摘要:

ii. 154 ABSTRACTS OF CHEMICAL. PAPERS. Nin er a1 ogieal Chemistry The Ultimate Composition of British Coals. THOMAS JAMES DRAKELEY [with FREDERICK WILLIAM SMITH] (T. 1922 Kasolite a New Radioactive Mineral. ALFRED SCHOEP (Compt. rend. 1921 173 1476-1477).-This occurs together with curite (this vol. ii 77) and torbemite a t Kasolo Katanga Belgian Congo. It forms compact crystalline aggregates with sometimes tufts and radiating groups of prismatic crystals on the The colour is ochre-yellow to brownish-yellow and the strea at- ochre-yellow. The crystals arc monocliiGc with the optic axial Nane perpendicular to the plane of symmetry and the acute bisectrix of the optic axes nearly perpendicular to a perfect cleav- age. dl' 5.962 H. 4-6. A4nalysis I is of translucent crystals showing no sign of alteration 11 of less fresh massive matel-ial and 111 of clear crystals 121 221-238).SiO,. PbO. UO,. H,O. Pe,O,. CaO. MgO. CO,. Total. I. 9.42 36.20 49-28 3.59 0.41 0.06 0.03 0.85 99'8.1 11. 9.14 34.44 49-00 3.77 0.58 - - 0.53 - 111. .9.00 32.16 ;48*2GZ 3.28 0.40 - - - IMINERALOGICAL CHEMISTRY. ii. 155 The simplest formula corresponding with the mean of these analyses is 3Pb0,3U0,,3Si0,,4H20. The mineral is decomposed by acids with the separation of gelatinous silica and of lead chloride or sulphate. Heated in the reducing flame on charcoal it fuses to a black glass with beads of lead. Its radioactivity is less than that of curite. L. J. S. WALDEMAR LINDGREN (Proc. Nat. Acad. Sci. U.S.A. 1921 7 249-251).- This occurs as bunches of black needles on a black shale from Minasragra Cerro de Pasco.The crystals are monoclinic with a perfect cleavage parallel to thc plane of symmetry. The streak is dark reddish-brown d1s 3.477 H. 2+. Only the thinnest splinters are brown and translucent under the microscope and the optical characters are masked by the strong absorption. Analysis by L. F. HAMILTON gives the formula 2Ca0,3V2Q,,2V,04. Melanovanadite a New Mineral from Peru. V,O,. V,O,. CaO. MgO. AI2O3,Fe2O3. SiO,. Total. 52.61 33.34 9-89 0.27 1-89 1-66 99.66 Before the blowpipe the mineral readily fuses to a brown liquid. It is readily soluble in acids giving an apple-green solution and in potassium hydroxide with a brown colour. A. F. BUDDINGTON (Amer. J. Sci. 1922 [v] 3 35-87).-To test Schaller’s hypothesis regarding the composition of the melilite group of minerals com- prising akermanite gehlenite hurnboldtilite sarcolite fuggerite and other varieties (A.1916 ii 632) more than one hundred synthetic crystalline mixtures of 2Ca0,Mg0,2Si02 (akermanite) 2Ca0,A1,0,,Si02 (gehlenite) and 3R’0,R,Q,,3Si02 (R’ =Ca or Na R=Fr or Al) were prepared from appropriate glasses a t tem- peratures above 1000”. The quenching method was used (cf. Ferguson and Buddington A. 1920 ii 621) and the glasses were crystallised by annealing a t a temperature just below the melting point or the dissociation point. The homogeneity optical char- acters and melting points were determined and the synthetic materials compared with the natural minerals. The gehlenite of Velardefia consists approximately of 76% of gehlenite 17% of akermanite and 7% of ferric and ferrous compounds and agrees very closely with artificial gehlenite having the same ratio of akermanite to gehlenite but free from iron cornpounds.Other natural gehlenites examined confirm the opinion that the artificial series of solid solutions of 2Ca0,MgQ,2SiQ2 and 2Ca0,A120Q,Si0 are pure synthetic analogues of the skermanite-gehlenite senes of minerals. Mixtures of akermanitle and gehlenite form a complete series of solid solutions with 3Ca0,A120,,3Si0 (grossularite) plus 10% of 3Na,0,A1,0,,3Xi02 except for a trace of inhomogeneity in some preparations high in akermanite. These mixtures when crystallised correspond in their properties with the humboldtilites which are interpreted as isomorphous mixtures of positive uniaxial akermanite and a negative uniaxial tetragonal moderately bire- fringent form of grossularite with minor amounts of gehlenite a L.J. S. Some Natural and Synthetic Melilites.ii. 156 ABSTRACTS OF CHEMICAL PAPERS. ferrous compound and 3R'Q,R2?,,3Si0 compounds. The com- positions of the humboldtilites he in a zone which exhibits the lowest temperatures of complete melting for the components involved. Artificial crystalline mixtures containing ferric iron (3Ca0,Fe20q,3Si0,) were found t o be quite different from the natural melilites of similar composition rich in ferric iron. The latter probably were formed at temperatures lower than those of the present experiments since some of them were found to decompose or invert at temperatures as low as 850". A new specimen of rnelilite rich in ferric iron from Capo di Bove differs in composition from any hitherto known. It contains SiO,. A1,0,. Fe,O,. FeO. MgO. CaO. Na,O. K20. Total. 40.03 5.66 7.76 0.4 9.43 32.17 2-83 1-72 100.0 The crystals have a tabular or pseudo-cubic habit and are intimately associated with nephclite and pyroxene. E. H. R.

ISSN:0368-1769    

DOI:10.1039/CA9222205154

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 156 ABSTRACTS OF CHEMICAL PAPERS. An a1 y t i cal Chemistry. The Graphical Representation of the Composition of Chemical Compounds. JULIUS I~UBSCMER (Chem. Ztg. 1922,46 19-20) .-The repeated calculation of the percentage of the various constituents of chemical compounds in mixtures can be avoided by calculating once and for all the percentage of the required constituent (for example anhydrous sodium carbonate in the decahydrate) and dividing a vertical line in these proportions. A square is then described with this line as its right-hand side and the points marked off joined to the left-hand top corner. From this co-ordinate system the weight of any Constituent corresponding with a given weight of any other constituent can be rapidly read off with sufficient accuracy for practical purposes.Should the given weights not lie between 0 and 100 they can be divided by a suitable factor and the corresponding weight read off the diagram and subsequently multiplied by the same factor. H. C. R. The Sensitiveness of Coloured Indicators at Temperatures above the Ordinary. I. M. KOLTHOFB (Rec. truv. chim. 1921 40 775-785 ; cf. Schoorl A. 1907 ii 388).-Indicators which are themselves weak acids are almost all as sensitive to hydrogen ions a t higher temperatures as a t ordinary temperatures. Those which are weak bases become less sensitive to hydrogen ions but retain the same sensitiveness to hydroxyl ions. Theoretical deduction of these facts is given in addition to experimental evidence. The suggestion is made that the results obtained may be of service in providing a colorimetric method of studying variations in dissocia-ANALYTICAL CHEMISTRY.ii. 157 tion constant and of hydrolysis constant with change of temperature and may also be of use in analytical work. H. J. E. Further Elaboration of the Indicator Method without Buffers. L. MICHAELIS and R. KRUGER (Biochem. Z. 1921 119 306-327) .-The salt error and temperature coefficient of m-nitro- phenol have been determined and a new one-colour indicator 2 5- dinitrophenol described. A theoretical and practical treatment of the effect on the PH of a solution of the addition of an indicator is given and instructions for the colorimetric estimation of PH in solutions weak in buffers for example sea and river waters. A discussion of the theory of the salt-error and of the activit)y theory of ions is also given.H. K. A Stable Single Buffer Solution p~ 1 to p~ 12. S. F. ACREE R. R. MELLON PAULINE M. AVERY and E. A. SLAGLE (J. Infect. Dis. 1921 29 7-1O).-The components of the buffer solution are (1) One mol. of potassium dihydrogen phosphate with dis- sociation constant K 1.1 x ; ( 2 ) 0.625 mol. of sodium formate K 2 x (3) 0.375 mol. of sodium acetate K 2 x 10-5; (4) the second group of dipotassium hydrogen phosphate K 2 x 10-7 ; (5) 1 mol. of sodium phenolsulphonate K 10-1O (approx.) ; (6) 0.005 mo1a.r thymol to saturation (for water 0-OS) K 0.5 x (approx.) ; (7) the third group of phosphoric acid K A curve is given from which the amounts of 0.5 molar hydrogen chloride or sodium hydroxide necessary to produce a given pH may be directly deter- mined.CHEMICAL ABSTRACTS. Colour Standards for the Colorimetric Measurement of Hydrogen-ion Concentration. LOUIS J. GILLESPIE (J. Bact. 1921 6 399405).-The recently published studies of Medalia are in disagreement with other published data (cf. ibid. 1920 5 441468). A colorimeter for two-coloured indicators is described for the measurement of the hydrogen-ion exponent of indicators. The optical assumptions underlying its use are practically the same as those on which ordinary colorimetry are based. The instrument is used as follows. The glass vessels A and C are fixed in position and B can be moved up and down the motion being measured by a pointer (not shown) fixed to B and moving on a scale divided into 100 parts. The pointer moves from 0 to 100 when B moves from contact with C to contact with A.The acidified indicator solution may be placed in B and the alkaline indicator solution of the same strength in C. A is left empty. If the scale reads 70 the path of light along the left dotted line passes through the alkaline form of the indicator for 10% of its path and the acid form for 30%. The light along the right-hand dotted line traverses an indicator solution in tube E again of the same strength and over a path equal in length to the total path on the left. The ' ' I Cii. 158 ABSTRACTS OF CHEMICAL PAPERS. solution the pH of which is unknown is placed in tube E in which titrations may be made. A New Apparatus for Colorimetric Estimations. 0. MANNEBACH (Chem. Ztg. 1922 46 20).-The apparatus consists of a wooden box open a t the top the inside of which is painted black.Into this fits a glass vessel filled with water. The bottom of the box has a hole cut in it allowing light to come up through the glass vessel and below is a rotating frame carrying a dead- white porcelain plate. The solutions to be compared are placed in glass tubes 16 mm. in diameter and 300 mm. long which are placed in the glass vessel in a slanting position. The apparatus is suitable for the colorimetric estimation of carbon in iron. A Gas Receiver of Convenient and Practical Form for Sampling Expired Air for Analysis. CHARLES CLAUDE GUTHRIE ( J . Biol. Chem. 1921,48 373-378).-Whilst less efficient than the mercury receiver the apparatus described has the advantage of being inexpensive.Expired air after storage in it for some hours gave results on analysis with an error of about 1% for carbon dioxide a'nd considerably less for oxygen. Apparatus for Estimation of the Gases in Blood and Other Solutions. DONA~D D. VAN SLYHE (Proc. Nut. Acud. Sci. 1921 7 229-231).-Essentially a much simplified form of the apparatus described in A. 1917 ii 422 and this vol. ii 78. The upper part of a large pipette (for instance 50 c.c.) ends in a tap funnel. The stem above the wide portion has a mark indicating a definite volume u from there to the tap (for instance 2 c.c.) and below the wide portion another mark indicating a volume A (for instance 50 c.c.) from it to the tap. The pipette is joined below to a tube of 800 mm. connected with an open manometer and through a tap with a mercury reservoir.A definite volume of solution (for instance 1 C.C. of blood) is sucked in through the tap funnel and then the necessary reagent (for instance acid for a carbonate solution) making a total solution of X C.C. (for instance 2.5 c.c.) and the mercury is allowed to fall to the lower mark. The lower tap is closed and the pipette is shaken for one to two minutes to establish equilibrium. Mercury is then let in through the lower tap until the gas volume is a C.C. and the pressure is read (m mm.). The zero point is then determined by expelling the gases or after absorbing one or more of them by introducing small measured volumes of gas-free absorbent solutions. The pressure is then lowered until the space above the solution is again u C.C.and read (n mm.). The volume at N.T.P. of the gas given off is V=u(m-n)/760 . (273/T+Xa/(A -X)). The term Scc/(A-S) in which cc is the volume of the gas dissolved in 1 C.C. of the solution at N.T.P. corrects for the portion of the gas remaining dissolved when equilibrium is reached. It is negligible for oxygen and nitrogen but not for carbon dioxide. The solubility of the latter gas also imposes an empirical correction for reabsorption of the gas while undergoing reduction from 50-8 to a C.C. With X=50 C.C. a= 2 C.C. the factor is 1.020 that is 2% of the carbon dioxide is reabsorbed. CHEMICAL ABSTRACTS. H. C. R. E. S. G. B.ANALYTICAL CHEMISTRY. ii. i59 The Use of Mercuric Nitrate instead of Silver Nitrate in the Estimation of the Halogens.I. M. KOLTHOFF and ADA BAK (Chem. WeeEbZad 1922 19 14-16).-The method proposed by Voto6ek (A. 1918 ii 238 272 330) in which mercuric nitrate js used with sodium nitroprusside as indicator gives very accurate results for chlorides (and for bromides cyanides? and thiocyanates) if a correction is applied for the excess of mercuric salt necessary to produce a precipitate under given conditions of composition and volume of solution. Tables of corrections are given. Neither dilute acids nor the common metals (except copper cobalt nickel and cadmium) interfere. The method estimates accurately chlorides in conductivity water and gives good results for as little as 9 mg. of chlorine per litre; it is suitable for the estimation of chlorides in urine. s. I.L. Use of Perchloric Acid as an Aid to Digestion in the Kjeldahl Nitrogen Estimation. BRALNERD MEARS and ROBERT E. HUSSEY ( J . Ind. Eng. Chem. 1921 13 1054-1056).- I n the estimation of nitrogen in such substances as milk urine casein gelatin dried blood etc. by the Kjeldahl method the time required for the digestion with sulphuric acid is reduced to about twenty minutes if perchloric acid is added to the mixture. For each gram of sample 25 C.C. of sulphuric acid 1 gram of copper sulphate and 2 C.C. of 60% perchloric acid should be used but the presencc of an excess of perchloric acid causes loss of nitrogen. Micro-Kipp Apparatus for the Preparation of Air-free Carbon Dioxide for Use in the Micro-estimation of Nitrogen by Pregl's Method. A. SCHOELLER (2. angew. Chem.1921 34 586).-The apparatus consists of two small cylindrical bulbs one above the other; the upper one contains fused potassium- sodium carbonate and is provided with a tapped delivery tube whilst a side tube on the lower bulb connects with an upper acid reservoir. Estimation of Very Small Quantities of Arsenic in Silicate Rocks. 0. HACKL (Chem. Ztg. 1921 45 1169).-Ten grams of the finely-powdered sample are heated at 250" in a tube through which a current of dry carbon dioxide saturated with bromine vapour is passed; the outlet end of the tube is connected with a receiver containing 10 C.C. of dilute nitric acid and the receiver may be connected with a vessel containing sodium hydroxide solution to absorb the excess of bromine. The contents of the receiver are subsequently evaporated with the addition of a small quantity of sulphuric acid the residue is dissolved in water and the arsenic in this solution estimated by the Gutzeit method.w. P. s. The apparatus is made all in one piece. W. P. S. w. P. s. Method for Direct Estimation of Carbon Dioxide and Oxygen in the Berthelot Bomb and its Importance for the Metabolic Balanm of Herbivora. W. KLEIN and MtLau STEUBER (Biochm. Z. 1921 120 81-89).-An extension of theii. 160 ABSTRACTS OF CHEMICAL PAPERS. work of Zuntz and co-workers on the use of the Berthelot bomb calorimeter for the analysis of organic substances the main feature now introduced being the determination of the oxygen used by weighing. It may prove useful for the analysis of the metabolic excreta of herbivora. H.K. Micro-elementary Analysis by Pregl’s Method. A. SCHOELLER (2. angew. Chem. 1921 34 581-583).