]7-NHBz and p-chlorobenxododecylamide C1*[ CH 2]12*NH Rz m.p. 6 5 O cdn be obtained in fair quantity. The yields were 40% 30% arid 30% of the theoretical in the heptane octane and dodecane series respectively D. F. T. Dibromides of Tertiary Amines. VLAUrMIR v. TSCHELINCEV ( J . Buss. Yhys. Chem. SOC. 1912 44 lS94-1905).-With a view to the comparison of dibromides obtained from tertiary amines with oxonium and thionium dtbromides (compare this vol. i 245) the author has investigated their solubilities in various solvents their molecular weights and their chemical and thermochemical relations. A general parallelism exists between the solubiiity of trimuthyl- amine dibromide and those of oxonium and thionium dibromides. Also in freezing acetic acid trimettylamine dibromide has the molecular weight corresponding with the simple formuh NMe,Br and is hence completely analogous to oxonium arid thionium compounds in this respect (compare Hantzsch and Graf A.1905 i 575). Amine dibromides are somewhat more stable than the oxoniuu compounds towards moisture and are decomposed by ethyl alcohol yielding hydrogen and ethyl bromides. When treated with excess of bromine dibromides of amines are converted into new com- pounds which possess peculiar properties distinguishing them from dibrornides and represent a different class of perbromides,i. 252 ABSTRACTS OF CHEMICAL PAPERS. The heat of formation of tripropylamine dibromide from its con- stituents is 39.72 Cal.per gram-mol. and that of triisoamylamine dibromide 38.76 Cal. ; the carbon tetrachloride employed RS solvent is without influence on the amount of heat developed (see this vol. i 245). Thermochemical investigation of the interaction of diethyloxonium dibromide or diethylthionium dibromide and tripropylamine in carbon tetrachloride solution shows that the tertiary amine displaces the ether or ethyl sulphide completely from oxonium or thionium compounds. Ether has no action on diethyloxonium dibromide and ethyl Pulphide none an diethylsulphonium dibromide but tertiary amine dibromides react energetically with tertiary amines forming compounds separating from carbon tetrachloride in a felted mass of slender pale yellow needles. The following thermochemical data were obtained 2NPr,Br2 + NPr = 23.6 Gal.and 2N(C,Hl,),Br2 + N(C5H11)5 = 22.9 Gal. The compounds formed in this way are being investigated further. Neither the structure suggested by Hantzsch (A 1905 i 576) nor that given by Cain (A. 1905 i 747) for these amine dibromides seems to explain the reactions better than the simple formula. T. H. P. Preparation of Oxan and the Properties of Salts of a- and p-Oxan. ALEXANDER P. LIDOV (J. Arnw. Chem. Soc. 1913 35 132-134. Compare Abstr. 1912 i 541)-Oxan is obtained most readily by t h e action of nitric oxide or nitrous oxide on charcoal at 150-3OOO. a-Oxan O*CiN is a stable gas and is not affected by hot platinised asbestos whilst P-oxan O*N iC is rapidly decomposed under these conditions. The sodium salt of a-oxan is stable when heated whilst that of p-oxan decomposes explosively The silver salt of p-oxan is pale yellow and darkens rapidly on exposure to light; that of a-oxan is white and is less susceptible to the action of light.The iron and calcium salts are also described. The sodium salt of a-oxan gives a white precipitate with manganous chloride or aluminium chloride whilst that of /3-oxan does not yield a precipitate. The salts of a- and p-oxan gradually cease to evolve gas and this is probably due t o polymerisation taking place. E. G. Action of Sulphuric Acid on Dicyanodiarnide. H J . LIDHOLM (Bey. 1913 46 156-160).-The interaction of dicyanodiamide with acids to form guanylcarbamide has been studied quantitatively and shown to ,be a bimolecular reaction.Guanylcarbamicle it! a sufficiently strong base to be titrated with sulphuric acid and methyl-orange. Concentrated bulphuric acid acts on dicyauodiamide liberating carbon dioxide and ammonia and forming guanidine. Guanylcarbamide is decomposed in a similar manner. These observations confirm the structure of dicyanodiamide as guanidinoformonitrile NH:C(NH,)*NH=CN. E F. A,ORGANIC CHXMISTRY. i. 253 The Tautomerism of Fulminic Acid. P. CARLO PALAZZO (Atti R. Accad. Lincei 1912 [v] 21 ii 713-719. Compare A. 1907 i 298 489 ; 1909 i 776).-The author's work on this subject has led him to conclusions similar to those of Ley and Kissel (A. 1899 ii 485) according to which fulminic acid is to be regarded as a tautomeric substance related to the pseudo-acids. I n the aqueous solution of f ulminic acid there is equilibrium between various saturated and unsaturated desmotropic forms.I n the present paper this opinion is developed and a new argument in its favour is drawn from the behaviour of sodium fulminate with azoimide for in this reaction the fulminic acid reacts sometimes as carbyloxime and sometimes in the desmotropic form of formonitryl oxide HCiNZO. The products oE the reaction are hydroxytetrazole (I) m. p. 145O and isooxytetrazole (11) m. p. 1 5 6 O and the relative proportions in which these two substauces are formed depend on the temperature at which the reaction proceeds. R. Y. 8. Catalysis. XIV. Reversible Addition of Alcohols to Nit riles Catalysed by Ethoxides. I. ELI K. MARSHALL jun. and SOLOMON F. ACREE [and in part C .N. MYERS] (8mer. Chem. J. 1313 49 127-158).-A study has been made of tjhe additiou of alcohvls to nitriles in presence of ethoxides as catalysts. It has been found that nitriles unite with ethyl alcohol in presence of sodium potassium or lithium ethoxide and that in every case the reaction is reversible. The percentage of imino-ester present when equilibrium is attained is the same whether t h e reaction IS started with the nitrile or the imino- ester. The equilibrium point varies widely with the different com- pounds the percentages of imino-ester formed with certain nitriles being as follows butyronitrile 0.90 ; propionitrile 1.75 ; acetonitrile 2.50 ; p-toluonitrile 6-8 ; benzonitrile 14.0 ; p-bromobenzonitrile 27.2 ; m-bromobenzonitrile 38.0 ; p-nitrobenzonitrile 63.0 ; m-nitro- benzonitrile 78.0 ; diisoamylcyanoamide 98.0. I n some cases the equilibrium point varies considerably with changes in the concentrn- tion of the nitrile and the ethoxide but in other cases shows but little fluctuation.Different ethoxides catalyse the reaction with different velocities and the equilibrium points also often vary in such cases. The velocity of the reaction varies greatly with the different nitriles p-nitrobenzonitrile reacting very rapidly whilst o-toluonitrile scarcely unites with alcohol a t all. Certain experiments are described which show that the velocity of reaction can be expressed as a function of both the ethoxide ions and the non-ionised ethoxide. E. G. Nitrile of Fumaric Acid and the Preparation of Methyl Maleate. EDWARD H.KEISER and L. MCMASTER (Amer. Chem. J. 1913,49 81-84).-Keiser and Kessler (A. 1911 i 949) have shown that fumaronitrile can be prepared by heating fumaramide with phosphoric oxide. It has now been found that the nitrile can bei. 254 ABSTRACTS OF CHEMICAL PAPERS. converted into fumaramide by treating it with a n alkaline solution of hydrogen peroxide. Methyl maleate which has only been obtained previously by the action of methyl iodide on silver maleate has now been prepared by heating a mixture of maleic acid methyl alcohol and sulphuric acid under a reflux condenser. When the ester is left with solution of ammonia for several days it gradually dissolves and on evaporation a yellow viscous mass is obtained which is probably maleamide.E. G. The A c t i o n of L i g h t on Pigments. 11. The Composition of Turnbull's Blue. ALEXANDER EIBNER and L. GERSTACKER (Chew. Zeit. 1913 37 137-139 178-179 1951-197).-As a result of their experiments the authors come to the conclusion that freshly prepared Turnbull's blue is not identical with Paris blue but ia a derivative of ferricyanic acid. I t is not the most Inbile of the ferricyanides of the heavy metals those of ferric iron zinc cadmium lead and copper being less stable. On long-continued washing or heating a change takes place between the constituents of Turnbull's blue resulting in the reduction of the ferricyanogen and oxidation of the ferrous radicle. The final result of such treatment is identical with Paris blue the velocity of change depending on the conditions. T.s. P. Spirocyclane its Synthesis and Behaviour on C a t a l y t i c Reduction. NICOLAI D. ZELINsKI (Ber. 1913 46 160-172 ; J. Buss. Phys. C'hena. Soc. 19 12 44 1873-1884).-The hydrocarbon formed by the action of zinc dust and alcohol on the tetrabromide of pentaerpthritol has been regarded by Gustavson (A. 1896 i 669) as vinyltrimethylene. Reasons are now given for formulating the com- pound as spirocyclane yHz>C<CH YH2 The only other possible con- stitution is that of methylenecyclobutane. The hydrocarbon is very readily and completely reduced in contact with nickelised asbestos and hydrogen at about 100'. No conden- sation product is formed the gaseous mixture consisting entirely of saturated hydrocarbons. This behaviour eliminates any other con- stitution than that of the spirocyclane.[With V. KRAVEc.1 -This is confirmed by effecting the synthesis of spirocyclane by closing the two trimethylene rings one after the other. By the action a t 0' of hydrogen bromide on pentaerythritol the dibronzohydrin C(CH2Br)2(CH2*OH)2 is obtained. This crystallises in well formed needlep m. p. 112'; the diacetpl derivative has b. p. 185'/13 inm. When reduced with zinc dust the diacetute of dirnethylolcyclo- propane is obtained b. p. 115'/15 mm. The ylycol ' CH2 yH2>C(CH2*OH )2 CH2 has b. p. 126-127"/16 mm. Dqo 1.0794 nm'5 1.4705. with permanganate i t yields cyclopropane- 1 1-dicarboxylic acid. When oxidisedORGANIC CHEMISTRY. i. 255 Phosphorus tribromide converts the glycol into dibromodimethyl- cyclopropane yH2>C*(CH2Br) b.p. 72-74'/13 mm. DY 1,8022 n= 1.534. I n addition a tribromide resulting from the opening of the cyclopropane ring is formed. On reduction of the dibromide spirocyclane is obtained b. p. 40-41.5' DY 0*7%66 n = 1.4120 in agreement with earlier values. [With B. SCHTSCHERBAK.]-W~€I~ a mixture of spirocyclane and hydrogen is passed over platinum black at 70' a mixture of ethyl- cyclopropane and pentane is formed. Using palladium black in the cold it is possible to restrict t'he reduction entirely to one ring and obtain ethylcycEopropane alone. ID order to reduce the second ring nickel must be used as catalyst-a temperature of 200' is necessary before isopentane is obtained. The reduction of spirocyclane thus takes place in two stages and selective catalysts are required.Nickel in the cold reduces it only to ethylcyclopropane. E. F. A. Preparation of the Three Cymenes (Methylisopropylbenzenes) and Three Menthanes (Methylisopropylcyctohexanes). PAUL SABATIEB and MARCEL MURAT (Compt. rend. 1913 156 184-187. Compare Sabatier and Senderens A. 1901 j 459).-Stltrting from the three tolyldimethylcarbinols C,H,Me*CLtIe,*OH the authors have prepared the three corresponding cynienes and menthanes and examined their physical properties. The three carbinols were prepared either (1) by the action of magnesium methyl iodide on the ethyl 0- m- and p-toluates or on the three tolyl methyl ketones or ( 2 ) by the action of acetone on the three magnesium tolyl bromides. The vapours of the three carbiuols were completely dehydrated under the influence of thorium oxide at 350" giving respectively 0- m- and p-P-allyltolueue C EI,Me*CMe:CH which by the action of slightly activated uickel at 200-220' yielded the corresponding cymenes.These substances underwent further hydrogenation when passed in the form of vapour over activated nickel a t 170-180' and the corresponding menthanes were obtained all of which have been previously described. I n certain cases t h e values of the physical constants now obtained differ from those previously given by other authors namely -o-fi-ailyltoluene has b. p. 175' Dk5 0.9181 ng 1.521 (compare Tiffeneau A. 1907 i 305). o-Cymene has b. p. 175" (corr.) DO 0.8902 ng 1.501 (compare Sprink- meyer 1901 i 519). o-Menthane b. p. 1713 (corr.) D 0.8326 D2,l 0.8135 ng 1.447 (compare 'Kay and Perkin T.1905 87 1066). r-rn-Menthane b. p. 166-167' (corr.) DS 0.7968 ng 1.440. d-?n-lilenthane was obtained by the hydrogenation of natural d-sylve- strene a t 200' by activated nickel and has b. p. 167-1668' D8 0.8235 0,8116 n z 1.446 [a] + 1.60" (compare Knoevenagel A. 1897 i 610). The para-isomwide has lo. p. 167-168" (corr.) D; 0.8134 DT 0.8028 ng 1.440 (compare Sabatier and Senderens Zoc. cit.). Systems Formed by Chloro- and Nitro-toluenes with Anti- mony Tnhaloids. BORIS N. MENSCHUTKIN (J. Buss. YIqs. Cham. Soc. 1912 44 1939-1963).-0- m- and p-Chlorotoluenes melt at - 36.2" CH2 W. G.i. 256 ABSTRACTS OF CHEMICAL PAPERS. (Haase A. 1892 ii 357 gave - 34O) - 47.8' and 6.2' (Hanse Zoc. cit. gave 7.4') respectively.With antimony trichloride o-chlorotoluene forms the compound SbCl,,C,H,MeCI crystallising in long plates or needles m. p. 3' and the eutectic points and compositions are (1) 37.5' and SbC1,,24*1 C6H,MeCl and (2) - 0.5' and SbC13,1.95C,H,MeC1. m-Chlorotoluene gives the compound SbCl,,C,H,MeCl which is much less stable than that formed by the ortho-derivative and decomposes before melting ; the eutectic points are (1) - 14' SbC1,,2*7C6H,MeC!l and (2) - 4Y0 SbC1,,24.1C,H4MeC1. p-Cblorotoluene and antimony trichloride form no compound the diagram showing only one eutectic point a t - 7*5' corresponding with SbC1,,2*3C6H,MeCl. With antimony tribromide none of the chlorotoluenes form corn pounds. The eutectic points and the corresponding compositions me for the ortho-compound - 38.5' and SbBr3,23*8C6H,MeC1 ; for tJhe meta-compound - 50' and SbBr3,32*3C6H4MeC1 and for the para- compound 2.5' and SbBr3,9.4C,H,MeC1. o-Nitrotoluene has m.p. - 8.5' (Knoevenagel A 1907 i 203 gave - 9.4' and Ostromisslensky A 1907 i 120 - 10.56') for the more stable a-modification and - 4' for the less stable @-form ; the solutions in antimony trihaloid always correspond with the a-compound. The meta- and para-isomerides melt at 16' and 52.5' respectively. o-Nitrotoluene and antimony trichloride give the compound SbCI,,C,H,Me-NO crystallising in slender needles m. p. 34.5'; the eutectic points are - 18*5O corresponding with SbC1,,7*28C6H,Me*N02 and 27.5' with SbCI 0.5 6 C6H4Me *NO,. m-Ni trotoluene and an timori y chloride form a compound which apparently melts at a higher temperature than the corresponding para-compound but could not be obtained crystalline.p-Nitrotoluene and antimony chloride form a compound SbCI C,H,bl (?*NO2! which crystallises with difficulty ; the eutectic points and compositions are (1) 7.5' and SbCl,,1.55C,H,Me*N02 and (2) 3' and S bC1,,0*76C,H4Me*N0,. With antimony tribromide o-nitrotoluene forms the compoynd SbBr,,C6H,Me*N0 crystallising in needles m. p. 32' (decomp.) isomorphous with those of the corresponding compound of antimony trichloride. The system exhibits one eutectic point - 13.5' corre- sponding with SbBr 10-8C6H,Me*N0 and one transition point 31' Corresponding with SbBr 1.3C6H,Me-NO,. m-Nitrotoluene and antimony tribromide form no compound the system showing only one eutectic point - 9' corresponding with SbBr 2C,H,Me*NO,.The para-derivative also forms no compound with the tribromide the diagram consisting of two curves meeting at the eutectic point 16' for which the composition is SbBr 1 '3c6 ,Me*N02. These results are discussed in relation to those obtained with benzene and its other substituted derivatives (Zoc. cit.). FRITZ STRAUS and LEO LEMMEL (Ber. 19 13 46 232-241).-1f A2-dihydronaphthalene which was obtained T. H. P. A1-Dihydronaphthalene.ORGANIC CHEMISTRY. i. 257 by Bamberger and Lodter (A 1888 292; 1896 i 99) by the action of sodium aud ethyl alcohol on naphthalene is heated with an alcoholic solution of $odium ethoxide it quaatitatively undttrgoes ieomeric change into the hitherto unknown Al-di hydronaphthalene. Crude A2-dihydronitphthalene was purified by shaking in ethereal solution with an aqueous solution of mercuric acetate ; the crystalline mercury compound after washing with ether wa3 dissolved in benzene when it slight insoluble residue waa obtained apparently of the mercury compound of hl-dihydronaphthalene due to a trace of this hydrocarbon in the crude starting substance.The pure mercury compound rn. p. 119- 120° obtained on evaporation of the solution when decomposed with a 30% solution of bydrochlolic acid gave pure h2-dihydronaphthalene leaflets xn. p. 34 5-25' b. p. 94..5'/17 mm. which on heating for eight ht,urs at 140-150° with sodium ethoxide in alcoholic solution was isornerised into Al-dihycEronc~~hthalene b. p. 84-85'/12 rnm. m. p.-8" to - 7O a n unpleasant-smelling liquid which immediately decolorises permanganate ; when bhaken with mercuric acetate i t is t.lowly converted into a white nzwcury deriv- ative which is insoluble in benzene and does not melt below 250'; the dibromide colourless crystals m. p. 70-71" is quite distinct from t h a t (m. p. 71.5-72') of the A2-isomeride and when boiled with alcoholic potassium hydroxide gives an oily substance of characteristic odour together with a little naphthalene. When an emulsion of Al-dihydronaphthalene in wdter i8 oxidised by the gradual addition of concentra ed potassium permmganttte d u t i o u o-carboxyphenylpropionic acid is obtained together with a quantity of a pungent substame of low m. p The furtfie~. reduction of' Al-dihydronaphthalene can be accornpiished by the addition of i t s alcoholic solution t o finely-divided sodium t,he product being tetrahydronaphthalene.The above luethod of formation of hl-dihydronaphthalene disposes of the diaculty of reconciling the reduction of naphthalene through A2- di hydronaph thalene to tetrahydronap hthalene with the behavio~ir of the analogous allylbeiizene aud propeuylbenze~e only the latter of which is reducible by sodium and alcohol to n saturated homologue of benzeae (Klages A. 1903 i 19 329 ; 1904 i 567); according to this A2-dihydronaphthale1ie should not be directly reducible. The prepara- tion of tetrahydronaphthalene by Bamberger and Kitschelt (A 1890 1146) is to be attributed to the reduction uccurring by the stages D. F. T. Triphenylmethyl.XXII. Ethers or Oxides in the Triphenyl- methane Series. MOSES GOMBERG (J. Amer. Chenz. Soc. 1913 35 800-2 lO).-lt is welt known t h a t diarylcarbinols can be converted into the corresponding ethers or oxides by heating them either alone or in presence of a dehydrating agent. h few oxides of the triaryl- VOL. c v. I. ti. 258 BHSI'RACTS OF CKEMICAI PA P E W . carbinols have also been reported in the literature but the results of the present work show that most of the compounds thus designated were not in reality triarylmethyl ethers. A general method is now described for the preparation of triaryl- methyl ethers. These compounds are as stable as the peroxides are not affected by exposure to the air or by heating them to temperatures below their m. p.; they are not decomposed by water or dilute alkali hydroxide even at loo' but are hydrolysed when boiled with dilute acids alcohol acetic acid or acetyl chloride.When triphenylmethyl chloride is treated with silver oxide oxidation takes place with formation of diphenylquinomethane and other products but the ether is not obtained. If triphenylmethyl chloride is shaken with zinc oxide and ether in sealed tubes it is reduced quantitatively to triphenylmethane and this reaction furnishes a simple and rapid method for preparing the hydrocarbon. The oxides of cadmium lead nickel cobalt and magnesium do not react with triphenylmethyl chloride. When however a triarylmethyl chloride dissolved in a dry solvent such as benzene ether carbon disulphide or chloroform is heated on the water-bath with mercuric oxide the corresponding triarylmethyl ether is readily obtained in a good yield.Tyiphenylmethyl ether CPh,*O*CPb m. p. 235-237" (decornp.) forms white crystals and is soluble in about 25 parts of benzene at the ordinary temperature or in 5 parts of boiling benzene; 1 gram dissolves in 11 C.C. of carbon disul~hide or in 325 C.C. of ether. PhenyZfEuorene ether (t:>CPh) 0 m. p. 232-2333' forms colour- A 9 less crystals and is solubliinabout 6'5 parts of benzene or 100 parts of ether; it is readily converted into the peroxide m. p. 193' (Gomberg and Cone A. 1906 i 822). The compound obtained by Kliegl ( A 1905 i 187) by tthe action of acetic and sulphuric acids on phenylfluorenol is not identical with the ether now described. Phenylxanthenol ether (O<$z:>CPh) 0 m.p. 250-2262' forms pale yellowish-pink crystals and is soluble to the extent of 1 gram. in 12 C.C. of cold or 5 C.C. of hot benzene or in 160 C.C. of ether. p-Met~oxytr~pherLyZmethyll et?ter m. p. 212' is soluble to the extent of 1 gram in 25 C.C. of cold benzene. p-Acetoxytriphertylmethyl chloride m. p. 85-86' obtained by the action of hydrogen chloride on a solution of the carbinol in benzene forms white crystals; when treated with mercuric oxide it is con- verted into p-acetoxytriiohsnylmeth~~ ether m. p. 123-124' (decomp.) which crystallises in white needles and is not identical with the sub- stance to which this constitution was aspigned by Bistrzycki and Herbst (A 1901 i 702) ; the latter was probably the carbinol as suggested by Auwers and Schroter (A 1903 i 821).Another method has alE;o been devised for preparing triarylmethyl ethers. When triphenylmethyl carbonate is heated under certain conditims carbon dioxide is evolved and a nearly quantitative yield of triphenylmethyl ether is produced. The details of this method wili be published subseqnently. E. G. 2ORGANIC CHEMISTRY. i. 259 Triphenylmethyl Ether. MOSES GOMBERG (Bey.. 19 13 46 225-828).-Although triphengZmethyl ether is not obtained in the act.ion of silver oxide on triphenylrnethyl chloride (compare Schlenli this vol. i 34) the application of mercuric oxide gives a n almost quantitative yield of this substance (m. p. 235-237O) The reaction with mercuric oxide is a general one for the production of triaryl- methyl ethers.Triphenylmethyl carbonate (m. p. 205-2 10’) when heated with copper as a catalyst to 140° also decomposes into triphenylmethyl ether and carbon dioxide. The opinion is expressed that the behaviour of triphenylmethyl and its analogues is best explained by an equilibrium between the three structures represented by the tervalent carbon the hexnphenylethane and Jacobson’s (A. 1905 i 186) formulze. D. F. T. Synthesis of Pyrene. RICHARD WEITZENBOCK (Monntsh. 19 13 34 193-223).-Two schemes for the synthesis of pyrene have been followed. The first which should have led to the preparation of diphenyl-2 2’-diacetaldehyde which might have <$) condensed in a manner analogous to the formation (Il2 I CH of P-phenylnaphthalene from phenylacetaldehyde \ P j \ (Auwers and Keil A.1904 i 26) mas unsuccess- 18 eCH ful. The tetramethylacetal of the dialdehyde was / \ 7 2 / / obtained but on hydrolysis it gave 4 5 6 7-dibenzo- 11;; 81 CpCHO A‘ :‘ :6-cycZoheptatriene-2-aldehyde (mnexed formula) the ready closing of the seven-mem bered ring recall- ing the formation of 2-imino-1-cyano-4 5 6 7-di- benzo-A4 ’ 6-cycZobeptadiene from diphenyl-2 2’-cliacetonitrile (Kenner and Turner T. 1911 99 2104). The other scheme was analogous to the preparation of 2 :S-di- hydroxychrysene from py-diphenyl-a8-dihydromuconic acid (Beschke A. 1911 i 874) and consisted in the condensation of diphenyl- 2 2‘-diacetic acid t o dihydroxypyrene which could be reduced by means of zinc dust or hydriodic acid and red phosphorus. Scheme A .-It was first attempted to prepare dipbenyl-3 2’-diacrylic acid by the distillation OF methyl o-iodocinnnnmte white needles m.p. 40° b. p. 300-310° with copper but the decomposition proceeded to the formation of phenanthrene. The ethyl ester could not be obtained pure and gave still worse results. The acid was obtained however by Perkin’s synthesis on 2 2’-dinldehydodiphenyl (compare Mayer A. 1911 i 870) being accompanied by the lactone of diphenyl-2-carbinol-2’-carboxylic acid (Kenner and Turner Zoc. cit.) and was converted into the dicmide C,,H,,O,N white needles by means of thionyl chloride and ammonia. A better way to arrive at diphenyl-2 2’-diacetaldehyde was sought in the application of Weerman’s method (A. 190’7 i 132) to the ccmide of o-iodocirnnccmic acid.This was obtained by the action of thionyl cbloride and ammonia on the acid in light brown quadratic leaflets m. p. 204-205’ the crude chloride having m. p. 63-64’ When treated with sodium hypochlorite in methyl alcohol methyl ‘W t 21. 260 ABSTRACTS OF CHEMICAL PAPELt3. o-iodost yrptcarbamate C6H41 CH CH NH* CO,Me was obtained in colourleas leaflets m. p. 128-130° which on hydrolysis gave o-iodo- phenylacetnldehyde C,HpO1 in pleasant smelling white needles m. p. 35-36O. When heated with copper extensive decomposition took place which was also the case with the ptieizylbensylhydraxone stout colourless needles m. p. 1 04-105°. However the dimethyl- acstal C,,H,,O,I which was obtained by Fischer arid Hoffa’s method (A* 1898 i 659) as a colourless mobile oil b.p. 144’/19 mm. gave tt good yield of diphenyl-2 2’-diacetaldehyde in the form of a viscid yellow oil b. p. 210-211°/13 mm. On bydrolysis an unsaturated aldehyde was obtained in white pleasant smelling needles m. p. 10S-109° which gave phenanthraquinone on oxidation with chromic acid and is therefore to be regarded as 4 5 6 7-dibeneo-A-’ ‘4‘6-cyclohe~tctt~.isne-l-ccldehyda rather than as phenanthryl-Cace taldehyde. It gives a stable dibrornide C1,Hl,OBr In colourless needlea m. p. 133’ (decomp.). Scheme B.-Diphenyl-2 2‘-diacetonitrile was hydrolysed by means of concentrated hydrochloric acid a t 130-140” (compare Kenner and Turner Eoc. cit.) and the acid was dehydrated with zinc chloride or better converted into the chloride with thionyl chloride and then condensed with aluminium chloride. The impure reddish hydroxy- product gave pyrene when distilled with zinc dust or heated with hydriodic acid and red phosphorus a t 200’.An attempt to convert dibromoditolyl into the nitrile by Rlttnn’s method for phenylacetouittile (A. 1881 1034) resulted in the formation of Kenner and Turuer’h 2-imino-1 -cyano-4 5 6 7-diben~o-A~~~-cycZoheptadiene. C21H19N21 C,,H,*[CH,*CH(OMe),] 5. C. W. Quaternary Salts of Alkylideneamines and a General Method of Converting Primary into Secondary Aminss. HEBMAN DECKER and PAUL BECKER (Annulen 1913 395 362-37’7). -The formation of a quaternary ammonium salt by the addition of an alkyl iodide to an alkylideneamine is practicable but the product is often contaminated by other substances formed by (i) the dissociation of the salt into its generators (ii) heterospasis (Decker aud Fellenberg A 1909 i 116) (iii) intramolecular change ring forrnation or polymerisation of the Yalt.Quaternary alkylideneammonium iodides are decomposed by water or alcohol in the sense of the equation CHR”:NRR’I + H,O = K”*CHO + NHRR’ + HI whereby a very satisfactory method is secured of converting primary into secondary amines without any possibility of the formation of the tertiary amines or the quaternary salt. The yield of the secondary amine is usually more than 75% being less however in the case of primary aromatic amines containing the amino-group i n the nucleus. P-Phenylethylamine reacts with benzaldehyde and with vanillin on the wat.er-bath to form P-phenyZeth~ZbeiLzylidensasnine CHL,Ph*CH,*N :CHPh m.p. 33-34” coloui less prisms and p-phenylet~~~lvunilly2ide.neam.ir~eORGANIC CHEMISTRY. i. 261 m. p. 108-109° leaflets respectively. The former and methyl iodide at; 100' yield an additive compound which is decomposed by boiling 95% alcoh 01 into henzalde hy de and /3-phenylethybmotluy lccmine hydriodide CH,Ph*CH,*NKMe,HI rn. p. 113-115O. The base which is also produced by heating P-phenylethylglycine above its M. p. forms a hydrochloride m. p. 156-157' (decomp.) platinichloride m. p. 225-226' (decomp.) aod picrate m. p. 141-143". P-Phenylethyl- ethylamine prepared in a similar manner forms a hydriodide m. p. 166-1 68". Methyl-p-toluidine prepared in a similar manner from benzylidene p-toluidine or heptplidene-p-toluidine forms a h,y&iodide m.p. 134-137' pale yellow leaflets and a picrate m. p. 130-132' (decornp.) which is very sparingly soluble in benzene. Ethylaniline methylaniline and methplisobuty lamine have also been prepared by this method. c. s. The Nitro-derivatives of o-Cresyl Oxide [o-Tolyl Ether] and o-Cresylene Oxide [ Di-o-tolylene Oxide]. ALPHONSE MAILHE (Compt. rend. 1913 156 241-243. Compare this vol. i 173)-On nitrating o-tolyl ether in acetic acid solution a viscous liquid is obtained which by distillation under reduced pressure yields 5-nitro-o- tolyl ether C,H,Me*O*C,EB,Me*NO yellow needles m. p. 125" ; this 011 reduction with iron and acetic acid gives the corresponding amine m. p. 98'. If the nitration is effect$ed in cold fuming nitric acid by gradual addition of the ether to the acid 5 5'-dinztro-o-t02yZ other C)(C,H3Me*S0,) is obtained as a white powder m.p. 270° which on prolonged nitration with fuming nitric acid containing a little sulphuric acid is converted into 3 5 3' 5'-tetranitro-o-tolyl ether m. p. 115'. Di-o-tolylene oxide nitrates very readily in acetic acid solution on warming giving nitrodi-o-tolylene oxide O<b&€,Me*NOz' m. p. 108-109" giving by reduction the corresponding amine m. p. 92' which gives a red coloration in alcoholic solution with calcium chloride. By warming di-o-tolylene oxide with fuming nitric acid a dinityo- derivative is obtained crystsllising in yellow needles m. p. 1'70". By warming this cornpound with fuming nitric acid tetranitrodi-o-tolylene oxide O< CH"1e(L'02)2 i C,KMe( NO,) o[C6H&Te*( NO,)] C6H,Me is obtained as a white powder m.p. 210". W. G. The Action of Aldehydes on Phenols. HERMANN WICHELHAUS (Ber. 1913 46 110-112).-A continuation of research as to the origin of tho dyes in certain moods (compare A. 1910 i 868). Formaldehyde has been detected in certain trees (Curtius and Franzen A. 1912 ii 978; Kleinstuck A 1912 ii 1202) and t h e author bas therefore examined the action on phenols of trithioform- aldehyde which possesses the advantage of a lower volatility. In the presence of zinc chloride condensation occurs with P-naphthol resor-i. 262 ABSTRACTS OF CHEMICAL PAPERS. cinol a- and P-anthrols and dihydroxynaphthalene producing deeply coloured fusions which are difficult to purify. It is probable that one molecule CH,S condenses with two of the phenol.If the aldehyde is 6rst combined with sodium sulphite (D.R.-P. 87335) tbe condensation follows another course involving two molecules of aldehyde and two of the phenol ; the products are colloidal substances often yielding fluorescent solutions and possess dyeing potvsr. P-Naphthol after conversion into the acid OH*C',oH,-CH,*S03H gives a condensation product which in solution poshesses a green fluorescence dyes wool a rose colour and gives brightly coloured lakes with aluminium manganese and zinc salts. The product from P-naphtholsulphonic acid dyes silk greyish red. 2 7-Dihydroxynaphthalene when converted into 2 7-dihydroxv- naphthylmethanesulphonic acid and heated slowly with zinc chloride solution in a vacuum undergoes condensation below looo giving a blue substance C,,H,,O,; this dyes silk and also can be converted into nitro-derivatives which also possess dyeing properties.D. F. T. The Silver Equivalent of Quinol. M. A. GORDON (J. Physical Chem. 1913 17 47-88).-The number of molecules of silver h a l t reduced per molecule of quinol varies with the conditions up to at least 10.5. I n presence of acid no reduction occurs. I n alkaline solution t,he amount of silver liberated from precipitated silver bromide depends on the efficimcy of stirring the time temperature and con- centration of the alkali but not on the incident light. A t 20' in presence of excess of sodium hydroxide the action appears to proceed in two stages namely up to about 6 equivalents of silver in a few hours and then to about 8 in eighteen days.A t ZOO0 at least 9 equivalents are liberated in six hours. The silver equivalent of p-benzoquinone is about two less than that of quinol. The liberation of 6 equivalents of silver by quinol corresponds with the formation of dihydroxy-p-benzoquinone thus C,H,(OH)q + 6AgBr + 6KOH = C:,H,(OK),~ + 6Ag + 6KBr + 4H,O. p-Benzoquinone and monohydroxy-p-benzoquinone may be intermediate products as suggested by Luther and Leubner (Brit. J. Photo. 1912 59 632-747) although the prezjence of neither monohydroxy- nor dihydroxy-benzoquinone has been demonstr'ited. p-Benzoqciinone is undoubtedly an intermediate product and by the action of the alkaline solution is transformed into quinol plus a peroxidised product which may be hydrogen peroxide (Mees and Sheppard) or hydroxybenzo- quinone (Luther and Leubner). The Mees and Sheppard theory demands an infinite liberation of silver by a swall amouut of quinol in presence of sodium sulphite and is inadmissible.The Luther and Leubner theory restricts the silver equivalent of quinol to 6 and therefore does not express the whole truth. In strongly alkaline solution an excess of sodium sulphite increases the silver equivalent of quinol by 2 (from 6 to 8) for short runs and by 1 (from 8 to 9) for long rum. The effecc on the equivalent of benzoquinone i6 about half a s great. When hulphite is added after the reduction by quinol has started its effect is restricted. HenceORGANlC CUEMZSTHY. i. 263 sulphite probably intervenes in the first and second stages of the oxidation of quinol equally.Some of the sulphits is oxidised pre- sumably to dithionrtte although sodium sulphite alone is without action on silver bromide. Ammoniacal silver nitrate silver sulphite dissolved in sodium sulphite and silver oxide in presence of sodium hydroxide give quinol equivalents of 7 8 and 10.5 respectively for five minute runs. Pyrogallol with and without sodium sulphite has a silver equivalent of a little over 3 when tested with silver bromide in a one hour run. Catechol under like conditions has an equivalent of 4.5 increasing to 5.5 in presence of sulphite. R. J. C. o-Nitrophenyl Selenocyanate and o-Aminophenylselenol. HUGO BAUER (BeT. 1913,46 92-98).-When a solution of potassium selenocyanate is added gradually to a diazotised solution of o-nitro- aniline in which the excess of free mineral acid has been neutralised by the addition of sodium acetate nitrogen is liberated and a quanti- tative yield of o-nitrophenyl selenocyanate yellow needles m.p. 1 4 2 O ia obtained. This action appears to be a general one and was also successful with p-nitroaniline (p-niti-ophenyl selenocyanate pale yellow leaflets IU. p. 1 3 5 O ) sulphanitic acid p-aminobenzoic acid and arsanilic acid. On moistetiing with alcohol and then adding sodium hydroxide solution 0- and p-nitrophenyl selenocyanates undergo hydrolysis form- ing coloured solutions (violet and red respectively) of the sodium salts of 0- and p-nitrophenyEseEenoZs; the free phenylselenols could not be isolated but the addition of a solution of lead acetate precipitated the lead salts both of an orange colour.The coloured a1 kaline solution of o-ni txophenylselenol soon loses its colour undergoing oxidation even in a hydrogen atmoqphere to di-o-nitrophenyl diselenide yellow needles m. p. 209O which precipitates. The alkaline solution of o-nitrophenylselenol cau also be obtained by the interaction of o-chloronitrobenzene and sodiu m hydroselenide in dilute solution in cold alcohol and the diselenide can then LEI again obtained the oxidation being aided if necessary by the addition of hydrogen peroxide. The former method is h)wever the more satis factory . If the alkaline solution of o-nitrophenylselenol is treated near its b. p. with sodium hyposulphite a clear yellow or colourless solutiori of the soclium salt of o-aminophenyZsdenoZ is obtained which on careful oxidation with hydrogen peroxide gives a precipitate of di-o-amino- qhenyl diselenide orange needles m.p. 81'. When a solution of this in hot alcohol is treated with hydrochloric acid and the resultant suspension of the hydrochloride reduced by zinc dust the addition of sodium acetate precipitates the stable xi9212 salt of o-aminophenyl- selenol ; the action of lead acetate on a suspension of this gives the orange lead salt. The reduction of the diselenide can also be effected by alkali and dextrose (compare Clam A. 1912 i 851). The action of benzoyl chloride on the zinc salt of o-aminophenyl- selenol in the presence of ethyl acetate produces 1-phenyZbenxoseEsrLazoZe C,H,c(Se>CPh colourless needles m.p. 11 6-1 17' which could not Ni. 264 ABSTRACTS OF CHEMICAL PAYERS. be obtained by the action of selenium on benzanilide (compare Hofmann A. 1880 386 ; 1887 839). With picryl chloride the zinc salt undergoes condensation with the formation of 3 Ei-dinitropherco- v selenazine CFH,<-Se->C6H,(NC)2)2 NH (compare Kehrmann A. 1900 i 61). D. F. T. Some Compounds of Cholesterol giving Liquid Crystals. PAUL GAUBERT (Compt. !rend. 1913 156 149-151. Compare A. 1907 ii 932 ; 1908 i 882; 1909 i 92O).-On heat'ing cholesterol with the different tartaric acids for one minute a homogeneous isotropic liquid substsnce is obtained which on cooling yieids elongated rhombic crystals possessing very great plasticity. The direction of the greatest refraction coincides w i t h the long diagonal.A.t temperatures near to the point of fusion the crystalline particles of the crystals arraiige themselves so that the optical axis is perpen- dicular to the glass slide and there are produced extensive irregular films exhibiting all the characteristics of a uniaxial optically positive substance. The hardness of the crystals rapidly increases up to that of gypsum as they become solid. Similar results are obtained by using malic and lactic acids instead of the tartaric acids. Maleic and innlonic acids but not fiimaric acid yield optically positive liquid crystals almost instantly on warming with cholesterol but they are only stable within narrow temperature limits. The same applies t o the compound obtained with succinimide and cholesterol.In order t o obtain liquid crystals with cholesterol and succinic cinnamic or anisic acids i t is necessary to keep the mixture molten at 160' for one hour when characteristic optically negative crystals are produced. W. G. Action of Magnesium on a Mixture of Ally1 Bromide and Benzoin. V. JAKUBOVITSCH (J. Russ. Phys. Chem. Soc. 1912 44 1 858-1 86 1 ).-Di~hen?/laZl~let~~ylene glycol [ 6 € - d i p ~ e r c p l Z - h a - ~ ~ n ~ ~ n ~ - d i d ] C3H,*CPh(OH)*CHPh*OH prepared by decomposing with water the product of the action of magnesium on ally1 bromide and benzoin forms fimall colourless crystals m. p. 89' has the normal molecular weight in boiling benzene and decolorises bromine. Wben boiled with 20% sulphuric acid it i8 converted into *he corresponding double ether which crystallises in small colourless needles rn.p. 125- 126'. f HPh-O--yHPh CPh(C,H,)*O*CPh *C,K,' T. H. P. Influence of Constitution on the Rotatory Power of Optically Active Substances. V. Esters of d-Carvoxime. HANS RUPE and GEORG WOLFSLEBEN (Anncclen 1913 395 136-148).-Tk~e following substxnces have been prepweci generally by the interaction of d-carv- oxime pyridine (2 mols.) and the acyl chloride in benzene. Only the acetyl compound can be purified by distillation under diminished pressure ; the others must be crystallised from absolute or dilute alcohol. Acetylcarvoxirne has m. p. 63-64' b. p. 158-161'/17 mm. and and [a] + 43.02'. Crotonylcnrvoxime C1 H,,:NO-CO*C:H:CHMe oil,ORGANIC CHEMISTRY. i. 265 [a] + 33.46'; c~ip?~enyZacet?lZcaruozime m.p. 65-66' [a] + 17.63' ; cinnamoylcarvoxims m. p. 79' [ u p + 15.44' ; P-phenyl~opion?/Zcarv- oxime oil [a] + 26.23' ; a-13henyZcznnnmo?