-A short review of the method with a detailed description of the apparatus used. w. P. s. Simplified Construction of the Metal Parts of the Apparatus used in Pregl’s Micro-analytical Method. A. SCHQELLER (2. angew. Chem. 1921,34 587).-Convenient methods of attaching the heating apparatus for the lead peroxide the micro-burner the drying chamber etc. to the stand are described the parts being provided with brass rods which fit into a boss on the stand. w. P. s. Solid Sodium Hydroxide as an Absorbent for Carbon Dioxide in Steel Analysis. G. L. KELLEY and E. W. EVERS (J. Ind. Eng. Chern. 1921,13 1052).-Powdered sodium hydroxide which will pass through a 5-mesh sieve but be retained on a 20-mesh sieve yields satisfactory results when used to absorb carbon dioxide in the estimation of carbon.w. P. s. The Separation of Silver from Mercurous Salts. I. M. KOLTHOFF (Pharm. Weekbkad 1921 58 1680-1683).-The treat- ment of the mixed chlorides precipitated in Group I with ammonia will not separate small quantities of silver from mercurous chloride. A better method is to treat the mixed chlorides after exhaustive washing with boiling water to remove lead with 2% potassium cyanide solution. Silver and mercuric cyanides dissolve in the reagent whilst black metallic mercury is precipitated. After filtering silver is again precipitated by means of hydrochloric acid; mercuric chloride remains in solution and may be detected after filtering by means of sodium sulphide.The test detects 0.05 mg. of silver in presence of 50 mg. of mercurous mercury and will also detect 0.5 part of mercury in presence of 100 parts of sj lver . s. I. L. The Titration of Zinc. E. MONASCH (Fham. WeekbZad 1921 58 1652-1656) .-The thiocyanate method of Kolthoff and van Dijk (ibid. 538) has been applied to the estimation of zinc in alloys. The potassium mercuric thiocyanate solution is prepared by dis- solving 23.7 grams of mercuric thiocyan.ate in a concentrated aqueous solution of 14.4 grams of potassinm fhiocyanate and is stable for many months. Compounds of all the common metals interfere but ferric and aluminium salts do not affect the reaction. Since the author uses aluminium in the separation of zinc from alloys the method is suitable for the estinlatians but iron salts must first be oxidised by means of peroxide.s. I. L.ANATAYTICAL CHEMISTRY ii. 161 Estimation of Minute Amounts of Lead in Water with Notes on certain Causes of Error. D. AVERY A. J. HEMING- WAY V. G. ANDERSON and T. A. READ (Proc. Austral. Inst. Min. Net. 1921 173-199).-By the following method it is possible to detect and estimate with considerable accuracy 1 part of lead in 100,000,000 parts of water. A known volume of the water is filtered and 2.5 to 5 litres of the filtrate are evaporated t o about 100 c.c. just neutralised with hydrochloric acid and 2 C.C. excess of acid are added the liquid is filtered and the filtrate cooled and made up to 250 C.C. Hydrogen sulphide is passed into the solution for one hour and after remaining over-night the pre- cipitate which is usually barely visible is collected and washed with cold water containing hydrogen sulphide in solution.Two portions of 2 C.C. of hot nitric acid (d 1-2) are then successively poured over the filter to dissolve the sulphides and the filter is washed with hot water. The filtrate is evaporated with 1 C.C. of sulphuric acid until the latter fumes strongly and the liquid after cooling is treated with 20 C.C. of cold water and 10 C.C. of absolute alcohol and the mixture set aside over-night. The precipitated lead sulphate is collected and washed with a mixture of 65 vols. of water 32 vols. of absolute alcohol and 3 vols. of sulphuric acid. It is dissolved off the paper by dropping succes- sively two portions of 5 C.C.of hot 33% ammonium acetate solution round the edges and then washing the paper thoroughly with hot water. The solution is transferred to a 50 C.C. Nessler tube and treated with 1 C.C. of 10% potassium cyanide solution 1 C.C. of ammonia solution and six drops of freshly-prepared ammonium sulphide solution. Into the standard tube are placed the same reagents in the same quantities ; the liquid which must be absolutely colourless is diluted to 45 c.c. and a standard solution of lead acetate (1 c.c.=0~00001 gram of lead) is added until the tint matches that of the assay. If more than 8 C.C. of the standard are required a proportionately smaller quantity of the sample should be used. To estimate the lead in the sediment it is evaporated to dryness with hydrochloric acid the residue is taken up with 2 C.C.of the same acid t'he solution filtered and the assay finished in a similar way to that of the water. The estimation of lead in urine is carried out by evaporating 1 litre of the sample with 50 C.C. of nitric acid to dryness first on a water-bath then on the hot-plate. The dish is then placed in a cool electrically heated muffle and gradually heated to 450-500" to destroy organic matter and nitrates. The residue is dissolved in water the liquid just neutralised with hydrochloric acid 2 C.C. more acid are added and the solution is filtered. The filtrate is treated for lead as described above. All the materials used in the above work should be re&stilled from lead-free glass apparatus the ammonium acetate should be made by neutralising freshly distilled ammonia with acetic acid and the ammonium sulphide must be made immediately before use.All filter-papers before use must be washed with hot dilute hydrochloric acid hot ammonium acetate solution and hot wafer VOL. CXXII. ii. 6ii. 162 ABSTRACTS OF CHEMICAL PAPERS. successively to remove the minute amounts of lead introduced by the acid washing process of rendering them ashless. A blank test must be made using the same quantity of redistilled water as that used for the assay and putting it through the whole of the operations A. R. P. New Method €or the Volumetric Estimation of Copper. S. MINOVICI and AL. IONESCU (Bul. Xoc. Chim. Rodnia 1921 3 89-93).-The salt CuS0,,4NH3 is quite stable a t the ordinary tem- perature and is quantitatively precipitated from aqueous solution by addition of eight volumes of 98% alcohol.The precipitate after thorough washing with alcohol is redissolved in water and titrated with N/lO-sulphuric or oxalic acid with methyl-red as indicator. J. K. Rapid Estimation of Mercury in Ores. ALFRED HEMZEL- MA" (Chem. Ztg. 1921 45 1226--1227).-The author has made comparative tests on the estimation of mercury in ores using a modification of Whitton's method (U.X. Bureau of Mines Bull. 78 1918) which consists in heating the ore with a mixture of 3 grams of fine iron filings and 3 grams of good lime and collecting the mercury on a cooled silver plate previously weighed and his own method (A 1921 ii 521) and finds that both methods give equally satisfactory results.[Cf. J. 8oc. Chem. Ind. 1922 6 1 ~ . ] A. R. P. The Analysis of Aluminium Alloys. H. MENDE (Chem. Ztg. 1922,46 49-50).-0ne gram of the alloy is heated with 5 C.C. of water and 12 C.C. of strong potassium hydroxide solution (the latter added gradually) on a water-bath until nothing further dissolves. The liquid is diluted with water the clear liquor decanted through a small filter-paper and the precipitate washed by decanta- tion first with dilute potassium hydroxide solution then with hot water. The filter-paper is burnt in a platinum spiral the ash added t o the metallic residue in the beaker and the whole dissolved in 5 C.C. of strong nitric acid and 15 C.C. of water; 75 c.c of water are added the liquid is boiled and the precipitate collected washed ignited and weighed as tin dioxide.It should be tested for traces of silica. The filtrate is evaporated with 5 C.C. of sulphuric acid until the latter fumes strongly the mass is treated with 150 C.C. of water and the precipitated lead sulphate estimated in the usual way. The filtrate is electrolysed with a current of 0.5 ampere a t 2.0-2.2 volts for one and a half hours a t 75" using a spiral anode and a gauze cathode. The gain in weight of the latter represents copper. The solution is neutralised with sodium hydr- oxide after adding any zinc found by treating the potassium hydroxide solution of the alloy with sodium sulphide and 50 C.C. of a 50% solution of sodium hydroxide are added in excess. The solution is again electrolysed using the same anode and cathode (the latter being coppered or silvered) for two to three hours a t 70° using a current of 1-1-5 amperes a t 4 volts.The gain in weight of the cathode represents zinc. Silicon is estimated in a separateANALYTICAL CHEMISTRY. ii. 163 trial in which 3 grams of the alloy are evaporated with 50 C.C. of a mixture of 2 parts of sulphuric acid 3 parts of hydrochloric acid 1 part of nitric acid and 4 parts of water. After the metal has dissolved the solution is evaporated with 30 C.C. of strong sulphuric acid until the latter fumes strongly the liquid is treated with 300 C.C. of water and the silica which separates in an easily filter- able flocculent form is collected washed ignited and weighed as usual. Iron is determined by treating 3 grams of the alloy in potassium hydroxide solution collecting the insoluble residue and dissolving it after thorough washing in nitric acid.The solution is evaporated to dryness the nitric acid destroyed by evaporation with hydrochloric acid the copper and heavy metals are removed by hydrogen sulphide the iron is precipitated from the oxidised solution by ammonia redissolved in acid reprecipitated as before and the final precipitate either weighed as Pe,O after ignition or dissolved in sulphuric acid reduced and titrated in the usual way. For the estimation of traces of iron in pure aluminium 3 grams of the metal are heated with 50 C.C. of strong potassium hydroxide solution 200 C.C. of 50% sulphuric acid are added the solution is heated until everything has dissolved then quickly cooled and titrated with N/10-potassium permanganate.Copper and silicon are estimated as described above for alloys. Germanium. 11. Identification of Germanium by its 'Visible Arc Spectrum. JACOB PAPISH (Chem. News 1922 124 3).-Photographs of the arc spectrum of germanium were obtained by means of a Hilger constant deviation spectrograph fitted with a flint glass prism (n,=1.7537) the arc being made between carbon electrodes the lower positive one carrying the material to be tested. Under these conditions the little-known germanium line in the blue X 4686 is very sharp and intense and very suitable for the identification of the metal. The line overlaps the prominent zirconium line of wave-length 4688. A. R. P. G. F. M. The Carrying Down of Calcium Oxide by Precipitates of Ferric Oxide. A.CHARRIOU (Compt. r e d 1921 173 1360- 1362 ; cf. Toporescu A. 1920 ii 450).-In order to get the minimum co-precipitation of calcium hydroxide with ferric hydroxide the concentration of the calcium salt should be as small as possible and the minimum amount of ammonium hydroxide requisite for the precipitation of the ferric hydroxide should be used. Estimation of Nickel in Steels. H. RUBBICIUS (Chem. Ztg. 1922 46 26).-From 2 to 5 grams of the borings are dissolved in 40-80 C.C. of nitric acid (d 1*2) and the solution is cooled and treated with 250 C.C. of ammonia (d 0.91). It is transferred to a graduated flask and diluted t o 500 C.C. of which 250 C.C. are filtered through a dry paper diluted to 500 c.c. slid the solution heated at 40° is treated with 20-30 C.C.of a 1% alcoholic solution of dimethylglyoxime. After half an hour the precipitate is atered W. G. 6-2ii. 164 ABSTRACTS 0%' CHEMICAL PAPERS. on a 15 cm. paper washed with hot water dried and ignited to nickelous oxide in a platinum crucible and weighed. 0.7858~ NiO=Ni. A. R. P. Estimation of Chromium in Ferrochromium by Electro- metric Titration. G. L. KELLEY and J. A. WILEY ( J . Ind. Eng. C'hem. 1921,13 1053-1054).-Twenty grams of sodium carbonate are fused in a nickel crucible and then cooled the crucible being rotated during the cooling so that the carbonate forms a lining. A mixture of 16 grams of sodium peroxide and L gram of the sample is then fused for three minutes in this crucible the heat being so regulated that the sodium carbonate lining is not fused; when cold the contents of the crucible are dissolved in 300 C.C.of water the solution is boiled for thirty minutes cooled 80 C.C. of sulphuric acid (d 1-58> are added the solution is boiled for a further five minutes cooled filtered and the filtrate diluted to 1 litre. One hundred C.C. of this solution are treated with 25 C.C. of sulphuric acid and titrated with ferrous ammonium sdpliate solution using the apparatus described previously by the authors and Adams Tungsten. HERBERT LAVERS (Proc. Austral. Inst.Min. Met. 1921 101-152).-The paper contains a short description of the chemistry and metallurgy of tungsten together with a summary of the various processes that have been described for the estimation of tungsten in low grade ores.A volumetric method is recommended in which the tungsten is precipitated with cinchonine hydrochloride from acid solutions and the precipitate dissolved in ammonium acetate an excess of lead acetate added and the excess determmed by titration with ammonium molybdate. [Cf. J. Xoc. Chem. Ind. 1922 Feb.] A. R. P. Estimation of Thorium in Monazite Sand by an Emanation Method. HOMER H. HELMICK ( J . ,4nzer. Chem. Soc. 1921 43 2003-2014).-A method of estimating thorium in monazite sand is described. The sample is sieved through a 40 per cm. mesh and dried a t 115-120". Two grams are well mixed with 5 grams of potassium hydrogen fluoride and 5 grams of anhydrous recently fused metaphosphoric acid and slowly brought to the highest temperature obtainable with a MBker burner in a 35 C.C.platinum crucible. A further 5 grams of metaphosphoric acid are slowly added during the heating; when the mass is clear it is allowed to cool. After cooling 20 C.C. of 80% orthophosphoric acid are added and the crucible is heated in an air-bath a t 250-255" for three hours the solution being automatically stirred mth a platinum wire; in this way a viscous solution is obtained. A small vessel made of glass and fitted with a ground stopper and inlet and outlet tubes is suspended in a vessel of concentrated sulphuric acid a t 190-200" and the liquid from the crucible poured in. The solution vessel is removed from the acid allowed to COO& and the remaining contents of the crucible are washed in with two quantities of 20 C.C. of water the total volume made up to 75 c.C.(A 1917 ii 512). w. P. s.ANALYTICAL CIIEMISTRY. ii. 165 and the vessel closed in an air-tight manner. The electroscope measurements are made (i) with a blank prepared in exactly the same way as the sample except that the monazite is omitted (ii) with a standard solution containing a known amount of thorium and (iii) with the sample solution The percentage of thorium is calculated by means of the expression X=ATs( Tb- Tu)/Ts(T~- T,) in which X is the percentage of thorium in the sample A the percentage in the standard T the time of discharge of the electro- scope by the standard TI by the blank and T by the sample under investigation. The main sources of error of Cartledge's emanation method (A. 1919 ii 120) were adsorption of thorium X by suspended matter in final solutions by filters and by the walls of the vessels used.These errors are avoided in the present method by producing a complete solution of the sand without filtration and in a single vessel. Other improvements made use of are a highly efficient form of vessel to contain the solution during de-emanation; t'he use of an automatic regulator to main- tain constant pressure in the ionisation chamber during measure- ments; maintenance of optimum pressure gradient along the air current line through the measuring apparatus thus assuring a minimum error on account of pressure variations and maximum speed of measurement; protection of the insulation of the electro- scope by means of a current of dry air. Analyses by this method gave results agreeing very well with results obtained by gravi- metric methods and required much less time for each determination.J. F. S. Detection of Bismuth in Urine. PIERRE AUBRY ( J . Pharm. C'him. 1922 [vii] 25 15-18).-Following the administration of bismuth salts the metal is a t least to some extent eliminated in the urine. In certain cases i t manifested its presence as a black precipitate of bismuth sulphide but in other cases no precipitation occurred and the metal was detected by evaporating to dryness calcining the residue dissolving the ash in hot dilute nitric acid and adding a reagent containing lo/ of quinine sulphate and 2./ of potassium iodide dissolved in slightly acidified water which produces an orange-red coloration or precipitate according to the amount of bismuth present.This reagent is sufficiently sensitive to detect 1 part of Bi,03 in 600000 parts of water. Estimation of Alcohols by Acetylation. H. WOLFF (Chew. Umscbu 1922 29 2-3).-The acetylation is carried out by weighing out 0.5 gram of the sample in a test-tube 0.6-0.8 cm. wide and 10 em. .long. One C.C. of acetic anhydride is added and the tube sealed the lower end being kept in cold water the while. The tube is heated for one hour in a boiling water-bath removed and allowed to cool. It is then placed in a well-stoppered thick- walled flask and broken by vigorous shaking. The stopper is bound on and the flask heated at about 50" for half an hour on the water- bath with constant shaking cooled and neutralised to phenolphthalein. Twenty-five C.C. of N/2-alcoholic potash are G.I?. M.ii. 166 ABSTRACTS OF CHEMICAL PAPERS. added and enough alcohol to make a clear solution. The flask is either left over-night or warmed for a quarter to half an hour at 50-60” cooled and titrated back with Nle-acid. The results obtained are within less than 1% of the theoretical. Solvents such as light petroleum or benzene have no effect on the result. If esters are present their saponification value must be allowed for. H. C. R. New Methods of Blood Sugar Estimation. Estimation of the True Sugar Content of Urine. D. G. COHEN-TERVAERT (Nederl. Tijdschr. v. Geneesk. 1921 65 ii 857-864 3065-3069).- I. The methods of Schaffer and Hartmann (A. 1921 ii 417) Folin and Wu (A. 1919 ii 308) and of Ponder and Howie (A.1921 ii 417) deserve full recommendation. The first-named has been worked out for 0-1-0-2 C.C. of blood. 11. Sumner’s method (A 1921 ii 564) has been compared with a fermentation method due to Nagasaki (Nederl. Tijdschr. *v. Geneesk. 1915 ii 1478) and found to be very accurate. A few small modifications were introduced. A Source of Error in Testing Urine for Dextrose with o-Nitrophenylpropiolic Acid. GEORGES RODILLON ( J . Pharm. Chirn. 1922,25 56-57).-Dextrose is not the only reducing agent likely to be found in urine which will reduce o-nitrophenylpropiolic acid to indigotin. The presence of hydrogen sulphide will both show this reaction and give a positive result in the sodium nitro- prusside reaction for acetone. It does not reduce Fehling’s solution. If the tests are carried out after clarifying the sample with lead acetate these misleading results are avoided. The Identification of Laevulose in Presence of Aldoses.I. M. KOLTHOFF (Chem. Weekblad 1922 19 1-2).-To 2 C.C. of the 1% sugar solution are added in succession 4 C.C. of N/lO-iodine solution and 5 C.C. of 2N-sodium hydroxide. This order of addition must not be reversed. The mixture after shaking is left for one to one and a half hours and the excess of iodine removed by addition of a few drops of N-thiosulphate. Two C.C. of Fehling’s solution No. I1 and 2 C.C. of Fehling’s solution No. I are added the tube is shaken and warmed in a boiling water-bath for not more than five minutes. A red coloration in one minute shows 5% fructose in presence of glucose; in two minutes 2*% and in four minutes 1% of fructose.After five minutes glucose alone gives the red colour. The test detects 0.2 mg. of Iavulose in presence of 10 mg. of Estimation of Sugar by Titration with Alkali of the Cuprous Oxide Precipitated from Fehling’s Solution. A. HANAK (Z. Unters. Nahr. Genussm. 1921 42 248-250).-The cuprous oxide obtained from the inverted sugar solution containing not more than 0.5% of invert-sugar and 50 C.C. of Fehling’s solution is washed dissolved in aqua regia diluted to 250-300 C.C. with water free from carbon dioxide and carefully neutralised with G. B. H. C. R. dextrose 10 mg. of sucrose and 10 mg. of lactose. s. I. L.ANALYTICAL CHEMISTRY. ii. 167 sodium hydroxide so that it gives a pale greenish-yellow colour with methyl-orange.Phenolphthalein is added and &/2-sodium hydroxide run in until the red colour remains for three minutes in the boiling solution. One C.C. of 3712-sodium hydroxide= 0-0159 gram of copper. Detection of Traces of Lactose in Urine by Formation of Formaldehyde. KURT HERZBERG (Biochem. Z. 1921 119 81-92).-The injection of lactose for testing the functioning capacity of the kidney necessitates a ready method for its recog- nition in urine. Concentrations of 0.2% can be recognised by isolation of the osazone oxidation of the latter with permanganate to formaldehyde which can be detected by a colour test for example the reaction with peptone and ferric chloride. VLAD. ST AN^ (2. Zuckerind. Cechoslov. 1921 45 4 1 7 4 2 3 ; 425431).-After correction for water ash invert-sugar error of the polarimeter etc. a normal solution of sucrose (recrystallised) polarised 99.9" Ventzke using a dichromate filter or 100*1" Ventzke when a filter was not used.Use of Invertase for Sucrose Estimation. T. SWA" HARDING (Sugar 1921 23 546-547) .-Errors in acid hydrolysis of sucrose by the Clerget method include the hydrolysis of other sugm present and the effect of the acidity on optical non-sugars. Using invertase no effect is found on compounds present other than sucrose. Invertase can be obtained of sufficient strength to invert a loo/ sucrose solution in two hours. The activity of invertase may be retained for a year and a half. H. C. R. H. K. Polarisation of Normal Sucrose Solution. w. P. s. CHEMICAL ABSTRACTS. Detection of Fatty Acids by the Formation of their Sodium Uranyl salts.J. BARLOT and (MLLE) M. T. BRENET (Cmpt. rend. 1922 174 114-11G).-Strengys reaction for the micro- chemical detection of sodium (cf. Ber. oberhess. Ges. Nut. Heilkunde 1883 22) based on the formation of a characteristic crystalline precipitate of sodium uranyl acetate with uranyl acetate in the presence of acetic acid gives positive results if acetic acid IS replaced by its homologues in which there is an even number of carbon atoms in the straight chain. In the case of derivatives of acetic acid the reaction depends on the nature of the substituent. The chloroacetic acids do not give the reaction but sodium phenyl- acetate and uranyl nitrate give a t once crystals of the double salt CH$'h-CO,Na,( CH,Ph*CO,),UO,.W. G. [Estimation of Arachidic Acid.] J. PRITZKER and R. JUNG- KUNZ (2. Unters. Nahr. Genussm. 1921 42 232-241).-See this vol. i 208. * rapid Method for Determining the Acetyl Value of Oils and Fats- ALEXANDRE LEYS ( J . Pharm. Chim. 1922 25 49- 66).-The following values are determined the saponificationii. 168 ABSTRACTS OF CHEMICAL PAPERS. value S of the oil or fat the saponification value S' of the acebylated oil or fat and the ratio K between the weight of the acetylated matter and that of the oil or fat from which it has been prepared. The acetyl value A is given by L4=X'-X/K. To determine K a weighed quantity of the oil or fat is boiled with ten times its volume of acetic anhydride under a reflux condenser for two hours cooled diluted with benzene and transferred to a tared dish.The benzene and excess of acetic anhydride are evaporated on a water-bath and the acetylated oil or fat is weighed. The acetyl value of an oil or f a t dissolved in a neutral solvent having no acetgl value may be obtained without evaporating off the solvent as follows. One weighed portion (1'') of the mixture is acetylated and the excess of acetic anhydride removed as above. The saponification value X' of this is then obtained. A further portion is saponified without acetylating giving a saponification value S. S'-S=A represents the quantity of potassium hydroxide required to neutralise the acetic acid which has combined with 1 gram of the mixture. This has increased its weight by 42 x A,/56=0*75 A,. Therefore P' grams of fat has become P"=Pf(1+0*75 A,) grams of acetylated fat.A saponification value S" can therefore be calculated based on the weight of acetylated oil or fat. The acetyl value A=X"-X/K. H. C. R. Detection of Vegetable Oils in Animal Fats. The Phyto- steryl Acetate Test. C. F. MUTTELET (Ann. Palsif. 1921 14 327-333) .-The cholesteryl acetate obtained from butter lard or beef fat (by treating the fatty acids a t 70" with alcoholic digitonin solution collecting the precipitated compound con- verting i t into the acetate and recrystallising the latter twice from alcohol) has m. p. 114.0" to 114.3" whilst the phytosteryl acetate obtained in a similar way from coconut oil or earthnut (arachis) oil has m. p. 124.5" to 126.5". This method will detect the presence Presence and Estimation in the Total Lipoid Ether- soluble Phosphorus of Phosphorus Compounds other than Phosphatides.(MLLE) ELIANE LE BRETON (Bull. SOC. China. Biol. 1921 3 539-546).-The ordinary indirect method of estimating lecithins as ether-soluble phosphorus is subject to an error unless the material is purified by precipitation with acetone according to MacLean (A. 1914 i 1197). About 20% of impurities remain in the acetone which contains free and combined glycerol as well as phosphorus. These impurities are not formed by hydrolysis of lecithin during extraction. Titrimetric and Spectrometric Analysis of Keto-Enol Mixtures. KARL VON AUWERS and HELENE JACOBSEN (Annulen 1922 426 161-336).-The general plan of the series of researches of which this paper forms a part has already been fully described (A.1915 ii 381) and it is now shown that by following the method of computation previously indicated spectrochemical data may be employed to estimate with moderate certainty the proportion of 10% of vegetable oil in an animal fat. w. P. s. G . B.ANALYTICAL CHEMISTRY. ii. 10'3 of end in a keto-enol mixture. It is true that the metliod breaks down in certain cases owing to the difficulty of estimating the optical constants for one or other of the pure constituents; K. H. Meyer's titration method also gives somewhat uncertain values in particular cases. However when the indications of both methods are definite they are in remarkably good agreement. The percentages represent t'he enol-content estimated spectrochemically whilst the figures in brackets are the values determined by titration with bromine ethyl acetylmalonate 70% (69) ; ethyl propionyl- malonate 43% (44) ; ethyl n-butyrylmalonate 557/ (55) ; ethyl isobutyrylmalonate 47 yo (47) ; ethyl isovnlerylmalonate 57 yo (55) ; ethyl hydroxymethylenemalonate 100 yo (94) ; ethyl hydroxymethylene-ethyl ketone ?yo (< 100) ; hydroxymethyl- enecyclohexanone assumed 100 yo (100) ; 3-methyl-6-hydroxy- methylenecyclohexanone < 100% (91 yo) ; 3 4-dimethyl-6-hydroxy- methylenecyclohexanone '1 yo (89) ; hydroxymethylenementhone 2% (97) ; acetylacetone 82% (84) ; propionylacetone 76% (72) ; methylacetylacetone 33% (36) ; ethylacetylacetone 31 yo (29) ; propylacetylacetone 31 yo (32) ; benzoylacetone 100% (100) ; propionylacetophenone 93 % (94) ; butyrylacetophenone 88 yo (90) ; isovalerylacetophenone 89% (85) ; methylbenzoylacetone 6% (9) ; methyl benzoylacetate 20% (19) ; ethyl benzoylacetate 24% (21) ; ethyl a-benzoyl-n-butyrate 2% (4).Colour Reactions of Phenacetin and Acetanilide. L. EKKERT (Pharm. 2entr.-h. 1921 62 735-737).-Under definite conditions phenacetin and acetanilide give different colorations when hydrolysed with sulphuric acid and then oxidised with potassium dichromate. If 0.1 gram of phenacetin is boiled for one minute with 5 C.C. of 10% sulphuric acid the solution then cooled diluted to 6 c.c. and treated with 2 drops of l:l0 potassium dichromate solution a violet-red or red coloration is obtained. Acetanilide under similar treatment but when boiled for two minutes yields gradually a greenish-blue coloration.The following substances have been examined. C. K. I. W. P. S. Alkalimetric Estimation of Amino-acids and Peptides. RICHARD WILLSTATTER and ERNST WALDSCHMIDT-LEITZ (Ber. 1921 54 [B] 2988-2993).-The acid of ammonium salts can be estimated alkalimetrically with phenolphthalein as indicator if the aqueous solution of the salt is mixed with a sufficient amount of alcohol since ammonia does not affect the indicator in alcoholic solution. It is essential that the solution should contain about 9776 of alcohol and that relatively much indicator should be used. Amino-acids and polypeptides show a similar behaviour. Character- istic differences are shown however in the concentration of the alcohol which is necessary for the elimination of the action of the amino-groups or of hydroxyl ions. The polypeptides peptones and proteins behave in the same manner as the ordinary carboxylic acids in solutions co,ntaining 40 yo of alcohol whereas amino-acids of the aliphatic series or of aliphatic character require an alcoholicii 170 ABSTRACTS OF OHEMLCBL PAPERS.concentration of about 97% to produce this effect. Ethyl alcohol can be replaced by propyl alcohol which appears to be even more effective but not by methyl alcohol. The behaviour enables amino- acids and polypeptides to be estimated simply in mixtures of the substances by titrating with alkali hydroxide solution to neutrality towards phenolphthalein in 50% and 97% alcoholic solution. If a and b are the volumes of alkali solution used the proportion X required by the amino-acids (since the majority of the latter and in any case those which predominate in the general mixtures neutralise in 50% alcoholic solution 28% of the amount required for complete neutralisation) is 100(b-a) /72 and the proportion used by the polypeptides is b - x .Estimation ‘of Urea. F. MEZGER (Phurm. 2entr.-h. 1921 62 719-721).-A simple gasometric method is described. One C.C. of the urine is placed in a small tube and this in turn is placed in a reaction bottle containing 30 C.C. of hypobromite solution and connected with the top of a burette; the latter is filled with water to the zero point by means of a levelling reservoir and serves as a measuring vessel for the nitrogen evolved when the urine and hypobromite solution are mixed. A definite volume (for example 1 c.c.) of 2% urea solution is treated in the same way and a t the same time in an exactly similar apparatus. This is taken as the standard and the amount of urea in the urine is calculated from the ratio of the two volumes of nitrogen obtained.H. W. W. P. S. Quantitative Gravirnetric Micro-analysis of Urea. Appli- cation to the Estimation of Urea in 1 C.C. of Blood. MAURICE NICLOUX and GEORGES WELTER (Cmpt. rend. 1921 173 1490-1493).-The use of Fossc’s xanthydrol reagent (cf. A. 1914 i 859; ii 506) is combined with Pregl’s micro-methods of analysis (cf . Die quantitative organische Milcroanulyse Berlin 1917). To 1 C.C. of solution containing not more than 0.2 mg. of urea are added 1 C.C. of glacial acetic acid and 0.2 C.C. of 5% xanthydrol solution in methyl alcohol.The mixture is stirred and after thirty minutes the precipitate is collected in a Neubauer micro- crucible and washed alternately with saturated solutions of xanthyl- carbamide in alcohol and water and finally with two drops of distilled water. The precipitate is dried at 105-110” and weighed on a micro-balance. For the estimation of urea in serum 1.0 C.C. or 0-5 C.C. is used. It is diluted with exactly five times its volume of water and a volume of Tanret’s reagent equal to the original volume of the serum is added. After five minutes the precipitate is filtered off and in 1 C.C. of the filtrate the urea is precipitated as above. The weight of xanthylcarbamide obtained is thus just equal to the weight of urea present in 1 C.C. of the original serum.W. G. Estimation of Uric Acid in Blood. CH. 0. GUILLAUM~N ( J . Pharm. Chim. 1922 [vii] 25 5-15).