/Zcczruoxime CIoH 4 N 0. CO CPh CHPh m. p. 139-140' [a] + 37.06' ; aP-diphsnyl;oi.opionl/lcnrvoxime m. p. 1 19-120' [a] + 12-52' ; P-phenyZcinnnmoylcnrvo.xim19 m. p. 74-75O [a] + 26.37' ; di-P-phenylpropionylcarvoxinte m. p. 89-90"? [a] + 20.09' ; a-methyZcinnamoy/lcarvoxime m. p. 68-69' [a] + 16.33" ; P~henyl-a-methy~~rop~onylcc;crvoxi?ne oil [a] + 23 85' ; P-metlqlcin- nam#oylcarvoxime m. p. 78' [a] + 22.45' ; /3-phenyZ-P-methylpi*opionyZ- carvoxime oil [aJ$ + 22.76'. Excluding the U- and the P-phenylcinnamoyl- and diphenylpropionyl- carvoximes the rotation of the saturated or the alkyl derivatives i R distinctly greater than that of the corresponding nnsaturated or phenyl derivatives. A parallelism cannot be traced between the carvoxime esters and the menthyl esters of the acids.The entrance of a phenyl group int)o acetic acid or phenylncetic acid or the replacement OF methyl by phenyl in acetic acid or crotonic acid diminishes the rotatory power of the carvoxime ; the entrance of phenyl into the U- or the P-position in cinnamic acid increases the rotatory power. Just the converse behaviour is observed with the menthyl estera of the acids. The author is of opinion that the work so far recorded proves the necessity of dealing with substances containing one or at most two asymmetric carbon atoms in connexion with the problem The Determination of the Configuration of the Stereo- isomeric Cinnamic Acids.CARL LIEBERMANN (Ber. 1913 46 214-216).-A reply to Stoermer and Heymann (A. 1912 i 974) indicating that theirs is not the first experimental proof of tho steric configuration of nllocinnamic acid. Fixation of the Alkali Hydrogen Sulphites by the Salts and Esters of the Acetylenic Acias. ED. LASAUSSE (Compt. rend. 1913 156 147-149).-Under given conditions the salts or esters of the acetylenic acids of the type R*CIC-CO,H will unite with one or two molecules of an alkali hydrogen sulphite giving an alkali salt of a monosulphonic acid containing an ethylenic linking or of a saturated disulphonic acid. On heating phenylpropiolic acid (1 mol.) with normal sodium sulphite (1.5 mol.) in aqueous solution in a sealed tube for eight hours a t 1 O O O crystals of disodi~m-P-suZphocin,?bclmate SO,Na* CPh CH*CO,Na are obtained which rapidly decolorise potassium permanganate in the cold.When heated in sealed tubes at 130' with concentrated hydro- chloric acid it is decomposed giving carbon dioxide sulphur dioxide and acetophenone. On frision with sodium hydroxide a t 200-220° it yields sodiiim benzoate sodium acetate. and sodium sulphite. The corresponding potassium salt has been prepared starting with potassium sulphite. Methyl phenylpropiolate and sodium hydrogen sulphite under similar conditions yield sodium methyl sulphodnmrazocte S0,Na*CPh:CH*C02hle. of the relation between constitution and rotatory power. c. s. D. F. T.i. 266 ABSTRACTS OF CHEMICAL PAPERS. If the heating is carried on for forty hours under reflux instead of in sealed tubes three compounds are obtained namely methyl disodium disuZphophe.nyl~opionate C,H,Ph(SO,Na),*CO,Me disodium sulpho- cinnamate and sodium phen~l%isu~phopropionnate C,H,Ph( SO,Na),* C0,Na.These three substances can be separated by their varying solubility in alcohol. The barium salt corresponding with the last compound has been prepared. By similar methods the author has prepared methyl disodium disulpho-octoate C,H11~C2H2(S03Na)2*C02Me which is saponified by cold aqueous sodium hydroxide giving Lhe corresponding trisodiuni salt which when heated with hydrochloric acid in sealed tubes at 120" yields the acid C,HlI*C2H,(S03Na)2*C02H. He also prepared methyzll disodiwn disulphononoate C,H,,-C,H,( SO,Na),*CO,Me the trisodium derivative and the w i d C,H,,-C,H,(SO,Na),*CO,H.W. G. Synthesis of P-m-Tolyl-a-methylhydracrylic Acid. A. GUBAREV (J. Russ. Phye. Chem. Soc. 1912 44 1865-1 867).-Ethyl P-m-tolyl- a-methylhydracrylute C,H,Me*CH( OK)*CH Mo*CO,E t obtained by decomposing with water the product of the action of zinc on a mixture of ethyl a-bromopropionate and o-tolualdehpde is a colourless viscous liquid with a pleasant odour b. p. 171-172'/15-16 mm. The acid forms crystals m. p. about go" but was not obtained pure. The potassium (+H,O) silver zinc copper aud lead salts were prepared and the first two analysed. T. H. P. Influence of Constitution on the Rotatory Power of Optically Active Substances. IV. HANS RUPE (Annulen 1912 395 have been prepared by heating menthol and the substituted ethyl acetoacetate; acetoacetate m.p. 36' b. p. 154"/10 mm. ; methylaceto- acetate CLI,*CO*CHMe*C:O,*C,,H,g In. p. 148-149°/8 mm. [u)z - 63.59O in benzene n 1.45436 n 1-45733 mp 1.46317 my 1.46797 DF 0.9697 violet coloratiou with alcoholic ferric chloride ; ethyl- acetoacetate b. p. 155'/8 mm. [.] - 60.26O in benzene violet colora- tion with ferric chloride. The following menthyl esters are prepared by heating menthyl sodioacetoacetate and the requisite alkyl haloid in ethyl alcohol propylacetoacetote b. p. 163"/5 mm. [a] -57.27' iu. benzene reddish-violet coloration with alcoholic ferric chloride ; sec.- octylacetoacetate b. p. 139O/0-1 mru. [a] - 47.82' in benzene brownish- red coloration with ferric chloride. iMenthyl phenykucetoacetate prepared from menthol and ethyl yhenylacetoacetate at 140' has m.p. 69O b. p. 131-133°/0.1 mm. and develops a violet coloration with alcoholic ferric chloride. A freshly prepared solution of +the ester in benzene is dextrorotatory [a] + 1 9 ~ 0 7 ~ but rapidly becomes laevo- rotatory and has [u] -6'7.55' constant after ten days. I n aDother experiment [u]g was initially + 28*70° and finally constant at - 67.1 6' after sixty-seven days. I n alcohol [uE is initially - 38-27" and becomes constant at - 67.15" after forty-seven hours. 87-1 35). -[With EDUARD LENZINGER.]-Th@ following mHIf;hyl estersORGANIC CHEMISTRY. i. 267 Menthyl benzykacetoacetate prepared from menthol and ethyl benzyl- acetoacetate a t 155' has m. p. 68') and [a] - 106*97' and produces with alcoholic ferric chloride a yellow coloration changing to greyish- yellow.By treatment with benzyl bromide and alcoholic sodium khaxide a< 0') it yields menthyl ~~benxylacetoacetats m. p. 70') [a] - 2 5 ~ . Menthyl sodioamtoacetate and the requisite haloid in alcohol yield the following menthyl esters /?-phenyleth ylacetoacetate CH,Ph* CH,* CHAc*CO Cl0Hl9 b. p. 143'/0.1 mm. [a] - 51.64' in benzene and - 53.79" in alcohol violet coloration with ferric chloride ; y-phenylprop~z/lacetoncettcte b. p. 157'/0.1 mm. [a] - 45.44' in benzene and - 48.99' in alcohol ; allyl- acetoacetate b. p. 169-171'/13 mm. [a] -56-2'7' in benzene; cinnamylacetoacetate CHPh:CH*CH,*CHAc*CO,*CloHl [a] - 41 -31' in benzene. Menthyl benxoykacetate CH,Bz*CO,* C10H19 prepared f rom ethyl benzoylacetate and menthol at 120° has m.p. 41' [uE n benzene initially - 55.36O and finally -63.97' after fifty hours [a] in alcohol initially - 56.41' and finally - 56.89' after six hours is slig htly soliible in alkalis develops n deep red coloration with alcoholic ferric chloride and forms a semicarbcmone m. p. 163') which produces a dark green coloration with ferric chloride. The following menthyl esters are obtained by treating menthyl sodiobenzoylacetate with the requisite alkyl hsloid in alcohol ; a-benzoylpropionate CHMeBz*C02*CloHls 111. p. 68') [a] - 5 7.73' in alcohol ; a-benxoylbutyrate b. p. 208'/10 mm. [a]; - 55.86' in alcohol and - 54.27" in benzene ; u-benzoylvalerate decomp. 180°/0 mm. [a] - 52-35' in alcohol violet-red coloration with alcoholic ferric chloride.Ethyl benzoylphenylacetate and menthol at 160-165' yield rnenthyl benzoylpJhenylacetote m. p. 116' [a] + 20.14' in benzene and - 12.12' initially and - 62.60' after eighty-nine hours in alcohol. The following menthyl esters are obtained from merithyl sodio- benzoylacetate and the requisite haloid in alcohol a-benxoyl-/?-phenyl- propionute m. p. 11 7" [a] - 60.83' in benzene ; a-benzoyl- y-phenyl- butyrate m. p. i"i' [a] - 56.70' in benzene ; a-benzoyl-6-phenylvakerate [a]:- 43.97'; a-benxoyl-Ay-pentenoate m. p. 53' [u]g - 51 *40° in benzene violet-red coloration with ferric chloride iu alcohol ; a-benzoyE-6- phenyl-AY-pentenoate m. p. 82-83' [a] - 48.10'. By esterifying a-benzoyl-6-phenyl-AY-pentenoic acid with menthol and repeatedly extracting the product with pasolin it can be resolved in the sparingly soluble 1-rnenthyl l-a-benxoyl-6-phe.nyl-AY-pentenoc6te m.p. 102-103' [a] - 86-66' in benzene colourless needles and the more soluble 1-menthyl d-a-benxoyl-8-phenyl-hY-pentenoate m. p. 77' [a] -25.95' in benzene; the esters do not develop a coloration with alcoholic ferric chloride. Menthyl benzoylacetate and benzaldehyde and a little pipedine cooled in a freezing mixture yield menthyl a-bmzoylcinnamate CHPh:CBz*CO,-C,,H, m. p. 65') - 77-43' in benzene white leaflet's. [With PAUL HAusf3~~~.]-a-Benzylcinnamoyl chloride and mentholi. 265 ABSTRACTS OF CHEMICAL PAPERS. in benzene containing pyridine yield menthyl a-benxy Ecinnanaate CHPh C( CH,Ph)*CO,* CloH19 m.. p. 64-65' [a] - 144.86' in benzene and a-honz?/lcinnarnic onhy- dr2de O[CO*C(CH,Ph):CHPh] m p.108-109°. The latter which is stable to boiling aqueous sodium carbonate and is only slowly esterified by boiling alcohol and sulphuric acid is also obtained directly from the acid chloride and pyridine. Menthyl P-phenyl-a-bonzylpropionate m. p. 42-43' [a]; - 24.41' in benzene is prepared from the acid chloride menthol and pyridioe in benzene. [ With GEORG ~~oLFSLEBEN.]-T~~ reaction between potassium y-phenylbutyrate and an excess of benzaldehyde and of acetic anhydride a t 106' for forty-eight hours and subsequently on the water-bath for 290 hours leads to the formation of y-phenyl- a- benxylidenebutyric cccid CH,Ph*CH,*C( CH P h )* CO,H m. p. 124-125'. Its menth,yE ester prepared from the acid chloride menthol and pyridine in benzene is a yellow oil.[a]! - 23-00'. Ethyl sodiomalonate and P-phenylethyl bromide in boiling alcobol yield ethyl P-phenylethylmalonate CH,Ph*CH,-CH(CO,Et) b. p. 1 7 9 O / 10 mm. which reacts with alcoholic sodium ethoxide and benxyl bromide to form ethyl ban,zyl-~-phenyZeth~?~Zmalate CH,Ph*CH,*C(CH,Ph)(CO,Et) b. p. 230G/10 mm. By hydrolysis with methyl alcoholic potasPium hydroxide the latter yields benzy~-~-phen?~~ethy~mcilonic a d m. p. 153' (decomp.) which is converted a t 160' into y-phenyl-a-bsnzylbutyrzc acid CH,Ph*CH,*CH(CH2Ph)*C02H m. p. 59-61' b. p. 330'/8 mm. The acid chloride of the latter yields the menthyl ester m p. IOZ' [a] - 36-69" by treatment with menthol and pyridine in benzene and is converted by distillation under 15 mm.partly into 2-P-phenyzethyl- hy%i.ndo.ne C,H,< co ->CH*CH2*CH,Ph m. p. 56-57" (semicarb- CH2 azone m. p. 227-228' [decornp.]). y-Phenylpropyl bromide and potassium cyanide yield y-phsnyZbzLtyro.natr?:Ee b. p. 132-133'/11 mm. The acid is converted by phosphorus trichloride in benzene into the chloride b p. 119'/9 mm. from which menthyl y-phenylbutyrate b. p. 201io/10 mm. [a] - 57*00" is obtained by means of merithol and pyridine in benzene. The variations with time of the rotations of the preceding menthyl esters of &ketonic acids inalcohol and in benzene have been measured in order t o gain some idea of the magnitude and the velocity of the keto-enolic transformation. The acetoacetate and benzoylacetate rapidly acquire a constant rotation in a alcohol but only after many hours or even days in benzene ; the methylacetoacetate henzoyl- propionate and benzoylphenylpropionate have constant rotations in benzene as well as in alcohol. An unexpected fact of great importance has been found in the resolution by crystallisation of the menthy1 esters of P-ketonic acids of enantiomorphous configuration.Such esters the phenylaceto- acetate benzylacetoacetate benzoylphenylacetate and beozoylphenyl- pentenoate all of which it will be observed contain a phenyl group must have the ketonic structure. The case of the menthyl phenyl-ORGANIC CHEMISTRY. i. 269 acetoacetate is interesting. Only I-menthyl d-phenylacetoacetate has been isolated and it is dextrorotatory. As i t changes to the enol in benzene the activity due to the acidic portion disappears the activity finally being due to the I-menthyl group only; the time required for the attainment of a constant lzevorotation varies in different experi- ments (probably owing to the action of a catalyst in the glass) in one case being ten dLtys and in another sixty-five days.The converse is observed with I-menthyl d-benzoylphenylacetate which has a constant dextrorotation in benzene but is laevorotatory in alcohol reaching a maximum after four days. Menthyl benzyl- dibenzyl- and benzylidene-acetoacetates and the methyl- phenyl- benzyl- s-phenylethyl- cinnamyl- and benzylidene- derivative3 of menthyl benzoylacetate do not develop a coloration with alcoholic ferric chloride. In some cases the enolisation must be repressed by the ferric chloride because menthyl benzoylphenylacetate for example which does not give a coloration with alcoholic ferric chloride shows in alcohol a laeoorotation which increases with time.The author’s results show that valuable conclusions regarding structure can be drawn from the molecular rotations provided strictly homologous esters are being cowpared ; comparisons are not justifiable a-Hydroxy- y-phenylcrotonic Acid. An Example of an Ether of a Ketone Hydrate. J. BOUGAULT (Compt. rend. 1913 156 236-239. Compare A 1912 i 770 and Fittig A. 1898 i 196).-By the controlled action of dilute sodium hydroxide on a-hydroxy-y-pheuylcrotonamide and subsequent neutralisation with acid an acid amide is obtained having the constitution when an alkyl group is replaced by a phenyl group.c. s. CH,Ph*CH,*C( OH) CO,H CK,Ph*CH,*C(OH)*CO*NH which on heating loses two molecules of water giving another acid amide C,oH,90,N. The first compound is readily decomposed by alkalis or alkali carbonates quantitatively into ammonia and benzyl- yyruvic acid but urilike the acid anhydrides is not hydrated by boiling with water or dilute acetic acid. Esters of Aromatic Keto-acids. GHETE EGEHEK and HANS lSlxYm (Monatsh. 1913 34 69-93. Compare A. 1908 i 26)- The pseudo- and normal esters of some beuzoylated benzoic acids are described. In most cases the +-methyl esters for which the sensitive colour reaction with concentrated sulphuric acid is characteristic are produced by the action of thionyl chloride but Goldschmiedt and Lipscbitz had already shown (A.1905 i 132) t h a t the n-ester resulted in the case of naphthoylbenzoic acid whilst +-ethyl esters were hitherto unknown. It is now demonstrated that the +-ester is the primary product in all cases but t h a t under the influence of alcohol and mineral acid3 it may undergo further changes which reault in the n-ester. ‘l’o prevent this rearrangement for example in the case of the naphthoyi- benzoate the mixture of the acid chloride and the alcohol is immediately poured into sodium carbonate solution. On the other hand any $-eater may be converted into its isoweride by the action of >o ? W. G.i. 270 ABSTRACTS OF CHEMICAL PAPERS. a mineral acid or thionyl chloride and an alcohol. I n this way R +methyl ester may be transformed into ft methyl ester which might be supposed to be due to the effect of mass action on the already rearranged n-methyl ester.Since however prolonged heating with methyl alcohol is necessary to convert ethyl n-benzoylbenzoate into the %-methyl ester whereas the +-ethyl ester gives the In-methyl ester in a short time the conclusion is drawn that the transformation of the @form into the n-form is not due to any instability of the chloride or of the ester but to the addition of alcohol to the lactone system under the catalytic influence of hydrogen ions and the subsequent elimination of alcohol from the methane carbon atom according to the scheme C-OMe /R C-OMe /R - - /\A MeOH /\/A I I + (HC1) = I I * \/\/ C-OMe /R c-0 /" v\/ 7'0" CO 0346 OM0 OMe Jt thus becomes evident why the action of ammonia on the iso- merides always results in the same amide namely that of the ketone acid (compare Meyer A.1905 i 133). Some of the acids employed were derived from the chlorophthalic acid which Auerbach obtained by the action of hypochlorites on phthalic acid. Since this may be condensed with benzene and trans- formed into @-chloroanthraquinone it is to be regarded as 4-chloro- phthalic acid. Whereas methyl pbenzoylbenzoate may be prepared without pre- caution by the action of thionyl chloride and methyl alcohol the formation of the $-ethyl ester only succeeds when the mixture of the chloride with excess of cold absolute alcohol is a t once poured into cold sodium carbonate solution. It crystallises in triangular tablets m. p. 5 1-53" and dissolves with lemon-yellow colour in concentrated sulphuric acid.The methyl ester (rhombic a b c = 1.9725 1 1,267) may be prepared by leaving the chloride with alcohol by the usual means or by boiling the +-methyl ester for a few minutes or the n-methyl ester for a few hours with alcohol and thionyl chloride or sulphuric acid. Conversely methyl alcohol and thionyl chloride transform the +.ethyl ester into the n-methyl ester in a short time whereas the n-ethyl ester must be heated for fifty hours. I n the same way methyl $-toluoylbenzoate and methyl +-methoxybenzoylbenzoate (Meyer and Turnau A. 1909 i 710; m. p. 83' and not 63") may be converted into the n-esters. The preparation of 4-chlorophthalic anhydride by Auerbach'sORGANIC CHEMISTRY. i. 271 method has been improved ; the compound has b.p. 291 -295" and when crystallised from dry ether has m. p. 94" but after contact with moist ether the m. p. rises to that of the acid. When condensed with benzene in presence of an excess of aluminium chloride i t yields ben8xoyl-4-c?dorobenxoic m i d m. p 180*5O which gives /I-chloroantlira- quinone (Graebe and RBe T. 1886 531) in conceutrated sulphuric acid. The acid chloride COPh*C,H,CI*COCI long needles m. p. 114-117" also readily yields the quinone on heating. The +-methyl ester forms colourless needles m. p. 68-5-69.5' and the n-ester forms monoclinic crystals (a b c = 1.8252 1 0.6878 ; p = 76'59') IU. p. 102-104°. The acid obtained by the condensation of 4-chlorophthalic anhydride with chlorobenzene dissolves in sulphuric acid with the formation of 2 6-dichloroanthraquinone and is therefore 2-p-chlorobenxoyt-4-chloro- benxoic acid which confirms the position of the halogen in the above benzoyl-4-chlorobenzoic acid.The acid bas m. p. 195*5" gives a well- defined acid chloride m. p. 115-120° from which however the +-ester could not be obtained crystalline. The n-methyl ester from the transformation of the crude isomeride or by direct esterification melts at 989 Methyl ~-p-chZoro&nzoylbcrzxoate m. p. 101-102*5O; the n-ester m. p. 109-1 lo" monoclinic crystals (a b c = 0.92461 1 ? ; /I = 73"40') and the n-ethyl ester m. p. SS' have also been prepared. Phthalic anhydride condenses with p-dichlorobenzene when boiled with an excess of aluminium chloride in nitrobenzene ; the 2-om-di- chlorobenxoylbenzoic acid radiating needles m.p. 1 6 8 O yields 1 4-di- chloroanthraquinone (Ullmann and Billig A . 191 1 i 490). Similarly 4chlorophthalic anhydride and p-dichlorobenzene give 2-om-dichloro- benxoyZ-4-chlorobenxoic ucid m. p. 157-1 60° which condenses t a form 1 4 7-trichloroanthraquinone and yields a +-methyl ester m. p. The constitution of the isomeric esters (A. 1908 j 26) receives support from the molecular refractions for methyl n-benzoylbenzoate [M.R.] = 61.98 being a benzophenone derivative shows exaltation (compare Auwers and Eisenlohr A 1911 ii 782) whereas the +-ester gives the theoretical value for a hydroxylactone [M.R.] = 65.4U. 115-1 20". J. C. W. Isomeric Esters of Trichlorobenzoylbenzoic Acids. STEPHAN JAROSCHY (Mormtsh. 1913 34 1-6.Compare preceding abstract). -The product of the condensation of 1 4-dichlorophthalic anhydride with chl or0 benzene 2 - p-chloro bemxoyl-3 6-dichlorobenxoic acid crystallises in colourless leaflets m. p. 1 5 7 O and yields 1 4 7415- chloroanthraquinone in concentrated sulphuric acid The $-methyl ester colourless crystals m. p. 153-154" and the $-ethyl ester n white crystalline powder m. p. 150-151° may be obtained by immedia ely adding the mixture of alcohol and acid chloride to sodium carbonate solution and may be transformed into the rz-esters by heating with thionyl chloride and the corresponding alcohol for some hours. The normal esters may also be obtained by the usual methods give no C,'P?*,C13~i. 272 ASSTRAC'fd OF CHEMICAL PAPERS. coloration in sulphuric acid and melt a t 90' and 105-106Q respectively.J. C. W. Preparation of Amides and Acylation of the Amino-group. HERMAN DECKER (Aiirtalen 1913 395 282-399).-Hofmann's classical method of preparing amides and substituted amides by heating the ammonium salts of carboxylic acids or their salts with primary and secondary amines which has fallen into dihuse owing to its supposed disadvantages is shown to be a simple and convenient method of preparation provided the optimum temperature (the temperature at Mhich water is eliminated it may be dowly from the salt whilst the dissociation of t,he latter is still hardly apprt- ciable) is obtained and is retained to the end of the reamion. A whole series of amides and substitutled amides have thus been prepared by simply heating the acid and the amine at the optimutn temgera- ture.The reaction which is analogous to the formation of an ester from an acid and an alcohol is accelerated as in the case of esterification by catalysts. [With WALTER KHOPP HEINRICH HOYER CLEMENS ZOELLNER and PAUL ~~c~~~.]-Formophenylethy~amide is o b tltined free from P-phenylethylamine formate and in 96% yield by heating P-phenyl- ethylamine and anhydrous formic acid in slight excehs a t 170-180' for four hours. I n a similar manner phenylacetyl-6-phenylethyl- amine (95% yield) is obtained from phenylacetic acid and the amirie a t lW0 aud acetyl-/3-phenylethylaruine from acetic acid and the amine. Piperoriylucetumide CH,O, C,H;CH,* CH,*CO*NH m. p. 122-1 23" colourless leaflets can be prepared from the acid chloride and 25% aqueous ammonia from ethyl piperonylacetude b.p. 5 0 3 O 3r.d aqueom ammonia a t 160-180O (bad yield) or from 3 4-~uethyletedioxy- phenylpropiooy 1 chloride and 25% aqueous ammonia is readily ob- tained by heating piperonylacetic acid for two hours at 200-220' in a current of dry ammonia. It is readily converted by the sodium hypochlorite method into homopiperonylamine (hydrochloride m. I). 207-208" ; picrate m. p. 174-176O ; curbonate m. p. about 110' ; platinichlorzde xn. p. about 225' [decomp.]). ~o?.rnol~omo~i~el.onylarnide C H,O C H CH,* C H ,*NH C H 0 m. p. 61-62' is obtained almost quantitatively from the amine and anhydrous formic acid a t 1 80-200°. Phenylacstohornop~peronyl~mide CH,O,:C,H,.CH,*C H ,*NH*CO*CH,Ph m. p.9 6 O is obtained from the aruine and phenylacetic acid at 160'. Homopiperono ylhomopiperon ylamim CH,O2:U,Hs*CH2*CH,*NH*C0*CH2*C~~~:CH,O~ m. p. 1 1 9 O is piepared from the amine and homopiperonylic acid a t 160' for eight hours. Homopiperonylic acid is obtained in 5% yield by oxidising safrole in well-cooled acetone with potassium permanganate and treating the precipitate with sulphurous acid whereby piperonylic acid is precipitated ; the homopiyeronylic acid is extracted from the filtrate by ether. Anhydrous oxalic acid react6 with p-phenplethylarnine at 180-200° to form oxalodi-/3-phenylethjltimide m. p. 186O in 61% yield and with homopiperonylamint! a t 1 iO-180° to form oxulodiho7tlopzyeron~~ORGANXC CHEMISTRY. i. 273 amide C,0,(NH~CH2dCH,*C,H,:CH202)2 m.p. 196-197' (corr.) colourless needles. Fagaramide (Thorns and Thumen A 1912 i 115) can be syn- thewed by heating piperonylacrylic acid and isobutylamine at 190-200° for two and a-half hours. c. s. The Oxidation of Substituted Aceanthrenequinones. D. kuTEscu - (Ber. 1913 46 212-214. Compare Liebermann and Butcscu A. 1912 i 467).-The substituted aceanthrenequiuones behave on oxidation in a similar manner to acennthrenequinone itself yielding anthraquinonecarboxylic acids (Liebermann and Zsuffa A. 1911 i 202). The oxidation is effected in acetic acid solution by chromic acid. P-MethylarLthraquinone-a-car~o~yZ~c acid yellow needles M. p. 2 9 5 O is obtained in the oxidation of P-rnethylaceanthrenequinone. P-Chloroanthraquinone-a-carbo~yZ~c acid yellow needles m.p. 260° obtained from P-chloroaceanthrenequinone is distinct from the P d l o r o - anthraquinonecarboxylic acid described by Heller and Schiiike (A 1908 i 994). a-Chloroanthraquinonc-a-carboxylic acid obtained by the oxidation of a-chloroaceanthrenequinone forms leaflets m. p. 2054 which can be sublimed to give yellow needles; it is distinct from the isomeric substances described by Heller and Schulke (loc. cit.) and Fischer and Sapper (A 1911 i 279). 1 5-Dichloroan~hraquino~-~-car~ox~Zic mid obtained from 1 5- dichloronceanthrenequinone has m. p. 250'. 1 8-Dichloroanthraquinone-5-carboxylic acid from the corresponding aceanthrenequinone forms yellow needles m. p. 240'. D. F. T. Action of Magnesium on a Mixture of Ally1 Bromide and Phthalic Anhydride. A. ORLOV (J.Russ. Phys. Chem. Soc. 1912 44 1868-1870. Compare Bauer Abstr. 1904 i 417; 1905 i 210). Diallylphthalide C6H4&(-2F&>0 prepared by the action of water on the product of the interaction of magnesium ally1 bromide and phthalic anhydride is a pale yellow slightly mobile liquid of pleasant odour b. p. 184-185'/14 mm. DF 1.0546 ng 1-53614 and develops fluorescence on prolonged keeping. It unites with 4 atoms of bromine giving a liquid bromide C,,H1,O2Br of pleasant odour. T. H. P. The Reaction between 5-Bromo-2 4 6-tri-iodo-1 3-dinitro- benzene and Ethyl Sodiomelonate. C. LORING JACKSON and F. C. WHITMORE (Ber. 191 3 46 67-70).-The explanation (Jackson and Bigelow A. 191 1 i 101) of the reaction between ethyl sodio- malonate and halogen-nitrobenzenes in which one of the halogen atoms of the latter becomes replaced by hydrogen is now tested by applying it to 5-bromo-2 4 6-tri-iodo-1 3-dinitrobenzene ; this substance is found in accordance with the hypothesis first t o form with the ethyl sodio- malonate an additive compound which probably has the constitution VOL.CIV. i. UIi. 274 ABSTRACTS OF CHEMICAL PAPERS. C0,Et*CHI*C(ONa)(OEt)*C6Br12( NO,) which when acidified under- goes scission into C6HBr12(N02) and UHI(CO,EG),? the latter substance then reacting with a second molecule of ethyl sodiomalonate with the formatiou of ethyl ethanetetracarboxylate. The additive compound could not be isolated but a mixture of 2-bromo-1 3 5-tri-iodo-4 6-dinitrobenzene and ethyl sodiomalonate in alcohol gives a deep red liquid ; if an excess of the halogen compound or of ethyl sodiomalonate is taken and a littleof the filtered red liquid is evaporated the percentages of sodium in the residue in the former case and of halogen in the latter are in accord with the above corn posi t ion.The direct coupling of the substituted benzene ring with the ethyl sodiomalonate is attributed to the possibility that the substituted ring is mom negative than the iodine atom and it i R held that the formation of p-toluenesulphinic acid and ethyl ethanetetracarboxylate from p-toluenesulphonyl chloride and ethyl sodiomalonate (Kohler and MacDonald A 1899 i 907) is in support of such a view. D. F. T. Polymerisation of Cinnamylideneacetic Acid by Light. C. N. RIIBER (Bev. 1913 46 335-338).-The author has obtained the.dimolecular form of cinnamylideneacetic acid by the action of light on cinnamylideneacetic acid. Cinnamylideneacetic acid was exposed to the action of light until the product had a mean mol. wt. of about 260 in acetone. The complex mixture so obtained was treated with a large quantity of benzene whereby considerable quantities of oxidation products were isolated. The residue obtained by evaporation of the benzene mother liquor after successive treatment with cold and boiling benzene left .a white crystalline residue of bisnolecular cinnamylideneacetic acid needles m. p. 219O mol. wt. in acetone solution 320 which mas purified by solution in methylal and addition of benzene. The acid is very sparingly soluble in the usual solvents. The silver salt was Ph*yH*$X€*CH:CH*CO,H is assigned to examined.The formula the acid since when oxidised by potassium permanganate in alkaline solution it yielded oxalic and henzoic acids and an acid which could not be obtained in the pure state but gave a silver salt C,,H90,Ag and a methyl ester O,,HlsOs. Since it was stable towards potassium permanganate its composition is probably represented by the formula Ph* VH* CH*CO,H CO,H*CK* bH*CO,H* allocinnamy lideneacetic acid is similarly but more readily poly- merised by the action of light. Bimolecular cinnamylideneacetic acid (m p. 219') differs greatly from the isomeric acid (m. p. 204') obtained by the action of light on cinnamylidenemalonic acid (A. 1902 i 617) particularly in regard to solubility in acetone. The latter acid when oxidised by potassium permanganate yielded benzoic and oxalic acids together with a saturated acid m.p. 134'. The formula CO,H* CH*CH*CH:CHPh a-Truxillic acid could not be isolated.ORGANIC CHEMISTRY. i. 275 Ph*~H*CH.CK:CH*Co2H is advanced for the acid m. p. CO H*CH:CH*CH*CHPh 204'. H. W. New Oxime of Santonin. GUIDO CUSMANO (Atti R. Accad. Lirncei 191 2 [v] 2 1 ii 796-800).-When nitrosohydroxylamino-p- santoninoxime (Prancescooi and Cusmano A. 1909 i 724) is heated with an equimolecular quantity of N-sodium hydroxide on the water- bath nitrous oxide is evolved and an oxime is formed which is identical with the santoninoxime of Cannizzaro (A 1886 '73). If however nitrosohydroxylamino-a-san toninoxime is similarly treated a new suntoninoxime of the same composition is produced; it differs from Cannizzaro's oxime in physical and to a certain extent in chemical properties and is regarded by the author as representing the oxime of formula 11 which is stereoisomeric with the oxime of formula I (Cannizzaro's oxime) adopting the formulae deduced from the work of Angeli and Marino (A. 1907 i 321).CMe CMe (1.) (11.; The new oxime crystallises with l*H,O in scales or in lustrous needies; on heating it becomes red towards 180° m. p. 230' (decomp.). I n addition this a-oxime differs from the p-oxime of Cannizzaro in having a bitter taste and in yielding the corresponding santoninic mid C,5H,,0,N,3&H20 m. p. SO0 when its solution in sodium hydroxide is exactly precipitated with acid. If this acid is kept a t 100' for twenty hours the original oxime is formed.The hydrochZos.ide of the oxime crystallises in colourless scales which change on keeping into large prisms ; on heating the hydrochloride undergoes gradual change until it melts at 168'. With water it yields t h e oxime together with santonin and hydroxylamine hydro- chloride. When treated with sodium nitrite and acetic acid the new oxime yields a pernitroso-derivative C H,,O,N H,O which forms prismatic crystals which become red at 175' m. p. 197' (with evolution of gas). This compound differs from that obtained from the other oxime in m. p. and in water of crystallisation but resembles it in giving santonin when heated with alkali and yielding a blue coloration with a solution of diphenylamine in sulphuric acid.Treatment of the p-oxime with methyl sulphate yields a mono- methyl ethur CI,H230,N (which forms silky acicular crystals m. p. 184') and also another substance having the same composition but crystallising in long thin needles m. p. 196O. Under the same conditions the a-oxime gives a methyk ether of the same composition which forms large prismatic crystals m. p. 185'. A mixture of this ether with tbat of m. p. 184' has m. p. about 160O. R. V. S u 2i. 2'76 ABSTRACTS OF CHEMICAL PAPERS. The Action of Oxalyl Chloride on Polynuclear Hydro- 198-212. Compare A 1911 i 202 387 656; 1912 i 464).- 2 4 2' 4'-Tetramethyldiphenyl when oxidised by prolonged boiling with sodium dichromate and diluted sulphuric acid gives in poor yield diphenyl-2 4 2' 4'-tetracarboxylic acid (compare Liebermann and Kardos A.1912 i 465); the same acid is obtained with still more diEculty by the oxidation of 2 7-dimethylphenanthraquinone in which phenanthraquinone-2-carboxylic acid can be isolated as an intermediate product. Oxalyl chloride reacts with 2 4 5 2' 4' 5'-hexamethyldiphenyl at the ordinary temperature in carbon disulphide solution in the presence of aluminium chloride giving a mixture of 1 2 4 5 7 8-hexamethyl- phena&ra-9 10-quinone yellow prisms m. p. 223-224' (the monoxime yellow flakes m. p. 178' when submitted to the Beckmann rearrangement gives a substance possibly the mononitrile of hexa- methyldiphenic acid ; the monophenylhydraxone exists in two forms a- red needles m. p. 187' p- yellow needles m. p.143' which are possibly cis- and trans-isomerides respectively) with 2 4 5 2' 4' :5'-hexa- nae 2 h y ldiphen yldicarboxy Zic acid a m ic r ocrys talli ne powder y .+ p. 284-285' which is turned yellow by light. This acid when oxidised in alkaline solution by potassium permanganate is converted into diphenyl-2 4 5 2' 4' 5' ? ; ?'-octacadoxylic acid a hygroscopic solid which gives a fluorescein reaction when fused with resorcinol ; calcium salt very soluble ; silver salt colourless ; when dried at llO' the acid loses carbon dioxide and water giving the monoanhydride of diphenyl- carbons. CARL LIEBERYANN and M. KARDOS (Be?'. 1913 46 the silver salt was prepared. 3 4 5 3' 4' 5'-Hexamethyldiphenyl was prepared from 5-amino- hemimellithene (Noelting and Porel A.1886 58 ; Limpach A 1888 464) ; in the preparation of this latter substance by heating a mixture of s-xylidine hydrochloride and methyl alcohol at 250-260' under 30-33 atmospheres' pressure a relatively large quantity of acridine bases was obtained as a high boiling feebly basic mixture which gave fluorescent solutions in organic solvents; there could be isolated from this mixture a substance m. p. 223' another substance (probably tetramethykc~cridine) m. p. 172-1 75' and a hexamethyl- acridine m. p. 220-225' ; hydrochloride yellow ; platimicidoride yellow and sparingly soluble. Aminohemimellithene was converted through the corresponding diazonium salt into 5-iodohemimeZlithene crystals m. p. 35' which on heating with finely divided copper (compare Ullmann A 1904 i 725) at 230-25O0 loses iodine with the formation of 3 4 5 3' 4' 5'-hexamethyldiphen?/l m.p. 132-133'. I n an experiment on a small scale in which hexamethyldiphenyl and oxalyl chloride were kept for six weeks in carbon disulpbide solution in coctact with aluminium chloride the product was a mixture of carb- ixylic acids with a neutral yellow substance doubtless the expected 1 2 3 6 7 8-hexamethylphenanthra-9 10-quinone. In extension of the earlier result with phthalic acid which was converted by acetyl chloride into phthalyl chloride (Liebermann A.,ORGANIC CHEMISTRY i. 277 1912 i 464) it is found that terephthalic and isophthalic acids in like manner with acetyl chloride a t 130' give terephthalyl chloride needles or leaflets m. p. 83-84' (compare Schreder this Journ.1874 990) and isophthulyl chloride prisms m. p. 43-44" respectively ; in the former case the product is accompanied by a little terephthalyl acid chloride C,H,*COCl*CO,H needles m. p. above 300'. Compounds of Benzaldehyde and Benzonitrile with Antimony Trichloride and Tribromide. BORIS N. MENSCHUTKIN (J. Russ. P f q s . Chern. Soc. 1912 44 1929-1938. Compare A . 1912 ii 930 and acnle).-For benzaldehyde Haase (A. 1893 ii 357) gave the m. p. -26' and Altschul and von Schneider ( A . 1895 ii 206) - 13.5'. The author finds that different preparations of the aldehyde melt a t temperatures varying from -26' to - 15'. This behaviour is probably due to the ready oxidisability of the aldehyde in the air most samples containing dissolved peroxide and acid.With t h e systems containing benzaldehyde difficulties were encountered in determining temperatures lying between the melting point of the aldehyde and the first eutectic point. D. F. T. Benzaldeh~de and antimony trichloride form the compound S bCI Ph* CHO m. p. 43.5' crystallising in elongated plates often united in stellar aggregates The eutectic point between this comporind and the pure trichloride lies at 25' and corresponds with the composition SbC13,0*44Ph*CH0. The compound SbBr,,Ph*CHO forms rhombic plates and crystals resembling rhombohedra m. p. 41-5" and the eutectic point lies at 37*8' and corresponds with the composition Sb Br Ph CH 0-S b Br SbBr,,O.63Ph0CHO. Benzonitrile has m. p. - 13.2' (Hofmann Jahresbericht 1862 335 gave - 17' and von Schneider A.1896 ii 290 and 1897 ii 304 The compound sbCl,,Ph.CN crystallises in quadratic plates m. p. 21*5' and the eutectic temperatures and compositions of the system are (1) for Ph-CN-Sbcl,,Ph.CN - 19' and SbCI,,1O.6Ph.CN and (2) for SbCI,,Ph*CN-SbCJ - 15' and SbCI,,O+59Ph.CN. The compound SbBr,,Ph.CN forms long plates or needles m. p. 38' and the eutectic points are 18' for SbBr3,8*7Ph*CN and 35' for - 12.9'). SbBr,,O.74Ph.CN. The diagrams of all the above systems have the form typical of the formation from the components of a single stable compound. T. H. P. New Synthesis of Syringaldehyde. FERDINAND MAUTIINEH (Annalen 1913 395 273-281).-Syringaldehyde is readily obtained in good yield by Guyot's process (A. 1909 i 935; 1910 i 40) A mixture of pyrogallol 1 3-dimethyl ether ethyl ruesoxalate anhydrous zinc chloride and a little carbamide is kept in glacial acetic acid for fourteen days whereby ethyl 4-hydroxy-3 5 -dimethoxyphnyltartronate OH*C,H2(OMe),*C(CO2Et),*OH m.p. 60° is obtained in almosti. 278 ABSTRACTS OF CHEMICAL PAPERS. quantitative yield. The ester by hydrolysis by boiling aqueous potassium hydroxide acidification below lo' and treatment with aqueous copper sulpbate finally a t the b. p. is converted into 4-hydroxy- 3 ; 5-dimethoxyp~~elz~Z~l~oxylic acid (ttyringoykarboxylic acid) OH*C,H,( OMe),*CO*CO,H m p. 126-129' yellow needles (p-nitrophenylb ydrazone m. p. 2 25' [decomp.] yellow needles) which yields syringaldehyde by treatment with boiling dimethyl-p-toluidine as in Guyot's method.The relative positions of the aldehydo- and hydroxyl groups in the aldehyde are proved by the fact that it yields gallaldehyde trimethyl ether by treat- ment with methyl sulphate in alkaline solution. Syringaldehyde forms a p-nitrophenylhydrazone m. p. 216-217' yellow needles and an uldazine C9Hl8O3N2 m. p. 208-209' yellow needles and reacts with 1 -phenyl-3-methyl-5-pyrazolone in hot glacial acetic acid to f oral 1 -phen yl- 4-p- h ydrox ydi-m-methoxybenzy Zidene- 3- methy1-5-py~uxoZone C,,H,,~,N m. p. 208-209' red leaflets with acetophenone and 33% sodium hydroxide in alcohol at 80' to form after acidification 4-hydroccy-3 5-dimethoxybenxylidelnebisacetophenone C25H2405 m. p. 112-113' faintly yellow leaflets and with P-naphthyl- amine and pyruvic acid in boiling alcohol to form a-p-hydroxydi-m- nzet~oxy~hRn?lZ-P-nap~thacinchonic acid C,,H170,N m.p. 275" (decomp.) yellow needles. c. s. a-Chlorocyclopentanone and its Derivatives. MARCEL GODCHOT and F ~ L I X TABOUEY (Compt. rend. 1915 156 332-334).-By pass- ing dry chlorine over cyclopentanone kept a t a temperature below 25' a mixture of substances is obtained which on fractionation yields 2-ch1orocyclopentctnone C,H,OCl b. p. SO0/lO mm. D1 1.870 n 1.4782 which on boiling with water or an aqueous suspension of barium carbonate is converted into cyclopentanone-2-01 C5Hs02 b. p. 80°/12 mm D 1.1680. It is very soluble in water and in solution gives a reddish-brown colour with potassium hydroxide and n violet-red with ferric chloride. It forms a phenylhydraxone yellow needles m.p. 142-143' and a sernicarbaxone a yellow powder decomposing at 170'. This hgdroxy-ketone is readily oxidised by 1% potassium permanganate to glutnric acid. Ou distilling 2-chlorocyc1opentanone either alone or better with diethylaniline it loses hydrogen chloride and is converted into A2-cyclo- pentenone a colourless liquid b p. 135-136' which gives a semicadazone m p. 214-215' and an oxime m. p. 52-53'. W. G. Terpenes and Ethereal Oils. CXIII. Autoreduction of Hydroaromatic Compounds at the Moment of their Forma- tion. OTTO WALLACH and PAUL FRY (Annulen 1913 395 74-86). -P-Methyl-AP-hcpten-[-one and zinc chloride form a t the ordinary temperature after two to three weeks a very viscous brown mass which is probably an additive compound since it is decomposed into its generators by water.A t loo' however methylheptenone reacts vigorously in the presence of zinc chloride or phosphoric oxide ; hyarogen is not evolved and the product is a complex mixture fromORGANIC CHEMISTRY. i. 279 which an oil is obtained by distillation with steam. By distillation t h i s oil yields a very large fraction b. p. 130-14O0 which is not 1 3~dimethyl~ycZo-A*~~-hexadiene as stated previously but is proved to be a mixture of m-xylene and 1 3-dimethyl-A3-cycZohexene by treat- ment with 3% pptassium permanganate a t Oo whereby the m-xylene is unattacked whilst the 1 3-dimethylcyclohexene is converted into 89O. The constitution of the glycol is proved by*the fact that it yields 1 3-dimethylcycZohexan-4-one b. p. 179-179*5O D210.9066 ng 1,4464 (semicnrbazone m.p. 189' ; oxime m. p. 98-99.) by treatment with warm dilute sulphuric acid. This ketone in an impure state (b. p. 176 5O D16 0.9124 n 1.446) has been described by Sabatier and Mailhe in 1906. By oxidation with chromic and dilute sulphuric acids on the water-bath i t yields a keto-acid (semicarbaxone m.. p. 136-1 37O) which is converted into bromoform and /I-methyladlpic acid by alkaline hypobromite. Since hydrogen is not evolved and 1 3-dimebhyl-A' '3-cycZohex~diene is not nbtnined by the aut,o-condensation of the methylheptenone i t follows that one molecule of 1 3-dimethylcyclohexadiene loses hydrogen and changes to m-xylene the hydrogen converting rz second molecule into 1 3-dimethylcycZo-A3-hexene. c. s. Synthetic p-Dialkylated Dihydroxyquinones and Hydroxy- perezone.FRITZ FICHTER MAX JETZER~ and ROBERT LEEPIN ( A m a h 1913 395 1-25. Compare A. 1904 i 678; 1908 i 658).-The following substances have been prepared by the reaction as described previously between sodium ethyl oxalate and a fatty ester in ether or benzene. The reactiou proceeds more slowly the greater the mole- cular weight of the fatty acid and reaches i t s limit with n-decoic ester ; ethyl laurate or palmitate do not yield a p-dialkylated dihydroxy- quiuone. 3 6-Dihydroxy-2 5-diisobutyZ-p-benzoquinone C14H2004 m. p. 217-218O (in closed tube) red spangles (diacetate m. p. 113*5' yellow crystals) from ethyl isohexoate develops a blue coloration in concentrated sulphiiric acid acd a violet in aqueous sodium hydroxide.3 6-Dihydroxy-2 5-dianayLp-benzoquinone Cl6HZ4O4 m. p. 164O red leaflets (diucetate m. p. %4" yellow needles) from ethyl n-heptoate ; 3 6-dihydroq-2 5-dihexyEp-benxoquinone C18H2804 m. p. 154O red scales (diacetate m. p. 6So yellow needles) frvm ethyl n-octoate; 3 6-dihydroxy-2 5-diheptyE-p-benxoquinon6 C20H3204 m. p. 145q red leaflets (diacetate m. p. 77.5' yellow needles) from ethyl n-nouoate ; 3 6-dihydroxg-2 5-dioctyZ-p-benxoquinone m. p. 141° red leaflets from ethyl n-decoate. I n the colour of their solutions and of their alkali salts and in their inactivity towards hydroxylamine and ortho-diamines p-dialkylated dihy droxybeazoquinones show a greater similarity to chloroanilic acid than to the unsubstituted dihvdroxvbenzoquinone. The same is true of their ethers ; 3 6-dimetho&y-2 i-diisoG*opyl-p- benzoquinone CPrKCO.C(oMe) C(o''e)*co>CPrfi m.p. 1424 prepared from the silver derivative crysthlisei in almost black leaflets.i. 280 ABSTRACTS OF CHEMICAL PAPERS. Ethyl isoualerylacstate CH,Pr+CO*CH,*CO,Et b. p. 99*5O/12*5 rnm. D15 0.964 prepared by hydrolysing ethyl isovalerylacetoacetate with aqueous ammonia is soluble in alkalis develops an intense red colora- tion with ferric chloride yields 1-phenyl-3-isobutyl-5~yraxolone CH2*70 CH2prS*C<N-Nph9 m. p. 105*5O with phenylhydrazine and condenses with resorcinol and concentrated sulphuric acid t o form 5-hydroxy-4-isobutylcournarin C1,H,,O m. p. 117" glistening needles which dissolves in alkalis with a blue fluorescence. By treatment with ozonised oGygen 3 6-dihydroxy-2 5-dialkyl- p-benzoquinones in dry chloroform at 0' do not yield ozonides but are decomposed in the sense of the equation C,R,(OH),O + 6 0 + 2H,O = 2H,C,O + SR*CO,H the necessary water being produced by the complete oxidation of a portion of the quinone ; thus dihydroxydiisopropgl-p-benzoquinone yields oxalic and isobutyric acids dihydroxy-p-xyloquinone yields oxalic and acetic acids (the same products are also obtained by the oxidation of the quinone by alkaline potassium permanganate) dihydroxy- diethyl-p-benzoquinone yields oxalic and propionic acids and di hydroxy- thymoquinone yields oxalic and isobutyric acids acetic acid not being detected.The study of dialkylated dihydroxybenzoquinones has thrown con- siderable lig ht on the constitutionof perezone (pipitzahoicacid).This sub- stance is converted through the anilino-derivative into hydroxy perezone by Mylius's method ( A 1885 777 805). Hydroxyperezone C1,H200 m. p. 138-1 39O yellowish-red needles resembles the dialkylated dihydroxy-p-benzoquinones in its colour in the colorations i t develops with concentrated sulphuric acid and with aqueous sodium hydroxide respectively and in its conversion into a tetra-acetate C23H3008 m. p. 97-98' colourless crystals by reductive acetylntion. By treatment in chloroform with ozonised oxygen it yields oxalic acid and not a volatile fatty acid as expected but up-diketobutyric acid which is isolated and identified by treating its aqueous solution with phenyl- hydrazine whereby up-diketobutyric acid phenylosazone (completely identified by its conversion by warm alkali into 4-benzenenzo-1-phenyl- 3-methyl-5-pyrazolone) is obtained.The formation of the diketo- butyric acid is accounted for if one of the side-chains in hydroxy- perezone is a propenyl group. Consequently the other side-chain must be a hex71 group since the sum of the carbon atoms in the side-chains is 9. Hydroxyperczone therefore has the constitution Since hydroxyperozone readily loses water to form perezinone (Mylius loc. cit.) whilst perezone does not suffer an analogous change perezone has the constitution C 6 H * ~ ~ ~ ~ ~ ~ ~ ~ ~ and pere- zinone is c(OH)-cO*~-cH>C€€. I I By reduction with sodium amalgam and aqueous sodium hydroxide at 1 OOO hydroxyperezone yields C(C6H1,)-CO*C.CH,ORGANIC CHEMISTRY. i.28,1 hexylpropenyldihydrwesorcinol C15H2*02 m. p. 140-1 4 4 O colourless needles. By similar treatment dihydroxythymoquinone yields methyl- isopropyldihydroresorcino,? C1,H,,02 m. p. 1 70° softening a t 145' colourlese leaflets. c. s. Camphor and its Derivatives. XII. JULIUS BREDT (Annalen 1913 395 26-63).-[With 6. HOUBEN P. LEVY and S. LINK.]- Hethyl 4-chloi*ocamphovate ~H2-CC1~co2nle)>~Me2 m. p. 56' b. p. CH CMe( C0,Me) 158'/15 mm. is prepared from 4-chlorocamphoryl chloride and sodium methoxide in methyl alcohol. By slow distillation a t 254-285' under ordinary pressure it yields hydrogen chloride and lnsthyl dehydro- camphorate C,,B.,,O b. p. 137'115 mm. and also methyl chloride and methyl camphanate the latter decomposition resembling that which occurs during the distillation of the ester of a y-halogenated fatty acid.Phenyl 4-chZorocamphorate C22H230,C1 m. p. 89' obtained in a similar manner from sodium phenoxide in petroleum (b. p. 70-100°) yields by slow distillation or by heating with quinoline only hydrogen chloride and phnyl dehydrocamphorate C22H2204 m. p. 155'. Phenyl dl-4-chloro- camphorate m. p. 74" yields phenyl dl-dehydrocampliorate m. p. 133O by similar treatment. By hydrolysis with aqueous methyl alcoholic potaesium hydroxide removal of the alcohol and phenol and subsequent acidification phenyl dehydrocamphorate yields d-dehydrocamphoric acid m. p. 202-203' [a) + 118.6O in chloroform and + 113.8' in alcohol CH*CH-CO which is converted into isodehydrocamphoic an- \o. hydride (annexed formula) m.p. 185.5-186' and camphonenic acid by distillation under ordinary 11 &Me2 CH*dMe*CO/ pressure. iaoDehydrocamphoric acid has m. p. 181-182' and readily yields the anhydride by treatment with cold acetyl chloride. Dehydrocamphoric acid yields camphoronic acid by oxidation with dilute nitric acid or alkaline potassium permanganate and forms a methyl hydrogen ester C,,H,,O rn. p. 96" silver salt C,Hi,(C0,Ag)2,H,0 and ccclciunz saltl C1!Hl2O4Ca 4 H,O. It does not form an anhydride and yields the chloride C,,,H,,02C12 b. p. 139'/135 mm. m. p. about 50° by treatment with phosphorus pentachloride or acetyl chloride. The non-formation of an anhydride and the fact that its chloride reacts with aqueous ammonia at 0' to form the diarnide CloH1,O2N,,H,O m.p. 1914 colourless needles (compare A 1912 i a l l ) show that dehpdrocamphoric acid has something approaching the cis-trans configuration. Reference to the tetrahedral model shows that the two carboxyl groups are in what the author terms the meso-trans position in which the spatial separation of the acidic groups is almost as great as in the cis-trans modificat,ion of the isomeric isodehydrocamphoric acid. The non-existence of dehydrocamphoric anhydride explains why hydrogen chloride or bromide cannot be eliminated from the C5-ring ot 4-chloro- or bromo-camphoric anhydride. With S. LINK and TH. Fussc+Am~~.]-When heated at 100' for IIi. 282 ABSTRACTS OF CHEMICAL PAPERS. six bours with hydrobromic acid saturated at O' d-dehydrocamphoric acid yields a mixture of cis-3-bronzocan~phor~~ acid m.p. 158-160° and trans-3-bromocccmphoric acid m. p. 232' of which the former is easily soluble in benzene. The cis-acid which is the chief product of the action of hydrobromic acid at O' yields cis-camphoric acid and the trans-acid yields tmns-carnphoric acid by reduction with zinc and glacial acetic and 24% hydrochloric acids. The action of hydrobromic acid at 100' on dZ-dehydrocamphoric acid yields a mixture of two stereoisomeric dl-3-bromocomphoric acids m. p 188-189' (decomp,) and 239-240' respectively of which the less fusible is the chief product is insoluble in benzene and yields t?*ans-dl-camphoric acid by reduction. Unlike the active acid dl-dehydrocamphoric acid is not attacked by hydrobromic acid a t Oo even after three months.By boiling with aqueous sodium carbonate and subsequently acidifying cis- 3- bromocamphoric acid yields 3 -h ydroxycamphoroZactone C10E11404 m. p. 228O whilst trans-3-bromocamphoric acid yields trans- 3-hydroxycan~phoric acid C1,,HI6O5 m. p. 194' and camphonenic acid m. p. 155" identical with that mentioned above and with the un- saturated acid obtained by Noyes from the nitroso-derivative of aminolauronolic anhydride (A 1906 i 397). The constitution of camphonenic acid is proved by the formation of camphorouic acid by oxidation with nitric acid or potassium permanganate. 3- H ydroxycam ph orolac tone boils unchanged b 11 t trans-3-hydroxy- camphoric acid yields dehydrocamphoric acid and isodehydrocamphoric anhydride by slow d i s ti1 la t i on.tran 8-3- H y droxy cam phoric anhydride yields only the latter by distillation. By heatiag equal molecular quantities of bromine and dehydro- camphoryl chloride at 100' for six hours decomposing the product with aqueous sodium carbonate and acidifying an unsaturated acid C,H,,O m. p. 149' colourless needles is obtained which is probably dchydrolaurolenic acid. From the behaviour of the two acids it is probable that in cis-3- bromocamphoric acid the two carboxyl groups are each i n the cis-position t o the bromine atom whilst in trans-3-bromocamphoric acid the bromine is in the cis-position t o the neighbouring carboxyl and in the trans-position t o the other carboxyl group because lactone formatiou does ncst occur by the distillation of its esters although the halogen is in the y-position t o the carboxyl group.c. s. Action of Magnesium and Ally1 Haloids on Camphor. METSCHISLAV CHOJN (J. Buss. phvls. Chem. Xoc. 1912.44.1844-1853). -At?lyZborneol (1 7 ; j-trirrLethyZ-~-aZZyl-l ; 2 2-bicy~loheptan-2-02) ' ClL-CH-CH CH,* CMe-6(OH)*CH2*CH CH obtained by decomposing with water the product of the interaction of magnesium ally1 bromide or iodide and camphor is a colourless viscous liquid with a pleasant camphor-like odour b. p. 118-1 19'/ 17 mm. 120-121°/21 mm. D?'* 0.9474 9 ~ ; ~ ' ~ 1.48943 and exhibits the normal molecular weight in freezing benzene or boiling ether. ItORQANIC CHEMISTRY. i. 283 unites with two atoms of bromine and when treated in ethereal solution and in presonce of anhydroiis sodium sulphate with dry hydrogen chloride a t Oo gives the analogous chloro-derivative which is converted into the corresponding unsaturated hydrocarbon when heated with dry pyridine. Oxidation of allylborneol with 1% potassium permanganate solution yields py-dihydroxypropylborneol ( 1 7 7-~rimeth~l-2-~opan-~y-dioZ- CH,-YH-CH 1 2 2-bicycloheptcc~z-2-02) I ?Me I CH2*CMe*C(OH)*CH,* CH(0H) CH,* OH which forms radiating or beard-like masses of tasteless odourless snow-white crystals m.p. 119-120° and exhibits normal ebullio- scopic behaviour in benzene. When oxidised with 4% potassium permangauate (4 atoms of oxygen) allylborneol is converted into the hydroxy-acid borneolacetic acid I ?Me I which was not obtained in the pure state; the ammonium silvey and calcium (+ 2H,O) salts of the acid mere prepared and analysed.Y CB,*YH-CH CH,*CMe*C(OH)*CH,* CO,H T. H. P. Bupleurol. The Alcohol from the Essential Oil of Bupleurum fructicosum. LUIGI FRANCESCONI and E. SERNAQIOTTO (Atti R. Accad. Lincei 1913 [v] 22 i 34-40).-This alcohol which the authors named bupZeuroZ can be isolated by the aid of phthalic anhydride from the higher fractions of the essential oil. It has the compositior C,,H,,O b. p. 209-210°/762 mm. D17 0,8490 nD 1.4508 and is optically inactive ; the substance has a slight pleasant odour of roses. From its physical properties the substance is probably a n olefinic alcohol and this is supported by the fact that it yields an oily dibromide. It forms a urethane which crystallises in lust,rous needles m. p. 45'. Oxidation of bupleurol with chromic acid yields (1) an aldehyde which shows Schiff's reaction and gives a semicarb- clxone m.p. 135' ; (2) an aldehyde of which the seniicarbazone has m p. 97' ; ( 3 ) a ketone (b. p. 2 17O vt 1.442 9) which yields a sernicarbaxone m. p. 189-190'; (4) a red oil b. p. 207' which is the ester of bupleurol and the corresponding acid which was also isolated. Bupleurol is isomeric with citronellol and wit'h androl and the authors assign to it the formula CHMe,-[CH2],*C(CH2)*CH2*CH2*OH which is t h a t of a dihydro-derivative of nerol. When the phthalic ester of bupleurol is dissolved in ammonia and treated with silver nitrate the silver salt C,,H,,O,Ag is obtained m. p. 135'. I n the isolation of bupleurol a substance C,,H1,O is als met with; it has an acrid odour gives a coloration with Schiff's reagent reduces ammoniacal silver nitrate and has D 0.9264 [a] 14*93O n 1,4909.R. V. S. Insoluble Constituents of Ceara- and Rambong-Caoub CLAYTON BEADLE and HENRY P. STEVENS (Xeitsch. Chem. Znd. chouc.i. 284 ABSTRACTS OF CHEMICAL PAPERS. KoZZoide 1913 12 46-48).-The influence of the insoluble constitu- ents on the properties of Ceara- and Rambong-caoutchouc has been investigated and the results compared with those of similar experiments carried out previously with Hevea-caoutchouc (A. 1912 i 789). “Benzine” was added to the caoutchouc and the products recovered from the upper clear solution and the lower turbid solution were separately examined the latter containing practically the whole of the insoluble constituent.The data compared are the nitrogen content the proportion of free and fixed sulphur in the vulcanised material and the mechanical properties. Although the relationships involved are of a complicated character it would appear that the insoluble constituents play an important part in connexion with the vulcanisation of the caoutchouc and are more or less independent of the percentage content of nitro- genous substances in the caoutchouc. H. M. D. Artiflcial Caoutchoucs. 11. CARL 1). HARRIES (Annakn 1913 395 211-264).-Replies are given to the remarks of Lebedev (A. 1911 i 959) Kondakov Ostromissleneki and Perkin (A 1912 i 636) in connexion with the author’s first paper (A 1911 i 798). [With MAX H A ~ E D O R N . ] - T ~ ~ identity of natural and of artificial caoutchoiics caunot be satisfactorily tested by a comparison of their derivatives except in the case of the ozonides. The products of their decomposition contain similar amounts of lwualdehyde and its acid and diperoxide.Also the comparison of the velocity of decomposition under proper conditions of the diozonides and dioxozonides (Harries and Neymann A. 19OS i 967 ; Harries A 1912 i 706) gives satis- factory results. The decomposition curves of the diozonides of Para caoutchouc (purified by twice precipitating its benzene solution by alcohol and by two extractions with acetone in a Soxhlet apparatus for twelve hours) of gutta-percha and of artificial caoutchouc obtained by the autopolymerisation of isoprene at 95” are the same; the decomposition curve of artificial caoutchouc obtaiaed from isoprene by the acetic acid process is slightly different.The decomposition curve of ‘‘sodium ” caoutchouc diozonide is quite different The same is true of the butadiene caoutchoucs. “ Sodium ” butadiene-caoutchouc (purified by the alcohol-benzene method) forms a diozonide the decom- position products of which do not contain a trace of succindialdehyde or lavulaldehyde and the decomposition curve of which is quite different from that of the diozonide of butadiene-caoutchouc polymerised by heat. Like natural caoutchouc artificial ‘‘ normal ” caoutchoucs form diozonides and dioxozonides. Artificial ‘‘ sodium ” caoutchoucs also form diozonides and dioxozonides although with greater difficulty ; the products of their decomposition by water are similar but the diozonides yield a larger proportion of aldehydes the dioxozonides a larger amount of acids.Gutta-percha purified by alcohol and chloroform and by prolonged extraction with acetone yields with washed 9-10% ozone a diomzde C,,H,,O which so closely resembles the diozonide of natural or of artificial caoutchouc that most probably they are identical. By further treatment with 18% ozone in chloroform gutta-percha diozonide yieldsORQANIC CHEMISTRY. i. 285 a dioxozonide CI,H1608 which behaves like the dioxozonide of Para caoutchouc. The authors have been able to account for a phenomenon which has frequently been observed. Caoutchouc diozonides prepared apparently in the same manner frequently yield by decomposition with water different amounts of the crystalline lzevulaldehyde diperoxide m.p. 196'; it has now been shown that the quantity of this product increases with amount of dioxozonide in the diozonide. I n partial agreement with Gottlob (A 1908 i 436) the authors find that the diozonides of African (Congo) caoutchoucs yield quantities of decomposition products distinctly different from those of the decomposition products of the diozonides of Para caoutchouc artificial caoutchouc and gutta-percha. Congo caoutchoucs yield dioxozonides only with difficulty. [With WILHELM ScHoNBERff.]-The exhaustive methylation of piperidine is not a suitable method for the preparation of piperylene in quantity. It can be obtained readily as follows (1) acraldehyde and magnesium ethyl bromide yield by the usual process the alcohol CH,:CH*CHEt*OH which is then dehydrated by phbhalic anhydride ; (2) the alcohol CHEt,*OH prepared in the usual manner from ethyl formate and magnesium ethyl bromide yields Ab-pentene by distilla- tion with phosphoric oxide; the olefine forms a cbibromide CHMeBr.CHEtBr b. p. 65-70°/15 mm. which is converted into piperylene by the sodium carbonate process at about 600'. By heating for about fourteen days at 105-110' in an atmosphere of carbon dioxide piperylene polymerises to ' I normal " pipwylene- caoutchouc Cl0Hl6 which is elastic and very closely resembles '' normal " iaoprene-caoutchouc in most of its properties. I t forms a nitrosite-a C,,H,,O,N (?) decomp. 118-12Y yellow powder insoluble in acetone or ethyl acetate and a nityosite-c 2CloH1507Na decomp.162-1649 easily soluble i n acetone or ethyl acetate and an unstable bromide Cl0Hl5 5r3 ('?) decomp. 150-160° palo yellow amorphous powder ; these three derivatives are almost indistinguishable from the corresponding derivatives of '( normal " isopreoe-caoutchouc. The ozonides of the two caoutchoucs however are quite dissimilar. By treatment with washed ozone in chloroform piperylene-caoutchouc yields the dioaonide C,,H,,O which explodes violently by heating and exhibits the usual properties of ozonides. It forms a dioxozonide o d y with very great difficulty. The decomposition curve of piperylene- caoutchouc diozonide is similar to yet quite distinct from that of normal caoutchouc diozonide but the decomposition products are quite different. The former diozonide does not 'yield lsevulaldehyde but a substance which is most probably methylsuccindialdehyde.Hence '' normal " piperylene-caoutchouc (which is a true structural iisomeride of " normal " caoutchouc piperylene being AaY-pen tadiene) is a derivative of 1 5-dimethyl-2 6-cycZooctadiene This is the best method. L 2C'HO*CH,*CH Me.CH.0.i. 286 ABSTRACTS OF CHEMICAL PAPERS During the polymerisation of piperylene by heating a by-product is obtained in the form of a terpene CIOHIB b. p. 58-59'/11 mm. D:'" 0.5313 VL:'~ 1.46916 72 1.46620 n 1.48373 which forms a crystalline bromide m. p. 178" and a white dioxonide Cl0H,,O ; the velocity of decomposition of the latter by water at 125" is very great but definite substances could not be isolated from the products owing to lack of material.The polymerisation of yiperylene by sodium at 60' yields a (' sodium " piperylene-caoutchouc which is brittle after purification ; it forms a nitrosite decomp. 140-145' and a bromide the analyses of which do riot correspond with the formulae of the normal compounds. [By the AuTHoR.]-T~~ proof of the presence of an &ring in " normal " caoutchoucs is of fundamental importance in the chemistry of caoutchoucs. To test this point the velocity of decomposition of " normal " butadiene-caoutchouc diozonide has been com- pared with that of the diozonide of Willstatter's 1 5-cyclo- octadiene. (A serious difficulty is encountered iu separating the " normal " butadiene-caoutchouc from the terpenoid hydrocarbon C8H12 obtained .as a by-product during the polymerisation.Both substances form almost colourless diozonides C,H,,O ; the diozonide of the terpenoid hydrocarbon is decomposed very rapldly by water at 1 2 5 O and the products of decomposition contain hydrogen peroxide but do not respond to the pyrrole test.) The comparison shows that both decompose at the same rate %(at first the normal " butadiene- caoutchouc decomposes more rapidly but this is probably due to the presence of a little of the easily decomposable diozonide of the terpenoid hydrocarbon) and yield practically the same amount of succindialdehyde. Since the decomposition curve of 1 5-cyclo- octadiene diozonide is very characteristic and since the decomposition products of the two diozonides are quite alike in not responding to the hydrogen peroxide test and in containing the same percentage of succindialdehyde the statement is made with considerable confidence that '' normal " caoutchoucs contain an $-ring.[With RICHARD S~~~z.]-Ahhough Zslinsky and Gorsky (A. 1908 i 619) have resolved l-methyl-A2 4-cycZohexatliene into its active forms their method of preparing the substance does not necessarily lead to the formation of a compound of this constitution (compare Harries and Neymann A. 1909 i 218). The authors therefore have used a method similar to that by which Harries obtained pure Al '3-cycZohexadiene (A. 1912 i 343). l-Methyl-A3-cycZohexene and bromine in acetic acid yield 3 4-dzbromo-l-rnetAylcyclohexane b. p. 94-95'112 mm. which reacts with 33% alcoholic trimethylamine (2 mo1s.) a t about 95' for twenty hours to form l-inethyZ-A4-cgclo- hexen y I- 3-trimeth y lammonizlm bromide or 1 -methyl- A2-c y clohcxen y Z-4-t~'- methylammonium bromide CloH20NBr m.p. 166 - 167'. The bromide whichever constitution it may have must yield 1-methyl-A2 *-cyclohexa- diene by treatment with water and silver oxide and subsequent distilla- tion. The hydrocarbon agrees well in its physical constants (b. p. 100~5-101~5° DY5 0.8252 na 1-46225 ng'6 1,46619 my 1.48519) with Zelinsky and Gorsky's compound (loc. cit.). By treatment with unwashed 18-20% ozone in chloroform it yields a diozonide C7HI0O6,ORGANIC CHEMlSTRY. i. 287 which is decomposed in ether by copper hydride yielding probably methylsuccindialdehyde and glyoxal ; these substances however could not be definitely identified.c. s. Comparative Researches on the Polymerisation Products of py-Dimethylbutadiene obtained Spontaneously and by Heat. CARL D. HARRIES (Annalen 1913 395 264-272).-[With ~ I A X HAGEDORN.]-‘‘ Nornial ’’ py-dimeth yl butadiene-caoutchouc pro- duced by heating py-diuiethyl butadiene in a closed vessel yields very readily the diozonide and the dioxozonide both of which are decom- posed by water giving an almost quantitative yield of acetonylacetone. Kondakov’s white insoluble polymeride produced by the prolonged keeping of by-tlimethylbutadiene at the ordinary temperature also readily forms a dioxosiide C12H2006 and dioxoxonide C12H200S by the decomposition of which by water only about 20% of acetonylacetone is produced. Also the decomposition curves of the two diozonicles are very different.By exposure to air for a few hours Kondakov’s polymeride changes to a yellow soluble resin. This forms a dioxonide C12H2006 and dioxozonide C12H,,0 by the decomposition of which about 36% of acetonylacetone is obtained. The author is of opinion that Kondakov’s polymeride is not a true caoutchouc and by analogy therefore that the caoutchouc obtained by Pickles (T. 1910 97 1085) by the prolonged keeping of isoprene is not true caoutchouc. c. s. Chlorophyll. LBON MARCHLEWSKI (A?z?zaZen 1 9 i 3 3 9 5 194-210). -A reply to Willstatter and lsler (A. 1912 i 710). The author maintains his contention that Willstatter’s phaeophytin is chloro- phyllan under another name. The heterogeneity of chlorophyllan was established by the author and Malarski (A.1909 i 947) before Willstiitter (A 1911 i 393). The proportion of the components a and b in chlorophyll is deter- mined far more conveniently by Marchlewaki and Jacobson’s method (A. 1912 ii 705) than by Willstatter and Isler’s process (loc. cit.}. c. s. Alkaloids of Aconitum Lycoct onum. HEINRICH SCHULZE and ERICH BIERLING (Arch. Pl~ccrrv~. 1‘313 25 1 8-49).-9 det,ailed resume is first given of the work of Biibschmann (Schweiz. Woch. Phaym. 1865 3 269) Dragendorff and Syohn (A 1885 403) Einberg (Diss. Dorpat. 1887) Dohrmann (ibid. 1888) and van der Bellen (ibid. lS90) on these alkaloids. The author’s results extend and to some extent confirm those of Dragendorff aud his pupils. It is shown that the alkaloids of this species differ from the typical ‘‘ aconitimes ” in not yielding two monobasic acids on hydrolysis.The coarsely ground roots were exhausted with 94% alcohol the extract concentrated and set aside to deposit sucrose the mother liquor further concentrated and diluted with three times its volume of water to separate resin and oil and the filtrate after extraction with ether to remove the last traces of oil made alkaline with sodiumi. 288 ABSTRACTS OF CHEMICAL PAPERS. hydroxide and the liberated lycaconitine extracted with ether. The. alkaline liquor was t,hen shaken with chloroform and the amorphous alkaloids so obtained freed from traces of lycaconitine by extraction with ether. This partly purified mixture of alkaloids was dissolved in dilute hydrochloric acid (3%) the solution treated with pottwium thiocyanate in excess t o remove an alkaloid giving an insoluble thiocyanate and the filtrate made alkaline with sodium hydroxide and extracted with chloroform which removed myoctonine. Lycaconitim C3RH46010N2 [a] + 42.47' in alcohol was decolorised by means of animal charcoal and thus obtained as a colourless powder easily soluble in alcohol or chloroform less so in ether; it is a weak base from which no crystalline derivatives could be prepared.On hydrolysis by water or dilute hydrochloric acid it yields succinic acid and anthranoyl-lycoctonine. Alkalis hydrolyse i t to lycoctonine and lycoctoninic acid. Myoctonine (C3,H4,0,,N?)2 [a] + 44.79' in alcohol is a colourless amorphous powder soluble in alcohol or chloroform but sparingly so in ether ; the solution in alcohol fluoresces bluish-violet. No crystalline derivatives were obtained.On hydrolysis by hydrochloric acid or alkalis it furnishes the same products as lycaconitine. The unnamed base giving an insoluble thiocyanate was not analysed; on hydrolysis by alkalis it also yields lycoctonine and lycoctoninic acid. Lycoctonine C,,H,,07N,H20 m. p. 131-133' [a] + 49.64" in alcohol crystallises in long colourless needles from dilute alcohol is a strong base contains four rnethoxyl groups and a methylimino-group and becomes amorphcus when dehydrated by drying at 100'/40 mm. The hydrochloride B,HCl,H,O m. p. 75' (decornp.) forms colourless prisms; the hydrobromide B,HBr,2H20 has m. p. 88-89' and the prchlorate B,HClO,,l &H,O m. p. 68-69' (decomp.) forms heavy prisms.The methiodide B,MeT m. p. 178' forms pale yellow needles from alcohol on addition of ether and the methochloride aurichZoride B,Me,HAuCl small heavy yellow prisms. Lycoctonine contains a t least two hydroxyl groups. Lycoctoninic acid C,,H,,O,N m. p. 179' forms bright brown needles or leaflets from dilute alcohol and appears to be succinanil- carboxylic acid (Riedel A. 1912 i 774). Anthranoyl lycoctonine C32H,,08N2 m. p. 154-155' forms bright brown glancing leaflets is easily soluble in chloroform but sparingly so in other solvents ; the solutions fluoresce bluish-violet. The alkaloid contains four methoxyl groups and a methylimino-group. The perchlmute B,2HC104 alone was obtained crystalline ; i t forms aggre- gates of colourless needles and does not meit completely even a t 235'.On hydrolysis by sodium hydroxide in alcohol the free base yields 1 y coc t on i n e and ant hran i 1 ic acid. Ant hranoy 1-ly coct oni ne is probably identical with Dragendorff's '' lycaconine," but as i t is not analogous with the other aconines," lycoctonine being the corresponding sub- stance in this instance it is proposed to abandon this name. The reactions of these alkaloids with the usual alkaloidal reagents and precipitants are tabulated in the original. Hildebrandt reports that in doses of 0.01 gram lycaconitine stills theORGANIC CHEMISTRY. i. 289 frog's heart in five hours and myoctonine in seven hours death occurring three hours later. Lycoctonine causes paralysis after seven hours but does not still the heart whilst the action of the relatively insoluble anthranoyl-lycoctonine only becomes apparent after six days.When paralysis of the heart's action does not come on too quickly all the alkaloids show the characteristic action of the aconitines on the heart. T. A. H. HERMAN DECKER and THEODOR EICHLER (Annalen 1913 395 377-381).-The reduction of an alcoholic solution oE LV-methyltiorprtpaverinium phenolbetaine (Decker and Dunant A. 190S i 204) by tin and concentrated hydrochloric acid on the water-bath yields the stannochloride C20H,50,N,HCl,SnC1 of a base C2,H2504N m. p. 111'. which has the constitution q-Laudanine. and is called t@azcdanine since it differs from laidanine only by the interchange in position of hydroxyl and a methoxyl group. The hydrochloride platinichloride chvomate picrate m.p. 162-1 63O and Syntheses of Dihydrokoquinoline Derivatives. HERMAN DECKER WALTER KKOPP HEINRICH HOYER and PAUL BECKER (AnnuZen 1913 395 299-320. Compare Pictet and Kay A. 1909 i 513 ; Decker and Kropp ibid. i 513).-Derivatives of 3 4-dihydro- isoquinoline are obtained by the interaction of acyl-P-phenylethyl- amides and phosphorus pen tachloride and phosphoryl chloride in boiling benzene toluene or xylene moisture being carefully excluded. Formo-P-phenylethylamide yields very little 3 4-dihydroisoquinoline (picrate m. p. 174-176') the chid products being P-phenylethylamiue and P-phenylethylaminomalon-P-phenylethylamide ( Decker and Becker A. 191 1 i 714). Plienylaceto-/3-phenylethylamide treated as in Decker and Kropp's method (Zoc.cit,) yields di-p-phenylethylamine (a) NH(CH,*CH2Ph)2,. b. p. 220-230°/30 mm. (picrate m. p. 229-23 lo) and 1-benzyl-3 4-dihydroisoquinoline (picrate m. p. 1 8 2 O not 1'74-175' [Pictet and Kay Eoc. cit.]). Oxalodi-P-phenylethylamide yields a substance (hydrochloride m. p. 191-193O ; picrate C2,H2,0,N m. p. 167-1 68' canary-green needles) which is probably 3 4-dihydroiso- quinolyl- 1 -carboxy - P-phenylethylamide C,NH,*CO*NH*CH2*CH2Ph since it yields P-phenylethylamine and ;t derivative of isoquinoline by hydrolysis by hydrochloric acid at 120". Even by energetic treat- ment the substance cannot be converted into bis-3 4-dihydroiso- quinolyl. Homopiperonoylhomopiperonylamine yields 1 -piperonyEnorhydras- tinine (annexed formula) m. p. 136-1 37' colourless plates (picrate m.p. 220-223' [decomp.] ; pZatini- chloride decomp. 175-1 80°) to- gethsr with another base picrate CH2*G6H3:02:CH2 Phenylacetohomopiperonylamide yields 1 - benzylnorhydrastinine perchlorate of the baee are mentioned. c. s. *2 CH,<O-/ I IN \/\/ m. p. 2 2 8 O . VOL. CIV. i 5i. 290 ABSTRACTS OF CEfEMlCAL PAPElIS. (picrate m. p. 205- 206" [ decomp.]) whilst benxohomopkperolaytamide CH,O,:C,H,*CH,*CH,*NH*C'OPh m. p. l22' colourless needles prepared by heating homopiperonylarnine beneoate m. p. 11 5" yellowish- green needles at 180' (compaze this vol. i 272) or from homo- piperonylamine by the Schottea-Baumenn method yields l-phenyl- norhydrastinine C,,H,,O,W m. p. 1 4 lo colourless prisms (methiodide m. p. 241'; picrate m. p.188-190'). Eormohomopiperonylamide yields by condensation norhgdrastinine 2 m. p. 90-9lo stout needles (picrate m. p- -CH2* FH CH202:CGH2<~~ =N 337-238' ; hydrochloride m. p. 192' ; pkatinichloride decomp- about 240°) the chief product however being honzopipei.o?zylccrr~ino- 71 ha1 ond iiiom op iperon y Id iu m id e CH,0,:C6H,:SH2* CH,*NN*CH( CO* NH.CH2*CH,*C6H,:CH,02) m. p. 124-126 (decomp.) colourless needles which forms a pzcralc IT]. p. 210-211° (decomp.) yellow plates and hydrochlmide m. p.. 182-1 83'. c. s. Syntheses of Hydrastinine and its lX-Homologues. HERMBK DECKER (Annalcn 1913 395 321-328).-Norhydrastinine (pre- ceding abstract) arld methyl sulphate react in toluene at 100' t o form 2-methylnorl~ydrastin~ne methosulphate (hydrastinine rtbethosdphate) C,,H,02NMe*80,RI e m.p. 117-119' pale yellow crystalline powder from which hydras- tiniae is liberated by 15% sodium hydroxide a t 0'. Norhydrastinine in alcohol reacts with benzyl chloride at 50' to form the benzp?ochZoride C,,H,0,NCI*CH2Pb m. p. 215O pale yellow powder and with ethyl iodide to form the ethiodide C,,H,O,NEtT m. p. 222O yellow leaflets ; 2-ethylnorhy~rastiizine picrate has m. p. 175O. c'. s. Synthesis of Cotarnine and Third Synthesis of Hydrastinine. HERMAN DECKER and PAUL BECKER (Anrtalen 1913 395 328-2342). -Forrnylhomorn yvisticylamine CH ,O, C,H 2( OMe) CH ,-CH 2*N H.CH9 m. p. 105-106° (corr.) colourless ueedlee obtained by heating homo- myristicylamine formate at 160-1 70' for three hours is converted by pbosphoryl chloride in boiling toluene and subsequently basifying the aqueous solution of the product into norcotarnim (picrate m p.182-184° yellow needles) the methiodide of which$. zu. p. 184-186O (decomp.) is identical with cotarnine hydriodide andl the met hosulphate of which is converted into cotarnine picrate (Salway T. 1911 97 1208) by alcoholic picric acid. Equal molecular quantities of homopiperonylamine and bsnz aldehyde react on the water-bath to form benxylidenehomopiperonyL arnine CH ,O,:C,H,*CH,*CH ,*N:CHPh m. p. 3 6 O pale yellow prisms which is converted by methyl iodide (without a solvent) at 100° into the rnetlriodide. The latter is hydrolyeed by boiling 95% alcohol or by steam yielding beu zaldeh y de and homopiperonylirLcthylccmine hydriodide,.ORGANIC CHEMISTRY. i. 291 m.p. 135-1 36' (corr.) colourless leaflets. Honzo~ipsronpl.methylccmine C1,H,30,N b. p. 156-158'/24 mm. pale yellow oil (carbonute m. p. 12-75' ; hydrochloride m. p. 183-185' ; picrate m. p. 166-167' [corr.]) is converted into formylhomopiperonylmethylamine by heating its formate at 150-160* for seven hours. By condensation with phosphoryl chloride in boiling toluene and basification of the product the forrnyl derivative is converted into hydrastinine. By processes similar to the preceding benzyliclene?'o,riopiz~:ron~ZanLino and its ethiodide Ihomopiperonylethylamincz hpldrioclde m. p. 126-1 2S0 white leaflets and the corresponding hydrochloride m. p. 183-185' and picrate m. p. 135 -1 36' orange-red leaflr?ts ~fbrm?llhorrLopiperonyl- ethylamine and 2-ethylnorhydrastinine (preceding abe tract) have been prepared.When a certain temperature or duration of heating is exceeded by-products are obtained in the interaction of benzylidenehomo- piperonylamine and an alkyl haloid. Their productlon is due t o the formation of homopiperonyl haloid which reacts with the benzylidene compound in the same manher as does the alkyl haloid a derivative of dimethylamine being produced simultaneously. As a n illustration of such heterospasis (compare Decker and Fellenberg A 1909 i 116) equal molecular quantities of benzylidenehomopiperonylamine and methyl iodide h,rve been heated in benzene at 140' for six hours and the product has been hydrolysed by steam whereby dihomopiperonyl- amine h y driodids N H { C €3,- CH C,H, C H 202)2 HI m .p. 2 3 4 - 2 3 6' pale yellow prisms has been obtained. The corresponding base has m. p. 72-75' (decomp.). Moreover quaternary ammonium haloids are formed when moisture is present during the interaction of benzylidenehomopiperonylamine and an alkyl haloid ; in the preceding example homopiperonyltrirnethyt- Syntheses of Tetrrthydroisoquinoline Derivatives. HERMAN DECKER and PAUL BECHER (AsmaZen 1913 395 342-362).-Homo- piperonylamine or a similar derivative of P-pbenylethylamine reacts readily a t the ordinary .temperature with an equal molecular quantity of an aldehyde to form the alkylidene derivative which is converted intoa tetrahydrozsoquinoline derivative by a suitablecatalyst ; homopiper- onylamine (or similar base) and the aldehyde reacting directly in the presence of the catalyst yield quite different products.By adding slowly a benzene solution of benzylidenehomopiperonyl- amioe to moderately warm concentrated hydrochloric acid the hydro- ammonium iodide m. p. 260-261' is formed. c. s. chloride m. p. 309-31 lo of 1 -phenytdihydroizol*h~drccslinine CH2-$! H2 CH202:C6H2<C.3pj- .NH ' m. p. 91-98' large hexagonal leaflets is obtained ; the nitrate and picrute m. p. 16 9- 1 70° (decomp.) dark yellow prisms are described. The same base is produced by reducing I-phenylnorhydrastinine (pre- ceding abstract) by alcohol and 2.5% sodium amalgam the solution being kept acid by the addition of glacial acetic acid. PiperonylidenehornopiperonyZarnine m. p. 11 7-1 1 So (unstable picrate m. p. 143-145') and cinnccmylidenehomo~i~eronylamine m.p. x 2i. 292 ABSTRACTS OF CHEMICAL PAPERS. 61-63O are respectively prepared from equal molecular quantities of the components on the water-bath The slow addition of homopiperonylamine to 20% formaldehyde yields homopi~eron?/lmet?