-The following modus operandi is recommended for the colorimetric estimation of uricANALYTICAL CHEMISTRY. ii. 171 acid in blood The blood or serum is first freed from albuminous substances by mixing 4 C.C. with 4 C.C. of lOyo sodium tungstate solution 28 C.C. of distilled water and 4 C.C. of 2*7y0 sulphuric acid shaking vigorously and filtering until a clear filtrate is ob- tained. For ordinary clinical work the uric acid may then be estimated directly in the filtrate by adding to 20 C.C. 1.5 C.C. of 40% solution of crystallised sodium carbonate 0.5 C.C. of the sodium phosphotungstate reagent and sufficient water to make 25 c.c.; and comparing in a colorimeter with a standard sulphite solution of uric acid prepared according to the directions of Folin and Wu (A.1919 ii 308). For a more exact estimation it is preferable to separate the uric acid from the dealbuminised blood by means of silver lactate as described by Folin (Zoc. cit.). This separation of the uric acid is however always necessary if working with a solution containing red corpuscles and by so doing it was demonstrated that blood usually contains a slightly lesser quantity of uric acid than serum. The author does not favour the dealbumin- isation of the blood by Grigaut’s method using 2074 trichloroacetic acid. G. P. M. Detection and Estimation of Morphine and Other Alkaloids in Animal Excreta and Organs. CURT WACHTEL (Biochem. Z. 1921 120 265-283).-Previous methods for the estimation of morphine in animal tissues are very laborious and time-con- suming.A new process is described which takes about one and a half days. Urine is submitted to a preliminary purification by basic lead acetate and the morphine in the lead-free filtrate pre- cipitated by phosphotungstic acid in weakly acid solution. The washed precipitate is decomposed in alkaline solution by sodium potassium tartrate and the morphine in solution oxidised to +-morphine by an excess of a standard solution of potassium ferri- cyanide. The excess of the latter is estimated iodometrically. When the morphine is present in tissues a preliminary extraction is made by means of acidified alcohol. The extract from brain and muscle in addition to purification by basic lead acetate has to be submitted to a further purification by boiling with copper sulphate the copper-free filtrate being then precipitated with phosphotungstic acid.The process is applicable to other alkaloids provided they are not adsorbed by the basic lead acetate precipitate. The Bliss Method for the Separation of Strychnine from Quinine. L. E. WARREN and A. H. CLARK ( J . Arner. Pharm. ASSOC. 1920 10 267-270; cf. A. 1920 ii 276).-The method is shown to be untrustworthy. The quinine fractions invariably contained strychnine. In most cases the strychnine fraction was comparatively free from quinine so that the method may have a qualitative value in detecting the presence of strychnine in mixtures. CHEMICAL ABSTRACTS. H. K. The Estimation of Proteins in Blood-a Micro-method.PAUL E. HOWE ( J . Biol. Chem. 1921 49 109-113).-The authorii. 172 ABSTRACTS OF CHEMICAL PAPERS. uses 0.5 C.C. of blood and the micro-Kjeldahl method. For the fibrinogen and non-protein nitrogen he follows the technique of Cullen and Van Slyke (A. 1920 ii 398). For the rest the method indicated in the following abstract. The Use of Sodium Sulphate as the Globulin Precipitant in the Estimation of Proteins in Blood. PAUL E. HOWE (J. Biol. Chem. 1921 49 93-107).-1n order to apply the Kjeldahl method more readily the author substitutes sodium sulphate for the ammonium salt. At 37" critical zones in the precipitation are observed when 13.5 17.4 and 21.5% of sodium sulphate are present in solution. These correspond respectively with the precipitation of euglobulin (as usually separated by carbon dioxide or saturated sodium chloride) and of that of two $-globulins I and 11. G. B. G. B. Reaction for Blood with Hydrogen Peroxide in statu nascendi. A. PATZAUER (Chem. Ztq 1921 6 1056).-A small quantity of magnesium peroxide is dissolved in very dilute acetic acid and when violent evolution of gas ceases guaiacum tincture or benzidinc dissolved in acetic acid is added followed by the ethereal extract of the blood. w. P. s. Measuring Soil Toxicity Acidity and Basicity. R. H. CARR ( J . I d . Eng. Chem. 1921 13 931-933).-The acidity or basicity of a soil and the amount of soluble iron and aluminium in the same may be estimated as follows 50 grams of the soil are shaken for two minutes with 30 C.C. of a saturated solution of potassium thiocyanate in 95% alcohol; if after settling the liquid has a red colour N/10-alcoholic potassium hydroxide solution is added until the colour disappears. Each C.C. of the alkali solution required is equivalent to 200 lbs. of calcium carbonate per acre. Should a red colour not appear on the addition of the thiocyanate the mixture is titrated with N/10-alcoholic hydro- chloric acid until a pink coloration is obtained. The relative amount of aluminium in solution is indicated by the depth of the blue colour produced when the thiocyanate extract of the soil is treated with a few drops of logwood tincture. Soluble iron and The Estimation of Tannin in Wines. aluminium salts seem to be toxic to plants. w. P. s. PHILIPPE MALVEZIN (Bull. SOC. china. 1921 [iv] 29 1087-1088; cf. A. 1912 ii 612).- A reply to Clarens (cf. A. 1921 ii 719). W. G.

ISSN:0368-1769    

DOI:10.1039/CA9222205156

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 173 General and Physical Chemistry. Visible Refraction and Dispersion in Aqueou Solutions of Salts particularly Coloured Salts. G. LIMANN (2. Physik 1921 8,13-19).-The refractive indices for the D Ha H and H lines have been measured for 0-3 0.5 1.0 2.0 and 4.ON solutions of ferrous chloride bromide and nitrate copper nitrate and chlorate ferric chloride manganous chloride bromide and nitrate ; nickel chloride bromide nitrate and chlorate cobalt chloride bromide nitrate and chlorate aluminium chloride and nitrate ; potassium chromate dichromate ferrocyanide and ferricyanide chromic chloride and bromide lithium sulphate chromate and dichromate magnesium chromate czesium bromide and nitrate glucinum chloride and nitrate mercuric chloride lead nitrate and sodium chromate. Two constants are deduced from the measure- ments by means of which the refraction of a solution may be calcu- lated if the equivalent conductivity for the particular concentration is known.The influence of temperature on the refraction and dispersion has been determined in the case of potassium bromide over the range 6-30'. The results show that the dispersion decreases markedly with decrease of temperature but the refraction is not much influenced. Thus over the measured range of temnera- ture the refraction changes only 1/1500 for a change"of lo. J. F. S. Eisenlohr 's Refractometric Constants. WOJCIECH SWIEKTO- SLAWSKI (Rocxniki Chemji 1921,1 104-115).-A theoretical paper in which the author attempts to prove the constancy of atomic refraction of the atoms of organic substances.An analysis of the experimental data leads the author to the conclusion that the method employed by Briihl and Eisenlohr is not a rational method. This method of determination of the atomic refraction based on the calculations of the mean value obtained from a large number of compounds only serves to cancel the individual differences of the compounds investigated. The author has used a different method. For the calculation of the atomic refractions he takes the molecular refractions of the eight compounds pentane isopentane hexane octane diisobutyl diisoamyl cyclohexane and cyclopentane and has calculated the most probable mean value of the refractivity of the group CH ( c ~ and that of hydrogen [H by the method of least squares the equations employed being of the type N=== n [ c ~ + 2 [ ~ + 8 A [ and M'~=n[c:c~,+xA[.In the solution of the equations it is assumed that the increment zlA%=O. The values thus obtained are compared with those of Eisenlohr <c= (2.418) 2.490 &= (1.100) 1.066 &H,= (4.618) 4.622 Eisenlohr's values being bracketed. The results show an agreement for the value of <cH* but a difference of about 3% for &. I n the case of compounds containing oxygen the equation MD=~&,+[~++A[ is used. The figures obtained show considerable deviations of the VOL. CXXII. ii. 7ii. 174 ABSTRACTS OF CHEMICAL PAPERS. value sac that is to say this increment cannot bc regarded as zero. Similar results are obtained for both alcohols and ethers. The agreement obtained on comparing the author’s value with those of Eisenlohr is explained by the dominant rcile of n&E and the insignificant influence of X& which corresponds with a residual refraction of the molecule in the equation ~ W D = ~ ( ~ E + X [ ~ + X A < .The author concludes that the methods employed by Briihl and Eisenlohr to determine the atomic refractivity mask the variability of this quantity and scarcely give any real knowledge of the refraction of the atoms. J. F. S. Molecular Coefficients of Refraction K. VON AUWERS and H. KOLLIGS (Ber. 1921 55 [B] 21-45).-h recent publica- tions Eisenlohr (A. 1920 ii 717; 1921 ii 1 229) has pointed out that the “ molecular coefficient of refraction ” N x n$ is more sensitive to constitutive changes than the generally employed molecular refraction and has calculated values for aliphatic benzenoid and polymethylene compounds ; this work is now exhaustively criticised.A protest is raised against Eisenlohr’s method of deriving cor- rected values. Thus in the case of the cyclohexane series he has assumed that the E values for the hydrocarbons may be derived from those of the corresponding analogously constituted alcohols and ketones by the deduction of 0.35. This rule is not fulfilled by 1 - methylcyclohexan-4- ol or 1 -met hylcyclohexan-4- one and the values for these substances have therefore been recalculated from the relationships that are supposed t o exist among position-isomeric cyclohexane derivatives. It is shown however that these re- calculated values lead to data for the refractive index which differ so widely from the experimental values that the latter could only have been obtained by the use of grossly impure material and that this assumption is devoid of experimental basis.The work on the benzenoid hydrocarbons has been examined in detail. In correcting the observed values for the refractive index to a temperature of Z O O Eisenlohr has preferred the factor 0.00065 or 0-00060 for each degree to the generally employed factor 0.00045. An exhaustive survey shows that this is generally unjustifiable. In the cases of benzene toluene and to a less extent of ethylbenzene the higher factor is to be preferred but in the cases of seventeen other hydrocarbons it is shown experi- mentally that the lower factor is in very close agreement with the observations.Since the bulk of Eisenlohr’s data for the constants of aromatic hydrocarbons are based on von Auwers’s observations which have been regarded as erroneous when they do not harmonise with the theory the values have been redetermined with more particular reference to m-ethyltoluene m-propyltloluene p-ethyl- toluene p -prop yltoluene and p-diethylbenzene. The previous specimens were obfained by the reduction of the corresponding ketones by Clemmensen’s method. The latter are prepared by the Friedel-Crafts method and also according to the scheme C,H,MeBr -+ C,H,Me*CHMe*OH -+ C,H,Me*COMe and theGENERAL AND PdiYSICAL CHEMISTRY. ii. 175 physical constants of the products obtairiecl ill either manner are found to be identical. The constants of the hydrocarbons obtained by their reduction are in good harmony with those observed previously.A second method of preparation consists in replacing the hydroxyl group of the carbinols CFH,Me*CIfR*OH by bromine and reduction of the bromides by sodium in the presence of moist ether ; the indices o€ refraction of these preparations are mostly lower than those of the first group practical identity being encoun- tered only with p-propyltoluene. Thirdly the Pittig synthesis is employed which gives specimens having refractive indices lower by 0-002-0.003 than those of the Clemmensen preparations. The discrepancies are far beyond the limits of experimental error. It appears impossible to decide which preparations have the greater claim to purity since on the one hand the Clemmensen products are generally obtained smoothly and in good yield whereas the “ Fittig ” specimens although isolated from more complex mixtures have constants which harmonise better with Eisenlohr’s rules. Examination of the new data obtained for the benzenoid hydro- carbons in accordance with Eisenlohr’s principles leads the author to the following conclusions. Ortho-derivatives can be easily recognised by the markedly higher refractive coefficient but this does not represent any advance since it has been shown previously that they me differentiated so sharply from their position isomerides by density refractive index and specific exaltation that any of these factors is alone suitable for this purpose.The older methods do not allow the distinction between meta- and para-compounds and in this respect Eisenlohr’s constant appears also to be useless; thus in the cases of m- and p-xylene the refractive indices do not differ by more than one part in a thousand parts and this position is not improved by multiplying them by their molecular weights.Position isomeric tri-derivatives are easily distinguished from one another by their different molecular refractive coefficients but this was easily possible previously. The relationships of sub- stances with four side chains cannot yet be elucidated. The molecular coefficient of refraction cannot replace the spectrochemical constants particularly the specific exaltation but can only serve as an amplification of them. If it is desired to assign a substance to a particular group or to elucidate the general character of a group of substances the most trustworthy data are to be derived from the specific exaltation since in this the influence of homology or position isomerism is but little noticeable. When on the other hand it is desired to elucidate questions of structure within a group of substances the molecular refractive coefficients are likely to be extremely valuable.Benzene n 1.50092. Toluene ~ ~ 2 9 ’ ~ 1.49653 nz 1.49647. Ethylbenzene ng 1.49606. Pro- pylbenzene n;; 1.49241. isoPropylbenzene ?? 1.49199. m-Xylene 12 1.49782. p-Xylene nf,”’ 1.49685 ng 1.49680. 1 -Methyl-2-ethyl- benzene n 1.50381. 1-Methyl-%propylbenzene nz 1049931. o-Cymene ng 1.501 ?GI 1.50188. p-Cymene (from camphor) ng’2 The following new data are recorded. 7-2h.176 ABSTRACTS OF CHEMlCAL PAPERS 1.48885 whence nz 1.48894 (from cymene-p-sulphonic acid) n;'' 1048942 whence n; 1.49222. p-Diethylbenzene ns 1,49671. $- Cumene n29'9 1.50527 whence n;; 1.50523. Mesitylene nz 1.49981. Prehnitol nz 1.51865. Ethyl-+cumene n$'75 1.51047 whence n$ 1.50556. 1 3 5-Methyl-2-eth.ylbenzene7 n$ 1.51167. m-Tolyl- methylcarbinol (from magnesium m-t'olyl bromide and acet- aldehyde) b. p. lW'jl2 mm. 1-.MethyZ-3-a-bromoethyZbenxene C,H,Me*C.H&Me a colourless liquid b. p. 101°/12 mm. (Py-Di- m-tolylbutane CsH4Me*CHMe*C,HMe*C,H,Me crystallises in slender lustrous needles m. p. 97".) 1-Methyl-%ethylbenzene (from m- methylacetophenone by Clemmensen's method) b. p. 159.7-160.5°7 0.8669 d;O 0.867 n2'9 1.49575 n:'g 1.49966 nF'9 1.51102 ny'9 162056 ; (from l-methyl-3-cr-bromoet~hylbenzene) b.p. 159" dig'8 043622 dj0 0.862 n2.Y 1.49279 n1,9'8 1.49650 nF'a 1.50767 n;" 1.51678. p-Tolylmethylcarbinol b. p. 108112 mm. is oxidised to p-methylacetophenone b. p. 105-106"/13 mm. di8'4 1.0045 d? 1.003 n;.' 1.52880 n1,8'J 1.53391 1.54835 ny'4 1.56127 ng 1.5332 which is identical with a product prepared by the Friedel- Crafts reaction. 1 - Methyl-4- 01- bromoethylbenxene a colourless liquid b. p. 105-106'/I2 mm. 1-Methyl-4-ethylbenzene (from p-methyl- acetophenone by Clemaensen's metlhod) b. p. 160.5' n::.5 1.49424 nz 1.49490 ; from the Friedel-Crafts ketone) b. p. 161' d:6'8 043650 whence d:"'9 0.8657 d;O 0.862 n2'g 1.49372 ng.g 1.49775 nr.9 1.50889 n;" 1.51833 ; (from l-methyl-4-a-bromoet~hylbenzene) b.p. 160" n2,4 1.49287 n","-49481. m-Tolglethylcarbinol b. p. 114'112- 13 mm. l-Methyl-3-cr-bromo~rolpyZbenxene7 a colourless liquid b. p. 114'/14 mm. 1-Methyl-3-propylbenzene (from the bromide) b. p. MOO 0-8646 d;' 0.863 n:'' 148968 n::'6 1.49340 ng6 1.5038; (from m-bromotoluene propyl bromide and sodium) b. p. 177- 178.5" di0 0.8601 n 148978 n$ 1.49321 n; 1.50392. p-Tolyl- ethyZcarbinoE is a colourless liquid b. p. 114"/12-13 mm. 1-Methy1-4-a-bromop~opylbe~xene7 a colourless liquid b. p. 108'/13 rnm. p-Propionyltoluene b. p. 114Ojl4 mm. 1-Methyl-4-pro- pylbenzene (from the corresponding bromide) b. p. 182" cl:*'8 0.8620 dy 04361 n2'8 1-49278 ni:'8 1.49655 nF'8 1.50765 ny8 1.51687 ; (from $1-propionyltoluene according to Clemmensen) b. p. 183" di0 0.860 d:K'8 0.8617 n?'' 1.49269 n:'* 1.49641 nf.8 1.50752; (by reduction of the ketone prepared by t'he Friedel- Crafts method) b.p. 152-5' ng 1.49542 ; (from p-bromotoluene propyl bromide and sodium) b. p. 181-151~5' di3'7 0.8554 d;"O 0.858 n?'' 1.48706 n2,3' 1.49065 n?'' 1,50119. 1-Methyl- cyclohexan-4-01 b. p. 172-173" d:6'3 0.9192 di" 0.916 n2'3 1.45742 ng.3 1.45959 nF'3 1-46558 nyj 1.47025 nz 14579. 1-Methyl- cycZohexan-4-one b. p. 169-2" dig'g 0.91685 di0 0.917 f12'9 1.44285 nF.9 1.44500 nF'9 1-45110 n?'' 1.45595 nz 1,4450. Occurrence of Spark Lines (Enhanced Lines) in the Arc. I. Lead and Tin. G. A. HEMSALECH and A. DE GRAMONT (Phil. iMag. 1922 43 [vi] 287-306).-A convenient method is H. W.GENERAL AXD PRYSICAL CHEMISTRY. ii. 177 described for obtaining the arc spectra of volatile metals. This consists in placing a piece of the metal on a sheet of copper (5 cm.X 10 cm. x 1 mm.) and connecting to the positive pole. The negative pole is a pointed carbon rod ; the arc is struck by lowering the point until i t touches the metal and then withdrawing it a little. The metal melts and forms a globule and the arc between it and the carbon point burns steadily. The heat generated is dissipated by the copper plate. Experiments are described which seem t o indicate that spark lines are brought out in the arc when the degree of ionisation is reduced as for example by blowing air through the arc. The effect of liquid media on the character of the arc spectrum of the metal has been studied by placing a drop of the liquid between the poles before striking the arc.The spark lines or so-called high temperature lines disappear from the arc when the cathode is formed by white-hot carbon but they are brought out prominently when the electrodes are cooled down to about -190" by immersion in liquid air. A detailed account is given of the observations on the relative behaviour of various types of lead and tin lines in the arc under various conditions of discharge. It is definitely shown that the presence of hydrogen is not essential for the excitation of spark lines. Spark lines att'ain a high degree of development only in a medium which offers a comparatively high resistance to the flow of electricity. When hydrogen is present in the medium either free or in coxbination its spectrum resembles that which is only observed with high tension condenser discharges ; namely its lines are symmetrically broadened as though under the influence of a strong electric field (Stark effect).Rontgen Absorption Spectrum of Chlorine. AXEL E. LINDH (2. Physik 1921 6 303-310).-The Rontgen absorption spectrum of chlorine has been examined using free chlorine and the compounds lithium sodium potassium and thorium chlorides potassium chlorate potassium perchlorate ammonium stanni- chloride and dich lorotetra-aquoch romium chloride (Cr[ H,O I4CI,) C1. It is shown that with univalent chlorine in all cases the absorption edge has the same wave-length within the limits of the experimental error. I n the case of quinque- and septa-valent chlorine a displace- ment of the absorption edge toward shorter wave-lengths is observed which is greatest in the case of septavalent chlorine.A metallic Rijntgen tube and new apparatus for photometric measurements both designed for measurements of the above-named type are described. J. F. S. J. F. 8. Series Regularities in the Resonance Spectrum of Iodine. R. MECKE (Z. Physik 1921 7 73-86).-A theoretical paper in which on the basis of Wood's measurements of the resonance spectrum of iodine (A. 1911 ii 82 950 ; 1912 ii 325 1018 ; 1913 ii 994; 1914 ii 233; " Researches in Physical Optics," 11 19191. which is shown t o consist of a series of doublets of the band type and is expressed by the series formula ~=A+Brn+Cm~+Bm3 the author has examined the series regularities of $his spectrum,ii. 178 ABSTRACTS OF CHEMICAL PAPERS.It is shown that the first constant is given invariably by the exciting line whilst the two final coefficients C and D maintain their values at all exciting lines. On the other hand the second factor varies but this may be represented in the form R=b,-bb,n in which n is a whole number so that a number of partial series can be differen- tiated. In the case of the most accurately investigated resonance spectrum that of the green mercury line eight such series of doublets can be characterised which can also according to the position of the components of the doublets be divided into two groups. In one group b has the value 0.655 and in the other 0.75 and n can have the values 0 1 2 and 3. For n=O an apparent triplet is indicated. Further regularities are probable in the series but they cannot be definitely characterised.It appears that the value of m represents an azimuth quantum number. In consequence of the very small moment of inertia however the rotation cannot be ascribed to the molecule itself; it is therefore assumed that the moment of inertia is due to a rotating electron ring. On this assumption the series formula can be developed and resolved into the two energy terms. Further it is shown that resonance spectra in the same way as line spectra are brought into existence by electron springs. J. F. S. Divergence from Stokes's Law during the Excitation of the Fluorescence of Iodine Vapour. PETER PRINGSHEIM (2. Physik 1921 7 206-216).-The resonance spectrum of iodine vapour has been examined. It is shown that on heating the vapour from the ordinary temperature to 320° the intensity of the anti- Stokes members increases many times and a t the same time also that of the members of positive order number some become stronger whilst the majority become less bright.It is thought probable that! these oppositely hehaving resonance lines belong to series which originate from some of the seven iodine absorption lines covered by the mercury line. Difference between the Absorption Spectrum and the Complete Fluorescence Spectrum of Iodine Vapour indicated by Lenz's Theory. PETER PRINGSHEIM (2. Physik 1921 8 126-131).-Theoretically it is to be expect'ed that the members of higher order number in tlhe resonance spectrum of cold iodine vapour will not be markedly absorbed; this conclusion is fully confirmed by experiment.Correspondingly the fluorescence spectrum of iodine vapour excited by white light is riot a simple reversal of the absorption spectrum but is considerably richer in lines and so the colour change of the fluorescence of iodine vapour of high density is explained by a partial reabsorption of the fluorescence light. I n iodine vapour a t higher temperatures resonance lines of higher order number are also stlrongly absorbed. The colour change in the emission spectrum of iodine vapour of constant density occasioned by fluoresence or electric discharge a t higher temperatures is considered and it is shown that the cause cannot a t present be indicated theoretically. J. F. S. J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii.179 Ultra-red Reflection Power of Silica. CLEMENS SCHAEFER and MARTHA SCHUBERT (2. Physik 1921 7 313-315).-The reflection spectra of various varieties of silica has been measured ; the varieties include quartz chrysoprase hornstein chalcedony opal and quartz-glass. It is shown that all varieties except the last two exhibit) an identical quantitative reflection power. The reflection maximum at about 9p exhibits about 90% of the metallic reflection. In the case of opal and quartz-glass the reflection maximum lies in the same position as in the other varieties but the reflection power has fallen to 40-50%. This result is attributed to a distortion of the space lattice in the amorphous varieties of silica. It is rcmarkalsle that the water maximum which lies a t 3-2p is not observed in the case of opal and it is suggested that this is to be attributed to the probable fact that the water is not arranged in tlhe space lattice in opal.WALTER GROTRIAN (2. Physik 1921 8 116-125).-IE”rom a consideration of the recent work on the systematics of examination of Rontgen spectra the view is put forward that only one permanent condition of unexcited atoms exists and that the different absorption band edges are to be explained not by different initial conditions but by different final conditions. From this the conclusion is drawn that of the inactive gases helium has one ionisation-potential neon three argon five and krypton seven. I n the case of neon it is shown that the doublet difference E,-L is identical with the constant A found by Paschen for the neon spectrum A=782 em-1.The absolute value of the ionisation potential of neon has as yet not been deter- mined with certainty. J. F. s. Characteristic Ultra-red Frequencies of Selenates and Chromates. CLEMENS SCHAEFER and MARTHA SCHUBERT (2. Physik 1921 7 297-308).-The reflection spectra of potassium manganese nickel copper zinc and cadmium selenates an iso- morphous mixture of lithium and sodium selenate magnesium ammonium selenate manganese ammonium selenate nickel ammonium selenate cobalt ammonium selenate nickel potassium selenate and zinc potassium selenate have been determined in the region of the ultra-red using ordinary light. It is shown that all selenates exhibit in the region l l p a definite maximum of the reflection power which is to be attributed to the vibrations of the selenate radicle.This maximum is analogous to the maximum at 9p exhibited by the sulphates (cf. A. 1916 ii 505 506; 1918 ii 282 315). I n those cases where the selenates contain water of crystallisation the water bands previously recorded (Zoc. cit.) are also observed. The crystals have also been examined in polarised light and it is shown that the reflection maximum at about l l p can be resolved into two groups of characteristic vibrations in the case of uni-axial crystals and into three in the case of bi-axial crystals. Similar measurements were made with potassium chromate sodium potassium chromate magnesium ammonium chromate and potassium dichromate. I n the first three cases J. F. S. The L Doublet of Neon.ii.180 ABSTRACTS OF CHEMICAL PAPERS. using ordinary light a single well-developed maximum is found which lies respectively a t ll.16p 11*2p and a t complex maximum 11.311. and 11.42~. In the case of potassium dichromate three maxima are observed the first two of which are complex and lie at 10.44~ and l l . l p 12.14~ and 13-22,1 and 18.12p. Magnesium ammonium chromate has been examined in polarised light and exhibits a maximum a t 11p which falls into three groups 11.46~ parallel to the u axis 11.28~ parallel to the b axis and 10.36~ parallel to the c axis. Characteristic Ultra-red Frequencies of Chlorates Bromates and Iodates. CLEMENS SCHAEFER and MARTHA SCHTJBERT (2. Physilc 1921,7,309-312).-The reflection spectra of sodium potassium silver and barium chlorates sodium silver cadmium and barium bromates and potassium iodate have been measured.It is shown that in all cases but that of sodium bromate where a single maximum is observed two reflection maxima are exhibited. The maxima have the following wave-lengths sodium chlorate 10*04p 16.04~ ; potassium chlorate 10*12p 16.22~ ; silver chlorate 10*76p 16.38~ ; barium chlorate 10*24,u 1 9 . 6 ~ ; sodium bromate 12.24~ ; silver bromate 12*62p 13.10,~ ; cadmium bromate 12*32p 13.20~ ; barium bromate 12*3p 12.64,~~ and potassium iodide 12*48p 13.16~. The values are discussed in connexion with those found for other acid radicles (cf. preceding abstract). J. F. S. J. F. S. Rontgen Spectra. ELIS HJALMAR (2. PhysiE 1921 7 341- 350).-Rontgen spectra of the elements copper to tantalum have been measured.lines of the K series of the lighter elements are not simple. This has been established in the case of sulphur. The new line is regarded by the author as the continuation of the p2 line of the next higher element and the theoretical significance of this is discussed. The valency of sulphur appears to have no action on the emission spectra but the experimental difficulties experienced in the work make it advisable to leave this question open. Exa,ct measurements of a number of lines of the K-series are recorded and the earlier measure- ments of lines of the L series are controlled. Two long tables of wave-lengths measured in the present work are included in the paper. J. F. S. D. COSTER (2. Physilc 1921 6 185-203).-The author has measured the Rontgen spectra of the elements tantalum tungsten osmium iridium platinum gold thallium lead bismuth thorium and uranium using the method adopted by Hadding (ibid.1920,3 369). The object of the work was to obtain measurements of the very weak lines and from these to examine various relationships and regularities obtaining among X-ray spectra. Tables of the lines measured are given in the paper and also of the L doublets; a table of the constant wave- length differences pz- p5 YJ-76 y2-y39 P4- P5 P2- Ps and P 2 - P7 is drawn up. The relationshlp (L,-L,)-My=L~3-L~ put forward It is shown to be probable that the Systematics of Rantgen Spectra.GENERAL AND PHYSICAL CHEMISTRY. ii. 181 by Smekal (A. 1921 ii 615) is evaluated and found to be only in moderate agreement with the experimental data ; the divergences between the two sets of values are attributed to errors in the (L3-L1) values. J.F. S. ADOLF SMEEAL (Z. Physik 1921 7 410-412).-A reply to Coster (preceding abstract). The author points out that Coster’s criticism is based on a misunder- standing of his method of treatment. Fluorescence of Cadmium Vapour. J. STEPH. VAN DER LINGEN (2. PhysiE 1921 6 403404).-Light from cadmium sparks was allowed to pass through an evacuated quartz globe a t 280” containing a scrap of cadmium. It is found that an absorption line 2288 A.U. appears a t this temperature and with changing vapour density a band symmetrical with this line appears. When the band extends to 2307 A.U. a second absorption line 3260 A.U. is observed.To ascertain whether the emitted light is due to resonance or fluorescence the cadium light around 2288 A.U. was isolated and passed through the globe. It was found that a t a density corresponding with that at which the line 2288 A.U. is emitted the vapour shows an ultra-violet fluorescence band which is sharply terminated ai; 2288 A.U. and fades a t 2314 B.U. At higher densities the head disappears a t 2288 A.U. and the band is then terminated at 2313 A.U. and extends to 3005 A.U. where it also ends sharply. Between 2745 and 3005 A.U. the band contains sixteen lines which are closer together the smaller the wave-length. Dependence of the Intensity of the Fluorescence of Dyes on the Wave-length of the Exciting Light. S. I. VAVILOV (Phil. Mag. 1922 [vi] 43 307-320).