~yZe~a~~n~ CH,O,:C,H,.CH,*CH,*N:CH a liquid which is converted by hydrochloric acid on the water-bath into the hydrochloride m. p. 274-2 7 6O of dihydronorhydrasti&ne C,,H,,O,N m. p. 81-83'. This base the hydrochloride of which is also obtained by reducing norhydrastinine with tin and hydrochloric acid forms a hydvobromide m. p. 256-258O picrate m. p. 229-231' (decomp.) and cavbonate m. p. 114-1 15' (decomp. corr.) and reacts in benzene with methyl iodide to form the hydriodide m. p. 239-241' (Freund and Will record 232') of dihydrohpdrastinine.Dihydronorhydrastinine and methyl sulphate react in benzene to form a crystalline substance m. p. 135-137O which is converted by successive treatment with sodium hydrogen carbonate and hydrochloric acid into dihydrohydra- atinine hydrochloride m. p. 276-278O. Dihydrohydrastinine in the form of its hydrochloride is obtained directly from homopiperonyl- amine hydrochloride by heating it with 40% formaldehyde a t 130' for three hours. The same hydrochloride is also produced from homopiperonylmothylamine hydrochloride or dihydronorhydrastinine hydrochloride and an excess of 40% formaldehyde at 120'. The paper closes with an explanation of Eschweiler's process of methylation by means of formaldehyde which is represented by the scheme /CH,*OH RR'NH,HX -+ RR'N-CH,*OH -+ \X /Me HO RR'N-C!HO -+ RRNMeX + H*CO,H.\X This explanation is in harmony with 'the fact that quaternary ammonium salts are not produced by Eschweiler's method and applied to phenols will account for the frequent occurrence of the methoxyl Synthesis of Pyrroles from Amino-ketones and Ketones or Ketonic Esters. OSCAR PILOTY and PAUL HIR~CH (Amncclen 191 3 395 63-74).-The synthesis of pyrrole derivatives by Knorr's method of condensing amino-ketones and esters of P-ketonic acids in glacial acetic acid fails in many cases. The authors now find that condensation in alkaline solution is much more satisfactory and that ketones can be used instead of ketonic esters. An aqueous solution of the amino-ketone hydrochloride is treated with an excess of an alkali hydroxide the ketone or ketonic ester is added and the closed vessel is kept at a gentle heat or left for several days at the ordinary temperature ; thus aminoacetone yields 2 4-dimethylpyrrole with acetone 2-phenyl-4-methylpyrrole m. p.152' with acetophenone 2 3 4-trimethylpyrrole with methyl ethyl ketone 3 6-dimsthyl- 2-ethyZpproZe an oil (picrute m. p. 122-5') with diethyl ketone whilst methyl a aminoethyl ketone yields 2 3 5-trimethyZpyrrob b. p. 75*5-76.5O/l(i mm. (and tetramethylpyrazine as a by-product) with group in plant substances c. s.ORGANIC CHEMISTRY. i. 293 acetone and 2 3 4 5-tstmnzet?~~lp?/roZe (picrate m. p. 125- 126O) and chiefly tetramethylpyrazine with methyl ethyl ketone. Aminoacetone yields ethyl 2 4-dirnethylpgrrole-3-carboxylate with eth y 1 ace toacetate and ethyl hydrogan 3-meth y Zp y ~ o l e - 4 5-d icar boxy la te NH<c(co,H)*bco,st m.p. 196' with ethyl oxalacetate; by hydrolysis the ethyl hydrogen ester is converted into 3-methyZpywoZe- 4(or 5)-carboxyZic acid m. p. 149' which yields 3-methylpyrrole by heating. Methyl a-aminoethyl ketone yields ethyl hydrogan 2 3-dimethyl- pyrrole-4 5-dicmboxylate m. p. 201' (decomp.) and tetramethyl- pyrazine with ethyl oxalacetate. By hydrolysis the ester yields 2 3-dimethyZpyrrole-~(or 5)-carboxpZic acid m. p. l t 3 8 O which decom- poses at 190-195' in carbon dioxide to form 2 3-dimethyZpyrroZe b. p. 62O111 mm. (picrot& 2C,H,N,C,H',(N02),*OH m. p. 146.5'). CH===CMe c. s. A New Method of Preparing Cyclamine-aldehydes and -alcohols.11. ADOLF KAUFMANN and LOUIS G. VALLETTE (Beg-. 1913 46 49-57. Compare A. 1912 i 655).-In the earlier paper the aldehydes obtained by the scission of the condensation products of nitrosodimethylaniline with 2-methylquinoline ethiodide or a-picoline methiodide were isolated only as phenylhydrazones ; processes are now described for the separation of the aldehydes in a free state. 6-Methoxplepidine ethiodide yellow or brown needles decomposing at 177-17g0 gives in dilute aqueous solution a beautiful blue fluorescence ; i t condenses with nitrosodimethylaniline when heated in alcoholic solution with the formation of the p-dimethyZanzinoaniZ of 6-methoxyquinoline-4-aEde?yde ethiodide green columns m. p. 214-2115' which gives blue solutions in alcohol and carmine-red i n water ; this substance dissolves in dilute hydrochloric acid undergoing scission into p-aminodimethylaniline and 6-methox~quinoZi~te-4-aldehyde ethiodide the latter of which can be easily separated as the plun?jZ- hydrazone red needles decomposing near 248'.The dimethylaminoanil of quinoline-2-aldehyde ethiodide (Zoc. cit.) is hydrolysed by mineral acid and phenylhydrazine precipitates the phenylhy drazono of quinoline-2-aldehyde ethiodide ; if the addition of the phenylhjdrazine be delayed for a time the precipitate obtained is a mixture of the above with thephenylhydraxone of quinoline-2-aZd&yde ethochloride red needles m. p. 180' (decomp.) which on reduction with zinc and dilute hydrochloric acid yields a pungent smelling oily base together with some aniline.The hydrolysis of the dimethylaminoa n il of pyridine - 2 -aldehyde methiodide likewise yields the methiodide and methoclhride of the aldehyde which can be separated as the phenylhydrazones that of the methochloride decomposing near 235' after previous fusion in its water of crystallisahion near 70'. If the phenyl hydrazone of I yridine-2-aldehyde niethiodide after previous careful removal of mat er of crystallisation is heated below its m. p. (244') under 0*1-0.2 mm. pressure (obtained by Wohl'si. 294 ABSTRACTS OF CHEMICAL PAPERS. method with liquid air and charcoal) methyl iodide is liberated with the formation oE pyridine-2-aldehyde phenylhydrazone yellow needles or leaflets m. p. 180-1 8 2 O ; hydrochloride orange-yellow needles m.p. 188O (decomp.). The methochloride can also be used for the reaction. I n a similar mauner the phenylhydrazone of quinoline-2-aldehyde ethiodide can be decomposed to produce quinolins-2-~ldeh?/~~p~~1zyl- hydrazone yellowish-brown needles or leaflets m. p. 203-204O ; /i?/dro- chloride red needles m. p. about 237O (decomp.) (compare von Miller and Spadg A 1886 370). Pyridine-2-aldehydephenyl hydrazone undergoes reversible h ydrot ysis when treated with warm mineral acid but the addition of dinitro- benzaldehyde causes the removal of the phenylhydrazine by forming a very sparinglp soluble phenylhydrazone and the hydrolysis then proceeds to completion ; free pyidine-2-ccldeltyde is a pungent liquid b. p. 210°/725 mm. which gives the usual aldehyde reactions except with Fehling's solution.Quinoline-2-aldehyde obtained by hydrolysis of the phenylhydrazone a t 120-130' under pressure forms colourless tablets m. p. 70-71' (compare von Miller and Spady Zoc. cit.). D. F. T. 4-Quinolyl Ketonefi. 11. ADOLF KAUFMANN MAX KUNKLER and HEINRICH PEYER (Ber. 1913 46 57-64. Compare A. 1912 i lOl7).-From a comparison of the cinchona alkaloids the conclusion is drawn that a substance of the structure 6-alkyloxy-4(/3-dialkylamino- a-hydroxyalky1)-quinoline should possess properties similar to those of quinine. 4-Quinolyl methyl ketone has b. p. 99O/O.O8 mm. and 4quinolyl phenyl ketone m. p. 5 9 O b. p. 142O/Oe12 mm. 6-Ethoxyquinoline (Kaufmann and Pey& A. 1912 i 650) readily unites with methyl sulphate with the formation of a yellow solid the 5uorescent solution of which when treated with potassium cyanide yields 4-cyano-6-sthoxy-1-methyl-1 4-dihydroquinoline ; the ethereal extract of this substance is oxidised by alcoholic iodine to red needles of 4-cyano-6-ethoxyquinoline methiodide m.p. 183-1 84' (decomp.) which when heated near its m. p. in a vacuum liberates methyl iodide leaving free 4-cyano-6-ethox~pui~oZi~e as yellow needles m. p. 1 IS0 which give 5uorescent solutions. When treated in benzene solution with an ethereal solution of magnesium methyl iodide the cyano- compound is converted into 6-ethoxy-Cquinolyl methyl ketone golden- yellow leaflets or needles m. p. 80-81° whilst with magnesium ethyl iodide in an analogous manner 6-ethoxyquinolyl ethyl htone golden- yellow crystale m.p. 92O is produced ; both ketones with dilute acids give yellow solutions with a greenish fluorescence. 6-Metboxy-Cquinolyl metbyl ketone dissolved i n acetic acid of 50% concentration is reduced by zinc dust to 6-methoxy-4-quinoly1 methyl carhinot needles m. p. 120-121° which gives a blue fluores- cence in dilute sulphuric acid and an emerald-green coloration with chlorine water and ammonia. 4-Quinoly l methyl ketone in alcoholic solution containing sodiumORGANIC CHEMISTRY. i. 295 ethoxide is converted by amyl nitrite into 4-puinolyl oximiNomethyl ketone colourless needles m. p. 237-242" (decomp.) which gives a /"\CH(oH)*cH2eNH2 yellow substance with phenylhydrazine and is reduced by an acid solution of 1 I i stannous chloride to P-amino-a-hydr- \/\/ 0x9-4-puinolyZetAane (annexed formula) ; hydrochloride a greyish-white powder m.p. 208-210' (decomp.) ; picrate leaflets m. p. 202'. N D. F. T. A Methylnaphthaisoquiooline. AM& PICTET and B. MANEVITCH (Arch. 8c;. phys. nat. 1913 [iv] 35 40-47. Compare Pictet and Gams A. 1909 i 671).-The preparation of 1-methyl-a-naphthaiso- quinoline (annexed formula) is described. A mixture of a- and P-naphthyl methyl ketones wits obtained by the addition of aluminium chloride to a solution of /\ naphthalene and acetyl chloride in carbon disulphide. 1 1 GH The two isomerides were separated by treatment of \/\/NOH their alcoholic solution with a saturated solution of I I IN picric acid whereby the a-naphthgl methyl ketone '\/\/ picrate was precipitated from which by decomposi- tion withsodium carbonate a-naphthyl methyl ketone b.p. 292-2934 was isolated in 25-30% yield. P-Naphthyl methyl ketone b. p. 171-173°/12 mm. m. p. 51" was obtained from the mother liquor the yield being 12-15%. Attempts to prepare the a-ketone by the action of acetyl chloride on an ethereal solution of magaesium a-naphthyl bromide were less successful. a-Naphthyl oximinomethyl ketone m. p. 183" was formed by the gradual addition of amyl nitrite to an alcoholic solution of a-naphthyl methyl ketone in the presence of sodium ethoxide and was trans- formed into a-nccphthgl aminomethyl ketone hydi*ochlm'de m. p. 245-250° (decomp.) by reduction with stannous chloride. The free ba8e was unstable a-Naphthyl acetylaminomthyl ketone C,,H?*CO*CH,*NHAc m. p. 103" prepared by the action of acetic anhydride and potassium hydroxide on a concentrated aqueous solution of the above hydro- chloride was reduced by means of sodium amalgam to the corresponding carbinol needles m.p. 145-146' which when treated with phos- phoric oxide in boiling xylene solution was transformed into 1 -methyl-a-naphthaisoquinoline m. p. 96-96". CMe H. W. Amino-Imino-Desmofropy. KURT H. MEYER and H A N ~ SCHLOSSER (Bey. 1913 46 29-32).-1t has already been shown (Meyer A 1911 i 193) that 9-hydroxyanthracene exhibits tauto- merism between its enolic and ketonic isomeric structures (anthranol and anthrone) and it is now discovered that similar tsutomerism can exist in the anthracene group with 9-aminoanthracene derivatives The oxidation of 9-aminoanthracene by amyl nitrite (Kaufler and Suchannek A.1907 i 225) or by bromine in alcoholic solution givesi. 296 ABSTRACTS OF CHEMICAL PAPERS. rise to a substance m. p. 204-205’ which from its lack of colour and of fluorescence must be dianthronedi-imine NH C<$2>CH*CH<c6H4>C:NH ; i t is a diacid base and the course of the oxidation is evidently analogous 6 4 C6H* to that of anthranol (Meyer Zoc. cit.). When t h e substadce is boiled for an hour with a methyl-alcoholic solution of potassium hydroxide i t is converted into the isomeric diaminodianthryl golden-yellow leaflets m. p.” 334’ (compare Gimbel A. 1887 1049) which dissolves in benzene to a solution with a green fluorescence. The same isomeric change can be induced less readily by boiling with acetic acid or by fusion but the reverse change from the amino- to imino-compound could not be accomplished.D. F. T. Er henylbenzylidenehydrazine. GEORG LOCKEMANN and FRANZ LUCIUS (Bey. 1913 46 150-152).-Thiele and Pickard (A 1898 i 474) obtained by the action of acetic anhydride and zinc chloride or sulphuric acid on phenylbenzylidenehydrazine an isomeric P-modifica- tion of the hydrazine m. p. 136’. On repetition the only product now obtained is a-acetyl-a-phenyl-P-benzylidenehydrazine m. p. 122’. E. F. A. Constitution of ‘‘ Anilipyrin 0,’’ EZIO COMANDUCCI (BoEZ. chim. Jarrn. 1912,5 l,741-’743).-Two ‘‘ anilipyrines ” have been described of which one was supposed t o result from the condensation of equi- molecular quantities of antipyrine and acetanilide and the other from two molecules of antipyrine with one molecule of acetanilide.By the method of thermal analysis the author now shows that these substances are neither compounds nor even mixed crystals but consist simply of crystalline mixtures. When fused mixtures of the adtipyrine and acetanilide are cooled an eutectic is observed corresponding with 45% of antipyrine and 45’. The behaviour of the “anilipyrines ” with solvents supports the above results. R. V. S. Constitution of ‘I Anilipyrine.” LINO METELLO ZAMPOLLI (Boll. chim. farm. 1912 5 1 780-782. Compare preceding abstract).- Polemical. The author appears to be in agreement with Comanducci’s conclusions as now stated. From his preliminary experiments however the eutectic temperature is a t least 48-59 R. V.S. Reaction Products from 1 -Phenyl-3-methyl-5-pyrazolone and Phthalic Anhydride. GUSTAV SCHULTZ and GEORGI ROHDE (J. pr. Chem. 1913 [ii] 87 119-142).-When crystallised from ethyl acetate or acetone the product formed by fusing 1 -phenyl-3-methyl- 5-pyrazolone with phthalic anhydride in equimolecular proportiono at 1 20° yields an orange-yellow crystalline substance which becomes red and melts at 202-204O and on crystallisation from methyl alcohol and acetic acid or on treatment with aqueous alkalis loses phthalicORQANIC CHEMISTRY. i. 297 acid and is converted into the red substance first observed by Knorr (A. 1887 601). The latter compound is best prepared by boiling the product of the fusion with water until it is completely soluble in chloroform. It crystallises in clusters of dark red prisms or thin lancet-shaped leaflets m.p. 208-210° or above according t o the rapidity of heating and when heated with phthalic acid in acetone or ethyl acetate solution is transformed into the above-mentioned yellow substance. The constitution of the red substance is represented by one of the following formulae C*C,H,*CO,H C*C6H,*C0,H >N* C Me*f\QH*CMe CMe*yH\g- CMe N'NPh*CO CO-NPh >N NqNPh*CO C(OH)*NPh It separates from methyl alcohol and chloroform i n red prisms containing the solvent and dissolves in aqueous alkalis and alkaline carbonates forming orange-red salts ; the red mono- and di-silver salts are mentioned With methyl-alcoholic hydrogen chloride it forms a methyl ester C29H2404N2 which crystallises in orange-yellow prisms or plates baving a bluish glance m.p. 178-179' and yields a red silver salt C,,,H,,O,N,Ag. When heated in nitrobenzene solution or in other solvents of high b. p. the red substance decomposes into 1 -phenyl-3-me t h y 1- 5 - pyrazolone and 1 -$en yl- 3-met h yl-4-p yraxol-5-onyl- idenephthalide ~=CMe>C:C<c6H4>C0. This crystallises in slender NPh* CO -0- red needles which sinter at 208' and have m. p. 212-219' accord- ing to the rapidity of heating. It combines with 1-phenyl-3-mrthgl- 5-pyrazolone in boiling cumene solution to form the original red compound and is resolved by aqueous alkalis into the ketonic m i d - - r;JI='CMe NPh* CO >CH*CO*C,H,*CO,H which forms lustrous yellow leaflets of variable m. p. (145.-160') and is reconverted by the action of acetic anhydride into the phthnlide.When warmed with acetic anhydride and a little sulphuric acid the original red substance is trans- formed into an anhydride (annexed formula) crystallising in slender colour- less needles m. p. 261'; the reverse transformation may be effected by boil- N'NPh*C-O-C*NPh'N ing the anhydride with alcoholic alkali hydroxides. F. B. CMe*f('g*CMe The Constitution of the Pyrazolinecarboxylic Acids. AUGUST DARAPSKY (Bey. 1913 46 218-225),-Polemical; a reply to Bulow (this vol. i 101). D. F. T. A New Example of the Reversed Pinacolin Rearrangement. HEINRICH BILTZ and KARL SEYDEL (Bey. 1913,46,138-142).-4:5-Di- phenyldihydroglyoxalone @:L::E>CO is oxidised by nitric acid toi. 298 ABSTRACTS OF CHEMICAL PAPERS. HO $!Ph*NH>Co HO*CPh*NH which in 4 5-dipheayldihydroglyoxalone glycol presence of alkaline hydroxides undergoes a normal pinacolin rearrange- >CO (compare Biltz A ment into 5 5-diphenylhydantoin 1909 i 525).When this bydantoin is energetically reduced with hydrogen iodide and phosphorus 4 :5-diphenyldihydroglyoxalone is obtained together with decomposition products the phenyl group returning to its original place. The decomposition products include diphenylacetic acid and dipheny 1- methane indicating that in the hydantoin the two phenyl residues are attached t o the same carbon atom. On reducing 5 5-diphenylhydantoin by distillation with zinc dust diphenylmethane and benzonitrile are formed the latter being due to the rearrangement into diphenylglyoxalone which gives rise to benzo- nitrile when distilled with zinc dust.Di-p-bromo-4 5-diphenylhy dantoin is very resistant to hydrogen iodide and phosphorus. Only bis-p-bromophenylmethane could be iso- lated from the reaction products ; the presence of di-p-bromodiphenyl- acetic acid and of diy-bromodiphenyldihydroglyoxalone was made probable. E. F. A. F;Ph,*NH GO-NH Phenazine. FRIEDRICH KEHRMANN and EM. HAVAS (Ber. 19 13 46 341 -352).-The authors have obtained good yields of phenazine by the action of o-aminodiphenylamine on o-nitrodiphenylamine in the presence of anhydrous sodium acetate and have examined several of its derivatives. o-Nitrodiphenylamine mas obtained in 85-90% yield by heating o-chloronitrobenzene aniline and anhydrous sodium acetate during twelve to fifteen hours a t 215’.Reduction OF its alcoholic solution by stannous chloride and hydrochloric acid gave o-aminodiphenyl- amine. For the preparation of phenazine o-nitrodiphenylamine o-aminodiphenylamine and anhydrous sodium acetate were heated a t about 250° when a violent reaction occurred. The phenazine was isolated by distillation of the crude product or better by treatment with superheated steam ; yield 60-70%. I n the absence of sodium acetate only traces of phenazine could be obtained. When dissolved in nitrobenzene and treated with methyl sulphate phenazine yielded methyZplAenazonium metl~osulphate as greenish-yellow prisms. The corresponding platinichlwide C,,H,,N,Cl~Pt and di- chrom8ate CZBH22N407Cr2 were analysed but the chlorzde bromide and nitrate were found to be so readily soluble in water that they could not be precipitated from a solution of the sulphate.When conceDtrated aqueous potassium iodide mas added to an aqueous solution of methylphenazonium methosulphate an orange-coloured solution was obtained which after a short time deposited greenish- black needles. The latter dissolved readily in hot alcohol with formation of a greenish-yellow solution which when rapidly cooled yielded bluish leaflets which could be ground to a dirty-green powder.ORGANIC CHEMISTRY. i. 299 Analyses of the crystals yielded figures agreeing with those required by the normal iodide C,,H,,N,I. The authors however are led to the conclusion that this substance is only contained in the yellow solution and that the crystals probably consist of a quinhydrone salt composed of 1 mol.of methylphenazonium tri-iodide and 2 mols. of met hyldi hydrophenazine. I n the presence of air sodium hydroxide transformed a solution of methylphenazonium methosulphate into phenazine mixed with small quantities of a red substance probably having the annexed formula. Similarly aqueous ammonia N /\'\/\ yielded mainly phenazine when brought into reaction I I ' with methylphenazonium salts but in the absence \)\H\/\o Me*N -- of water salts of 3-aminomethylphenazonium were readily obtained. Of these the following were isolated namely the chloride bromide and nitrate green needles which yielded magenta-red solutions and the platinichloride. 1 3-Dinitrophenazine was obtained by cautiously heatbg phenazine wihh sulphuric acid and rather more than the calculated amount of nitric acid to 130'.It crystallised in yellow needles wbich had no definite m. p. but decom- /\/\/\ posed above 200'. Reduction of this substance I by hydrogen sul phide in ammoniacal alcoholic \/\ )\,,h02 solution led to the formation of dinitrodihydro- NH phenazine (annexed formula) the constitution of which follows from its identity with the com- pound prepared by Kehrmann and Messinger (A. 1894 i 55) and by Leemann and Grandmougin (A. 1908 i 478) from o-phenylene- diarnine and picryl chloride. Attempts to reduce 1 3-dinitrophen- :rzine or its dihydro-derivative to diaminophenazine were unsuccessful. The authors have re-investigated the acetylation of dihydro- phenazine (compare Hinsberg and Garfunkel A 1897 i 123; Tichwinski and Wolochowitsch A 1905 i 383 ; Hinsberg A.1905 i 840). They find that pure acetic anhydride and pure dihydro- phenazine yield only a monoacetyl derivative whilst the diacetyl derivative is immediately formed if a trace of zinc chloride is added. They consider that dihydrophenazine and its diacetyl derivative possess a symmetricul structure whilst the yellow monoacetyl deriv- ative and dihydrophenazine sulphate are probably /\I/\/\ A solution of dihydrophenazine diacetate in glacial I I acetic acid was mixed with concentrated nitric acid \ / I \ / \ / and warmed on the water-bath whereby a mixture of 2-nitrophenazine m. F. 2 14' and nitrodiacetyldiAydro- phenazzne m. p. 166" was obtained. The latter sub- stance yielded 3-aminophenazine when warmed with concentrated sulphuric acid.2-Aminophenazine (compare Fiscber and Hepp A. 1889 500) was obtained by reduction of an alcoholic solution of nitrodiacetyldihydro- phenazine by stannous chloride and hydrochloric acid oxidation of the tin salt so obtained by ferric chloride solution and liberation of the base by means of ammonia. NH NO H NH derived from the annexed unsymmetrical form. N H. W.i. 300 ABSTRACTS OF CHEMICAL PAPERS. New Methods of Preparation of Asymmetric aB-Naph- thazine. FRITZ REITZENSTEIN 'and FRANZ ANDRE (J. pr. Chem. 19 13 [ii]. 87 97-1 18).-as-ap-Naphthazine (Fischer and Junk A. 1893 i 283) has been prepared (1) from P-naphthylamine by the action of sulphur monochloride or sulphuryl chloride in pyridine solution and also by distillation over magnesium and barium peroxides; (ii) from a-naphthylamine by heating with calcium oxide and (iii) by sublimation of aceto-P-naphthylamide over a mixture of barium peroxide and calcium oxide.It forms greenish-yellow crystals m. p. 27S-28lo according to the method of preparation and yields a dinitro-derivative m. p. 330-332" which is reduced by aqueous sodium sulphide to diaminonaphthazine (compare D.R.-P. 166363). When warmed with alcohol and hydrochloric acid it forms au unstable red hydrochloride. I n pyridine solution sulphuryl chloride reacts with a-naphthylamine yielding a red rrubstarzes m. p. 169" and with aceto-P-naphthylamide to form aceto-1 -chloro-P-naphthylamide. When distilled over a mixture of barium peroxide and calcium oxide benzidine yields a substance m.p. 122" probably identical with the azine N ~ 2 ~ C ~ ~ 4 g C H 3 < ~ C 6 H 3 * c 6 ~ ~ * ~ H 2 isolated by Kal b (Digs Miinchen 1905) from the product obtained by oxidising benzidine. The action of sulphuryl chloride on benzidine in pyridine solution gives rise to a substance m. p. 126" which is considered to be a chloro- derivative of benzidine or of the above-mentioned azine. Synthesis of Two Isomeric Oxytetrazoles from Azoimide and Fulninic Acid. F. CARLO PALAZZO and G. MAROGNA (Gaxxetta 1913 43 i 69-80).-The interaction of azoimide and fulminic acid yields not only the 1 - hydroxytetrazole previously described (compare Palazzo A 1910 i 342) but also an isomeride of this substance. Its formation is favoured by a low temperature.The sodium salt of iso- oxytetraxoEe CHON4Na,3H20 forms large crystals which have been described by Rosati (this vol. i 207). It yields other saIts by double decomposition and gives also a bensoyl derivative which crystallises in needles m. p. 94". The sodium salt is stable towards water and alkalis but with sulphuric acid or with fuming hydrochloric acid suffers a decomposition analogous t o that of its isomeride. The iso- oxytetraxole CHON,:NH is obtained by treating the sodium salt with cold dilute sulphuric acid; it has m. p. 155O (softening a few degrees previously). The decomposition of this substance with sulphuric acid is similar to that of the isomeride but hydrochloric acid acts some- what differently. The acid and its salts explode on percussion and also when heated.The 1-hydroxytetrazole previously described forms when treated with diazomethane an ether containing a methoxyl group; it has m. p. 93-94". The authors consider that the isooxytetrazole probably has the following structure F! H:No>NH. They regard the production of these two isomerides from fulminic acid a s a further proof of the tautomeric nature of that substance. F. B. The isooxytetrazole forms an N-ether. N=ZN R V. S.ORGANIC CHEMISTRY. i. 301 Halogen Substitution Products of Azo-dyes. 5. WEBER (&fOnd8h. 1913 34 243-254).-The influence of halogen substitu- tion on the shade and usefulness of some dyes has been systematically studied. Group A.- 0- m- and p-Chloro- bromo- and iodo-anilines diazotised and coupled with P-naphthol-8-sulphonic acid in sodium carbonate solution give yellow to red dyes the p-compounds boing darker and the m-compounds lighter than the o-members whilst the shades deepen from chlorine to iodine.Group &-The same bases give redder dyes with a-naphthol-2 8-di- sulphonic acid but the same generalisations may be made. Group C.-Aniline m- and p-bromoaniline do not couple so readily with 1 -amino-~-naphthol-6-sulphonic acid and the dpee are dark red tinged with blue. Group 0.-2 4-Dibromoaniline is less easily diazotised and coupled than the mono-derivatives but gives deeper colours with the above sulphonates. The dyes are faster than the unsubstituted analogues and their colouring power is much enhanced. The ortho- and para-compounds are more valuable than the meta- and the bromo- and iododerivatives are much more effective that the chloro-dyes. J.C. W. Congo-Red. I. Experimental Part. F. I. BOGOJAVLENSKI. 11. Theoretical Part. VLADIMIR G. SCRAPOSCBNIKOV (J. Russ. Phys. Chern. Soc. 1912 44 1813-1844).-The action of either strong or weak acids (even carbonic acid) on Congo-red results in the replace- ment of the sodium by hydrogen. With strong acids the action proceeds rapidly and yields a dark blue precipitate which when washed gives a blue colloidal solution; the latter cannot be freed from admixed impurities by washing or dialysis. This solution of Congo-blue exhibits electrical conductivity which is however probably conditioned by the impurities present. The action of weak acids gives the same product but in a crystalline condition Very small crystals of Congo-blue are capable of forming suspensions which closely resemble the colloidal solutions ; both the colloidal particles and the crystals carry negative charges both are coagulated without change of structure by acids or acid salts and both the colloidal solution and the filtered crystalloidal suspension show Brownian movement under the ultramicroscope the crystals passing through the filter.The theoretical considerations of Part I1 lead to the following conclusions. The change in colour of substantive bisazo-colouring matters is conditioned by change in their intramolecular structure. The red forms of amino- and hydroxybisazo-colouring matters of the Congo-red type correspond with the azoid configuration of the molecules whilst the blue forms correspond with the quinonoid structure.The instability of these forms and their ready inter- conversion are regarded as due to the agency of so-called ‘‘ suspensive ” linkings and of mobile hydrogen. T. H. P.i. 302 ABSTRACTS OF CHEMICAL PAPERS. Aniline-Black and Allied Compounds. 111. ARTHUR G. GREEN and SALOMON WOLFF (Ber. 1913 46 33-49).-See P. 1912 28 250. The Density and Solution Volume of Some Proteins. (Miss) HARRIETTE CHICK and CHARLES J. MARTIN (Biochem. J. 19 13 7 92-96).-A comparison was instituted in the caGe of four proteins caseinogen egg-albumin serum-a1 bumin and serum-globulin between the density directly determined with dry specimens and that calculated from the specific gravity of concentrated solutions. The latter is found to be 5 to 8% in excess of the former showing the exteut of shrinkage in volume taking place when these proteins enter into colloidal solution.W. D. H. The Hydrolysis of Organic Phosphorus Compounds by Dilute Acid and Dilute Alkali. R. H. ADERS PLIMMER (Bio- &em. J. 19 13 7 72-80).-Ethyl dihydrogen phosphate glycero- phosphoric acid and phytic acid are bydrolysed by acid but are stable t o alkali. Hexose-phosphoric acid and phospho-protein behave so differently to alkali from the other three compounds mentioned that they are probably not esters. In phospho-proteins the phosphoric acid is probably united to one of the amino-acids. Hexose-phosphoric acid reduces Fehling’s solution which points to the presence of a functioning aldeh5.de or ketone group Some suggestions as to atomic grouping are made to explain the differences in reaction referred to.W. D. H. Protein Compounds. WALTER H. EDDY (Biochem. Bull. 1912 2 11 1-122).-A description is given of protein salts formed by combining organic bases (strychnine morphine etc.) with acid reacting proteins (mucoids nucleoproteins) and by combining the latter with basic reacting proteins such as histone. It is pointed out that so- called histone however is itself probably a protein salt.. W. D. H. Bilirubin and Hzemin. HANS FISCHER (Zeifsch. physiol. Chtm. 1913 83 170).-Polemical. A reply to Kuster (this v&i i 210). E. F. A. The Action of Pepsin-Hydrochloric Acid on Proteins Partly Digested with Trgpsin. VALDENAR HENRIQUES and J. K. GJALD- BAE (Zeitsch. physiol.Chm 1913 83 83-92).-Egg-white and caseinogen partly digested with trypsin behave differently when sub- mitted to the subsequent action of pephin-hydrochloric acid the former being more readily changed and the yield of formaldehyde-titratable nitrogen being greater. Activity of Koji Sucrase [Invertase] in the Presence OL Different Acids. GABRIEL BERTRAND M. KOSENBLATT and (Mrne. ) A1. ROSENBLATT (Compt. rend 1913 156 261-263. Compare A. 1912 i 148 337 $Ol).-A study of the diastatic activity of the W. D. H.ORGANIC CHEMISTRY. i. 303 sucpase known as taka-diastase,” extracted from the Japanese Koji in the presence of various acids. This sucrase unlike thom obtained from yeast and A a p e r g i h ~ niger shows a maximum activity in solutions the concentration of which with respect to hydrogen ions practically corresponds with neutrality to helianthin and is independent of the nature of the acid.W. G. Enzymic Decomposition of Glucosides and Galactosides. HENRY BIERRY (Cornpt. rend. 1913 156 265-267. Compare A 1909 ii 747).-A r6sum8 of the work already published on the enzymic hydrolysis of a- and P-glucosides and galactosides by various ferments. The author finds that the digestive juice of the Helix attacks both a- and P-galactosides. The lactase obtained from the intestine of a dog appears to be much more specific in its action only attacking derivatives of galactose and of these only the P-derivatives from which it seems to make a restricted choice in that it hydrolyses lactose itself but neither a- or P-methyl galactoside.The Rate of Destruction of Ptyalin by the Direct Electric Current. W. E. BURGE (Amer. J. PhysioZ. 1913 31 328-333).- The passage of the direct electric current destroys ptyalin but this is not due to electrolytic products. The rate of destruction is uniform and was 2.5% per coulomb for the Eolutions used W. G. # W. D. H. Resistance of Emulsin to the Action of Heat in Presence of Strong Alcohol. EMILE BOURQUELOT and MABC BRIDEL ( J . Yfkavrrb. Chim. 1913 [vii] 7 65-67).-1n a previous paper (this vol. i 2121 it was shown that the temperature at which emulsin is rendered iractive falls as the concentration of alcohol increases to 50% but that with stronger alcohols the tern perature of inhibition rises with the concentration of the alcohol. It was suggested t h a t this phenomenon is due to the fact that in the stronger alcohols the ferment is precipitated and in this condition is more resistant to beat.Experiments are now described which prove this contention ; thus it was found t h a t emulsin was scarcely weakened in action when mixed with dry alcohol and the latter heated slowly to the boiling point and maintained a t this temperature during two minutes. In sterilising plants containing enzymes therefore it is best to use alcohol of such u strength as to produce a liquid containing about 60% of alcohol when the plants are immersed in it allowance being made for the water in the plants. T. A. H. Enzyme Action. 111. Action of Manganous Sulphate- on Castor Bean Lipase. K. GEORGE FALK and MARSTON L. HAMLIN (J. Amer.Chem. SOC. 1913 35 210-219. Compare Palk and Nelson A. 1912 i 523 59S).-Experiments are described which show t h a t when a preparation oE castor bean lipase which has been rendered inactive by heating with water is treated with rnanganous sulphate it becomes slightly active again. In order to explain this behaviour it is suggested that although the active enzyme is hydrolysed by the action of hot water the inactive zymogen present in the pre-i. 304 ABSTRACTS OF CHEMICAL PAPERS. paration is not wholly deetroyed and that the manganous sulphate effects the conversion of the inactive zymogen into active enzyme by a process of oxidation. E. G . Enzymic Decomposition of Hydrogen Peroxide. IV. PERCY WAENTZG and OTTO SrECHE (Zeitsch. physiol. Cham. 1913 83 315-337. Compare A 1911 i 759 ; 1912 i 228 ; ii 839).-The action of several proteoclnstic and other enzymes on active prepara- tions of catalase has been studied.Trypsin alone destroys the catalase indicating the protein nature of this substance. The experi- ments are not in favour of the possible destruction of a protective colloid by the trypsin thereby destroying the catalase as well. The resistance of catalase to hydrolysis by pepsin suggests that it has a polypeptide structure but it is possible that the experimental condi- tions were adverse to the action of pepsin since the solutions could not be made more than faintly acid. The gastric juice of the cray fish was especially active in destroying catalase-this confirms its tryptic nature. The action on catalase affords a method of detecting and possibly of measuring tryytic enzymes. Differences are noted in the resistance of blood catalase to the tryptic ferments of vertebrates and of the crayfish and also in the behaviour of catalases of different origin to the same trypsin. E. F. A. Neutralisation of Solutions of Diaminodihydroxyarseno- benzene Hydrochloride. J. CHARLES BONGRAND (J. Pharrn. Chirn. 1913 [vii] 7 49-55).-Theoretically this drug requires 4 mols. of sodium hydroxide to neutralise it by conversion into the disodium derivative The author shows by means of cryoscopic and electrical conductivity determinations that in dilute solutions as used in practice hydrolytic dissociation occurs and that more than the theoretical amount of sodium hydroxide is then required to main tain the drug i n solution as the disodium derivative. PAUL C A R R ~ (Bull. Xoc. china. 1913 [iv] 13 102-104).-Magnesium phengl bromide reacts with antimony tri- chloride to form triphenylstibine together with the cblorides of phenyl- stibine and diphenylstibine the first being almost the sole product when a small proportion of the magnesium compound is used whilst with 1 or 2 mols. larger quantities of the two latter substance8 are simultaneously produced. Phenglstibine and diphenylstibine chlorides are decomposed by heat into antimony trichloride and triphenylstibine (compare Michaelis and Gunther A 1911 i; 1056). T. A. H . Irhenylstibines. T. A. H. Mercury Dibenzyl. PAUL WOLFF (Be?. 1913 46 64-66).- The description of mercury dibenzyl given by Carnpisi in 1865 is erroneous and endeavours t o prepare this substance by the action of sodium amalgam on benzyl chloride have been futile producing only dibenzyl. The substance has beea successfully obtained by the application of magnesium benzyl chloride [see Pope following abstract].PHYSIOLOGIICAL CHEMISTRY. i. 305 Mercury dibenzyl is formed and crystallises in long colourless heedles m p. 111' [Pope and Gibson give 104'1 which decompose above the rn p. into mercury and dibenzyl. When heated in alcoholic solution with mercuric chloride mercury benxyl chloride leaflets m. p. 104O is obtained ; mercury benxyl bi-omide and mercury benzyl iodide prepared in an analogous manner also form coiourless leaflets m. p. 119' and 117' respectively; mem.wy benzyl cyanide needles m. p. 1 2 4 O for its formation requires mercury dibenzyl and mercuric cyanide to be heated together in alcoholic solution at 130'. MAT CUT^ benxyl acetate is produced by the interaction of mercury dibenzyl and mercuric acetate in alcoholic solution and also of mercury benzyl chloride and silver acetate in alcoholic solution. Mercury dibenzyl when heated with acetic acid for two or three hours at 170' undergoes decomposition into mercury toluene benzyl acetate and dibenzyl. D. F. T. Mercury Dibenzyl. WILLIAM J. POPE ( B e y . 1913 46 352).- Mercury dibenzyl has been obtained previously to Wolff (preceding abstract) by Pope and Gibson using the same method (T. 1912 101 735). T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9130400241