-It has been shown by Nichols and Merritt (Physica,E Rev.1910,31,376,381) that thespecific fluorescence of resorufin and eosin increases toward long wave- lengths. The present paper describes experiments with fluorescein eosin-S extra and rhodamine-B extra designed to test how far this result is general. It is shown that within the limits of the errors of observation the specific fluorescence of the dyes mentioned is independent of the wave-lengths of their absorption bands. This result is equivalent to the conclusion that the absorption curves of the dyes are physically simple ones. Einstein’s theory is not con- firmed but the deviations required by this theory are so small that they are only a little greater than the experimental errors and consequently no very definite statement can be made.The intensity of fluorescence radiated by a definite molecular resonator depends only on the value of the absorbed energy and on the mechanism of the resonator. In the case of excitation by white light the in- tensity of fluorescence P can therefore be expressed by the equation F=K I A . xc.e-xc” dh where Ih is the energy of the exciting source in the wave-length interval A . . . A+dh xc the coefficient of absorp- tion of the solution over the same wave-length interval C the Systematics of R6ntgen Spectra. J. F. S. J. F. S. I: 7’ji. 182 ABSTRACTS 0 [1' CHEMICAL PAPERS. concentration and K the specific fluorescence. The result of Nichols and Merritt (Zoc. cit.) probably only shows the physical complexity of the bands of the dyes examined by them.J. F. S. GERHARD C. SCHMIDT (2. Physik 1921 8 160-164).-1t is shown that quinine nitrate as well as quinine sulphate (Le Bony Compt. rend. 1900,130 891) emits light on warming and makes the surrounding air a conductor ; other salts of quinine have no such action. All quinine salts when heated to just above the melting point change into a modification which gives intensely green fluorescent solutions instead of the usual violet fluorescent solutions. Quinine hydrogen sulphate in aqueous or chloroform solution gives a violet fluorescence but when heated at 50" for an hour the fluorescence is light blue; when heated to the melting point this changes to an intense green which is maintained at very high dilutions. I n the case of quinine valerate the green colour changes back to violet on dilution when in water solution ; in chloroform solution the heated salt gives a green fluorescence but a violet fluorescence in benzene.The absorption spectrum of the green fluorescing solution is different from that of the violet fluorescing solution. The following hypothesis is advanced to explain the luminescence of the nitrate and sulphate when warmed and its absence in other salts. On heating these two salts pass into a new modification which on stronger heating passes into the green fluorescing variety ; the change into the intermediate modification is accompanied by the emission of electrons or ions. I n the case of the other salts there is no intermediate compound formed but a direct change into the green fluorescing variety without emission of ions or electrons.Action of Eight on Silver Chloride Bromide and Iodide. PETER PAUL KOCH and FRITZ SCHRADER (2. Phys'ik 1921,6 127- 131).-The results of experiments made to ascertain the loss of weight of particles of silver chloride silver bromide and silver iodide on illumination previously published (A. 1921 ii 289) and a large number of other experiments made by the same method are collected and considered. The experiments were made with the suspended particles in air dried air dry nitrogen moist nitrogen moist argon and dry argon and a number of improvements were made in the technique of the method. The results show that silver chloride illuminated by intensities up to 3,000,000 silver bromide up to 12,000,000 and silver iodide up to 5,600,000 candle metre seconds (the light coming from the positive crater of an arc through 80 em.of 1% copper sulphate solution) do not undergo a change in weight greater than 1-2y0. The larger changes previously recorded are attributed to disturbances in the earlier experiments among which the secondary reaction of silver bromide with the surrounding gas is mentioned The rate of colouring of the silver haloids by light has also been determined; it is shown that silver bromide after an illumination of 5 seconds by a light of intensity 3200 candle metre seconds shows a definite coloration silver chloride shows a coloration in three minutes when illuminated by Ponisatioia brought about by Quinine Salts. J. F. S.GENERAL AND PHYSICAL CHEMISTRY.ii. 183 940 candle metre seconds and silver iodide after ten minutes' illumination by the same light shows only a weak greyish-black coloration. I n all cases the coloration increases with the duration of the illumination. Luminous Path of cr-Rays in Crystals. H. GEIGER and A. WERNER (2. PhysiE 1921 8 191-192).-An experiment is described which answers the question " Is the number of metallic centres which are excitcd by an a-particle on its entry into a crystal sufficiently great in every case to bring about a visible scintillation ? " A thin highly polished section of artificial willemite was arranged in the field of a microscope so that the a-rays from a polonium preparation should strike it at a small angle. At a magnification of 400 point scintillations were not seen but luminous lines of 0.02 mm. length.These represent the path of the a-particle in the crystal and show that the number of centres is extremely large and in the case of perfect crystals sufficient to ensure a scintil- lation for every a-particle hitting the crystal. The Meitner Nuclear Model of the Radio-elements as the Basis of a Relationship between the Range and Total Number of Nuclear Particles of the a-Radiators. MAXIMILIAN CAnmLo NEUBURGER (2. physikal. Chem. 1921,99 327-331).-A theoretical paper in which on the basis of the Meitner nuclear model a relation- ship between the range and the total number of nuclear particles of the a-radiators is deduced. The range of iaost of the a-radiators of the uranium thorium and actinium families is calculated by means of this new relationship and found to be in good agreement.The divergence of the two sets of values lies between IJt0.8% and 5 1 . 8 %. Applying this relationship to the hypothetical elements uranium I11 and uranium IVY it is found that the former is practically inactive whilst the latter has a much shorter life than uranium I. This is further evidence against the existence of these hypothetical isotopes (cf. this vol. ii 85). J. L. GLASSON (PhiE. Mag. 1922 [vi] 43 393-396).-A theoretical paper in which the re- lationships between the atomic absorption a and the atomic scattering p of p-rays respectively and the atomic number are considered. The values of a p the atomic absorption a=aA/D the atomic scattering b=PA/D the atomic weight A the density D and the atomic number N are tabulated for a number of elements from magnesium to bismuth.It is shown from the table that the values of a are approximately coiistant for elements of the same period of the periodic system ; the elements examined fall into four groups which have values for a in the ratio 1 2 3 4. These groups are magnesium and aluminium a=89 ; iron cobalt nickel copper and zinc a= 172-196 ; palladium silver and tin a=260-268 ; and platinum gold lead and bismuth a=348-372. It therefore seems likely that the value of a is a periodic function of the atomic number. The value of b increases with the atomic number of the J. F. S. J. F. S. J. F. S. Beta Rays and Atomic Number. element and on plotting log b against log N a curve is obtained 7"-2ii.184 ABSTR,ACTS OF CHEMICAL PAPERS. which is represented by log b=2*09 log N-0.44 and therefore b=0°36 x N2.09. Scattering of R6ntgen Rays by the Atoms of a Crystal. W. L. BRAGG R. W. JAMES and C. H. BOSANQUET (2. Physik 1921 8 77-84).-A theoretical paper in which the experimental results previously published (A. 1912 ii 477) on the scattering of Rontgen rays by the sodium and chlorine atoms of rock-salt crystals have been used in connexion with the arrangement of the electrons inside the atom. In the case of the sodium atom the expected amplitude curve has been calculated for the case that of the eight exterior electrons four vibrate in di-quantic circular orbits and four in di-quantic elliptical orbits and it is shown that such a model has a very satisfactory agreement with the experimental facts.J. P. S. Characteristic X-Rays from Boron and Carbon. A. LL. HUGHES (Phil. Mag. 1922 [vi] 43 145-161).-The photoelectric effect of the radiation from carbon and boron bombarded by electrons has been measured as a function of the energy of the electrons. Two slight but definite breaks in the curves for both carbon and boron were obtained. These are considered to cor- respond with the K- and L-absorption wave-lengths. The breaks occur a t 215 volts (h=57.5) and 34.5 volts (h=358) for carbon and 148 volts (h=83*5) and 24.5 volts (h=505) for boron. The L point for carbon is in good agreement with the measured values recently obtained by Millikan (Astrophys. J . 1920 52 47) for the L emission lines of carbon vapour. The K points for carbon and boron are approximately where they would be expected on extra- polating the known values of the K critical absorption wave-lengths for elements heavier than magnesium.Absorption of the K X-Rays of Silver in Gases and Gaseous Mixtures. P. W. BURBIDGE (Phil. Mug. 1922 [vi] 43 381- 389).-The total absorption coefficient of silver K radiation has been measured in air carbon dioxide sulphur dioxide and methyl iodide vapour. Using the same silver K radiation it has been shown with mixtures of sulphur dioxide and air carbon dioxide and air sulphur dioxide and carbon dioxide and methyl iodide and air that the absorption in gases is atomic (as in the case of solids and liquids) and therefore additive in mixtures and compounds. J. F. S. J. I?. S. J. F. S. Experimental Decision of the Question of the Radioactivity of a11 Elements.G. HOFFMANN (2. Physik 1921 7 254- 259 ; cf. A. 1920 ii 575).-Making use of the very sensitive method of measuring a-ray activity previously described (Zoc. cit.) the author has extended his measurements to platinum. The measuring instrument itself shows an a-ray activity represented by 0 . 3 4 . 5 a-particle per hour. Using a cleaned platinum dish of 39 sq. cm. surface an activity of 14.6 per hour for the whole dish is recorded or 0.39 per sq. cm. The measurements were made over a period of about fifty hours. The results are analysed for ways which 11.QEXERAL ASD PHYSICAL CI-IEMISTRY. ii. 185 may come from known a-radiators of all ranges uniformly distributed through the mass of the platinum and for a-radiators situated on the surface of the platinum and the analysis indicates a definite a-ray activity of platinum.J. F. S. Protactinium Content of Pitchblende Residues and the Branching Relationship of the Actinium Series. OTTO HAHN and LISE MEITNER (2. Physik 1921 8 202-204).-A criticism of the value put forward by St. Meyer (Mitt. Inst. Rad. Porsch. 1920 127) for the branching relationship of the actinium series. The value 4.2y0 is about 25% higher than that found by the present authors 3*0.3y0. It is shown to be probable that Meyer’s pre- paration contained 1-2% of ionium which would explain the difference in the two figures. Existence of Isotopes of Uraniuim and the Meitner Nuclear Model. MAXIMILIAN CANILLO NE UB URGER (2. physikal. Chem.1921 99 321-326).-The author discusses the position of uran- ium-2 in the disintegration series from the point of view of Meitner’s nuclear model. The position given by Hahn (A. 1921 ii 498) in the series U, -\ UZ -5 UZ -8 U is criticised and it is shown for several reasons that only two elements of the uranium type uranium I and uranium 11 can possibly exist. The elements uranium I1 and uranium I11 are shown to be identical and the disintegration series U >+ is put forward to represent the disintegration of uranium. A method for the detection of isotopes of the fourth order (this vol. ii 107) is described. It consists in determining the number of particles emitted by the disintegrat’ing substance ; should this number be in keeping with the disintegration constant then the substance does not consist of isotopes of the fourth order but of a single element J. F.S. A. PICCARD and E. STAREL (Physikal. Z. 1922 23 1).-A quantity of uranium-X separated from uranyl nitrate by the ether-water method has been repeatedly measured with respect to its p-radiation for a prolonged period. It is shown that in addition to the hard p-radiation of uranium-X there is a soft radiation which with increasing age of the preparation decreases more and more slowly; this indicates the presence of a substance of longer life than uranium-X. This substance has been provisionally named uranium- V . It has an approximate half life of forty-eight days or about twice as long as uranium-XI. The P-radiation due to this element is half absorbed by an aluminium sheet 0.003 mm.thick that is the absorption coefficient is 2300 cm.-l Al. It is shown that this substance may be a member of the actinium series but it has not been decided whether it or uranium- Y is the first thorium isotope in the disintegration series put forward by one of the authors. J. F. S. ‘ ux,_s,ux a I0 Q U Z - ~ U Z / a ‘5L UY A New Radioactive Substance. J. F. S.ii. 1% ABSTRACTS O F CHEMICAL PAPERS. Some Oxidising Properties of Thoriurn-,X. PIERRE LEMAY and LBON JALOUSTRE (Compt. rend. 1922 174 171-172).- Thorium-X exerts a very marked catalytic action in the oxidation of adrenaline and morphine the oxidation being much more rapid than in the presence of manganese salts. Oxidation could not however be proved in the case of the primary alcohols of the fatty series W.G. PAUL KNIP- PING (2. Physik 1921 7 328-340).-The ionisation tension of hydrogen cyanide chloride bromide and iodide has been deter- mined by the method previously described by Franck and Knipping for helium (A. 1920 ii 72). The following values are recorded hydrogen cyanide 15.5 volts 357 Cal. ; hydrogen chloride 14.4 volts 331 Cal.; hydrogen bromide 13.8 volts 317 Cal.; and hydrogen iodide 13.4 volts 308 Cal. The electron affinity in Cal. and volts the limiting wave-length and frequency have been calculated for chlorine bromine and iodine and the values com- pared with those of other investigators. The following values are recorded chlorine 98 Cal. 4-26 volts h=2890 v=34600; bromine 68 Cal. 2.96 volts h=4150 v=24100 and iodine 61 Cal.2.65 volts h=4600 v=21500. Ionisation and Excitation Tension of Nitrogen. ERICH BRANDT (2. PhysiE 1921 8 32-44).-The ionisation tension of nitrogen has been found to be 17*75&0.1 volt with reference to the resonance tension of helium 20.5 volts. Higher ionisation stages have been found a t 25.41&0.1 volt and 30.72&0*2 volt both with reference to the value 17.75 volts. The limits of light excitation of the nitrogen molecule by electron collisions have been investigated and an analogy between the light-electric curve and that of band emission is pointed out. Electrical Conductivity of Zinc Sulphate Solutions in the Presence of Sulphuric Acid. HERMAN V. TARTAR and HARMON E. KEYES (J. Ind. Eng. Chem. 1921 13 1127-1129).-The conductivity of zinc sulphate solutions increases with the sulphuric acid concentration but the conductivity of sulphuric acid is de- creased by the addition of zinc sulphate ; when magnesium sulphate is added to a strongly acid zinc sulphate solution an additional decrease in conductivity occurs.The addition of small quantities of gelatin does not affect the conductivity. The temperature coefficients of conductivity vary and are a function of the acid and zinc concentration. During the electrolysis of zinc sulphate solutions there is an increase in the volume of the solution the Ionisation Tension of the Halogen Hydrides. J. F. S. J. F. S. increase amounting to 1.5% for each 100 grams of zinc deposited. w. P. s. Anomalous Dissociation in Aqueous Solutions. A. J. RABINOWITSCH (2. physikul.Chem. 1921 99 338-360).