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 261 General and Physical Chemistry. Change in Refractive Index with Temperature. 111. K. GEORGE PALK (Zeitsch. physikd. Chenz. 1913 82 504-505).-In the two previous papers'(A. 1909 ii 197 629) an account was given of measurements of the refractive indices of a number of organic liquids. The present paper deals with a theoretical consideration of these results on the basis of new determinations of the atomic refractions by Eisenlohr (A. 1910 ii 365; 1911 ii 81). The author compares the observed molecular refractions of the substances diisoamyl n-heptyl alcohol n-bu tyric acid methyl hexyl ketone isobutyl acetate ethyl n-butyrate and isoamyl acetate with those calculated from Eisenlohr's atomic refractions. It is shown that for the vslues at 20° there is a small but generally unimportant difference between the two values.The Lorentz-Lorenz formula is considered. It is written (n2-l)/(m2+a)d and the value of a is calculated from the experimental values of the specific refraction of the substances mentioned above. It is shown that a varies between 3.6 and 6.9 but the value for the two isomeric substances isobutyl acetate and ethyl n-butyrate is practically the same for the a- P- and y-hydrogen lines and for the D-sodium line and is equal to 4.5 as a mean. J. F. S. The Spectrochemistry of Compounds with a gem-Dialkyl Group. KARL VON AUWEHS (Be?.. 1913 46 494-514).-1t is foutrd that the presence of a gem-dialkyl group in a molecule generally causes a depression of the rnolccular refraction and dispersion the effect being most marked when the group is substituted into a conjugation of double linkings ; thus ethyl d-cis-camphorate ethyl I-trans-camphorate and dimethyl isodehydrocamphorate (Bredt A 1909 i 498; this vol.i 338) show such a depression whilst methyl d-dehydrocamphorate and ethyl dZ-dehydrocamphorate although containing conjugated double linkings show no sign of exaltation ; ethyl bornylenecarboxylate in which the dimethyl group is outside the conjugation exhibits an exaltation. The influence of the gem- dimethyl group is less marked when present in a substance of normal spectrochemical behaviour but becomes more appreciable as the size of the alkyl radicles increases; for example although ethyl dimethylacetoacetate is normal a slight depression is observable with ethyl methylethylacetoacetate and this becomes still more marked with ethyl diethylacetoacetate.Especial care was taken to ensure the purity of the last three substances and hence probably arises some divergence in the figures quoted below frbm those already published by Briihl (A. 1894 ii 433). With ethyl malonate also the introduction of two ethyl groups or of a methyl and ethyl group has a marked depressing effect whilst two methyl radicles have no apparent action on the refraction. The refraction of the following substances was measured for the VOL. clv. ii. 18ii. 262 ABSTRACTS OF CHEMICAL PAPERS a- p- y- and D-lines but only t,he value for the last is quoted below. >CMe b. p. ?H:C(CO,Me)-- CH *CMe(CO,Me) Methyl d-dehydrocamphorate 132-132-5"/9 mm. D:j'4 1.0915 ng'4 1.47509' ; ethyl dl-dehydro- camphorate,'b.p. 145-146"/10 mm. Di63 1.0400 ng'4 1.116588 ; rncthyl >CMe b. p. 128-129",'s 5 isodehydrocamphorate EH * CH (C0,Me) CH*CMe(CO,Me) nun. Di7 ' 1.0852 1 ~ ' ~ 1.46'782 ; ethyl-bornylc~ccarhouglntc CH,-~H-C*CO,Et I 1 CH,-CMe-CH 1 CMe2 ' / b. p. 122'/16 mm. Die" 0.9826 Ethyl methylacetoacetate b. p. 75-5-765O/12 mm. Dia0 1.0008 ng8 1.42066; ethyl ethylacetoacetate b. p. 80°/10 mm. 0.9831 n:.l 1.42366 ; ethyl dimethylacetoacetate b. p. 78"/14 min. DiB1 0.9'777 ng'8 1.41828 ; ethyl methylethylacetoacetate b. p. 85"/12 mm. DiTa 0.9734 ng'7 1.42586 ; ethyl diethylacetoacetate b. p. 92-92*5"/10 mm. Di6'7 0.9710 ng'l 1.43266; methyl acetoacetate b. p. 7%-72*5"/12 mm. DF'6 1.0755 n:" 1.41837 ; methyl met'hylacetoacetate b.p. SOo/20 mm. DqS'3 1.0308 n:"" 1-41 689 ; methyl dimethylacetoacetate b. p. 74'/15 mm. D?'* 1.0002 n2.l 1.41789. Ethyl malonate b. p. 198-198-6O DP6 1.0566 r21,7" 1.41508 ; ethyl methylmalonate b. p. 201.2- 201*4O Dts7 1.0192 ng'7 1.41369 ; ethyl dimethylmalonate b. p. 88.7'/21 mm. DY'O 0.9910 9 i g . l 1.41049 ; ethyl methylethylmalonate b. p. 102'/17 mm. Di8" 0.9970 r ~ " ' ~ 1.41896 ; ethyl diethylmalonate b. p. 109-l10°/21 mm. Di6'6 0.9880 ng6 1-42516 ; methyl dimethylmalonate b. p. 71"/22 inm. Dyg 1.0591 n;;'2 1.41312 ; methyl diethylmalonate b. p. 97-9So/2S mm. DqJ.' 1.0315 7if:'5 1.42528. D. F. T. 1.47604. Arc and Spark Spectrum of Lead. FHITZ KLEIN (Zeitsch. wiss. Photocheru. 19 13 12 16-30).-These spectra have been re- examined in order to obtain data expressed in terms of the Inter- national normal lines.The measurements were made with a Row- land concave grating the spectrum of the second order being used for the great majority of the lines which covered the region between h=7228 and h=2088. The recorded data are compared with the results obtained by previous observers. The existence of three groups of ten lines in the arc spectrum the corresponding members of which show the same difference in frequency on passing from one group to another is clearly shown by the author's data which thus confirm the relationship first indicated by Kayser and Runge. H. M D. Selective Dispersion of Mercury Vapour at the h = 2536 Absorption Line. ROBERT W. WOOD (Physikccl. Zeitsch. 191 3 14 191-195).-Quantitative measurements have been made of the dis- persion produced by mercury vapour in the immediate neighbour- hood of the mercury line h=2536*5.The observations were carriedGENERAL AND PHYSICAL CHEMISTRY. ii. 263 out with mercury vapour saturated a t temperatures between 34O and 58O the iron lines of wave-lengths ~=2535*6 ~=2536*9 and A = 2639.0 being submitted to exa.mination. For these three lines the displacement increases as the wavelength becomes more nearly equal to that of the absorption line being greatest for the second and least for the third line. The displacement is not proportional to the pressure of the mercury vapour but increases much less rapidly than this. I n the case of the iron line h=2535'6 the dis- placement was found to increase in the ratio 1 3 when the pressure was raised from 0*0031 to 0.0215 mm.that is in the ratio 1 7 . From this it would appear that the molecules which are directly responsible for the dispersion in the neighbourhood of the absorp- tion line are not the normal molecules of mercury. Whether the active molecules are complex aggregates or ionised molecules cannot be determined. H. M. D. Relationship between the Absorption Spectrum and the Constitution of Complex Cobaltammine Salts. KOBERT LUTBER and ANDREAS NIKOLOPULOS (Zeitsch. physikaE. Chenz. 1913 82 361-378) .-In determining the absorption spectrum of twenty complex cobaltammine salts the visible portion of the spectrum was measured by a spectro-photometer using a mercury vapour lamp as the source of light and the ultraviolet portion was measured by Hartley's method using a quartz spectrograph and an iron spark ils source of light.The various errors of the method are discussed and an approximate estimate of their dimensions is made. It is shown that the light absorption is only dependent on the composi- tion of the complex. The replacement of NH3 by NO H,O (21 and Br in the complex causes a displacement of the absorption toward the red end of the spectrum. Replacement of NHS by NO causes a displacement toward the violet end. In accord with the electron theory the stability of analogous compounds is greater the further the absorption bands extend toward the violet and the photo- chemical hnsitiveness is greater the steeper the absorption cuive. J. F. S. Quantitative Investigation of the Absorption of Ultra- violet Rays by the Fatty Acids and their Esters in Aqueous and Alcoholic Solutions.JEAN BIELECKI and VICTOR HENRI (Compt. rend. 1913 156 550-552).-In continuation of this investi- gation (compare this vol. ii 86) the authors have studied the absorption by the fatty acids and their esters in alcoholic solutions and by sodium formate and acetate in aqueous solutions and from the results have calculated the molecular coefficients of absorp- tion. The figures are tabulated and show that the absorption of the ultraviolet rays is almost the same for the esters as for their acids the absorption of a compound of the type C,H,,,*CO,R being determined by the acid group the alcohol radicle having only a feeble influence. Alcoholic solutions have a stronger absorptive power than aqueous solutions due probably to the displacement of the absorption bands in alcoholic solution towards the red end 18-2ii. 264 ABSTRACTS OF CHEMICAL PAPERS.of the spectrum. The acids arranged in ascending absorptive power are acetic propionic formic butyric and valeric or leaving out formic acid the absorption increases with addition of CH to the molecule. No change occurs in the form of the absorption curve but a displacement of the bands towards the red is produced. The sodium salts of the acids studied are less absorbent than the acids themselves probably owing t o the greater ionisation of the salts in aqueous solution. W. G. Spectrographic Studiesin the Anthraquinone Group. RICHARD MEYER(BW. 1913 46 617. Compare this vol. ii 168).-The author acknowledges that Forminek has dealt with the anthraquinone dyes in a work entitled ( ( Investigation and Identification of Organic Dye-stuffs by means of the Spectroscope,” and points out the differ- ence between the aims of this investigqtion and of his own.H. W. Absorption Spectra of Fluorescein Eosin Erythrosin and Rose-Bengal in the Visible and Invisible Regions. GUSTAYE MASSOL and A. FAUCON (Bull. Xoc. chim. 1913 [iv] 13 217-221).- The authors have examined the absorption spectra of fluorescein eosin erythrosin and rose-bengal (dichlorotetraiodofluorescein). In the visible portion the spectra obtained closely resemble one another giving a band extending over the blue and green portion the limits of which have been defined with regard to the yellow sodium green thallium blue strontium and violet potassium lines.I n the ultra- violet fluorescein gives three bands between A=260 and ~ = 3 3 5 depending on the thickness of the layer; eosin gives only one band between A = 325 and h= 345 only visible in thickness above 50 mm. ; erythrosin and rose-benzal only show a progressive absorption with- out bands the latt,er being much the more powerfully absorptive. All the substances were examined in aqueous solution (concentra- tion 1 in 10,000). Optical Investigations of Diazo compounds. BRI HUE HABTZSCEI and ISRAEL LIFSCHITZ (Ber. 1913 46 414-416. Compare A. 1912 ii 1116)-Polemical; a reply to Cain (this vol. i 169). The authors dissent from Cain’s views and reaffirm the correctness of their own interpretation of the phenomena.The Theory of Fluorescence. HUGO KAUFFMANN (Zeitsch. Elektroclwn. 1913 19 192-196).-PoIemicaI. An answer to Stark (this vol. ii 2) and a further criticism of Stark‘s theory of fluorescence (A. 1911 ii 786). H. W. D. F. T. J. F. S. The Theory of Fluorescence. J OKANNES STARK (Zeitsch. Elektwchenz. 19 13 19 196-19$).-~olernical. An answer to Kauffmann (see preceding abstract). B1~Fct~ochen~ 191 3 19 197).-Polemica1. preceding abstract). J. F. S. J. F. S. The Theory of Fluorescence. HUGO KAUPFMANN (Zeitsch. An answer t o Stark (seeUENERAL AND PHYSICAL CHEMISTRY. ii. 265 [Rotation Dispersion.] JOH. PLOTNIKOV (J. pr. Ciiem. 1913 [ii] 87 236-237).-A note on the author’s light filter the efficiency of which was called into question by Deussen (this vol.ii 88). ’ F. B. Energy Absorbed and Mass Formed in a Photochemical Reaction. MARCEL BOLL (Compt. rend. 1913 156 691-694).-A mathematical paper in which the author deduces the following laws (1) When an absorbent substance is the seat of a chemical reaction the emergent energy decreases according to the exponential function of the thickness of the layer and the concentration a t each instant. (2) The mass formed m = ( k s t ) / x . cWa where s=surface t =time x = coefficient of absorption W a = incident energy c = con- centration. (3) I n the case of a bimolecular reaction Grotthus’s law of photochemical absorption does not hold good there being no ratio between the mass formed and the energy absorbed. W. G. Photochemical Behaviour of Colloidal Tungstic Acid.ALEXANDRA WASSILJEWA (Zeitsch. wiss. Photochenz. 191 3 12 1-15)- If dilute hydrochloric acid is added to a solution of sodium tungstate until tho liquid becomes slightly acid a colloidal solution of tungstic acid is obtained which in presence of various organic substances such as formaldehyde sucrose dextrose dextrin etc. undergoes reduction on exposure t o light with the formation of an intense blue solution. If the undialysed solution is kept for some time it is found that the above reduction process does not occur when the solution is exposed to light; on raising the temperature however the blue reduction products are obtained as in the case of the freshly prepared colloidal solution. It is suggested that this is due to the existence of two forms of colloidal tungstic acid one of which is photochemically sensitive and the other not.The former changes spontaneously into the latter but the reverse transformation is brought about by a rise of temperature. The absorption spectra of the two modifications are found to differ appreciably the region of ultz-aviolet absorption extending further towards the visible spectrum in the case of the photo- chemically sensitive modification. Kinetic experiments have also been made in order to ascertain the nature of the change in which the photochemically active form is converted into the inactive modification. These show that the change proceeds in accordance with the equation for a unimolecular reaction. The rate of transformation was ascertained by measure- ments of the photochemical activity of the colloidal solution after measured intervals of time.This was effected by exposing the colloidal solution containing dextrose as reducing agent to the light from an arc lamp for five minutes and estimating the amount of the reduction which occurred during this period by titration with a permanganate solution. From the photochemical sensitive- ness obtained in this way it was possible to ascertain the correspond- ing concentration of the active form by reference to a curve con-ii. 266 ABSTRACTS OF CHEMICAL PAPERS. necting the two quantities this curve being plotted from data obtained in experiments which were carried out to determine the connexion between the two factors. By similar measurements it has been found that a colloidal solution which had become quite inactive at 7O regained 31% of its origilial photochemical activity when heated to 43O and 81% when neated to 96O.That this is not due simply to an acceleration of the photochemical change with rise of temperature is shown by measurements of the influence of temperature on the reactivity of the freshly prepared colloidal solution. I n common with all photochemical reactions the temperature-coefficient was found t o be very small the velocity increasing by only 1% when the temperature was raised from 8 O to 96O. As regards the chemical relationship between the active and inactive colloids very little information has been obtained. The spectroscopic data would seem to show that both are colloidal and of similar composition and i t is suggested that.the change from the active to the inactive form may consist in the addition of water or in the combination of the tungstic acid with sodium salts according to 3w03 + N%WO = Na,0,4W03 which substance was obtained by Sabaneev (A. 1897 ii 456) by subjecting the solution to dialysis. H. M. D. The Activation of Oxygen by Radiation. FRITZ WEIGERT ( H e i s . 1913 46 815-820).-1n order to investigate the photochemical reaction of ozone it was necessary to use a part of the spectrum where ozonisation of oxygen does not occur. This was attained by using a quartz-mercury lamp and allowing the rays to pass through a layer of air before entering the reaction vessel. The apparatus was similar to that previously used by tlfe author (A. 1912 ii 715) in the in.vestigation of the decomposition of ozone by ultraviolet light and the particular reaction used was that between ozone and hydrogen.No trace of hydrogen peroxide was formed (compare Coehn A. 1910 ii 608) and there was only an extremely slow reaction in the dark. I n ultraviolet light however about one-third of the ozone originally present disappeared in two minutes ths disappearance being due to the two reactions 2 0 3 = 3 0 and H,+O3=H2O+0,. The total amount of ozone decomposed is proportional to the ozone concentration whilst the amount of hydrogen oxidised approached asymptotically an upper limit which was attained at an ozone concent.ration which was the lower the lower the concentration of the hydrogen. This limit is approxi- mately proportional to the concentration of the hydrogen (compare Clausmann A.1910 ii 608). The above results indicate that in the activation of oxygen by ultraviolet rays two photochemical reactions occur. I n the f orma- tion of water from hydrogen and oxygen the oxygen is first ozonised by the short rays and then reacts with hydrogen under the influence of the long rays. I n the photochemical dissociation of water vapoiir a further photochemica.1 reaction plays a part. namely H,O = HZ + 0,GENERAL AND PHYSICAL CHEMISTRY. ii. 267 which is affected by the short rays. The complicated relations observed by Coehn (Zoc. c i t . ) are thus explained. It is possible that the deviation of t-he nitric oxide equilibrium from the position calculated thermochemically is due to the photo- chemical action between nitrogen and ozone the latter being formed from oxygen by the ultraviolet rays as for example in the experi- ments of Fischer and Hene (this vol.ii 317). T. S. P. Absorption of the Ultraviolet Rays by Acetylene. VICTOR HENRI and MARC LANDAU (Compt. rend. 1913 156 697-699).-A study of th4 ultraviolet absorption spectra of acetylene first in a gaseous state a?; the ordinary temperature under a pressure of one-tenth t o one atmosphere using a thickness of 40 cm. of gas and secondly in alcoholic solution. I n the first case there are three distinct groups of bands. The first extends from h 3157 to 2880; the second beginning to appear a t h 2960 and being most marked between ~2800 and 2500; the third extends from ~2327.5 to 2236-4 and is in turn capable of resolution into a series of very fine bands.Between ~2500 and 2327.5 acetylene in the gaseous state under the given conditions shows no sensible absorption. I n alcoholic solu'tion acetylene presents only one very broad band commencing a t ~ 2 8 5 0 and attaining a maximum at ~2631. The ultraviolet absorption by acetylene commences approximately at the region where t h s solar ultraviolet spedrum ends. W. G. The Inversion of Sucrose by Ultraviolet Rays. DAHIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 1913 156 468470).-A rgsum6 of work already published (compare A. 1910 ii 813; 1912 i 750 ii 1120; this vol. i 16 ii 4) and a reply to Bierry Henri and Ranc (this vol. ii 4). W. G. A Lavulose Actinometer for Ultraviolet Rays. Influence of Concentration on the Rate of Photochemical Action.DANIEL BERTHELOT and HEKRY GAUDECHON (Compt. rend. 19 13 156 707-710)-A 10 per cent. aqueous solution of lzvulose can be used to give a direct measure of the intensity of the radiation the volume of the gas evolved being directly proportional to the time for any given radiation and inversely proportional to the (distance)3I2. Further for diluh solutions (4.5 to 18 grams per litre) the velocity of the reaction is proportional to the concentra- tion whilst for strong solutions (720 to 1080 grams per litre) it is constant and independent of the concentration. These facts are best explained on the hypothesis that the velocity of reaction is proportional to the quantity of light absorbed per unit of time. W. G. The Most Recent Value for the Atomic Weight of Radium.STEFAN MEYER (Physikal. Zeitsch. 191 3 14 124-! 25).-Honigschmid has verified his atomic-weight value 225.97 found from the determinations for radium chloride by determinations for radium bromide and in common with Haschek shown by spectro-ii. 268 ABSTRACTS OF CHEMICAL PAPERS. scopic tests that not more than 0.004% of barium can be present. Theoretical grounds can be adduced for the value 226. From magnetic deviation experiments and the value of the faraday it can be deduced t h a t thel atomic mass of the a-particle is 3.8 or 5% smaller than that of helium. Subtracting five times 3-8 from 226 gives 207.0 agreeing with the atomic weight of lead. This suggests an error in the determination of the atomic weight of helium but the possibility is referred to that helium and the a-particle may represent " non-separable " elements (Soddy). The value 3.8 however makes the atomic weight of uranium 237.4 instead of 238.5 and until the complex (UI+UII+UX+UY) has been further studied arguments from the atomic weight of uranium are indefinite.There is no ground for doubting the value 226.0 for the atomic weight of radium or the purity of the International Standard (Marckwald A. 1912 ii 323). Revision of the Atomic Weight of Radium by Analysis of Radium Bromide. OTTO HONJGSCHMID (Monntsh. 1913 34 283-309).-The material which had given the value Ra =225*95 by analysis of the chloride (A. 1912 ii 523) was converted into bromide and fractionally crystallised thirty times. No change of atomic weight occurred during the process.Very full details are given of the analytical operations. Six analyses with nearly a gram of radium bromide in which the ratio RaBr,/AgBr was deter- mined gave the mean value Ra=225*96 with a mean variation in the separate experiments of 0.01 and a mean error of 1 in 40,000 of the weight of the radium bromide. Two analyses in which the ratio RaBr,,/Ag was found gave in both cases Ra=225.97. The purest preparations of bromide did not show the barium line 4554.2 and were absolutely free from barium so far as spectroscopic test revealed. It is calcula-ted t h a t not more than 0.004% of barium could have been present. The results of Whytlaw-Gray and Ramsay (A. 1912 ii 413) are criticised in detail and corrected for a constant error in the reduc- tion of the.weigh& to a vacuum. Their mean value recalculated should be 226.26 with a mean error of 20.21. Two determinations by their method converting the bromide into the chloride by heating in hydrogen chloride the second with nearly a gram of radium bromide gave the value Ra=225*94. It is estimated t h a t the heat generated by the radium compounds may raise the atomic weight by 0.01. Seventeen analyses of radium chloride and bromide by two independent methods in which the extreme values are included between 225.99 and 225'93 give the final value 225.97 (Ag= 107.88 ; C1= 35.457 ; Br = 79.916). The mean departure from the mean is k0-012. F. S. The Purity of the International Radium Standard. EnuARD By means of a large Rowland grating radius of curvature 15 feet with 72,000 lines at 20,000 t o the inch the spectrum in the neigh- bourhood oe 4500 A .units was examined of the purest radium bromide used in the atomic-weight determinations (preceding F. S. HASCHEK and OTTO HONIGSC!HMID (hfonalsh.. 1 !! 13 34 35 1 -35f) -.- GENERAL AND PHYSICAL CHEMISTRY. 11. 269 abstract) and of the mother liquors in which all the impurities in the material which was that employed in the atomic-weight deter- minations on the chloride (A. 1912 ii 523) had been accumulated after twenty-five crystallisations of the bromide. A rod of electro- lytic copper which was completely free from barium was used f o r the electrode. The rod was 7 mm. thick and provided with grooves and one drop of the purest bromide solution containing 0.15 mg.of radium (metal) was tested with a powerful spark discharge. No trsce of the barium line 4554.24 was seen in the photograph. On a new electrode a drop of a barium solution of strength 0.1% of the radium solution previously tested showed this ling faintly but clearly. The mother liquors containing 75 mg. of radium bromide were tested as in the first case a drop containing 0.25 mg. of radium (metal) being employed. The barium line was plainly visible. Addi- tion of 0.1% barium increased the intensity of the line four times. If the original barium content of the mother liquors is taken as 0*03?4 i t follows that the original chloride out of which the Austrian standards have been prepared does not contain more than O.O047L and the radium bromide used in the final atomic-weight estimations not more than 0*002% of barium. This can make no appreciable difference in the values found.A similar degree of purity can be assumed for the International radium standard as for the Austrian standards and for the barium to cause any error in the radioactive determinations methods a hundred times more sensitive than the present must be employed. F. S. Heating Effect of Radium a n d i t s Emanation. I ~ N E S T ~?UTHEHFORD and H. RosrIvsoN ( P h d . M a g 19 13 [vi] 25 312-330). -The heating effect of any a-ray would not be a measure of the energy of the expelled a-particle if the a-particle lost energy before escaping from the atom. Experiments on the distribution of the heating effect among the emanation and its first three products were made to see if the observed emission of heat agreed with that calculated from the energy of the radiations expelled and also to determine the heating effect of the p- and y-rays.The relative calculated heating effects of the emanation ra.dium-A and -C 28.8 30.9 and 40m3% agree with the observed values 29 31 and 40% but as the &rays of radium-B are included in the results for radium-C i t follows that the percentage for this number should have been about 43.6 instead of 40.3. The difference is small but it may prove to be significant. The heating effect of one curie of emanation and its products in terms of the Vienna standard is 103.5 gram-calories per hour when more than 90% of the energy of the &rays is included. Under these conditions 99.2 calories are estimated to be due to a-rays 4.2 t o &rays and 0.1 t o y-rays.The total heating effect of 1 gram of radium is estimated to be 134.7 calories per hour made up as follows 25.1 due to a-rays of radium-B 28.6 to the a-rays of the emanahion 30.5 t o the a-rays of radium-4 39.4 to the a-rays 4.7 to the @rays and 6.4 t o the y-rays of radium-B and -C. F. S.ii. 270 ABSTRACTS OF CHEMICAL PAPERS. Decomposition of Water by a-Rays. WJLLIAM DUANE and OTTO SCHEUER (Compt. rend. 1913 156 466-46'i*).-A study of the decomposition of water in the solid liquid and gaseous state by a-rays care being ta.ken to avoid excess of water to have it in as thin a layer as possible and to remove the gaseous products from the radiation as soon as formed. With ice a t - 1 8 3 O hydrogen and oxygen are obtained in the proportion of 2 l by volume.With water the hydrogen is a t first in excess due to the formation of hydrogen peroxide this in its turn being decomposed and giving oxygen in excess. With water vapour the hydrogen is largely in excess and may amount to 50% of the total volume of gas liberated. A radiation capable of producing an ionisation current of one ampere in air decomposes water giving 0.1594 C.C. hydrogen and 0.0797 C.C. oxygen per second these amounts being of the sa.me order as those obtained by the electrolysis of water a t 15O. W. G. The 0-Rays of Radium-B -C -D -E. JEAN DANYSZ (Le Radium 1913 10 4-6).-The experiments before carried out with thin- walled glass tubes of radium emanation (A 1912 ii 219 220) have been repeated with thin wires of silver and platinum made active in the emanation. There was no difference in the results but the photographs with the glass tubes are much superior in sharp- ness.Tables are given of the character value of Hp velocity and energy of twenty-seven groups of P-rays from radium-B and -C and of five groups from radium-D and -3. These results are corrected for slight retardation of the P-rays in passage through the walls of the tube. Some of the original photographs are reproduced. F. S. The Penetrating Power of the 7-Rags of Radium-C. ALEXANDER S. RUSSELL (Proc. Ho?. Soc. 1913 A 88 75-82).- Experiments were carried out with 300 millicuries of radium emana- tion in the attempt to detect the presence of a radiation more penetrating than the y-rays of radium-C after passage through great thicknesses of mercury.With from 1 t o 22.5 cm. of mercury the y-rays are absorbed strictly according to an exponential law and over this range are reduced in intensity from 3.6 x LO5 to 1. The value of p / d is 4-38 x lO-Z(cm.)-l. This value is practically the same as that previously found for lead over the range from 2 to 22 cm. namely 4.37 x 10-2 (A 1909 ii 851). I t is calculated that after passage through 28.6 cm. of mercury the y-rays unabsorbed from 10 grams of radium would produce an effect less than 5 per cent. of the natural leak. I f any ionising radiation exists more penetrating than the y-rays its intensity must be less than 2 x 10-6 of the initial y-rays. F. S. The Chemical Action of Penetrating Radium Rays.V. Influence of Penetrating Rays on Sterilised Aqueous Sucrose Solutions ANTON KAILAN (Moncttsh. 191 3 34 359-364. Compare this VOI. ii 8).-Normal sucrose solutions were sterilised by long heating a t 100° and subjected to the action of the penetrating * and Lc Radium 1913 10 33-46.GENERAL AND PEYSICAL CHEMISTRY. ii. 271 raps of radium in closed flasks in the absence of light for several months blank experiments without the radium being also per- formed. Formation of acid and a decrease in the rotation still took place in the solutions after sterilisation although it is much smaller than in unsterilised solutions rather less effect being produced after 2800 hours' exposure to the rays than formerly after 500 t o 700 hours. The acid so produced must be relatively feebly dissociated but its quantity is completely sufficient t o account f o r the loss of rotatory power of the sucrose through the inversion brought about by the hydrogen ion.The solutions after exposure to the rays reduce Fehling's solution and the amount of invert sugar present as so determined agrees a.pproximately with that calculated from the decrease of rotatory power. F. S. Theory of the Concentration Variations in Radioactive Solutions EGON VON SCHWEIDLEH (Phy~ikccl. Zeirsch. 19 13 14 198-200) .-The mathematical theory of the von Schweidler varia- tion in the emission of rays from a radioactive solution is con- sidered in which the instantaneous concentration also undergoes a probability variation. Experimental complications for example when only a small part of the total radiation is for various causes observed by the observer do not affect the general character of the results to be expected as regards t-he relative magnitude of the variations and the law of distribution of the rays in time.F. S. The Solubility of Radium Emanation in Water a8 Re- gards its Dependence on the Temperature. MARTIN KOFLER (Monutsh. 1913 34 389-400. Compare A 1908 ii 80).-The following results have been obtained showing the variation of the solubility of radium emanation in water with temperature Temperature ...... 0.5" 17'5" 35' 41" 51" 60" 74" 79" 82' 91" Solubility ......... 0.526 0.283 0.185 0.161 0.138 0.127 0.112 0.111 0'111 0.1G8 Both the solubility and the change of solubility with temperature decrease with increase of temperature.It is shown that the per- centage change of solubility between Oo and 1 8 O for a large number of gases increases with the molecular weight of the gas. It is 7% for helium 33% f o r argon and 49% for the radium emanation. Above 70° the solubility changes so little that i t may be considered practically constant but no evidence of a minimum solubility as in the case of hydrogen and helium was obtained. The solubility of gases generally is discussed. F. S. A Relation between Ionisation by Cathode Rays and Certain Chemical Effects. E. JACOT (Phil. Mag. 1913 [ v i l 25 215-234).-The investigation is concerned with the proportion of the chemical zction of the cathode rays due (1) t o direct action as supposed by Schmidt (A. 1902 ii 237) of the negative charge neutralising the positively charged ion and causing chemical dis- sociation (2) to thermal effects (3) to the secondary action of theii.272 ABSTRACTS OF CHEMICAL PAPERS gases in the tube. I n the case of yellow phosphorus the rapid transformation into the red variety is attended by rapid exhaustion of the nitrogen in the tube. The mass of phosphorus so trans- formed exceeds the a-mount that could be formed as a direct thermal effect assuming the energy of the cathode rays to be quantitatively converted into heat and whstl the phosphorus is screened from direct impact of the rays the transformation attended by absorption of gas still goes on. The absorption is proportional to the equili- brium ionisation of the nitrogen. The ionisation is inversely propor- tional to the kinetic energy of the cathode rays for a range of velocities from 2.92 to 4.76 ( x lo9 cm./sec.) and varies linearly with the pressure from 0.083 to 0.025 mm.But the total number of active atoms or molecules in the gas is of a much higher order than the number of ions. Most probably the absorption is not due to the ions but to an atomising effect of the rays the active agent being monatomic nitrogen and the number of such molecules being proportional to the ionisation of the gas. F. S. Positive Ionisation Produced by Platinum and by Certain Salts when Heated. FRANK HORTON (Proc. Roy. Soc. 1913 A 88 117-146. Compare A 1910 ii 176).-The thermionic currents resulting from the emission of positive ions by heated platinum aluminium phosphate sodium phosphate and sodium pyrophos- pha.te have been investigated a t 1080° and 1 1 9 0 O .I n the case of platinum and pure aluminium phosphate the initial thermionic emission decreases very rapidly with time and after a few hours becomes extremely small. With sodium phosphate the emission increases at first this stage being followed by one in which the effect slowly decreases but even after many hours’ heating a very considerable thermionic current is obtained with this substance. The view is put forward that the positive ionisstion exhibited by platinum (and by metals generally) is largely due to the emission of absorbed gases but that in the case of sodium phosphate a considerable part of the effect is due to the emission of positively charged sodium atoms.This view is discussed in reference to the observations of other workers on the ionic emissive power of heated substances. H. M. D. Ionisation Produced by Heated Salts. CHARLES SHEARD (PkiE. Mag. 1913 [vi]. 25 370-359).-An examination has been made of the ions which are emitted by cadmium iodide when this substance is heated out of contact with metal. The observations show that both positive and negative ions are emitted by the salts under these circumstances. The initial emission consists almost exclusively of negative ions but when the temperature is main- tained for some time a t 350° to 500° the positive ionisation increases reaches a maximum and then gradually diminishes ; the negative ionisation on the other hand falls away continuously. I n addition to the emission of ions from the heated salt i t is found that the observed ionisation must be partly due to ionisation ofGENERAL AND PHYSICAL CECEMlSTRY.ii. 273 the vapour. This may arise from the action of the vapour on the cblectrodes or i t may be a volume ionisation or possibly is a com- bination of the two effects. The distilled salt is less active than the undistilled and successive distillations are found to exhibit alternations in their power of emitting positive and negative ions. These distillations which give rise to a comparatively large negative thermionic current exhibit a small positive emission and vice versa. The fact that continued distillation leads to a diminution in the percentage of iodine in the substance and that iodine itself exhibits ionisation effects of a similar kind seems to show that the negative ionisation observed with cadmium iodide is largely due to the negative constituent. H.M. D. Separation of Corpuscles in Chemical Reactions. SEBASTIAN M. TANATAR and E. BURKBER ( J . Russ. Phys. Chenz. SOC. 1913 45 1-6).-Immersion of a charged conductor connected with an electroscope ifi to the gas evolved during the catalytic decomposition of hydrogen peroxide by platinum-black shows the gas to be strongiy ionised. A thin aluminium plate placed under the base of the glass vessel retards the loss of charge. Similar experiments were also made on the oxidation of sodium sulphite or arsenic trioxide by hydrogen peroxide solution. The results do not allow of any definite sta.tement concerning the cause of the ionisation observed.T. H. P. A New Method for Coilcentrating Polonium. FRITZ PANETII (,llo?aatsh. 1913 34 40 1-402).-Pure polonium formed from radio- lead may be obtained as well by the electrolysis of lead nitrate as lead acetate solution when the voltage and acid concentration are such that lead is no longer deposiked on the cathode. Polonium diffuses either not a t all or only in extremely minute amount through animal bladders or parchment paper and may be separated from lead and radio-lead by this method. By dialysing a solution of radio-leGd through thin parchment paper it may be obtained practically free from polonium which remains behind in the cell. F. s. Solubility of the Active Deposit of Thorium in Various Solvents. CHARLES FREDERICK HOGLEY ( P l d Mag.19 13 [vi] 25 330-332).-Water solutions of salts hydroxides and acids always dissolve thorium-B in relatively larger amount than thorium-C especially in the case of short treatments. Boiling water for fifteen minutes dissolves about 3576 and for an hour 70%; potassium iodide solution dissolves the deposit about twice as fast as water; dilute acids dissolve it much more rapidly. Organic solvents dissolve it a t the same rate as water but thorium-C is dissolved more easily than thorium-B the latter being insoluble in carbon disulphide and methylene iodide which dissolved some 20% of the thorium-C in ten minutes. Benzene bromoform etc. behaved very similarly but the thorium-B was slightly soluble. F. S.ii. 214 ABSTRACTS OF CHEMICAL PAPERS.The Chemical Properties and Relative Activities of the Radio-products of Thorium. HERBERT N. McCoy and CHARLES H. VIOL (Phil. n//ccg. 1913 [vi) 25 333-359).-The results of experiments on the chemical nature of the various thorium products agree with the known behaviour of these substances. Meso- thorium-I1 is separated from thorium by hydrogen peroxide at 60° or 70° and is left in the solution. It is carried down by a precipitate of barium sulphate in slightly acid solution. I n absence of thorium radiothorium is partly precipitated with barium sulphate in acid solution up to SO% and to about 5% by mercuric or lead sulphide. Very numerous other reactions are given confirm- ing previous knowledge. A comparison of the a-activities of thorium-B -C and -D with that of thorium-X emanation and - A gave the ratio of the first to the second as 0.427.The products of radiothorium are 5'23 times as active as radiothorium itself. A redetermination of the range of the a-particles of thorium-X gave the value 4.1 cm. (of air a t Oo and 76 cm.) instead of 5.7 cm. as previously found. The new value agrees with what is t o be expected from the period of the substance. The values found for the activities of the various groups of producbs are in excellent agreement with the theoretical law that the total ionisation produced by an a-particle is propor- tional to the two-thirds power of its range. The following is the distribution of the a-activity among the separate products Th 11'4%; Ra-Th 14.4%; Th-X 15.5%; Th Em. 17.6"; Th-it 18.6%; Th-C' 22.5% as calculated from this relation and in agreement with the determined values.B. s. Tables of Radioactive Constants. LBON KOLOWRAT (Le Xadium 1913 10 1--4).-These tables are similar to those published in former years and give the present knowledge with regard to the radio-elements their periods and radiations together with parti- culars of the physical constants of the latter and some other data relative to radioactivity. F. S. ALEXAKDER S. RUSSELL (Chenz. News 1913 107 49-52).-The known rule as regards the change of family in the Periodic Table of an element undergoing ail a-ray change is modified and supplemented by a similar rule with regard to the &ray changes. (1) The a-ray change results in a product belonging to a family the nuniber of which is either two units greater or two units less than that of the parent.(2) The &ray change or rayless change results in a product the number of which is either one unit. greater or one unit less than that of the parent. Tables are given showing how well these rules are obeyed in the three series. Branch products are not considered. Uranium-X is put intermediate between uranium-1 and -11 and a new member uranium-X2 in group VS of the table is predicted. The recent results for radioactinium (Russell and Chadwick Nature Dec. 26th 1912) are discussed. Radioactinium-IZ a new member giving a- and &rays is placed in group VA and its product actinium-X in group 114. The rules were obtained independently Periodic System and Radio-elements.GENERAL AND PHYSICAL CHEMISTRY.ii. 2 i 5 of and are supported by Fleck’s results on the chemical nature of the B-members the C-members radium-E and mesothorium-11 (see Radio-elements and the Periodic Law. FREDER~CK SODDY (Chern. News 1913 107 97-99*).-The known disintegrdtion series many of the members of which have recently been shown by Fleck t o be non-separable from other elements (T. 1913 103 381) agree with the author’s a-ray change rule and the corollary with regard to the P-ray change (Russell preceding abstract). The expulsion of the. a-ray lowers the number of the group in the Periodic Table to which the radio-element belongs by two and the expulsion of the &ray increases the number of the group by one. This holds throughout the disintegrations including the branch series which conimence at the C-members.The emanations in the zero group which expel a-rays furnish short-lived d -members which i t is pre- dicted are in the VIU group in the place already occupied by polonium. Fleck’s results (lor. cit.) are in accord with the rules and for the members the chemical nature of which cannot be directly determined owing t,o too short period of existence i t is predicted that the .4-members and the C’-members are in group VIR and will be non-separable from polonium whilst thorium-B actinium-D and the corresponding member in the radium series radium-C2 are in the I I I B group and should be non-separable from thallium Whenever a radio-element falls in a place in a Periodic table occupied by another it is chemically identical with and non- separable from that element independently of the atomic weight of the radio-element and of the series in which it originates; thus occupying the place in the IVA group already occupied by thorium are ionium radiothorium radioactinium and uranium-X a group the members of which vary in atomic weight by about 6 units.The unknown product of uranium-X (group IVA) by a P-ray change is called “ eka-tantalum,” and occupies a vacant place in the table in the group V-4 the heaviest member of the family known being tantalum. It should prove to be separable from tantalum. Actinium should also be separable from lanthanum. All the members expelling a-rays occupy even-numbered groups except the C-members in group VB non-separable from bismuth. These dis- integrate dually in one mode a P-ray change preceding and in the other mode following an a-ray change.It is suggested that ek* tantalum may disintegrate similarly in one mode a rayless change producing uranium-ZZ (group VIA) and in the other an a-ray change producing actinium (group 111.4). Evidence is given of an excessively minute growth of actinium over a term of years from the old preparations of uranium-X separated in 1909 from 50 kilograms of uranyl nitrate. The six end-products all occupy the place in group IVB occupied by lead and the atomic weight; of lead 207.1 is intermediab between the calculated atomic weights 206.0 and 208.5 of the main end-products of the uranium-radium and the thorium disintegra- * and Jahrb. Radioaktiv. Elektronik. 1913 10 188-197. T. 1913 103 381).F. s.ii. 276 ABSTllACTS OF CEEMICAL PAPfiRS. tion series. These end-products should be non-separable from lead and lead may be a mixture of these end-products. I n Dhe case of thorium and ionium the two elements possess so far as can be seen identical spectra. A chart is given showing graphically the passage of the radio-elements from place to place through the Periodic Table. The prediction with regard to the non-separability of thorium-D and thallium has since been confirmed by Fleck who finds that thorium-D can be quantitatively separated from the B- and C-members by precipitating in the solution potassium by means of platinum chloride. F. S. The Position of the Radio-elements in the Periodic System. KASIMIR FAJANS (Physsikal. Zeitsch. 1913 14 136-142*).- Soddy’s a-ray change rule that the position of the radio-element changes into the next group but one from right to left in the hori- zontal row of the periodic system is shown to be general.I n the same way the P-ray change in general causes a change of one from left to right in the system. By the aid of these rules all the radio- elements can be placed without uncertainty in the Periodic Table. I n all properties the disposition of the elements so obtained corre- sponds with what is t o be expected for the members of the last two horizontal rows of the periodic table which shows that these two rows are the expression of the law of change of the elements. The only difficulty in the application of the a-ray rule is in the change of the alkalineearth elements as radium into the emana- tions which occurs with expulsion of both a- and &rays. From the rules mesothorium-IZ is placed in the third group and radium-E in the fifth.The shortrlived Cr-members come into the sixth group. Tha change from radium-A to lead is written VI IV V VI IT V VI IVY which is analogous t o the change of uranium-Z into ionium VI IV V(?) VI IV. The unknown fifth group member is regarded as a short-lived element intermediate between uranium-X and uranium-IZ which is supported by the fact that uranium-X gives two types of P-rays one very hard such as would be given by it short-Iived element. The members Ra-C Th-D and Ac-D are placed in the third group with thallium. The remarkable fact shown by the table so constructed is that places which elsewhere in the Periodic Table contain only one element here contain several in some cases six. All the elements of one group with atomic weights differing from one another by two units are so completely similar that it has not been possible to separate them by chemical or crystallisation methods and a mixture of such elenents separated from a mineral behaves chemically as one element.The atomic weight found for such a complex element would be nearest to that member with the longest period of life and therefore present in the greatelst quantity. It is sug- gested that thallium is formed in an a-ray change from bismuth itself regarded as the product of (‘ thorium-D ” in a &ray change. The discrepancy between the atomic weight of lead 207.1 and that of the end-product of the uranium series 206.5 would be * arid Le 12adiuna 1913 10 61-65.GENERAL AND PBYSICAL CHEMISTRY.ii. 277’ explained if common lead were a mixture of the latter and “ thorium-D?,” which is the product of thorium-C’ and must be very similar to lead. The question of the origin of actinium is discussed and two possible alternatives are considered. The results throw much new light on many questions arising out of the Periodic Law Radioactive Changes and the Periodic System of the Elements. KASIMIR B’AJANS (Bey. 1913 46 422).-The paper contains a fuller account of the author’s views (preceding abstract). It is probable that what holds good among the radio-elements applies also in other parts of the Periodic Table and that elements there may aiso be mixtures of unseparable groups of elements.The position of the rare-earth elements in the Periodic Table is discussed at length. It is supposed that these elements may be in process of continuous change with loss of hydrdgen nebulium or proto- fluorine atoms rather than of helium. Tantalum appears as the parent of the rare-earth group and columbium of yttrium. The anomalies in the Periodic Table such as tellurium and iodine are also referred to. F. S. F. S. Some Relatiorj s between the Radio-elements giving a-Rays. RICHARD SWINNE (Phyysikal. Zeitsch. 19 13 14 142-145).- The experimental values for the velocity of the a-particles found by Geiger and Nuttall are compared with the values calculated from the periods of the elements producing them according to the three relations proposed by Geiger and Nuttall Swinne and Wilson and it is shown that all three formulae show nearly equally good agreement with the observed values.From the author’s formula it can be deduced that the difference between the initial velocity of the a-ray member of one series and that of the analogous member in another series is approximately constant for the two series. Expressing this diflerence as Ava for the radium and thorium and Awla for the radium and actinium series respectively the values of these two constants are 0.13 and -0.20 ( x l o 9 cm./sec.). The calcu- lated value for the velocity of the a-ray of the unknown C”-member of actinium is 2-27. The disintegration constants of analogous a-ray-giving members of different series stand in constant ratio to one another.The logarithm of this ratio between the radium and actinium series is 1 . 3 ~ 10-5 and between the radium and the thorium series 4-8 10-5. F. S. A Relation between the Kind of Radioactive Change and the Electrochemical Behaviour of the Resulting Radio-element. KASIJIII~ FAJANS (Physikal. Zeitsch.. 1913 14 131-136*).-Tmo rules ara proposed and shown t o be followed in all cases where they can be tested (1) An a-ray change gives a product more electropositive than the parent substance. * and Le Radium 1913 10 57-60. VOL. CIV. ii. 19ii. 278 ABSTRACTS OF CHEMICAL PAPERS. (2) A 8-ray change gives a product more electronegative than the parent substance. The rule with regard to the P-ray change is considered to apply also to rayless changes and &rays of very low velocity not yet detected may be supposed to be emitted in these cases also.The three disintegration series are discussed in detail in so far as there is evidence of the electrochemical character of the members. It is assumed that uranium-X is intermediate between uranium-] and -ZZ which then conform t o the rules. The change of radium and of thorium-X in which both a- and P-rays are emitted is sup- posed to be complex an alkali-metal first resulting as the product of the a-ray change which then in a subsequent @change suffers trans- formation into the much more " noble " emanations. It is predicted that radium-C' should be nobler than radium8 or -D. Such simple relations the change in the character of the atom being analogous to electrochemical changes are very unexpected for it has always been comidered that these atomic changes are concerned with regions of the atomic structure quite different to those conditioning chemical changes.F. S. The Radioactivity of tbe Mineral Springs of Tyrol. IV. Compare A. 1911 ii 1049).-Tables are given of tlie amount of radium emanation of numerous Tyrolese springs in Mache units together with particulars of the locality the kind of rock in which the spring occurs and its temperature. R. GRENGG contributes the results of a petrographic study of the rocks. The decay curves of the active deposit from the iron spring of Bad Ratzes and the strongly active potable water of Schreiberhof in Tscherms are shown and are in agreement with that due to radium. F.S. MAX BAMBERGER and KARL KRUSE (MORatsh. 1913 34 403-423. Electrical and Chemical Effects of t h e Explosion of Azo- imide. PAUL J. KIRKBY and JAMES E. MARSH (Proc. Roy. Soc. 1913 A 88 90-99).-Measurements have been made of the quantity of electricity which is set free when azoimide is exploded by the passage of an electric spark through the vapour contained in a vessel provided with electrodes which were connected in series with a ballistic galvanometer and a potential difference of about 100 volts. The galvanometer readings show that the number of ions set free is exceedingly small in comparison with the number of molecules decomposed in the explosion. The ratio was always less than 1 to 100,000 and this seems to indicate t'hat dissociated atoms do not in general carry electrostatic charges.It is supposed that the forma- tion of the ions i8 due t o those impacts between the dissociated atoms which occur under specially f avourable conditions amongst which a relatively high velocity is probably the most important. Except under these circumstances the combination of the dissociated atoms takes place without the production of ions. From experiments a t different pressures it was found that the azoimide could not be exploded when the pressure was less thanGENERAL AND PHYSICAL CHEMISTRY. ii. 279 about 10 mm. I n the case of pure azoimide this limiting pressure would probably be smaller. The value of the limiting pressure is much smaller than that obtained in previous experiments with electrolytic gas for which 80 mm. was observed as the lower limit.I n drying the gas i t was observed that azoimide is very readily absorbed by phosphoric acid although no change in volume occurs when fresh phosphoric oxide is employed as drying agent. After the explosion experiments copper azoimide was found to be present in the gold-plated brass explosion vessel and it is shown that this is probably formed in the actual explosion the dissociated N,-group being driven through the layer of gold into the brass as a conse- quence of the forces developed in the molecular disruption. H. M. D. Duration of Luminosity of Electric Discharge in Gases and Vapours. (Hon.) ROBERT J. STRUTT (Proc. 120~. Soc. 1913 A 88 llO-l17).-Some experiments are described which show that; the luminosity accompanying the electrical discharge persists for an appreciable period after the cessation of the discharge. This is not only the case for discharge through vapours of metals and non-metals but can be observed when the discharge takes place through gases such as hydrogen oxygen carbon dioxide and air between non-vola.tile electrodes. The luminosity gradually fades away when the discharge ceases but there is no immediate altera- tion in the spectrum although a change may sometimes be observed in the later stages in consequence of a difference in the rate of decay of the lines.The effects in question the duration of which is less than one-thousandth of a second are quite distinct from the after-glow effects in nitrogen and in gaseous mixtures containing oxygen or hydrogen. H. M.D. Electrical Discharge in Helium and Neon. HERBERT E. WATSON ( Proc. C'amb. Phd. SOC. 19 13 17 YO-lO7).-Measurements have been made of the sparking potentials in pure helium and neon a t different pressures the discharge taking place between plane aluminium electrodes 15 mm. apart. The minimum spark potential was found to be 184 volts for helium and 200 volts for neon the pressures corresponding with these minima being 2.4 and 2.8 mm. respectively. For pressures greater than 10 mm. the relation between the spark potential and the pressure is represented graphically by a straight line the increase in the potential being 30 volts per cm. pressure in the case of helium and 22 volts per cm. for neon. With a cathode of sodium-potassium alloy the minimum spark potential in neon is near to and not greater than 145 volts and the cathode fall amounts to 85 volts.With aluminium electrodes which have been run f o r a sufficiently long time the cathode fall is a t most 164 volts for helium and 170 volts for neon. The cathode fall in neon with cathodes of copper carbon magnesium and calcium is approximately 221 217 150 and 150 volts respectively. The electrodes have been found to exhibit marked fatigue effects 19-2ii. 2SO ABSTRACTS OF CHEMICAL PAPERY. and these appear to be of two kinds one representing a t ~ u e fatigue and the other a reluctance to allow the current to start for a second time wben one discharge has already taken place. I n view of the brilliancy of the discharge through pure neon some measurements were made of the efficiency of the negative. glow but the data showed that the actual intensity of the light was much smaller than the estimated intensity.At pressures between 10 and 16 mm. the efficiency was raised to about 4 watts per candle by making use of a sodium-potassium electrode. The light emitted by both helium and neon under the influence of the discharge produces very marked physiological effects. When for instance the light from a tube of about 0.1 candle power was allowed to fall on the unprotected eyes for about fifteen seconds i t gave rise to a violent headache followed by temporary blindness. On this account i t was necessary to wear dark brown glassee during the whole of the experiments. Similar effects have been noticed with argon krypton and xenon and i t is suggested that the pheno- menon may be connected with the fact that the spectra of these elements contain a comparatively small number of intensely bright lines.H. M. D. The Hall Effect. JOHANNES KOENIOSBERGER and G. GOTTSTEIN (I’hysikal. Zeztsch. 1913 14 232-237).-Evidence is brought forward to show that the Hall effect can be accounted for on the basis of the electron theory. By reference to the data for graphite molyb- denite and a silicon-iron alloy (containing 5.2% of iron) i t is shown that the €€all effect changes with temperature to about the same extent as the number of electrons. It is further found that the ratio of the Hall effect to the specific resistance is of the same order of magnitude for metalloids metals and alloys although the two quantities vary to the extent of 1 to 1-10’ when the extreme members of the composite group are compared.The behaviour of alloys such as German silver and constantan suggests that the low conductivity which they exhibit is not due to the smallness.of the free pa,th or the energy of the electrons but to the presence of a very small number of electrons. H. M. D. The Changes in the Electrical Resistance of Wires which have been Drawn and Subjected to Torsion and also of Drawn and Twisted Wires on Warming Gold Silver Copper Nickel and Iron. FMTZ CHEDKER (Zeituch. pir,ysikal. Chem. 19 13 82 457-503).-The paper commences with a critical r6sum6 of the work which has been done on this subject. The experimental part of the paper consists in an account of the changes in the resistance of wires which have been warmed to definite tempera- tures for measured periods of time.It is shown (1) That the resistacce of drawn wires of gold silver and copper falls a t a constant temperature and the rate of decrease. is more rapid the higher the temperature. After a time the resistance reaches a constant minimum ; on further increasing the temperature after the minimum has been reached an increase in the resistance takesGENERAL AND PHYSICAL CHEMISTRY. ii. 281 place; for gold the increase commences a t 300° and for silver and copper at 400O. (2) On successively warming drawn wires for periods of three minutes and measuring the cold wires it is shown that a minimum specific resistance is obtained at a definite tem- perature and that this minimum specific resistance is independent of the cross-section of the wire.F o r gold the minimum is found a t 480°; silver 450O; and copper 450O. The temperature at which the minimum occurs is the same as that at which the coarse recrystallisation of the crystallite begins and so is the same as the temperature a t which small crevices begin to be formed in the wires which naturally cause an increase in the resistance. I n the case of nickel the minimum value of the specific resistance is obtained at 550° and remains constant whilst the temperature is raised 300O. The minimum for iron wires is found a t 600° and this increases on increasing the temperature due t o chemical changes in the substance of the wire. (3) Lamina are produced on drawing a wire due to a movement of parallel crystallite surfaces and a t the same time an increase in the resistance is brought about.On warming such drawn wires to the temperature of the minimum resistance the laminze are destroyed and replaced by an irregular crystallite mass and the resistance falls to its original value before drawin,p. (4) On bending or subjecting a wire to a strong torsion the resistance of a wire is increased due to the formation of small crevices ; this increased resistance is not changed by warming. (5) On lowering the temperature the resistance in the direction of the axis of a wire made up of lamina decreases more quickly than the resistance in the direction at 90° to the axis. ( 6 ) The greater specific resistance of drawn wires is due to the orienting laminz lying in the direction of their poorest conductivity and is appa- rently uninfluenced by the loosening of the crystals.(7) Permanent changes in the resistance only occur when there is a definite change in the crystal structure. The hypothesis that on working metals a new phase appears is shown to be incorrect. J. F. S. The Theory of Electrolytic Ions. VI. The Conductivity of Pure Water. RICHARD LORENZ (Zeitsch. physikcd. Chsm. 1 9 13 82 612-620. Sea A. 1912 ii 323 and also Festschyift W. N e r n s t 1912 276).-The author calculates the mobilities of the hydrogen and hydroxyl ions a t various temperatures from molecular kinetic considerations ; the values obtained are compared with those obtained from the Kohlrausch measurements. It is shown that in every case the Kohlrausch value is much larger than the calculated value in many cases the Kohlrausch value being more than four times as large as the calculated. A theory of the migration of ions resembling t.he Grotthus theory is then considered. I n this case the passage of an ion is supposed to be partly due to its own actual motion and partly due to colliding witch an undissociated molecule with which it combines and sets free the corresponding ion of the undis- sociated molecule.I n this way part of the distance proportional t o the number and diameter of the undissociated molecules lying in the path is covered a t an extremely high velocit.y thus makingii. 282 ABSTRACTS OF CHEMICAL PAPERS. the apparent velocity much larger than that calculated on the molecular kinetic hypothesis.On comparing the values obtained in this way with the experimental results the former are found to be somewhat larger than the latter. Hypotheses are considered which would slightly reduce the calculated values. J. F. S. Conductivity Dissociation and Temperature-coefficients* of Conductivity of Certain Inorganic Salts i n Aqueous Solution as Conditioned by Temperature Dilution Hydra- tion and Hydrolysis. E. J. SRAEFFERMI~ HARRY C. JONES (Anzer. Chew. J. 1913 49 207-253. Compare Hosford and Jones A. 1911 ii 960; Winston and Jones A 1911 ii 961; Howaxd and Jones this vol. ii ll).-In continuation of earlier work con- ductivity measurements have been made a t temperatures between Oo and 65O of ammonium hydrogen sulphate tetraethylammonium iodide ammonium sodium hydrogen phosphate sodium chloride chlorate and perchlorate disodium hydrogen phosphate potassium chlorate perchlorate and phosphate calcium chloride strontium chloride barium bromide and f ormate magnesium chloride and sulphate manganous chloride and nitrate aluminium chloride nitrate and sulphate the violet forms of chromic chloride nitrate and sulphate lead nitrate nickel nitrate copper ammonium sulphate and uranyl sulphate.The results confirm the more important relations established by the earlier work. The dissociation was found to decrease with rise of temperature in all cases except that of potassium phosphate. It has been found that the hydrolysis of chromium salts increases rapidly with rise of temperature and that the hydrolytic products only slowly recombine as the solution cools.It follows therefore that in purifying a chromic salt for conductivity experiments i t must not be heated to a higher temperature than that at which the conductivity is to be determined since the dehydrolysis time factor persists for months. This precaution does not appear to be necessary in the case of other salts. It is shown that considerable error may be introduced into conductivity measurements unless the proper water corrections are applied. The purity of the air in the room must be the same when the water-cell is filled as when the solutions are prepared. Care should also be taken to ensure that the air is as free from impurities as possible. The influence of hydration hydrolysis and polynierisation in conductivity determinations is discussed and it is pointed out that the Kohlrausch method is not suitable for measuring the dissocia- tion of highly polymerised sulphates or for determining the disso- ciation of any electrolyte which is both hydrated and hydrolysed. E.G. Citrophosphate Solutions. 11. Electrical Conductivity of Aqueous Solutions of Citric Acid and Phosphoric Acid. UGO YRATOLONGO ( A t t i I?. Accnd. Lincei 1913 [vl 22 i 86-89. Compare A. 1911 ii 865).-The paper records the results of con-GENERAL AND PHYSICAL CEEMISTRY. ii. 283 ductivity measurements of binary mixtures of citric acid with phosphoric acid arsenic acid and hydrochloric acid in aqueous solution. The curves present no abnormality and therefore show no evidence of t-he existence of complex ions.Electrical Conductance of Non-aqueous Solutions. LEON IRWIN HHAW (J. Physical Chem. 1913 17 162-176).-The con- ductivities of mercuric chloride iodine and lithium chloride in acetone and of mercuric chloride and iodine in epichlorohydrin were compared with the dielectric constants of the purified solvents. The molecular conductivity of lithium chloride in acetone first increases then decreases and finally increases again on dilution. None of the solutions examined approached a constant molecular conductivity a t infinite dilution so that the (‘ degree of dissocia- tion ” could not be calculated. The dielectric constants of acetone and epichlorohydrin accord- ing to Walden are 21.0 and 26.0 respectively. Neglecting the question of ionic mobility mercuric chloride is in accord with Nernst’s hypothesis in having a higher conductivity in epichloro- hydrin than in acetone but iodine on the contrary has a much higher conductivity in acetone.The author did not make any measurements of dielectric capacity but it is to be noted that his solvents by the conductivity test were somewhat purer than Walden’s . Solutions of a number of metallic chlorides iodides etc. in ten organic solvents of various t y p a were examined qualitatively. No relationship appears t o exist between the dissociating power of a solvent and its dielectric constant degree of association or residual affinity. R. J. C. R. V. S. Abnormal Electrical Conductivity Changes. IV. ALEX- ANDER NICOLAEVITSCH SACHANOV (J. Ruse. Phys. Chem. Soc. 1913 45 102-136.Compare A. 1912 ii 422 730).-Theoretical considera- tions together with the results obtained on investigating the con- ductivity and viscosity changes of solutions in aniline acetic acid etc. with dilution lead to the following conclusions. The molecular conductivity increases with dilution in the more concentrated solutions and later diminishes continuously with dilution ; the maximum value is reached at a dilution corresponding with x=((m-2)/(2m-2) m being the number of molecules of dissolved salt in th9 complex mC,pB (see A. 1911 ii 689) and x the number of polymerised molecules. The rate of diminution occurring on dilution increases with m that is with the complexity of the group conducting the current.. This appearance of a maximum conductivity in concentrated solutions is regularly met with in cases of abnormal conductivity cliaages.The formation of a minimum molecular conductivity with increasing dilution is also a regular phenomenon increase of dilution beyond the point of minimum conductivity being accom- panied by normal increase of the latter. It is shown that cases of masked abnormality in the change ofii. 284 ABSTRACTS OF CHEMICAL PAPERS. molecular conductivity on dilution may occur when either the con- centration of the polymerised molecules is not high at any rate for low dilutions or the degree of electrolytic dissociation of these moleculeq is not considerably higher than that of the simple molecules. Those cases must also be termed abnormal in which dy /dv has a positive value (the molecular conductivity increasing with the dilution) and d2p/dc2 changes its negative sign at a certain dilution.Xasked anomalies may also give rise to a fold in the molecular conductivity-dilution curve dp /dv assuming the value zero although positive for all neighbouring dilutions. T. H. P. The Addition of Alkyl Halogens to Thiocarbamides. HEINRICH ~OLDSCRMInT and HANS KHF. GRINI (zeit.wh. E'laktvochern. 1913 19 226-234).-The electroconductivity of allylthiocarb- amide ethiodide C3H5*NH=CS*NH,EtI is determined in aqueous solution a t 25O. It is shown that this substance is not hydrolysed in aqueous solution and has a value A = 102.2. From this value the migration velocity of the cation C,H,*NH*CS-NH,Et is calcu- lated as 25.9. The electrocondnctivity is also determined in absolute alcohol and in alcohol containiiig water ; the water concen- trations measured are 0*02N? 1-03 2*ON and l O * O N .It is shown that small additions of water do not effect the conductivity; the 2*O~Y-water-alcohol solution shows an' increase which is compara- tively small whilst in the case of the l0.0N-solution there is a great increase. I n the very dilute solutions of the salt i t is shown that in all cases the conductivity is approximately the same. The change in the conductivity is shown to be due to an increased ionisation and not to a change in the migration ve1ocit;ies of the ions. The equivalent conductivity of a number of thiocarbamide derivatives was determined in absolute alcohol and in alcohol containing 0-02N-water. The following values for A in absolute alcohol were obtained.Allylthiocarbamide ethiodide h rc = 43.8 ; ethobromide A = 41.5 ; methiodide hl(n4 = 38.63. Phenylthiocarbamide eth- iodide A = 39-26 in 0*02N-water-alcohol; ethobromide h,, = 37.19 in O.02N-water-alcohol ; methiodide A,,,,= 37.83 in 0.02N- water-alcohol. Thiocarbanilide methiodide A = 48 in absolute alcohol. The velocity of combination of the various thiocarbamides with alkyl haloids was determined by measuring the conductivity in water-alcohol solutions at measured intervals of time and so deter- mining the amount formed from curves obtained in the above- mentioned conductivity determinations. Allylthiocarbamide reacts with ethyl and methyl iodides at approximately the same rate; diphenylthiocarbamide reacts with methyl iodide much more slowly.The addition of water to the alcohol solutions makes only a small difference in the velocity constant; up to 2.0N-water there is no appreciable change in the velocity constant but with a 1ON-water- alcohol solution in the formation of allylthiocarbamide ethiodide the constant increased from 0.253 to 0.296. The slight influence of water on the velocity of reaction is remarkable in view of its great influence on hydrolysis in non-aqueous solutions. J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 285 The Reduction to Hydroger Peroxide of Oxygen Dissolved under Pressure. FRANZ FISCHER and OTTO PRIESS (Rer. 19 13 46 698-709).-The authors have confirmed the experiments of Moritz Traube with respect to the formation of hydrogen peroxide a t the cathode when air is led through the catholyte.When the air is replaced by oxygen at atmospheric pressure a 0.32% solution of hydrogen peroxide is obtained as again& a 0'26% with air the current density being 0.02 ampere per square dcm. The eff& of various conditions on the yield was studied in detail The current yield is diminished by rise in temperature and increased by vigorous stirring. The best electrolytes are sulphuric acid (0.1%) and phosphoric acid; boric acid may also be used. Solutions of neutral salts are not suitable owing to the formation of alkali a t the cathode unless an insoluble derivative of hydrogen peroxide is formed as for example calcium hydroperoxide from an ammoniacal solution of calcium chloride. The best electrode material is mercury ; when however the catholyte is stirred mercury goes into solution so that all the experiments were made with amalgamated gold electrodes.The current yield diminishes with time and the concentration of the hydrogen peroxide increases to a maximum and then falls owing to the reduction of the hydrogen peroxide formed. The current-yie3d increases with diminution in current density. A special steel apparatus was constructed which permitted electrolyses in a divided cell being carried out under pressures up to 100 atmos. th5 catholyte being stirred by means of an electro- magnetic attachment. Under high oxygen pressures the current yield and concentration OF hydrogen peroxide increase with the pressure the voltage neces- sary diminishing a t the same time. A t 100 atmos.pressure and a current density of 2 amperes per sq. dcm. using 2 volts 2.7% solu- tions of hydrogen peroxide can be obtained that is 3 0 0 4 0 0 grams of hydrogen peroxide per kilowatt-hour and a current-yield of 83%. A 5% solution is obtainable when the best currentryield is not insisted on. Experiments with various electrolytes and electrodes gave the same resulk as a t atmospheric pressure. The investigation of the effect of 1% sulphuric acid under an oxygen pressure of 25 atmos. on the various materials used for electrodes showed that all metals with the exception of tin and iron which go into solution without current being necessary produce hydrogen peroxide a t the same time. Zinc amalgam gives the most hydrogen peroxide nickel gives a third as much and then follow the other metals.T. S. P. The Form of Electrolytically Deposited Metals. I. Silver- black. VOLKMAR KOHLSCH~~TTER and THEODOR TOROPOFF (Zrritsch. EErktrochPm. 1913 19 161-168. Compare A 1912. i i 253 845).- An account is given of the formation of silver-black by electrolyti- cal methods of its properties and the transformation of it into grey crystalline silver. It is shown that silver-black can be obtained by the action of organic reducing agents on ailver solutions andii. 286 ABSTLXACTS OF CHEMICAL PAPERS. also by the action of zinc copper and cadmium on dilute solutions of silver salts. Electrolytically silver-black is best obtained from dilute solutions by the use of coniparatively high current density. Silver-black cannot be preserved ; no matter how prepared it speedily changes into grey or white crystalline silver.The rate of passage into the crystalline variety is about ten times as rapid in the presence of dilute acid as in the presence of dilute alkali whilst in the latter case the change is quicker than in pure water. Black silver is regarded as in a condition between the colloidal and the crystalline states. This substance when examined microscopically during the electrolytic preparation is seen to be crystalline but it behaves as a colloid towards electrolytes. A t the moment at which the current is stopped in the preparation of silver-black it begins to pass over into the grey crystalline variety as evidenced by the change in colour and by the shrinking together of the mass. Experiment shows that there is no real volume change in the passage from coherent massive silver to silver-black and to grey crystalline silver.To obtain evidence which should indicate the reason for the formation of silver-black a number of measurements were made on the potential difference of the electrodes during deposition and from these results it was deduced that the formation in dilute solution is due to the relative lack of crystal centres so that each discharged ion finds itself more or less isolated and consequently deposits as such and does not attach itself to a crystal centre with the formation of the grey crystalline silver. The sudden change to grey silver on breaking the current is explained as an electro- surface tension phenomenon. The silver-black with very large surface takes up the form of smallest surface on stopping the current but while the current is flowing and it is negatively polarised the electrostatic repulsions of the charged particles over- come the tendency to a surface diminution.J. F. s. The Form of Electrolytically Deposited Metals. 11. Silver Deposited by Metals. VOLKMAR KOHLSCR~TTER THEODOR TOROPOFF and W. PFANDER (Zeitsch. Elektrochem. 1913 19 169-172. Com- pare preceding abstract).-It is shown that different metals precipi- tate silver in different but perfectly definite conditions which depend to some extent on the concentration of the silver solution. The experiments were carried out with copper zinc cadmium iron tin aluminium a i d magnesium. It is shown that the observed differences are due to the velocity with which the precipitation takes place.The addition of neutral salts causes an increase in the velocity of precipitation. This Is explained in the following way I n neutral salt solution when copper is the metal a colloidal copper hydroxide is formed by hydrolysis; this is adsorbed by the copper and so prevents it8 further rapid solution but by the addition of an electrolyte this colloidal substance is removed either by chemical solution o r by coagulation. The addition of such substances as sugar starch gum and gelatin cause the reaction to take place more slowly but at the same time they cause a very dark powderGENERAL AND PHYSICAL CHEMISTRY. ii. 2S7 to be formed which is more stable than that usually obtained. The course of the reaction is followed in all cases by means of potential difference measurements between the depositing metal and the solution.J. F. S. The Form of Electrolytically Deposited Metals. 111. The Influence of Foreign Substances on the Deposition of Silver. VOLKMAR KOHLSCHUTTER and HERMANN SCHACHT (Zeiisch. Elektrochsm. 1913 19 172-181. Compare preceding abstracts).-Silver was deposited electrolytically from a O.05N-solution of silver nitrate to which had been added just sufficient ammonia to redissolve the precipitated silver oxide ; 100 C.C. of this solution were electrolysed after the addition of one or two drops of sodium hydroxide solution and a small amount of the solution of the metallic nitrate. The nitrates used in the various experiments were those of copper zinc cadmium lead glucinum chromium aluminium and thallium.The solutions were electrolysed by a current of 3 milliamperes which corresponded with a cathode current density of 0*001-0*005 ampere per sq. cm. The silver was deposited in different forms in each cas? which were easily reproducible ; micro-photographs of the various forms are given in the paper. It is shown that if the solutions are kept more than fifteen to twenty hours quite different forms are obtained so that in all the experiments described freshly prepared solutions were employed. It is also shown that the amountl of silver deposited under these conditions is more than that demanded by Fa.raday’s Law and that it does not contain more than the merest trace of the added metal. The action of the added subst.ances in producing the different deposits is held to be due to the formation of colloidal metal hydroxides which are deposited on th6 cathode and form a type of filter which conditions the distribution of the centres of crystallisation.The excess of silver deposited above bhat required by Faraday’s Law is supposed to be due to causes other than electrolysis since i t does not increase with the concentration of the silver solution. J. F. S. The Form of Electrolytically Deposited Metals. IV. The Deposition of Silver from Solutions of Complex Salts. VOLKMAR KOHLSCHUTTER (Zeitsch. Elektrochem. 1 9 1 3 1 9 1 8 I - 184. Compare preceding abstracts) .-The reasons for the. compact adhesive deposition of silver in the electrolysis of complex solutions of silver are discussed in the present paper.It is shown that in the first stages of the deposition colloidal silver in the complex silver compound is deposited ; this is demonstrated by the reddish-violet coloration on the cathode which is the characteristic of the swalled ‘‘ subhaloids.” It is aIso shown that if a platinum cathode on which this deposit has been formed is removed from the electrolyte and washed the blue colour vanishes but that if such an electrode is now placed in a solution of a non-complex saver salt such as silver nitrate the further deposition is of the same compact form characteristic of silver deposited from complex solutions such as KAdCN),.ii. 288 ABSTRACTS OF CHEMICAL PAPERS. It is thought that this first deposit determines the number and position of the crystal centres on which the further deposition takes place.It is shown from theoretical grounds and from analogy to the results of the addition of foreign metals (see last abstract) that the silver salts are also present in the colloidal form in the complexes and that these colloids are determinative of the peculiar form of the silver deposition. Experiments in confirmation of the author’s views were made with complex cyanide thiosulpliate and ammoniacal solutions. The author’s views all confirn the work of Danneel (Zeitsch. Elektrochern. 1903 9 762) Haber (A. 1904 ii 607 SOS) and Bodlander and Abegg (A. 1904 ii 713) which point to t,l10 fact that silver deposi- tion is not a secondary reaction due to the primary deposition of potassium which then reacts chemically to produce silver.J. F. S. Variation of Magnetic Susceptibility with Temperature. 11. Aqueous Solutions. A. E. OXLPY (Yvoc. Cnmb. Phil. SOC. 1913 17 65-89. Compare A. 1912 ii 325).