-By anomalous dissociation is understood the phenomenon which occasions a decrease in the molecular or equivalent conductivityGENERAL AND PHYSICAL CIIE3IISTRY. ii. 187 with increasing dilution that is the degree of dissociation as expressed by cc= h/h decreases with increasing dilution. With the object of finding a connexion between the viscosity and the electrical conductivity of solutions of salts in water the author has determined the density viscosity and electrical conductivity of aqueous solutions of czsium chloride cadmium chloride cadmium bromide cadmium iodide zinc bromide zinc iodide and sodium iodide a t 0" 25" and 50". It is shown that in the case of caesium chloride the viscosity and the conductivity are very closely con- nected.A comparison of the corrected molecular conductivity curves and the relative viscosity curves a t 25" and 50" for the halogen salts of cadmium with one another and with those of other salts shows that the iorm of t,he relative viscosity curve has a strong influence on the form of the ~ q ~ curve. I n those cases with a high value for 7imY the introduction of the usual viscosity correction of the hya curves can lead to an anomalous form of the curve because of over-correction. This anomaly is general in the case of highly concentrated aqueous solutions. The over-correction is explained as follows In introducing the correction it is assumed that the ionic mobility is inversely proportional to the viscosity of the medium. This assumption however does not hold because zt reduction of the ionic diameter is brought about by increasing concentration due largely to a dehydration of the ions.With increasing temperature the anomaly extends over a considerable portion of the hya-V curve. This is in opposition to the view that the anomaly is due solely to the over-correction on account of a reduction of the ionic diameter. If the over-correction is due alone to the inapplicability of Stokes's law to all concentrations then it is to be expected that the minimum displaced on warming should correspond with higher viscosity values; but since this is only observed in the case of caesium chloride it follows that this cause of over-correction does not explain the anomaly in all cases. It is held that the anomalous form of the conductivity curve is not to be explained by the over-correction alone but is due to several causes.It is suggested that the causes which bring about the " true anomalous dissociation " in non-aqueous solutions are operative in aqueous solutions also. This suggestion would explain the displacement of the minimum with increasing temperature since with increasing temperature water in respect of its dielectric constant approaches in behaviour the other solvents. It is also shown that in concentrated aqueous solutions in addition t'o the over-correction of the conductivity values there is also a typical anomalous progression of the molecular and equivalent conductivity which in all probability has its origin in the same causes as in non-aqueous solutions. J. F.8. Electrolytic Dissociation of Salts in Concentrated Solutions and in the Fused and Solid States. A. J. RABINOWITSCH (2. physikal. Chern. 1921 99 4 1 7 4 3 3 ; cf. preceding abstract).- The conductivities viscosities and densities of aqueous solutions of cssium chloride silver nitrate ammonium nitrate thalliumii. 188 ABSTRACTS OF CHEMICAL PAPERS. nitrate and thallium silver nitrate were determined at high con- centrations. In the case of thallium ammonium nitrate the results were extended to the fused salt. The molecular conductivities were extrapolated to the pure salts. After the application of the viscosity correction all the molecular conductivity curves assumed an abnormal form and on extrapolation to pure salt gave high values of pya where p is the molecular conductivity and yn the relative viscosity.The values of pqQ/pm = a were therefore abnormally high. The true values of a for the salts probably lie between the values calculated from the corrected and the uncorrected (p/pm ) conductivities and nearer the former. The course of the dissociation in very concentrated solutions is thus abnormal. The extrapolation was confirmed by the form of the curve for thallium silver nitrate which continued smoothly up to the fused salt. J. R. P. Reversal of the Molecular Conductivity Curve and Abnormal Dissociation. A. J. RABINOWITSCH (2. physikal. Chem. 1921 99 43M-453 ; cf . preceding abstract).-Abnormal dissociation occurs when the degree of dissociation (or the molecular con- ductivity) decreases with increasing dilution.It is most commonly observed with non-aqueous solutions and is most marked when the dielectric constant of the solvent is small. The various hypo- theses which have been advanced to account for the phenomenon are reviewed. In the ordinary method of represenOation of con- ductivities the dilution V is taken as the variable volume of solution in which a constant weight of one gram equivalent of solute is dissolved. The author considers the results obtained when a constant weight of one gram equivalent of solvent is taken and the volume V of solution containing it is taken as the dilution. If lc is the specific conductivity the product kVl=pl is the newly- defined molecular conductivity. The curves representing the values of p1 and V are called “reversed conductivity curves.’’ When only one constituent of the solution is capable of ionisation and the other is a strong ioniser (for example acetic acid in water) the original molecular conductivity curve is normal but the reversed curve is abnormal exhibiting a maximum but not a minimum after correction for viscosity.When the ionising constituent is also a strong ioniser (for example silver nitrate in aniline or water) the original curve is abnormal without a maximum or apparently abnormal (without correction). The reversed curve is normal (water in silver nitrate and thallium silver nitrate) or in conse- quence of the uncorrected increase in viscosity is apparently abnormal (aniline in silver nitrate). When neither constituent is ionisable but when its polymeride or solvate is ionisable then in both cases abnormal curves result in the latter case with a maximum the position of which indicates approximately the maximum content of solvate in the solution. To the right and left of the maximum the conductivity decreases in consequence of the diminution of solvation due to insufficient quantity of solvent and to depolymerisation respectively.Examples of such curves areGENERAL AND PHYSICAL CHEMISTRY. ii. 189 furnished by acetic acid and aniline and by acetic acid and pyridine. A definition of abnormal dissociation is given. Effective Potential Difference of Electro-osmosis and Allied Phenomena. H. FRETJNDLICH (Trans. Faraday SOC. 1921 16 Appendix 146-149).-A theoretical paper in which the author discusses the nature of the potential difference at work in electro-osmosis cataphoresis and allied phenomena.A great deal of experimental work is reviewed and i t is shown that the Nernst potential difference E is in no sense identical with the electrokinetic potential difference [ ; the Nernst potential represents the total difference between the interior of the first phase and that of the second phase the electrokinetic potential represents that portion of the difference which falls within the displaceable liquid layers. Selenium [Cells]. WILHELM SPATH (2. PhysiE 1921 8 165-183) .-The influence of illumination on the dielectric constant of selenium has been investigated in connexion with the fatigue and inertia of the element. It is shown in all selenium cells that the change in conductivity on illumination runs parallel with a change in capacity.The final capacity value and the final con- ductivity are reached with similar inertia phenomena. The conduc- tivity of the cells increases two- or three-fold on illumination but the capacity increases only 5%. A cell which with respect to its conductivity exhibits fatigue also exhibits the same phenomenon with respect to its capacity. The dependence of the change in capacity on the intensity of illumination is much the same as that of the conductivity. With increasing intensity of illumination the sensitiveness of the capacity increases in a parabolic manner. The inertia on darkening the cell is greater than the inertia on illumination as far as the capacity effect is concerned and further it is considerably smaller in soft cells.The fatigue effect in soft cells on intense illumination is more marked both with regard to the capacity change and the conductivity. The author has put forward an hypothesis of the mode of action of the selenium cell and has calculated the equilibrium of the cell for illuminated and dark conditions. J. F. S. Fatigue of Alkali Metal Cells in the Neighbourhood of the Discharge Potential and the Influence of this on the Results of Photometric Measurements. H. ROSENBERG (2. Physik 1921 7 18-64).-Sodium potassium and rubidium photo- electric cells have been examined in connexion with the fatigue effects often noticed in these cells. It is shown that these cells when filled as usual with an inactive gas rapidly exhibit fatigue effects and also a rapid recovery.The effects are apparently not proportional to the intensity of the light or to the photoelectric current. In addition slow changes of the sensitiveness of the cells are observed which must be regarded as a type of fatigue effect. The cause of the fatigue is found t,o be due to the adsorption of a positively charged layer of gas by the alkali metal but it is J. R. P. J. P. S.ii. 190 ABSTRACTS OF CIIEMICAL PAPERS. not decided whether electron absorption or a reduction of the field is the ultimate cause of the fatigue effect. The process appears to be intimately connected with the appearance of a powerful collision ionisation. The pure photo-eEect is shown to be strictly proportional to the amount of light which has entered the cell.Taking into account these phenomena a photometric process has been tested which lends to intensity ratios which are accurate to o*lyo. J. F. S. Equilibrium Law of Electrolytes. M. JABLCZ-SKI and F. J. WI~NIEWSKI (RocsniEi Chemji 1921 1 116-134).-The authors have deduced a dilution law of the form n4/3/n,=E and have used this to calculate the value of E for potassium sodium and lithium chlorides using data obtained from cryoscopic measure- ments. It is shown that only in the case of potassium chloride is the value of E constant whilst in the case of the other two salts it may have even negative values. These facts are explained by hydration of the ions. Correctlions which take into account the hydration have been introduced into van't Hoff's equation and lead to a remarkably constant value for E in all three cases; thus for potassium chloride lc = 3.09 for sodium chloride 3.10 and for lithium cliloride 2.93.Furthermore the number of molecules of water combined with the various ions has been calculated as follows potassium 0; sodium 3 ; lithium 11 ; chlorine 0. Hydrochloric acid behaves in the same way as the salts mentioned and when the hydrogen ion is taken as combined with nine mole- cules of water a very constant value 4.74 is obtained for k. The equation has been applied to those weak electrolytes which apparently follow Ostwald's dilution law. The value of k has been calculated for acetic acid from cryoscopic measurements and a remarkably constant value 0.00504 obtained whereas the value of k calculated from Ostwald's equation increases considerably with increasing concentration.On applying the equation to ebullioscopic data of solutions of the chlorides mentioned above it is shown that the value of k increases even more strongly than when cryoscopic data are used. This is explained by assuming that the ions are more heavily hydrated a t 100" than a t 0". This is shown to be in keeping with facts. The value of k a t 100" is smaller than that a t 0" which shows that the degree of ionisation decreases with increase of temperature. This the authors attribute to a fall in the dielectric constant of water with increase of tem- perature. A rule has been deduced in keeping with facts which shows that the equilibrium constant of salts in aqueous solution is proportional to the dielectric constant of the solvent.J. 3'. S. Velocity of Sound in Air and Hydrogen at 8" and 1 Atm. E. GRUNEISEN and E. MERKEL (Ann. Physik 1921 [iv] 66 344- 364).-The velocity of sound in air is found to be 331.57 m./sec. and in hydrogen 1260-6 m./sec. The ratio of the specific heats for air is Cp/Cv=1.4034 and for hydrogen 1.408 both a t 0" and 760 mm. J. F. S.CIEXERAL AKI) WIYSICAT CEIEMISTRY. ii. 191 Specific Heats of Ammonia Sulphur Dioxide and Carbon [vi] 43 369-38@).-The ratio of the specific heats k=cp/c for ammonia sulphur dioxide and carbon dioxide has been deter- mined by a method depending on t'he relative velocities of sound in the gases and in air. The specific heats have been calculated using Berthelot's equation of state in all calculations. The following results were obtained a t one atmosphere pressure ammonia a t 14*5" cp/cv 1.308 Cp 8.77 cal.C 6.70 cal.; sulphur dioxide a t 13-2" cp:plcL 1.290 Cp 9.47 cal. C 7.34 cnl.; carbon dioxide at 20° cp/c 1.303 Cp 8-76 cal. C 6.72 cal. Numerical Values of the Gas Constants. F. HENNING (Z. Physik 1921 6 69-72).-The data on which the gas constant is based have been critically discussed and on the basis of the most trustworthy experimental data the value of this constant in different units has been calculated. The following values are recommended for general use as the most accurate R=0~08204+0~00003 litre- atm./degree mol. ; R= (8*3l3&O.0O3)1O7 erg/degree mol. ; and R= 1-986&0*001 cal. /degree mol. Theoretical Determination of the Chemical Constants of Monatomic Gases.E. BRODY (2. Physik 1921 6 79-83).- The author have deduced a mathematical expression for calculating the chemical constants of ideal monatomic gases on the basis of the first quantum theory and from statistical considerations. The expression obtained is the same as that deduced by Stern (A. 1919 ii 219) and Planck (Sitxungsber. Preuss. Akad. Wiss. Berlin 1916 653). The expression has the form C=log ( 2 ~ r n ) ~ 2k5 2/h3. J. F. S. Chemical Constants of Sodium and Potassium. R. LADEN- BURG and R. MINKOWSKI (2. Physik 1921 8 137-141).-The chemical constants of sodium and potassium have been calculated from existing data on the specific heat vapour pressure and latent heat of fusion of these elements. In the case of sodium the value of the chemical constant C is found to be 0.846 and on inserting this value in the equation C=Co+l*S log ill where M is the mole- cular weight the value of the constant Co is found to be -1.20 instead of -1.59 as in the case of mercury argon hydrogen cadmium and zinc.The data on which the calculation is based are analysed with the object of finding the cause for the discrepancy. I n the case of potassium the value of C is found to be 1.016 which gives the value of Co as - 1.37. J. F. S. MAX PLANCK (Ann. Physik 1921 [iv] 66 365-372).-An answer to the criticism of Ehrenfest and Trlcal (ibid. 1921 65 609) in which the difficulties in calculation of entropy experienced in the author's book (" Theorie der Warmestrahlung," 1921) are pointed out. It is also doubted whether the equation s=E log W in which W is the thermodynamic probability will give the value of the entropy.The author answers the objections and criticisms and points out that they arise from a confusion of terms. Dioxide. J. R. PARTINGTON and H. J. CANT (Phil. Mag. 1922 J. F. S. J. F. S. Absolute Entropy and Chemical Constants. J . F. S.ii. 192 ABSTRACTS OF CHEMICAL PAPERS. Equation of Condition. RUDOLF WEGSCHEIDER (2. physikal. Chem. 1921 99 361-382.)