-The influence of tempera ture OG the magnetic susceptibility of aqueous solutions of ferric chloride ferrous sulphate and ferric nitrate has been examined. On the assumption that the susceptibility is independent of the intensity of the magnetic field and that complex molecular aggre- gates containing water of hydration are formed the composition of which varies with the temperature in accordance with van Laar’s theory a formula is deduced for the susceptibility x which may be written in the form x = A / O + 3 + C8 where 8 denotes the absolute temperature.I n the case of dilute solutions this reduces to the simpler form x = A / 8 + B. The experimental observations are shown to be satisfactorily represented by means of these formulze and this would seem to indicate that if the Curie-Langevin theory is strictly applicable to aggregates the composition of which is inde- pendent? of the temperature the complexity of the aggregates present in the aqueous solutions which have been examined varies with the temperature in accordance with a linear formula. H. M. D. Magnetic Double Refraction and Chemical Conatitution. A. COTTON and HmRr MOUTON (Ann. Chim. Phys. 1013 [viii] 28 209-243).-A rQsum6 of work published in A. 1906 ii 146; 1907 ii 727; 1908 ii 745; 1909 ii 773; 1910 ii 368; 1911 ii 4; 1912 ii 426. H. W. The Critical Points of Iron WITOLD BRONJEWSKI (Compt.vend. 1913 156 699-702).-Using electrolytic iron the author has studied the variation of its thermoelectric force with respect to copper and platinum its electrical resistance and its dilatation with variation in temperature and curves are given showing these variations. He finds three critical points on the curves one corre-GENERAL AND PHYSICAL CHEMlSTRY. ii. 289 sponding with a-iron stable below 730° another with &iron stable at 950° and the third with y-iron stable above 1020O. W. G. The Thermoelectric Properties of Some Irreversible Nickel and Manganese Steels. SJEGFRIED HILPERT and FRITZ H ERRMANN (%e,itsch. h’lek/rochem 19 13 19 215-219).-~teels containing 13.6% and 27.5% of nickel and 4*58% 11*7% and 20.8% of manganese were examined as to their thermoelectric properties after they had been subjected to definite temperatures. The steels after treatment were made into thermo-couples with either constantan or copper and the two ends subjected to different but not widely separated temperatures and the B.M.F.produced by the temperature differ- ence measured. With the steel containing 27.5% nickel i t is shown that after subjecting the steel to -75O a difference of lo between the ends of the couple produces an E.M.F. of 21.1 microvolts whereas after cooling to -185O lo difference gives 7.7 microvolts. . From this temperature up to 400° the same thermo-electromotive force is produced for lo difference between the ends; after treatment a t 500° the value rises to 16 microvolts and a t 600° it reaches 36-4 microvolts. This case is analogous t o the behaviour of the magnetic properties of this steel when it has been subjected to various temperatures (L4.7 1911 ii 1057; 1912 ii 229).Steel with 12.6% nickel showed similar properties to a very slight extent. Steels containing 4.58% and 11.7% manganese which are strongly magnetic do not show these properties. It is suggested that the observed differences in the EJ4.F. have their cause in a consider- able volume change which is accompanied by an internal tension and that there is a marked hysteresis of the specific volume. J. F. S. The Gas Thermometer as the Basis for High-teniperature Measurements. FRITZ HENNING (Zeitsch. A”Zekt~~ochem. 19 13 19 185-192).-A theoretical paper in which the following points relating to the gas thermometer for use a t high temperatures chat is up to 1500° are discussed (1) Material of which the thermo- meter is to be made.(2) Gas with which i t is t o be filled. (3) Pre- cautions to be taken in use. (4) The dead space. (5) Fixed points to be used in the calibration of such a thermometer. (6) Subsidiary thermometers for controlling temperatures and for determining the temperatures required for the calculation of the necessary corrections. It is shown that a platinum iridium vessel is the best for this purpose and that the dead space can conveniently be brought down to about 1 cubic centimetre. A platinum-platinum rhodinm (10% rhodium) thermocouple is recommended as subsidiary thermometer for temperatures up to llOOo for which the formula for calculation of the temperature is E = - 310 + 8.048t + 0.00172t2 microvolt.Above l l O O o to 1600O it can still be used but the temperature is obtained from the formula E = 306001og(1-3 + t 2 x 10-6) - 1590. As fixed points for controlling the temperatures the following melting and boiling points are recommended Naphthalene b. p. 21800~;ii. 290 ABSTRACTS OF CHEMICAL PAPERS. tin m. p. 231.8O; benzophenone. b. p. 305.9O; cadmium m. p. 320.9O ; zinc m. p. 419.4O; sulphur b. p. 444.5O; antimony m. p. 630O; aluminium in. p. 658O; silver ni. p. 961O; gold m. p. 1064O; copper m. p. 1084O; nickel m. p. 1452O; cobalt m. p. 1490O; and palladium m. p. 1587O 1 2 O . J. F. 8. A Simple Method for Maintaining Constant Temperatures in the Region of t h e Room Temperature.FRITZ BAXR (Zeitsch. angew. Chem. 1913 26 135).-Tl:e action of the gas regulator in a thermostat working at the ordinary temperature may be assisted by regulating the flow of water by means of a sensitive syphon. For this purpose a hole is blown in a piece of glass tubing which is then drawn out at this point and cut off across the narrow slit. The tube is then bent near the end through 360° so as to form a syphon which is then hung in the full thermostat. OTTO HAUSER and W. STEGER (Zeitsch. anorg. C / m t . 19 13 80 &6).-'I'h specific heat of bismuth oxide Bi,O has been determined by heating the oxide enclosed in a silver case to a temperature of 100-507° in an electric furnace and then rapidly dropping into a copper calori- meter enclosed in a vacuum vessel.The values obtained are It has not been found possible to dehydrate bismuth peroxide without loss of oxygen. Effact of High Pressures on t h e Physical and Chemical Behaviour of Solids. JOHN JOHNSTON and LEABOK H. ADAMS (-4mer. J. Sci. 1913 [iv] 35 205-253*).-1n any discussion of the influence of pressure on solid systems it is necessary t o distinguish between the effects of uniform pressure and of non-uniform pressure. The effects produced by non-uniform compression are in general such that the original state of the system is not re-established when the pressure is released. Most of the work on the influence of high pressures on solids has been carried out under these conditions and i t seems probable that many of the apparently contradictory state- ments recorded in the literature are due to the disregard of the distinction between the two types of compression.I n general uniform pressure raises the melting point by an amount which seldom exceeds loo per 1000 atmospheres; its effect on solubility is also very slight. Non-uniform pressure on the other hand always lowers the melting point and raises the solu- bility and by amounts which are many times greater than the corresponding variations produced by the application of uniform pressure. The actual cause of the phenomena recorded as occurring when solid systems are subjected to high pressure is supposed to be the local melting produced by non-uniform compression and on the assumption that permanent deformation of a crystalline aggre- gate is always conditioned by liquefaction it is found that the pressure required to produce this change a t the ordinary tempera- ture is well within the bounds of probability.* and Zeitsch. anorg. Chew. 1913 80 281-334. J. C. W. The Speciflc Heat of Bismuth Oxide. 20-100° 0.0568; 20-312° 0.0604; 20-50307 0.0623. C'. H. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 291 Prom an examination of the available data and in particular of the results obtained by Spring the authors draw several conclu- sions with respect to the physical and chemical behaviour of solids under high pressures. The pressure necessary to produce local melting of crystalline sggregates depends mainly on the melting point the heat of fusion the density of the substance and the temperature a t which the compression is applied.Generally speaking those substances which a t a given temperature require the largest pressures to weld them are those which have the highest melting points. Compression alone will not in general produce crystallisation or bring about the transformation of one modification of a substance into another. If the conditions are such that the velocity of trans- formation is appreciable it may give rise to such changes in certain cases; and if further the conditions are such that partial melting may occur then the compression will be followed by a partial transformation. I n regard to chemical reactions between solids non-uniform pressure will also have a much greater effect than uniform pressure. I n the latter case the reaction can only occur a t the surfaces of contact between the solids whereits the conditions obtaining with non-uniform compression will assist the reaction by a renewal of the contact surfaces in consequence of local melting and the flowing away of the fusion.With reference to the alleged reaction between barium sulphate and sodium carbonate and between potassium nitrate and sodium acetate it is pointed out that the methods adopted in the examination of the product after compression afford no certain information as to the actual condition of the dry mixture. Apart from the question of the direct influence of pressure on reactions between solids it is probable that the more intimate contact which is attained under pressure will result in an increased rate of interdiffusion of the substances and to this extent pressure will have an influence on the reaction.The formation of alloys may be referred to as a special case of such interaction. Where the formation of solid solutions is possible pressure will have an effect by promoting indirectly the rate of diffusion but there is no evidence in the available data t o show that compression itself has any specific influence on the formation of alloys. H. M. D. Fusibility of Natural Fats. HENRI LE CHATELIER and (Mlle.) CAVAIGNAC (Compt. rend. 1913 156 589-594).-The aiithors have made a careful study of the temperatures of fusion and solidifica- tion of two natural fats vegetalin and stearin under varying con- ditions and find that they obey the general laws of change of state in that their fusion and solidification is a reversible phenomenon the temperature of which can be determined to one-tenth of a degree by sufficient experiments.The melting point as rapidly determined does not as a rule differ by more than a degree from the true value ; the solidification temperature however shows greater variation. Foreign substances have a marked effect on theii. 292 ASSTBACTS OF CHEMICAL PAPERS. melting point and these fats exhibit the phenomenon of super- fusion. W. G. Influence of Chemical Constitution on the Thermal Pro- perties of Binary Mixtures. 11. Mixtures containing Un- symmetrical Constituents. PAUL PASCAL and LEON NORMAND (Bull. Soc. chim. 1913 [iv] 13 20?-216).-The authors have examined the melting-point curves of a series of mixtures composed of the following pairs of constituents (1) dibenzyl and benzyl- aniline (2) azobenzene and benzylideneaniline (3) stilbene and benzylideneaniline (4) benzylideneaniline and benzylaniline (5) phenyl henzyl ether and benzylaniline (6) phenyl benzyl ether and dibenzyl (7) benzylaniline and hydrazobenzene (8) dibenzyl and benzylideneaniline (9) hydrazobenzene and benzylideneaniline (lo) tolane and benzylideneaniline (11) benzylaniline and azo- benzene (12) benzylaniline and stilbene and (13) tolane and benzyl- aniline.I n every case a eutectic mixture was obtained. I n the first seven cases in which the constituents of the mixtures have either different central atoms or different central linkings the extent of the region of syncrystallisation (defined by the difference in percentage of either of the c’onstituents of the mixed crystals which form the eutectic mixture) lies between 20% and 40% whilst in the last six cases in which the constituents of the mixtures possess different central linkings and central atoms i t lies between 40% and GO% attaining a maximum of 65% in the case of mixtures of tolane and benzylaniline. H.W. The Fusion Curves of Several Substances. Eamw AUGUST BLOCK (Zeitsch. p h y s i k ~ l . Client. 1913 82. 403-433).-A method due to Tammann is used for the determination of the equilibrium pressure in the melting of the substances veratrole p-chloro- toluene p-iodotoluene p-bromotoluene anethole diphenylmethane dichlorobenzene benzylaniline thymol and menthol It is shown that the equilibrium pressure is independent of the proportions of crystalline and liquid substance and a method is given for ascer- taining whether the substance under examination is pure.I f the substance is pure the equilibrium pressure is constant for all proportions of melted and crystalline substance but if impure the equilibrium pressure increases very rapidly when only a small proportion of the subst-ance is melted. The fusion curves of the ten substances mentioned above are determined for pressures 1-3000 kilog. by Tammann’s method and the temperature read- ings compared with those calculated by the Tammann formula t = tPZlkq + up - bp2. The agreement is very good the differences being in every case sma.ller than the mean probable error. The substances examined are according to the Eotvos formula non-associated when molten and according to the Tammann theory (this vol.ii 193) should only form one kind of crystals. This statement is confirmed by the melting curves obtained. It is however Ternarkable that two of these substances menthol and veratrole are known to exist in aGENERAL AND PHYSICAL CHEMISTRY. ii. 293 second unstable form. The fusion curve for benzene is determined by means of a series of determinations of p2' curves a t constant volume. The method is due to Tammann (A. 1912 ii 630). The curve is determined for pressures up to 3050 kilog. and the tem- perature values are found to agree with those calculated by the Tammann formula t =5*40 + 0.0283~ - 0~0000019G~ within limits of +0*25O and -0-26O the mean divergence being 0.03O.It is shown that the coefficient d p / d t is smaller f o r the molten substance than for the crystalline substance and that the value increases for both with increasing pressure These two facts are both in accord with the Tammann theory (Zoc. cit.). The value dp? is not constant for the different pT curves but increases with increasing tempera- ture. It is shown that the quantity of material employed is without influence on the p and T values of the equilibrium point between liquid and crystals but that the dp. values are smaller a t low tem- peratures f o r smaller amounts of material than for larger amounts. This is explained by a change in the apparent compressibility of the material. The volume change AvpT a t constant temperature and constant pressure in melting is redetermined f o r benzene.The values obtained confirm the Tarnmann formula (Zoc. cit.) and are also in good agreement with those of Tammann and Cowper (A. 1910 ii 20). The fusion curve of Glauber's salt is determined by means of pi" curves and agrees well with that calculated from Tammann's formula t = 32.6 + 0*000507p - 0*00000055p2. A method is described by which impurities may be removed from the substances examined. Finally the relationship between the fusion curves of different substances is discussed. It is shown that the ratio between the absolute melting points 0"f two substances a t the same pressure is a constant. This formula is of the same nature as that given by Ramsay and Young for the vapour pressures. The relationship is examined for twenty pairs of substances up to pressures of sbout 3000 kilog.and for a given pair shown to hold very well. The constant varies for different pairs between 0.9733 for aniline and water and 1.2240 for diphenylamine and aniline. It is further shown that T,/T,-Tf2/Tf1=c where T and Tz are the melting points a t a given pressure f o r a pair of substances and T f and TI are the melting points of the same substances at a second pressure and c is a constant. The value of c varies from zero for the pair benzylaniline aniline to +0*0060 for aniline water whilst sodium potassium gives - 0*00139 the divergence being in all cases well within the experimental error. J. F. 8. Molecular Attraction. K. K. J~~RVINEN (Zeitsch. p h y s i k d . Chen?. 1913 82 541-574).-A mathematical paper in which an attempt is made to deduce a formula which shall give the molecular attrac- tion.The general form of the Newton Law of Gravitation F=mzk/rn is made the basis of the calculations. It is found that if n=5 6 or 7 the formula represents in some cases the observed conditions obtained from the heat of vaporisation. In general the value m = 6 is better than the other values. A formula is also deduced for calculation of the heat of vaporisation which has the VOL clv. ii. 20ii. 294 ABSTRACTS OF CHEMICAL PAPERS. form (C-2.52-C2),/LP=IT=1.63 in which B is the coefficient of cubical expansion L the heat of vaporisation C the molecular heat 2-52 cal. the quantity of heat used up in increasing the velocity of the molecules and C the quantity of heat used in intra- molecular work.The formulae which are deduced from considera- tions of the potential of the moleculw are used for calculating the heat of vaporisation of several substances and shown to hold within 2-3%. J. F. S. The Latent Heat of Vaporisation of Metals. EDMOND VAN AUBEL (Compt. rend. 191 3 156 456-457).-Tho author has calcu- lated the constant in Trouton’s Law for the metals mercury cadmium zino and bismuth using the values obtained by Wehnelt and Musceleanu (this vol. ii 23) for their latent heats of vaporisa- tion and finds that they obey the above law. Taking the value for this constant as 20 he calculates the boiling point of magnesium as 1792O. W. G. Mechanism of Evaporation. RENE MARCELIN (J. Chim. phys. 1912 10 680-690).-The rate a t which the meniscus is lowered by evaporation in capillary tubes containing “ superheated ” ether or carbon disulphide at a constant pressure is measurable by cathetometer and stop-watch. The surface layer is cooled by evaporation to the temperature a t which it is in equilibrium with the vapour a t the given pressure.The rate a t which evaporation takes place is therefore governed by the rate a t which heat is conducted through the glass tube from the thermostat under the temperature gradient which establishes itself near the meniscus ; thus the rate of evaporation v,=M(Tb-T,)/rdL where M is a constant depending on the thickness and heat conductivity of the glass T b is the temperature of the thermostat Tp is the temperature of the surface layer corresponding with vapour pressure p for the given liquid T is the radius of the tube d the density of the liquid and I its latent heat.This formula was verified experimentally and the same constant M was obtained with ether as with carbon disulphide a t a variety of temperatures and pressures and also with tubes of different bore but the same thickness of wall. The real rate of evaporation is apparently a t least ten times as great as the apparent rate in these experiments. It is deduced from the kinetic hypothesis that in a liquid of molecular weight TV and vapour pressure P a t temperature 1’ evaporating into a vapour phase a t pressure p the rate of evapora- tion V = a ( P - p ) / 4 d ’ x 4/(3W/RT) where a is a fraction represent- ing the proportion of the gaseous molecules which are re-absorbed on collision with the liquid surf ace.The highest values of u observed lead to a= 1 / 100 as a minimum but in view of the lowering of the surface temperature in the experi- ments a is probably greater than 1 / 10. The author’s method lends itself to the evaluation of the boiling points or vapour prespures of pure liquids. The variation of vGENERAL AND PHYSICAT CBEMISTRT. ii. 295 with T a t any constant pressure p being a linear function the curve can be exterpolated t o v = O when T becomes the boiling point at pressure p . R. J. C. Chemical Affinity. VIII. Crystalline Change of the Alkali Salts. JOHANNES N. BRONSTED (Zeatsch. physikaf. c'/wna. 191 3 82 621-640. Compare A. 1911 ii 381 856; 1912 ii 736).-A con- tinuation of the work contained in the previous papers.The double decomposition of various pairs of alkali salts is investigated in the present paper. The solution affinity and the affinity of the double decomposition are determined. To arrive a t these quantities the values of the dilution affinity solubility and vapour pressure of the solutions at the temperature of the experiments must be known. These values have been determined in the present work. The dilution affinity is calculated from freezing-point measurements f o r sodium chloride sodium nitrate sodium chlorate sodium bromide sodium sulphate sodium fluoride potassium iodide potassium fluoride potassium chlorate potassium sulphate potassium nitrate and potassium chloride. From these measurements it is seen that work of dilution is generally less for a potassium salt than for the corresponding sodium salt.The solubilities of the above-mentioned salts a t looo are determined and the following values obtained in grains per 100 grams water EBr=105-3; NaC1=39'22; NaI= 303.4; NaBr=121-9; NaClO,=204*9; NaNO,=176.3; KC1=56*05; KI = 207.7 ; KClO = 57.7 ; KNO,= 244.8 ; Na2S0 42-19 ; K,SO = 24.1. The vapour pressures of the saturated solutions of the above sdt3 at looo were also determined and the following values obtained NaCl= 561-5 mm. ; NaBr = 382.9 ; NaI = 174.4 ; NaF = 734.0 ; NaCIO,? 410.0 ; NaNO =418.9 ; Na,S04 = 684.7 ; KCl == 567.8 ; KBr = 926.3 ; KI = 427.0 ; KF = 174.3 ; KClO,= 668.3 ; KNO = 496.0 ; K,SO From these data the energy change in the double decomposition of pairs of the salts mentioned is calcu- lated and the following results obtained NaF + KC1 -+ NaCl+ KF - 6E30 cal.; NaF -t- KBr -+ NaBr + K F - 8520 cal. ; NaF + KI -+ KF + NaI - 10150 cal. ; NaCl + KBr -+ KC1 + NaBr - 1690 cal. ; NaCl + K I -+ R C l + NnI - 3320 cal. ; NaBr + K I -+ NaI + KBr - 1630 cal. ; NaCl + KNO -+ NaNO + KC1 - 840 cal. ; NaCl+ KClO -+ NaClO + KC1 - 2270 cal. ; NaCl + $K2S04-+ $Na@O + EC1- 340 cal. ; NaNO + RClO,-+ NaC103 + KNO - 1430 cal. The values obtained above by the new method are compared with those obtained by the older electrochemical method (Zoc. cit.) and a very good agreement is found between them. I n the double decomposi- tion between haloids of sodium and potassium the tendency is that the two elements of lowest atomic weights and those of highest atomic weights will combine.723.9. J. F. S. Fractional Distillation with Steam. L. G URWITSCH (Zeitsch,. urzgew. Chem. 2913 26 102-11)3).-Frorn a consideration of the formula put forward by Vresvski (A. 1910 ii 1038) for the composition of the vapour given off from a mixture of volatile liquids the author deduces that when the temperature of 20-2ii. 296 ABSTRACTS OF CHEMICAL PAPERS. vaporisation of such a mixture is lowered the proportion of the constituent with tlie lesser niolecular latent heat of vaporisation should increase in the vapour phase. The temperature of vaporisa- tion is lowered by steam distillation and therefore in the case of a mixture of liomologues the proportion of the more volatile con- stituents should increase in the distillate.The abov9 deduction has been verified by experiments with a purified Russian illuminating oil (Meteor oil) consisting of a mixture of saturated hydrocarbons and naphthenes. I n order to avoid dephlegmation the whole of the distilling flask together with the greater part of the side-tube was immersed in the oil-bath. Instead of passing steam through the flask water was added to the contents together with numerous pieces of pumice stone so that the surface of contact between the water and the oil should be a great as possible. T. S. P. Triferrocarbide (Cementite) Fe,C. OTTO RUFF and EWALD GERSTEN (Bey. 1913 46 394-40O).-Jermilov (J. Buss. Metall. Soc 1911 357-366) has found that the molecular heat of formation of triferrocarbide is + 2-27 Gal. whereas the authors have previously found i t to be -15.1 Cal.(A. 1912 ii 260). I n the authors’ calculations the only thermochemical datum which had not been determined by theinselves was the heat of oxidation of ferrous oxide to ferroso-ferric oxide (Fe304) the value used being that due to Le G‘hatelier. They have consequently redetermined this value and find 28*6+1.8 Csl. as the heat of oxidation of FeO to iFe304 which is in fairly good agreement with Le Chatelier’s value 25-7 Cal. Using this value the molecular heats of formation given in the previous paper (Zoc. cit.) are corrected to the following values Fe304 267.1 k0.2 Gal. ; FeO 60.4 & 1.8 Cal. ; Pe,C (from a-irbn and graphite) - 15.3 +_ 0.2 Cal. The value for triferrocarbide is thus practically unaltered.Jermilov’s value is due to the fact that he has taken too high values for the molecular heats of formation of Fe30 and FeO. T. S. P. Heat of Formation of Additive Organic Compounds. I. Picrates. BARTOLO L. VANZETTI ( A t t i R. Accad. Lincei 1013 [v] 22 i lOS-l09).-The following heats of formation have been determined naphthalene picrate (in two experiments) 1450 cal. 954 cal. (compare Bronsted A. 1912 ii 21); isosafrole picrate 4430 cal. (mean of five experiments); eugenol picrate 5940 cal.; 2-methylindole picrate 2082 cal. Physico-chemical Investigations with Aromatic Stereo- isomeric Acids. I. WALTER A. ROTH and RICHARD STOERMER (Rer. 1913 46 260-280).-The mol. heats of combustion dissociation constants and solubilities of a number of carefully purified isomeric acids have been determined.The general rule indicated by Stoh- mann (A. 1892 ii 153) that the stable acids have the lower heats of combustion and smaller dissociation constants is confirmed. Some liquid esters have also been calorifically and optically R. V. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 297 examined. The results are given in the following table where V min. is the reciprocal of the solubility that is the number of litres of water required to dissolve 1 Mol. at 25O. Subst an ce. Ciniiamic acid ..................... cclloCitinamic acid ............... Methylcoumarinic acid ......... Ethylcouniaric acid ............ Ethylcoumarinic acid ......... Propylcoumaric acid ............ Propy lconniarinic acid ......... * Butylconmaric acid ............"Butylconmarinic acid ........ i- A mylcoumaric acid.. .......... i-Amylconmarinic acid ......... Acetylcoumaric acid ............ Acetylcouniarinic acid ......... Piperonylacrylic acid .......... aZloPiperonylacrylic acid ...... 2'-Hydr oxycinnamic acid ...... a I lo -p- H ydroxy cin namic acid p-Methosycinnamic acid ...... allo-p-Methoxycinnamic acid M e thylcoumaric acid.. .......... RI. p. 132-133" 58" 182 -183 91-92 133-134 101-102 105-106 83-81 89- 90 53 -54 79-79 -5 80-80'5 154-155 85 238 99-100 206 126-127 170 66 Heat Dissociation tion. x Vmin. 1041.4 Cal. 3.81 210 of cornbus- constant 1048-1 1162.4 1168.6 1317.9 1324.4 1472.0 1477'9 1632'4 1638.8 17925 1795.1 1209'0 1213.1 1068'8 1077.8 992'4 997'5 1164.2 1173.6 14-10 17-5 2.07 2120 5'40 (250 2'12 2110 4.54 333 - - - - 1 '4 11900 4-24 2070 5.0 1430 11 (approx.) 180 2 5 7000 (appros.) 10.61 (400 2'34 126 8.44 41.6 2 -1 2500 9-29 90'6 Ethyl methylcoumarinate b.p. 291-292.5O. Heat of combus- tion 1495'7 Cal.; D:6'7 1.1016; ptc 1.54697; TL 1.55399; nF 1.57303. Methyl ethylcoumarate b. p. 306-307O. Heat of combustion 1491-8 Cal.; D:8T5 1.0998; l a c 1.56318; n 1.57188; n 1.59680; nG 1.6233. Methyl ethylcoumarinate b. p. 288.5-289.5O. Heat of combus- tion 1496.5 Cal. ; D;'j4' 1.0981 ; nc 1'54724 ; i t D 1'55431 ; ?aB 1.57381. The compmnds marked with an asterisk are new and will bo described in a future paper whilst the majority of the others are the fruit of Stoermer's researches (A. 1910 i 114; 1911 i 295). The " heat values " for particular substituents agree with Stoh- mann's; for example the heats of combustion of the methyl esters are about 173 Cal.higher than those of the free acids. The proximity of the substituent to the carboxyl group has a great influence on the dissociation constant. Whereas o-methoxybenzoic acid has the constant 8.15 x 10-5 methyl coumaric acid has the value 2.07 x 10-5 and methyl coumarinic acid 5.4 x 10-5. A rela- tion is established between the amount of transformation which takes place when the stable acid is exposed to ultraviolet light and the ratio of the dissociation constants. When this ratio is smallest the transformation is most complete. The optical properties of the three esters agree with those of the esters of non-sttbstituted cinnamic acids described by Briihl (A. 1897 ii 129).The stable forms have the higher densities and refractive indices whilst a11 ether group in the ortlio-position raises the specific exaltation slightly and the dispersion considerably. J. C. W.ii. 298 ABSTRACTS OF CHEMICAL PAPERS Densities at the Critical Point. MAURICE PRUD’HUMME (J. CI~inz. yhys. 1912 10 636-639).-Accordin~ to van der Whals’ equation the critical volume should be three times the volume a t absolute zero but as is well known for many substances it assumes a value in the neighbourhood of four times. When van der Wads’ equation is solved for density it is found that the three roots d + d2 + d = m/ 6‘= a constant = m/nlb -I- n z /n2b + m/?@ where m is the molecular weight. A t the critical point where tho densities of vapour and liquid become equal dl=d2.Hence 2/n + l/n,= 1. This equation has only two solutions in integers namely nI = n3 = 3 and nl = 4 .n3 = 2. The first solution is the ordinary one where V = 3 b . The second solution corrwponds with the exceptional cases (formates methyl acetate fluorobenzene etc.) where V=4b but it remains to give an explanation of the third root namely V=2b the density d3 being twice the critical density that is d3=dl + d2. According to Cailletet and Mathias (d,+d,) is a linear function of the tempera- ture whether m is normal or not. Hence d3 is also a linear function of the temperature and in the exceptional cases an infinitesimal variation in the temperature corresponds with a variation in d which is the sum of the variations in d and d2. The author interprets d3 as representing the density of the surface film separating the liquid from the vapour.A t the critical point the density in the surface film must be twice the critical density for the substances mentioned. R. J. C. Pressure Density and Expansion of Saturated Water Vapour. KONRAD W. JURISCH (Zeitsch. physikal. Chem. 19 1 3 82 385-402).-A theoretical mathematical paper in which the rela- tionships of the pressure density and expansion are discussed. J. F. S. The Influence of Dissociation on the Density of Saturated Water Vapour. KONRAD W. JURISCH (Zeitsch. physikrd. Chem. 1913 82 575-580 ; see also preceding abstract).-A mathematical paper in which it is shown that the maximum density of water vapour lies at; T=985O. The diminution of density at higher temperatures is shown to be due entirely to a dissociation of the water vapour; a minimum density lies approximately a t T=2260° a t which point 55.66% is dissociated.J. F. S. The Influence of Dissociation on the Expansion of Saturated water vapour. KONRAD w. JURZSCH (Zeitsch. physikal. Chem. 19 13 82 581-586 ; see also preceding abstracts).-A mathematical paper in which i t is shown that there is a maximum of the expan- sion a t 1’’=1000° and a minimum a t T=1170°. It is shown that t,his is due entirely to the dissociation since this is the only volume changing function which is operative in the region mentioned (see last abstract) J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 299 The Temperature-coefficient of the Molecular Surface Energy and the Molecular Cohesion.PAUL WALDEN and RICHA~~D SWINNE (Zeitsch. physikdZ. Cliem. 2913 82 271-313. Compare A. 1911 ii 97; 1912 ii 628).-New determinations of the density and surface tension of a number of substances are given for temperatures between 20° and 100°. The substances investi- gated are octinene undecinene hexa-ethylbenzene myricyl alcohol the triethyl ester of aconitic acid diethyl ester of sebacic acid diisoamyl ester of sebacic acid Lamyl ester of bromo-n-butyric acid tetrachloroethane tetrabromoethane and dichlorobromomethane. The specific cohesion free surface tension free molecular surface energy and the temperature-coefficients of the free molecular surface energy (dMG/dt) and molecular cohesion dE,/dt were calculated. The results obtained in these experiments are compared with similar values calculated by other investigators and it is shown (1) That the coefficients dMa2/cEt and dE,/dt increase as an homologous series is ascended.(2) .That the substitution of hydrogen by the ethyl group causes an increase in the coefficients for members of the benzene series. (3) For alcohols the coefficient dMaz/dt increases very much as the series is ascended. (4) The replacement of hydrogen by chlorine iodine or bromine causes an increase in the coefficients which is greatest in the case of the iodine substitution and least in that of chlorine. It is also shown that replacement of oxygen by sulphur causes the value cEMa2/dt to increase. The replacement of an atom of lower atomic weight by one of higher atomic weight causes the coefficient dMa2/dt to increase.This is demonstrated in the case CCI - + SiCl -+ SnC1,. For eight of the substances investigated the value dE,/dt exceeds the normal value given by Ramsay and Shields and in consequence these substances ought to be regarded as dissociated. On the other hand the Dutoit-Mojoiu vapour pres- sure expression (A. 1909 ii 470) and the Walden expression for the value dE,/cFt (A. 1908 ii 1014) point to these liquids being normal. The Ramsay-Shields formula for the normal value of dE,/dt is discussed as also is the Guye theory of the dissociation in the surface layer. It is shown that the values dMa2/dt and dE,/dt are of an additive nature and from an examination of 316 substances formulz are deduced which give a means of calcu- lating these coefficients.dMa2/dt = - [0.00027( 8 d’) + 0*0103] dE,/dt = - [0’011( 2 +/X) + 1-90] where 2 4 A is the sum of the square roots of the atomic weights of the component atoms. The agreement between the values of the coefficients calculated by the above €ormulae and those obtained from experimental results is on the whole good. For dements and halogen derivatives the agreement is best; for hydrocarbons a variation of about 12% is fourid in some cases; esters 6% is about the maximum divergence; oxides 9% divergence but the agreement is generally good; amines The formulae for normal liquids are:ii. 300 ABSTRACTS OF CHEMICAL PAPERS. a mean divergence of about lo% but some amines differ far more than this figure. Nitro-compounds acid amides nitriles and hydroxy-derivatives are less in aclSord with the formulae.J. F. S. Dimensions of the Suiface Energy of Solid Substances. WILLIAM J. JONES (Zeitsch. p h @ d Chem,. 19 13 82 448-456).- The formulz used by Ostwald (A. 1900 ii 730) Hulett (A. 1901 ii 493) and Freundlich for calculating the surface energy of solid substances are critically discussed. The author deduces a formula from considerations of a thermodynamical reversible process which he applies to the experimental data of Hulett (Zoc. c i t . ) . The formula is given by in which r1 and rZ are the radii of the solid particles which are dissolving and being formed in the saturated solution CT the surface energy per unit area p the density of the solid y1 and yz the degrees of dissociation of the solid substance of radii r1 and rZ in the saturated solutions m is a constant having a value between 1-36 and 1-55 M is the molecular weight n is the number of ions furnished by the salt and R and T have their usual meanings.ThO surface energy for gypsum calculates to 1050 ergs. per sq. cm. and for barium sulphate the value 1300 ergs. per sq. cm. is obtained. J. F. 5. Method of Determining a ” of van der Waals’ Equation from the Surface Tension. ALBERT P. MATHEWS (J. Physical Chem. 1913 17 154-1 61).-The various known methods of corn- pxting a involve the assumption that b the real molecular volume is unaffected by changes of temperature and pressure. The author’s method which is based on the surface-tension formulae of Young and Eotvos is independent of any assumption as to the value of b.Young’s formula S=rR/3 equates the surface tension to the radius of action r of cohesive attraction and the total cohesive pressure K . The rival formula S=3rK/20 due to Rayleigh is rejected by the author because it leads to improbable values of a according t o his method of treatment. van der Waals’ constant a which expresses the cohesive power may be equated to Nh?K where N is the number of molecules in volume V . Hence a/?72=il!PK/u2 where v is the space occupied by a single molecule. A t absolute zero when the molecules are in contact T= v,+. By equating the two values of Su,% and assuming N t o have the value 6.21 x 1023 the author deduces that M2K=9.045 x 10-1G(T,-6)v,. From MZE a and 7 can readily be calculated. The values of b thus calculated for ether pentaae and isopen- tane are shown to be a constant fraction of the critical volumes ‘V,/b,=2.074.This figure is very close to the various estimates by Hence Su,% = .M2K/3w0. Now according to Eotvos’ formula S V ~ = 2’19(T - 6)/NQ.GENERAL AND PHYSICAL CHEMISTRY. ii. 301 van der Waals and departs considerably from the theoretical value namely 3. The values o€ X2K calculated by the author for twenty-seven substances with the aid of Young's surface-tension data are very similar to the values obtained by the ordinary formula but in some instances differ markedly from these. The new formula is con- sidered to give the more accurate values because these exhibit more clearly the relationship of cohesion to molecu1a.r weight and valency deduced by the) author.Properties of a Liquid Connected with its Surface Tension. RICHARD D. KLEEaIAN (Proc. Camb. Phd. L~OC. 1913 17. 149-159. Compare this vol. ii 26).-In the previous paper a formula was deduced for the surface tension of a liquid on the assumption that there is no transition layer at the surface. By substitution of the experimentally determined surf ace tension the formula may be inversely applied to calculate the absolute weight of a molecule. From the data f o r ethyl ether carbon tetrachloride methyl formate and benzene ths mean weight of the hydrogen atom which is obtained from the formula is 1.56xlO-24 gram. This is in good agreement with the value 1-61 x 10-24 gram obtained by Rutherford from experiments on the a-particle. A number of relations have also been obtained connecting the surface tension of a liquid with its internal heat of vaporisation compressibility coefficient of expansion and other quantities.Some of these may be utilised for the detection of association and estima- tion of the extent to which association occurs. Determination of the Viscosity of Caoutchouc Solutions. J. G. FOL (Chsm. Wepkblad 1913 10 154-174*).-From the results of a number of determinations of the viscosity of a specimen of caoutchouc from Java the author makes the following inferences (1) I n the determination of relat'ive viscosity the type of visco- meter employed has an important influence on the results. (3) The diameter of the capillary in Ostlwald's viscometer should not be too small. (3) Violent shaking during the making of the solution considerably affects the viscosity.(4) There is a remarkable relation between the relative viscosity of caoutchouc solutions of similar concentration. ( 5 ) The viscosity is affected by the length of time which has elapsed between the preparation of the solution and the determination especially for solutions of high concentration. (6) The relative viscosity of the solutions of the samples examined was affected by the temperature but not the absolute viscosity. (7) With concentrated solutions the time of efflux diminishes between successive determinations the greatest difference being observed between the first and second reading. Det'ails of a method of determining the viscosity of caoutchouc solutions are given. Relationship between Molecular Weight and Turbulence Viscosity Constant.WALTITER S~RRAU (Plwsiknl. %le;twl,,. 1 91 3. 14 147-162. Compare A. 1912 ii 793; 1912 ii 900).-From ++ and Zcitsch. Chena. I ~ i d . Koll. 1913 12 131-147. R. J. C. H. M. D. A. J. W.ii. 302 ABSTRACTS OF CHEMICAL PAPERS experiments on the hydraulic flow of methyl propionate propyl acetate and butyl acetate at temperatures between 1 5 O and 40° it is found that the connexion between the time of flow (t) the pres- sure ( p ) and the temperature (0) in the primary stage of turbu- lence is expressed by t The value of C for ethyl acetate is 114.3 methyl propionate 115.2 propyl acetate 125.8 and for butyl acetate 130.2. The constant G appears to be related to the molecular weight ( M ) by means of the equation C= 12-25 J M .I n tho third stage of turbulence in which under very high pres- sures the liquid appears to be projected through the capillary like a frictionless solid cylindrical column the time of flow is given by t = C ’ / J p in which C’ is equal to 33.4 for butyl acetate 34.0 f o r propyl acetate 34.6 for ethyl acetate and 34.5 for methyl propionate. The sequence which is obtained when the esters are arranged according to the viscosity constants is thus seen to be reversed when the numbers relating t o the primary stage are replaced by those characteristic of the third stage. e0/273. H. M. D. The Adsorptive Power of the Hydroxides of Silicon Alu- minium and Iron. VI. PAUL ROHLAND (Zeitsch. nnorg. Chem.. 1531.3 80 174-175. Compare. A. 1912 ii 1145).-The colloids of clay have very little adsorptive power for azo-dyes and the colouring matter of unknown constitution which is present in the waste water from sulphi te cellulose is not adsorbed.C. H. D. Adsorption. VIII. Adsorption by Starch in Mixed Solu- tions. ADAM V. RAKOVSKI (J. IZuss. Yhys. Chem. Soc. 1913 45 7-12. Compare this vol. ii 114).-The author has investigated the adsorption by starch of alkali in presence of salts and of two ltlkalis simultaneously. Potassium and sodium salts of organic and inorganic acids cause considerable increase in the amount of sodium hydroxide adsorbed by starch the carbonates being appreciably less effective than the other salts ; the extent of the adsorption increases continuously with the concentration of the salt. The adsorption of the large propor- tions of alkali thus occurring is not accompanied by appreciable gelatinisation of the starch.Barium salts exert a similar influence on the adsorption of barium hydroxide by starch but the small amount of ammonium hydroxide adsorbed by starch is scarcely affected by the presence of ammonium salts. A more complicated course is followed by the adsorption when the hydroxide and salt possess dissimilar cations. The systems NaOH + &BaCI and $Ra(OH),+ NaCl give identical results. With the system Ba(OH) + NaOH both alkalis are adsorbed the former to a higher and the latter to a lower extent than when present alone so that the adsorption of barium ions is raised and that of sodium ions diminished by excess of hydroxyl ions. Ammonium hydroxide is practically without influence on the adsorption of sodium or barium hydroxide.T. H. P.QENERAL AND PHYSICAL CEEMISTRY. ii. 303 Adsorption. IX. Adsorption and Hydrolysis. ADAM V. assumption is made that the action of alkali on starch yields “ starchates ” o r chemical compounds analogous to alkoxides and sucrates. Since starch adsorbs both alkali and water simultaneously in the solid phase hydrolytic decomposition of the starchate would occur these changes being represented by the equation AmH + MOH AmM+ H,O where AmE indicates starch and AmM the starchate. I f the initial concentration of the alkali is a milli-equivalents in volume v and the weight of starch 772 grams o r 1000m/162*08n or N milli-equivalents and if further after the establishment of equilibrium there are present x milli-equivalents of starchate N - x of free starch and a-x of free alkali then x/(N-$)(a-x)=k should give constant values.The index n of the constant represents the number of C,H,,O groups present in the given starchate per equivalefit of metal. With potato and St. Vincent and Bermuda arrowroot starches constant values are obtained with lithium sodium and potassium hydroxides for k if n=3. I n the case of starches with small granules such as rice starch the constancy is less satisfactory and with wheat starch constant values are obtained for k,. The starchates formed by the two latter starches hence differ in type from those given by potato and arrowroot starches. With barium strontium and calcium hydroxides less concordant numbers are obtained but these ar0 in fairly good agreement with the value n = 1.The constancy of the values of k the negligible influence of change of temperature on the adsorption of alkali hydroxides by starch and the intensification of the adsorption in presence of salts (compare preceding abstract) render highly probable the existence of starch a tes . T. H. P. RAKOVSRI (J. KUS8. I’hys. ChelYL. SOC. 1913 45 13-21).-The Influence of the Geometric Form of Solids on the Chemical Reactions which they Undergo. G. REBOUL (Compt. rend. 1913 156 548-550. Compare ibid. 1912 155 1227).-The author has measured any change of rate of attack of a gas on a solid by varying the curvature of the solid in such cases as the action of iodine vapour on silver and finds that either at the ordinary pressure or under reduced pressure the action of the gas on the solid is most rapid a t those points where the mean curvature is the greatest and explains the phenomenon on the grounds of capillarity the gaseous concen- tration being greatest at the points where the radius of curvature is least.W. G. Capillary Phenomena in Gases. Extension of Laplace’s Formula to the Contact Solid-gas. G. REBOUL (Cowpt. ~-e3~d. 1913 156 688-691).-Working with copper cylinders of different diameter subjected to the gas from vulcanised caoutchouc tho author shows that the amount of copper compound formed is given by aq = b/2R + c where Q is the thickness of the layer of copperii. 304 ABSTRACTS OF CHEMICAL PAPERS. compound formed R the radius of the cylinder and a 6 c three constants varying slightly with the pressure of the vapour.Assum- ing that there is an increase in the concentration of the gas at the surface of the metal he obtains & = k T + c where F is the concen- tration of the reacting gas which is thus a linear function of 1/22; thus there is at each point of the surface of separation of solid-gas an excess of pressure proportional to the mean curvature and so Laplace’s formula holds good for such cases. W. G. The Differential Tonometry of Solutions and the Theory of Arrhenius. EUGENE FOUARD (Corn@. rend. 1913 156 623-625. Compare A. 1911 ii 267 1071; 1912 ii 436).-A photograph and description is given of a tonometer in which the author has made determinations on equimolecular solutions of potassium chloride and sucrose and has obtained results which are in agreement with his measurements of osmotic pressure (Zoc.cit.) and thus opposed to the ionic theory of solution. W. G. [Stratifled Systems.] RAPHAEL E. LIESEGANG (Zeitsch. Chem. Ind. Kolloide 1913 12 74-77).-It is shown that the experiments described by Hatschek (A 1912 ii 439) cannot be accepted as disproving Ostwald’s view that the formation of stratified layers of insoluble substances as a result of slow diffusion in jellies is due to the intervention of supersaturation phenomena. The slow interaction of copper nitrate and sodium carbonate which occurs when silicic acid jellies containing the two substances are brought into contact has been found to give rise to irregularly stratified precipitation layers of basic copper carbonate the structure of which resembles closely that shown by certain malachites.H. M. D. New Apparatus for Quantitative Dialysis. A. GOLODETZ (Chenz. Zeit. 1913 37 259-260).-ln order to dialy~e a substance exhaustively using a small volume of water the material is enclosed in a suitable membrane which is so placed in a modified Soxhlet apparatus that i t presents as large a surface as possible to the water. Should it not be advisable to heat the product above 50° a capillary tube may be attached and ebullition maintained under reduced pressure. J. C. W. Influence of Chemical Constitution on the Thermal Pro- perties of Binary Mixtures. I. PAUL PASCAL and Liox NORMAKD (BUZZ. Soc. chirn. 1913 [iv] 13 151-161).-This is the first of a series of papers in which tho authors propose to deal with binary mixtures of compounds of the type R-a-@-R’ where R and R’ are aromatic nuclei and a and fi may be *CH,* *CH *Ci *NH* ON or *O*.Such investigations have been made already by Beck (A. 1904 ii 646) and by Bruni (A. 1912 ii 1043). The authors propose to ascertain (1) whether “ mixed crystals ” are formed and if so over what range o€ temperature and (2) what relationship exists between the structures of the two components and theGENERAL AND PHYSICAL CHEMISTRY. ii. 305 property of simultaneous crystallisation. The mixtures now examined are (1) stilbene with (n) dibenzyl ( b ) tolane ( c ) azo- benzene (d) hydrazobenzene; (2) tolane with ( a ) dibeneyl ( b ) azo- benzene ( c ) hydrazobenzene ; (3) dibenzyl with ( a ) hydrazobenzene ( 6 ) azobenzene; and (4) azobenzene with hydrazobenzene.Tables and graphs showing the fusion curves of these mixtures are given. They show that compounds of the type R-a-a-R taken two a t a time give a continuous series of mixed crystals and are probably strictly isomorpilous although there are shades in this isomorphism thus in the case of a binary mixture of two compounds having the same multivalent central atoms or the same central linkings the fusion curve generally shows no minimal point whilst a minimal point develops more and more clearly ,as differences in the two constitutional characters mentioned become more noticeable and is most marked in a mixture of-hydrazobehzene NHPhONHPh and tolane CPhiCPh. Further hydrazobenzene shows an unforeseen tendency to produce minimal points on the curves possibly owing t o tlie ease with which its ON atoms may become quinquevalent.T. A. H. Chemical and Crystal Molecules. EVGRAF S. FEDOROV ( Z d s c h . J l j y s t . Min. 1913 52 22-43).-Several examples are quoted from the author’s tables (A. 1912 ii 772). I n considering the symmetry relations of the chemical molecule the arrangement of the peri- pherically piaced radicles must be taken into account in addition t o the nucleus itself. As a rule the symmetry relations shown by the crystal cannot be expressed by the chemical molecule alone and two or more of these must be united to form the crystal molecule. L. J. S. Formation of Crystal Faces. A. BERTROUD ( J . Chim. ph?is. 1912 10 624-635).-4ccording to Curie crystals take the habit which gives them the minimum of superficial energy so that the relative areas of the faces depend on their capillary constants.A crystal departing from the equilibrium shape when placed in a solution of suitable strength should dissolve from some faces and grow on others. Actually the differences of solubility in crystals are so minute as to be without influence on their crystalline habit in comparison with the effect of different rates of crystallisation along different axes. Taking the surface energy of two faces of a crystal in its normal habit as of the order 100 and 800 ergs per sq. cm. respec- tively (Hdlett) the author calculates that even in crystals depart- ing very considerably from the normal habit an appreciable differ- ence in solubility can only arise when the dimensions are micro- scopic.Surface energy might come into play in extreme cases as for example in preventing a substance from crystallising in thin plates when normally it crystallises in slender needles. The main factors which influence crystalline habit are the internal structure of the crystals and the degree of supersaturation and the nature of the concentration and other currents in the solutionii. 306 ABSTRACTS OF CHEMICAL PAPERS. during deposition. According to Noyes and Whitney (1897) the dissolution of a crystal is governed by the rate of diffusion of the dissolved molecules across the zone of falling concentration which being replenished instantaneously from the crystal remains satur- ated on one side. Le Blanc has applied this theory to the reverse process of crystallisation.The author agrees with Wagner that Le Blanc's theory fails to account for the varying rates of crystal growth on different faces. Wagner suggests that the thickness 6 of the diffusion zone varies from one face to another but 6 being at least 0.03 mm. with the most violent agitation (Brunner) is not likely t o be influenced by forces of molecular magnitude a t the crystal surface. The rate at which equilibrium tends to establish itself between a ,given area of crystal surface S and the solution is proportional to the difference in the concentration of the saturated solution co and the solution in immediate contact with the crystal c'. Thus dx/dt=kS(c' - c g ) = ~ ~ ( c - c g ) l ( ~ + D l k ) where k is the velocity conetant of crystallisation of the given surface D the diffusion constant and c the mean concentration in the diffusion zone.This formula reduces to that of Noyes and Whitney when B / k is very small in comparison with 6 that is when the solution is absolutely still. The more nearly this condition is attained in practice the more nearly the crystal faces approximate t o equal rates of growth and facets may then appear which are not seen when the solution has been agitated. R. J. C. Chemical Analogies of Substances Showing a Crystallo- graphic Relation t o Potassium Sulphate. EVGRAF S. FEDOROV (Zeitsch. Kryst. Min. 19 13 52 11 - 21) -A variety of substances of the hypohexagonal type having nearly the same symbols as potass- ium sulphate fall together in the author's tables (A 1912 ii 772) for example S0,K2 BeF,(NB,) HgBr4Cs2 ZnCl,K CuCl,(NMe,) etc.These exhibit the same type of chemical formula (although the numbers of atoms and the valencies differ); and they are described as isotectonic substances and their crystals as isogonal. L. J. S. Efflorescence of Crystals under Water. MORRIS FORT (Chenz. Neim 1913 107 86).-1f slightly effloresced crystals of sodium sulphite Na2S03,7H20 are placed in an excess of water in a test- tube the opaque outer crust dissolves and the crystals become clean and bright. On gently warming the crystals rapidly become opaque and powdered in appearance and analysis shows them to have effloresced to a considerable extent. The author considers that the best explanation is that dehydration of the crystals due to rise in temperature takes place faster than solution can be effected.T. S. P. Liquid Crystals of Ammonium Oloate. A. MLODZIEJOVSKI (Zeitsch. Kvyst. Min. 1913 52 1-lo).-The so-called liquid crystals of ammonium oleate may be obtained by the evaporation at theGENERAL ARD PHYSICAL CHEMISTRP. i;. 207 ordinary temperature of a solution in water and alcohol. They are only formed in the presence of water or at a sufficiently high tem- perature and by the addition of more water they exhibit m y e h forms. The conclusion is drawn that the structure observed is of t8he nature of an emulsion rather than that of liquid crystals (compare A. 1912 ii 109). Nature of t h e Electrical Synthesis of Colloids. CAXL BENEDICKS (Koll. Chem Beihefttiz 1913 4 229-260.Comp:tre Kutscherov A. 1912 ii 1148; Benedicks this vol. ii 99).-The micro-structural changes which are exhibited by the surfaces of the electrodes after electrical disintegration have been investigated with the object of throwing light on the nature of the disintegration process. The apparatus employed was practically identical with that described by Svedberg ethyl ether being used as dispersive medium and the current passed between erectrodes of various metals and alloys. The results obtained indicate that the process is essentially thermo-mechasical. When the conditions are such that arc discharge hkes place for a very short time interval as may easily be arranged i f the current is furnished by an inducZlion coil and a Leyden jar is placed in parallel with the discharge gap i t is found that the surfaces of the electrodes exhibit well-formed eruptive craters which are attributed to the melting of the metal under the influence of the discharge.When the discharge ceases the surrounding liquid comes in contact with the hot metal and this is supposed to Ke directly responsible for the disintegration of the electrodes. In support of this view i t has been found that exactly similar crater-like structures can be obtained when a gentle current of hot air is allowed to impinge on the surface of a highly viscous substance such as asphalt I n accordance with the thermo-mechanical nature of the process the most important factors in connexion with the electrical disin- tegration process are the latent heat of liquefaction and the thermal conductivity of the disintegrating metal.Ultra-microscopic observations made with the colloidal metal solutions obtained by Svedberg’s method have shown that the particles are spherical the diameter varying over a wide range with an upper limit of about 5p. [Preparation of a Dispersoid Solution of any Substance.] theoretical paper in which the author discusses the conditions under which it is possible to obtain any substance in the form of a dispersoid solution. H. M. D. Physical Properties of Colloidal Solutions. JOSEF PRANK (Koll. C h m . Beihefte 1913 4 195-2.38).-Measurements have been made of the volume changes which accompany the absorption of water by colloids of the heat of liquefaction and the coefficient expansion of various colloids and also of the viscosity of certain colloidal solutions. The absorption of water by gelatin or starch and of colophony L.J. S. H. M. D. I). P. VON WEIMARK (Kdl. Chem. Be&pfle 3913 4 175-194).-Aii. 308 ABSTRACTS OF CHEMICAL PAPERS. by oil of turpentine is attended by contraction the magnitude of which when referred t o unit volume of the gelatin starch or oil of turpentine is independent of the composition of the mixture. The transition from the solid to the liquid state shows no appreciable absorption of heat according to experiments with colophony mixtures of colopliony and oil of turpentine and mixtures of gelatin and water. The coefficient of expansion of gelatin-water mixtures increases with rise of temperature to a maximum afterwards falling to a minimum and a t still higher temperatures increasing again.The maxima and minima become more sharply defined as the pro- portion of gelatin in the mixture increases and a t the same time the temperatures a t which they occur are found to rise. I n the case of colophony and its mixtures with oil of turpentine the coefficient of expansion rises with the temperature at first quickly then more slowly and later again more rapidly. As the proportion of oil of turpentine in the mixture increases the coefficient of expansion becomes greater but the rate a t which the coefficient increases with temperature becomes less. From thO examination of a large number of colloidal solutions of dyes dissolved in water and alcohol it has been found that the effect of the dye on the viscosity is in general greater for alcoholic than for aqueous solutions. The viscosity of solutions of malachite- green and safranine was found t o vary with time.H. M. D. Thermo-chemical Researches on Solution and their Bearing on Theoretical Gonsiderations coucerning the Rela- tions between the Chemical Properties of Solutions. NICOLAS A. KOLOSOVSKI ( J . Russ. Phys. Chem. SOC. 1913 45 22-52.* Com- pare this vol. ii 22).-On the assumption that the change of any property for mixtures or chemical compounds is an external mani- festation of the action of chemical affinity it may be asserted that in the case of aqueous solutions of electrolytes the divergence of any property from the mean of those of the solvent and solute is a consequence of the formation of hydrates. Assuming further the formation of hydrates of the ions all such divergences must neces- sarily follow an additive law.I n order to ascertain the limits of applicability and a memure of the general character of this proposition the author examines the relations between the values obtained for various salts of (1) the lowering ( V ) of the coefficient of distribution of acetic acid between water and ether under the influence of 1 gram-equivalent of dissolved salt (compare A. 1911 ii 591 705); (2) the change ( V ’ ) in the temperature of separation of an aqueous solution of isobutyric acid produced by a half gram-equivalent of dissolved salt (compare Smirnov A. 1907 ii 334); (3) the change (Vll) in the absorbability of carbon dioxide by water caused by one gram- equiva.lent of dissolved salt (compare Setschenov A.1875 864 1159; J . Russ. Phys. Chem. SOC. 1886 18 and 1887 19). The con- stancy exhibited by the two ratios Vl/V=Kl and VIlIV=R/l is regarded as evidence of the chemical nature of these properties. ’ and BUZZ. Acad. roy. Belg. 1913 86-67.GENERAL AND PEYSICAL CHEMISTRY. ii. 309 With other properties such as density capillarity etc. no such simple relations were obtained. Measurements have been made of the heats of solution and specific heats of sodium and potassium chlorides and nitrates in water and in various mixtures of water and ethyl alcohol. In each of these solvents the differences between the heats of solution of (1) sodium and potassium nitrates and (2) sodium and potassium chlorides are very nearly equal. Approximate equality is also exhibited between the differences for (1) potassium chloride and nitrate and (2) sodium chloride and nitrate.T. H. P. Influence of Temperature on the Velocity of Chemical Reactions. A . BEKTHOUD (J. Chim. phys. 1912 10 573-597).- According to Arrhenius’ theory the “ active part ” in chemical change is formed reversibly in accordance with van% Hoff’s equation for static equilibrium. The active part is supposed to be trans- formed chemically a t a definite rate in accordance with the law of mass action. If Icf is the rate of formation of the active part and k‘f of the reverse action and k the rate of chemical transformation of the active part the concentration C of the latter is proportional to ?c’/ (k + k”).It is not permissible to assume with Arrhenius that li is independent of temperature. The modificat.ion of Arrhenius’ theory put forward by Trautz (A. 1911 ii 381) in which the active part consists of molecules undergoing a preliminary dissociation is open t o a similar objection as also is the additive compound hypothesis. According to Gold- echmidt (A. 1909 ii 390) only those molecules react the velocity of which exceeds a certain minimum. The author proposes a modi- fication of this theory in which velocity is replaced by “energy of internal atomic vibration.” Those molecules the atoms of which are in an unstable configuration or are vibrating beyond a certain critical amplitude constitute the [‘ active part.” I n gaseous actions other than intramolecular actions i t is necessary to assume that transient additive compounds are formed which are dissociated again into the original constituents or into new constituents accorcl- ing to their content of energy or their configuration.The ordinary temperature-equation is modified by the addition of a new factor f ( T ) and thus becomes logli’/kf’=A/T+~/logT+ CZ’+ I) + f(2”). The new term f(7’) is intended t o take account of the effect on k of various factors such as thO increase in the propor- tion of active molecules exceeding the critical energy the increase in the average energy of the molecules which exceed the critical energy and in the case of solutions the viscosity. I n practice f ( 1’) is usually negligible in comparison with experimental errors. R. J. C. Action of Low Temperatures on Explosives ANDRI~ KLINCI and DANIEL FLORENTIN (Compt.rend. 1913 156 694-696).-A study of the influence of coding on the sensitiveness of different explo- sives and the force and rate of their explosions comparison being made between results obtained a t the ordinary temperature and VOL C ~ V . ii. 21ii. 310 ABSTRACTS OF CHEMICAL PAPERS. a t - 190° (liquid nitrogen). The sensitiveness to percussion is considerably diminished at low temperatures the cooling effect being shown both by the detonator and the explosive- itself. The force of the explosion does not appear to be diminished by cooling providing that the percussion is sufficiently powerful to produce tot.al deflagration of the explosive. When detonation occurs the propagatioii of the explosion wave is not affected by cooling.W. G. The Oxidation of Complex Cobalto-organic Compounds H. COLIN and A. SENECHAL (Compt. rend. 1913 156 625-627).-A study of the rate of oxidation of solutions containing a cobalt salt and either glycerol or lactic acid to which an excess of alkali hydroxide has been added the amount of oxygen fixed by the cobalt in a given time being determined. The reaction is uni- molecular and the value of the constant K is independent of the concentration of the cobalt salt but decreasm rapidly with increase in concentration of the alkali. The authqr considers that the mechanism of the oxidation is similar to that in the case of the cobaltocyanides (compare Manchot and Herzog A. 1901 ii 549). W. G. Velocity of the Reaction between Sodium Thiosulphate and Sodium Bromoacetste.SERGIUS KRAPIVIN (Zeltsch. physikal. Chem. 1913 82 439-447).-The velocity of the reaction betweeu sodium thiosulphate and sodium bromoacetate is determined by the same method as that employed for determining the velocity between sodium thiosulphate and chloroacetate (A. 1912 ii 926). The reaction is bimolecular the velocity constant depending on the concentration ; for 0*25N-solutions k = 1.605 ; 0*05N-solutions k = 0.697 and for O'OlN-solutions k = 0.456. Doubling the concen- tration of either the bromoacetate or the thiosulphate brings about the same change in the velocity constant. The addition of O*OlN- sodium bromide sodium iodide sodium nitrate or sodium sulphate effects the velocity constant to the same extent as the addition of the same quantity of either sodium thiosulphate or sodium bromoacetate.The addition of alcohol to the reaction mixture causes an increase in the velocity constant. J. F. S. Hydrolysis of Metallic Alkyl Sulphates. GEOKGE A. LINRART (Amar. J . Sci. 1913 [iv] 35 283-289. Compare A. 1912 ii 927). -The rate of saponification of sodium ethyl sulphate by sodium hydroxide and of barium methyl sulphate and strontium methyl sulphate by barium hydroxide has been examined in aqueous solution at 60°. The data indicate that the reaction proceeds in all three cases in accordance with the equation for a bimolecular change. This result differs completely from that obtained in similar experiments by Kremann (A. 1910 ii 596) and the author draws the conclusion that Kremann's data are untrustworthy and that the interpretation of the results is consequently without foundation.H. M. D.GENERAL AND PHYSICAL CHEMlSTRY. ii. 311 Re investigation of the Velocity of Sugar Hydrolys's. 11 The RBle of Water. A'rARTrN A . KOSANOFF and H. 11. Y o ~ ~ l s i i ( J . Arn.~9*. Chem. Soc. 1913 35 248-258).-1n an earlier piper ( A . 1912 ii 34) it was shown that tho hydrolysis of sucrose is a strictly unimolecular reaction. Various explanations including those of Cohen (A. 1897 ii 484) and Arrhenius (A. 1899 ii 359) have been offered for the fact that the velocity of hydrolysis of sucrose is a function of the initial concentration but i t is now shown that none of these is adequate. A new theory is therefore proposed which states that water plays a double r6le in the reaction (1) it takes part in the reaction and contributes tto its velocity in accordance with the law of mass-action and (2) it acts as a negative catalyst by its disso- ciating power.I n accordance with this view the mechanism of sucrose hydrolysis appears to depend on the existence of a molecular complex the concentration of which determines the velocity of the reaction. Water retards the reaction by dissociating this complex. E. G. SYDNEY H. HIGGTNS (J. Soc. ,!?yers 1913 29 85-S9).-See P. 1912 28. 130. H. M. D. Action of Neutral Salts on Bleaching Solution. Neutral Salt Reactions. I1 A Double Neutral Salt Re- action and the Action of Glauber's S a l t on Wool. MORRIS FORT (J. SOC. Dyws 1913 29 80-85. Compare A. 1912 ii 1047). -According to the views brought forward in the previous paper salts which do not give an alkaline reaction with litmus or alizarin should exhibit alkalinity when more strongly acid indicators are added t o the boiling solutions.I n support of this i t has been found that a hot solution of sodium chloride which is inactive towards alizarin gives a feeble alkaline reaction with nitroalizarin and a distinctly alkaline reaction with dinitroanthrachrysone sulphonic acid. Although no alkalinity is indicated on the addition of alizarin to boiling solutions of either sodium chloride or calcium sulphate yet when the solutions are mixed an alkaline reaction is immedi- ately developed. This is attributed to double decomposition sodium sulphate being formed in sufficient quantity to give the alizarin reaction.The action of aqueous solutions of sodium sulphate on wool has been investigated with reference to its tensile strength and dyeing properties and the results are supposed to show that the basic properties of wool enable i t to react with sodium sulphate in boiling solution in much the same way as other organic bases. Neutral salt reactions arc3 considered to play a part in other technical processes and also in physiological changes. Cjolour Changes Among Dyes of the Triphenylmethane Series as Influenced by the Hydrogen Ion Concentration of Acids of Different Dissociation Constants. HENRY C. BIDDLE (J. Amer. Clmn. Suc. 1013,.35 273-281. Compere A. 1913 i 296; ii 1048).-A study of the conversion of the benzenoid forms of H.M. D. 21-3ii. 312 ABSTRACTS OF CHEMICAL PAPERS. certain dyes of the tripheuylmetliane series into the quinonoid forms by acids of different dissociation constants has shown that there is a marked similarity between the action of the acids in this case and their catalysing influence in the case of the cinchond alkaloids. The rate of development of colour in a solution of magenta in sulphurous acid to which a little formaldehyde has been added increases in equivalent solutions with acids of decreasing dissocia- tion constant and is retarded by acids of increasing disrsociation constant. The reaction forms a useful lecture experiment for demon- strating the accelerating catalytic action of the slightly dissociated organic acids and the inhibiting action of the highly ionised mineral acids.The velocity of the reaction appears also to increase with the molecular concentration of an organic acid. The action of excess of an acid on a rosaniline dye or its carbinol base leads to an equilibrium between the coloured and colourless forms which is largely dependent on the concentration of the hydrogen ions of the acid. The velocity of the reaction in the case of methyl-violet with acetic or chloroacetic acid seems to increase with the decreasing dissociation constant of the acid. E. G. Xanthic Acid and the Kinetics of its Decomposition. HANS VON HALBAN and ALEXANDER KIRSCH ‘zeitsch. physikal. Chern. 1913 82 325-360).-Xanthic acid usually 3ecomposes violently in several minutes after preparation. It is shown that this is due to autocatalysis in which the alcohol fornied as a product of the decomposition is the catalyst.The authors show that if xanthic acid is intimately mixed with phosphoric oxide it becomes stable and can be kept for weeks The rate of decomposition of the acid is determined in solutions in benzene chlo,roform carbon disulphid3 light petroleum (b. p. 65-80°) ether nitrobenzene acetone and alcohol at temperatures Oo 4 * 7 O 25O 45O 65O and SOo. The course of the reaction is followed by titrating portions of the solution with a standard iodine solution when the undecomposed acid can be estimated according to the equation I,+ 20Et*CS*&H= 2HI + OEt*CS*S*CS*OEt. The velocity of decomposition in solutions where the decomposi- tion is rapid is in accordance with a reaction of the unimolecular type but for those solutions in which the reaction is relatively slow the constant calculated by the equation for unimolecular reactions gradually increases thus pointing to an autocatalysis.The velocity constant varies enormously in the different solvents; thus if a t 25O the constant f o r ethyl alcohol is 1,000,000 acetone gives 25,980 ether 485 nitrobenzene 315 benzene 5.15 chloroform 3.64 light petroleum 1-50 and carbon disulpliide 1.0. It is shown that there is no connexion between the dielectric co~lstants of the solvents and the velocity of the reactions. The effect of adding quantities of various substances to the various solutions is also investigated. The addi- tion of alcohol t o the benzene solutions causes an increase in the velocity of the reaction.The addition bf many other substances causes a similar increase; thus the constant for a pure benzeneGENERAL AND PHYS1C.AL CHEMISTRY. ii. 313 solution a t 2 5 O is 0.0000068 for a 0.01 normal solution of xanthic acid ; if the following substances are added in quantities sufficient t o form a 0.2 normal solution the following values are obtained methyl alcohol 0.0028 ; ethyl alcohol 0.0036 ; propyl alcohol 0.0023 ; acetic acid 0.00021 ; acetone 0.000075 ; tribromophenol 0*000015 ; triphenylcarbinol 0.000031. I n ethereal solution sulphuric acid causes a considerable increase in the velocity whereas acetic acid and hydrochloric acid increase it t o t-he same extent wliicli is however much less than with sulphuric acid. The tern- l~erature-coefficient of the reaction is much smaller than that usual for unimolecular reactions; it conforms well with the formula of Arrhenius.The molecular weight of xanthic acid was determined in solutions of benzene and carbon disulphide and shown t o be normal. J. F. S. Structure of Some of the Elements. HAWKSWORTH COLT~TNS (Chem. News 1913 107 99-100).-Reforence is made to the advertisement coliimns of Natum and Chem. News 1906. for priority of the idea t h a t “ t h e acidity or non-metallic nature of an element is always due to a pair or pairs of electro-positive forces each pair emanating from a portion of the element ” of mass 4. Eleven pairs of elements are cited differing in mass by four units and in valency by two units such as phosphorus and aluminium aluminium and sodium etc.The combination of oxygen and helium t o form neon is cited in support of these views of atomic structure. Twentieth Annual Report of the Committee on Atomic Weights. Determinations published during 19 12. FRANK W. CLARKE (J. Amor. Chem. Soc. 1913 35 22?-?35).-A siimmarv of t,lie atomic-weight investigations carried o u t during 1912 and the results obtained. E. G. F. S. A New Source of Error in the Determination of Atomic Weights. ICILIO GUARESCHI ( A t t i R. h a d . Sci. Torino 1913 48 128-131).-AppIying his reaction for the detection of bromine (A 1912 ii 989 and this vol. ii 333) the author has been unable t o find chlorides which do not contain bromides or clilorates or iodates free from bromates. From preliminary colorimetric deter- minations it is probable t h a t even the purest potassium chlorate contains bromate to t h s extent of one or two parts in ten thousand. This would be enough t o cause perceptible error in atomic weights involving an analysis of these substances.The Development of Avogadro’s Theory. CARL GRAERE (J. p r . Chem. 1913 [ii] 87 145-208).-Historical. The author traces the position and development of the above theory from the time of its advancement in 1811 until its general acceptance more than fifty years afterwards. F. B. W h a t are Bases and Acids? RICHARD MEYER ( J . pr. Chem. 1913 [ii] 87 250-286).-A criticism of Vorlander’s definitions (this vol. ii 130). R. V. S. F. B.ii. 314 ABSTRACTS OF CHEMICAL PAPERS. Gas Generator. FRANC SOUTHERDEN (Chenz. News 191 3 107 86).-The apparatus has been designed more especially for tho generation of hydrogen sulphide. The ferrous sulphide is contained in a tower fitted a t the top with a delivery tube and stop-cock; the constriction in the lower part of the tower contains a radially grooved plug so that a drainage chamber is formed underneath. The side-tube from this drainage chamber is connected with a side- tube opening into the upper part of tho acid reservoir with the result that the dense stale liquor tends t o sink in the reservoir as returned relatively fresh acid being available on restarting. T. S. P. A Reflux Condenser. S. W. WILEY (J. lnd. Eng. Chem. 1913 5 151).-The a.pparatus consists of tubes of block tin connected with bell-shaped condensers of spun copper. The bell is composed of two sections which are separated by a perforated partition. The bell is surrounded by cold water and condensation takes place on the upper surface of the bell. The condenser is very efficient and can be used for ether extractions. T. S. P. A New Form of Laboratory Extraction Apparatus. A. E. PERKIKS (J. Ind. Xng. Chem. 1913 5 148-149).-The xpparxtns consists essentially of an extraction flask with a long neck which is constricted a t the base. The flask is flabbottomed and has a diameter of 22 inches and a height of 2 inches to the base of the f F I G . 1 F I G . I 1 neck. The constriction is about half-an- inch in diameter as well as in height and the neck above the constriction is 12 inches long by 18 inches in diameter. A tube through which cold water flows fits into the upper part of the neck and acts as a condenser. The extraction thimble fits on to the constriction at the base of the neck. The apparatus is much simpler than t h e ordinary extraction apparatus and rapid and complete extractions can be carried out. T. S. P. A Modified Extraction Apparatus. G . IT. MACNIDER-(J. Ind. Eng. Chem. 1913 5 150-151).-The apparntm combines the best features of the Soxhlet and Knorr extractors a; small siphon extraction tube of the Soxhlet type fitting into a Knorr adapter. The principle is readily under- stood from the accompanying diagrams. T. 8. P. A Useful Valve. NATHAN SMITH (J. lnd. Eng. Chem. 1913. 5 235).-The valve is placed between the desiccator and the safety-bottleINORGANIC CHEMISTRY. i i . 315 when using a water-pump. A piece of glass tubing drawn out evenly at one end (the delivery tube of a pipette answers very well) is fitted with a piece of rubber which acts as a valve. A piece of wire is drawn through the centre of the rubber and then coiled into a spiral outside the tube so that the rubber is allowed some play but cannot be sucked back right up the tube. Another piece of glass tubing is then fitted over the valve tube by means of a collar of rubber tubing and connects with the desiccator. T. S. P. New Separating Funnel. C. €3. PARKER (J. An7er. Chewt. SOC. 1913 35 295-297).-1n order to overcome the difficulty due to the formation of persistent emulsions which are often produced when animal or vegetable extracts are shaken with immiscible solvents a special form of separating funnel has been devised. The separators are of flat shape and are held in a horizontal position during the extraction and in a vertical position when the contents are to be withdrawn. The advantage of this form is that the liquids are distributed in thin layers over a large area so that the con- tiguous surfaces are from eight to ten times as great as with the same amounts of liquid in separators of the ordinary kind. A gentle movement of the liquids in contact with one another can be effected by means of a nearly horizontal disk making 20 revolutions per minute. The separators lying on the rotating disk are tilted about gently in such a way that no actual mixing of the liquids takes place E. G.

ISSN:0368-1769    

DOI:10.1039/CA9130405261

出版商:RSC    

年代:1913

数据来源: RSC