-A theoretical paper in which the equation of condition put forward by Wohl (this vol. ii 117) is discussed and criticised. It is shown that this equation of condition leads to results which can scarcely be accepted; for example the decrease of pressure a t constant volume with increasing temperature in liquid systems consequently this equation can have no theoretical significance.The critical point is always given by equations of condition which yield isotherms of the van der Waals form by the coincidence of the three roots of the equation v=f(p. T). The equality of four roots involves the introduction of a relationship between the constants; the equality of two roots leads to con- ditions which include in addition to the critical point also the maxima and minima. Physical Properties of Vapour-Liquid Systems. I. WOJCIECH SWIENTOSLAWSKI (Rocxniki Chemji 1921 1 276-296). -Starting from relationships based on van der Waals's hypothesis of corresponding conditions T= T/Tc and dc/d=K=f(T). Where T d T and dc are the temperature and corresponding density and T and d the same critical values the author has deduced the following regularities from the experimental work of Young Amagat Mathias Villard Kamerlingh Onnes and Crommelin.(1) The value of K or log K increases with increasing molecular weight of the liquid and also when the liquid is associated. (2) Oxygen and argon have small values for K . In the case of associ- ated liquids it is shown that the concentration of non-associated molecules y is given by y%=lOOK/KB where K=dc/d for a non-associated liquid and KA is the same ratio for an associated liquid a t the same relative temperature (T=const.). The con- centration of non-associated molecules in methyl alcohol and propyl alcohol increases proportionally to the temperature but this is not true for ethyl alcohol. Ramsay's results for water and ethyl alcohol are satisfactory if it is assumed that the associated molecule of water contains three simple molecules and that of ethyl alcohol two simple molecules.The value of K plays an important r6le in all cases where the physical state of a system liquid-vapour is characterised. The relationship between the surface tension y and the reduction of pressure below the meniscus in a capillary tube of radius r is given by (2~/~Af)r=const.=~=c~nst. and in the case of osmotic pressure (P/Af);=co,t.=K=const. The constant of Trouton's rule may be calculated by the equation Wmol.=bB log,K=20*4 in which R=2 cal. log,K=2.303 log&= 2.203 x 2-38 or 2.38 depending on the ratio K=d,/d for the liquid a t the relative boiling point ~=0*65 under a pressure of one atmosphere.* J. I?. S. Physical Properties of Vapour-Lipid Systems. 11. WOJCIECH SWIENTOSLAWSKI (Rocxniki Chemji 1921 1 297-304 ; cf. preceding abstract).-It is shown that over the range of relative temperatures ~=0*50 to ~=0.95 the expression d,2/Z'log,K=B is constant where d is the density of the liquid and K the ratio dJdP in J. F. S.GENERAL AND PHYSICAL CH-EMISTRY. ii. 193 which dp is the density ctf the vapour a t the absolute temperature T'* The deviations of B ncver exceed a mean amount of &2*3%. A minimum value of B is found between T=O% and 0.90 and a maximum about ~=0*60-0*65. Associated liquids are exceptional ; these show a continual increase in the value of B from ~=0'50 to the critical temperature T= 1. Vaporisation Coefficients of Solid and Liquid Mercury.M. VOLMER and I. ESTERMANN (2. Physik 1921 7 l-l2).-The authors have determined the velocity of vaporisation of mercury a t temperatures from 59" to -180". This demands the determin- ation of the fraction (a) of the vaporised mercury which is con- densed on a cooled surface whilst the rest (1 -.) is reflected. It has been previously shown by Knudsen (Ann. Physilc 1915 [iv] 47 697; 1916 50 472) that a t 19-45" cc=0?35 but a t -140" cc= 1.00. For the temperature range 59-0" the rate of vaporisation and consequently the value of cc has been determined by measuring the rate a t which a small globule of mercury deposited on the interior of the outside wall of a highly evacuated Dewar vessel filled with liquid air decreases. The Dewar vessel is kept in a thermostat a t the required temperature during the experiment and the temperature of the bath up to 40" is taken as the tem- perature of the mercury but for higher temperatures a correction is applied to the bath temperature to get the temperature of the mercury.This method is inapplicable a t temperatures below 0" and above 60". For these temperatures 0" to -64" the rate of vaporisation is determined by measuring the rate of change of the electrical resistance of the condensed film of mercury. A third method is also described which depends on the difference of readings in a graduated capillary tube due to vaporised mercury. The results show that for pure liquid mercury irrespective of the temperature the value of a is unity but for solid mercury it is less than unity and decreases with decreasing temperature.It is shown that with sulphur phosphorus and benzophenone the value of a lies between 0.2 and 0.5. It is also shown that there is a close connexion between cc and the extent to which a liquid may be supercooled. J. F. S. Coefficients of Vaporisation and their Relationship to Ostwald's Step Rule. M. VOLMER and I. ESTERMANN (2. physikal. Chem. 1921 99 383-394).-The coefficient of vaporis- ation a has been determined for mercury over the temperature +59" to -64" and found for the liquid phase to be equal to unity irrespective of the temperature. The known expression G= l/z/%R . W T . p expresses actually the velocity of vaporisation for all temperatures If this equation yields results for other substances similar to those obtained for mercury then it becomes the first strictly true reaction velocity equation.In the case of solid mercury a is found to be approximately 0.9. The ratio cc (solid)/. (liquid) has been determined for sulphur phosphorus and benzophenone and the values 0-3-0*4 0*4-0*5 and 0-25 respectively have been obtained. The Ostwald step rule and the J. F. S.ii. 194 ABSTRACTS OF CHEMICAL PAYERS. limits of its applicability to the separation of the liquid and solid phases from the vapour condition are shown to be due to the different a-valucs of the solid and liquid phases. The Separation of Miscible Liquids by Distillation. 11. ARTHUR FELIX DUFTON (T. 1922 121 306-308). Divergences of the Value of the Mechanical Equivalent of Heat. WOJCIECA SWIENTOSLAWSKI (.hcZZiki Chernji 1921 1 171-177).-The author gives a short description of facts which show that the value of the mechanical equivalent of heat requires exact verification. It is shown to be probable that the values obtained by electrical and mechanical methods are not in agree- ment.The measurements of Jaegcr and Steinwehr show that in bomb calorimetry conditions often exist which increase the amount of heat obtained by the introduction o€ electrical energy into a calorimeter. It is also pointed out that adiabatic Calorimetry has not been employed in the measurement of this constant. J. F. S. Heat of Vaporisation of Sodium and the Probability ~f the Transition of the Sodium Atom from the Resonance to the Normal Condition on the Basis of Optical Measurements.R. LADENBURG and R. MINKOWSKI (2. Physik 1921 6 153- 164).-The authors have measured the magnetic rotation of the plane of polarisation in the immediate neighbourhood of the D line by the method described by Senftleben (Ann. Fhysik 1915 [iv] 47 949) a t various temperatures of the emitting vapour. The sodium used was contained in an air-free glass tube in an electric furnace the temperature of which was constant to &O.l". It is shown that the dependence of N (the number of electrons which vibrate with the atoms) on the temperature can be regarded as a relative vapour pressure curve if the theory that N is pro- portional to the number of sodium atoms present is accepted. Calculation from the experimental results leads to the value for the heat of vaporisation of sodium Ei.=o=25-9 Cal.This value is probably uncertain to about 2%. J. F. S. Action of Forces between Separated Atoms in Diamond and Aliphatic Molecules. I<. PAJANS (2. physikal. Chem. 1921 99 395416).-A theoretical paper in which it is shown that if in analysing the results of heat of combustion experiments the assumption is made as a first approximation that only neigh- bowing atoms have a noticeable energetic action on one another then it appears that the firmness of a C-C linking in the diamond is somewhat greater than that in aliphatic hydrocarbons. Prom this it follows that the heat of combustion of hydrocarbons with branched chains should be somewhat smaller than that of the straight chain isomerides a conclusion which is in keeping with experimental data.To explain the above relationships it is assumed (1) that the energy of the C-C linking in aliphatic sub- stances and diamond is constant irrespective of whether or no the carbon atom is bound to further carbon atoms or also with hydrogen. (2) That separated and distant atoms have a notice- J. F. S.QENERAL AND PHYSICAL CHEMISTRY. ii. 105 able energetic action on one another. As a second approximation in the quantitative analysis only those linkings which lie on a common edge of the tetrahedron are cansidered. From a corn- parison of diamond with the hydrocarbons the relationship ym- Bxm+h - 1-2 Cal. between the energies of the three types of edge linkings (C-C C-H H-H) where ym x,,~ and h are re- spectively the energies of formation of the three types of linking.This relationship indicates a method of explaining t'he difference in properties of the chain isomerides and also the exceptional position of the first member of homologous series. In the case of aliphatic hydrocarbons alcohols ketones and esters of mono- basic acids the chain isomerides with low boiling point and heat of vaporisation possess a lower heat of combustion a stronger saturation of the forces in the molecule corresponding with a weaker intermolecular force. The difference in the boiling points and the specific heats of the chain isomeride is therefore brought into relationship with the difference in the intramolecular energy and the latter is attributed to the mutual action between separated and distant atoms. The Meaning of the Atomic Constants of Heat of Com- bustion and Molecular Refraction.WALTER HUCKEL (J. pr. Chem. 1921 [ii] lO3,241-248).-A theoretical paper in which the author states the various relations that have been found by Steiger (A. 1921 ii 473) and others between the various " atomic " and " linking " constants of organic compounds and of the elements forming them and points out some relations that seem to follow. J. F. S. W. 0. K. New Data in the Thermochemistry of Organic Substances. WOJCIECH SWIENTOSLAWSKI (Rocxnilci Chemji 1921 1 305-315). -The heat of dissociation of hydrogen chlorine bromine iodine and solid carbon into individual atoms determined during recent years has been used to obtain the value of the constant E of the equations (C-1)=(13-1)+~-3 ; (C-Br)=(H-Br)+c-3 ; H)-(-~+15.The symbols (C-I) (H-I) indicate the heat of formation of the single link between the atoms named. When the values 81.3 Cal. 106 Cal. 46 Cal. and 36 Cal. are taken as the heat of formation of the molecules of hydrogen chlorine bromine and iodine respectively as represented by 2X- =X,+& Cal. and the heat of formation of solid diamond as -6- =Csol x 287 Cal. it is possible to calculate the heat of formatioh of the links (C-C) and (C-H). According to Fajans (A. 1920 ii 354) (C-C)=137*5 Cal. and (C-H)=117.0 Cal. Using the above data in the equations a mean value of 20.6 is obtained for E . From the heat of formation of the linkings (H-C1)=115.5 Cal. (H-Br)= 72.0 Gal. (H-1)=52.7 Cal. it is shown that (C-C1)=136.3 Cal. (C-Br)=S9-7 Cal. and (C-1)=703 Cal.An analysis of the above results shows that the heat of formation of a link is an additive (C-C1)=(H-Cl)+E; (C-C)=(H-C)+c; (C-N)=(H-N)+c ; (C-S)=(H-S)+€+2 ; (C-Q)=(H-O)+E+~; (C-H)=(H-ii. 196 ABSTRACTS OF CHEMICAL PAPERS. quantity made up of parts due to the links of the atoms concerned. These parts have been calculated as follows (C-)=6S.S Cal. (H-)=48*2 Cal. (C1-)=67.4 Cal. (Br-)=23-8 Cal. (1-)=4*4 Cal. The heat of formation of a link between two atoms is the sum of the two atomic values. This regularity is probably existent in inorganic compounds also for if the above atomic values of the halogens are subtracted respectively from the heat of formation of the corresponding haloids of potassium the value of (K-) is found to be 91.2 94.5 and 93.7 Cal.and by the same method the value for sodium (Na-) is 83.3 84.0 and 82.7 Cal. Heat of Coagulation of Ferric Oxide Hydrosol with Electro- lytes. FREDERICK L. BROWNE and J. HOWARD MATHEWS ( J . Amer. Chem. SOC. 1921 43 2336-2352).-The heat of coagulation of ferric oxide hydrosol of various concentrations and purity by various concentrations of sodium oxalate sulphate chloride and hydroxide potassium ferricyanide and sulphuric acid has been determined. It is shown that the dilution of ferric oxide hydrosols of varying purity is accompanied by measurable heat effects until the purity exceeds 21 or 22 (the ratio of gram equivalents of ferric oxide per litre to gram equivalents of chlorine per litre is termed the purity of the sol) beyond which point the heat of dilution is zero.If the heat of dilution per gram-equivalent of chlorine in the sol is plotted against the chlorine content the curve is of the same nature as that for the heat of dilution of ferric chloride solutions of varying concentration. The thermal behaviour of ferric chloride solutions on dilution confirms the observations of Goodwin (Physical Rev. 1896 9 251 ; 1900,11 193) to the effect that the hydrolysis of ferric chloride takes place in two steps the first an instantaneous and the second a slow reaction. The mixing of ferric chloride solutions with common electrolytes involves very significant heat changes. The heats of coagulation have been reduced to curves showing the heat of coagulation as a function of the purity which vary widely in shape with the nature of the coagulant; the heat effect is usually positive but with sodium sulphate and sodium chloride at low purities it is negative.As the purity increases the heat of coagulation becomes smaller and finally becomes negligible except in the case of sulphuric acid. The peculiar behaviour of this last electrolyte is due to solution of the ferric oxide. When the heat of coagulation is plotted against the concentration of the coagulating electrolyte smooth curves are obtained which show no break at the point of limiting concentration. The heat effects observed on coagulating ferric oxide sols with electrolytes are to be attributed to the action of the electrolytes in the coagulants on the electrolytes particularly ferric chloride present in the sol. The change in dispersity of the ferric oxide on coagulation does not involve a greater heat change than 1-2 cals./gram-equivalent of ferric oxide. In the case of ferric oxide hydrosols there is no heat of peptisation analogous to the heat of solution of crystalloids. RICHARD LORENZ (2. Physik; 1921 6 269-270).-A criticism of the work of Gunther-Schulze J. P. S. J. F. S. Kation Volumes in Permutite.ii. 197 OEPJERAL AND PHYSICAL CHEMISTRY. on the determination of the kation volumes in permutite (A. 1921 ii 624). It is pointed out that the value found for the alkali ion is practically the same as that of the alkali atom. It is suggested that the alkali ions in permutite fill only a small amount of the space and have a large space to vibrate in. This great mobility is characteristic of permutite. The kation radii calculated by Gunther-Schulze are probably too large for the new determinations of Fajans and Herzfeld and also those of Land6 are much smaller and lie very close to those calculated from the ionic mobility by Lorenz and Born.J. F. S. The Velocity of Extension of Thin Layers of Oils on the Surface of a Sheet of Water. PAUL WOOG (Compt. rend. 1922 174 162-165).-For fatty oils where all the molecules intervene the velocity of extension is practically proportional to the ratio (the carboxyl groups of the glycerides+ the double linkings+the acidity) /viscosity. In mineral oils however the velocity of extension depends only on the unsaturated molecules which are few in number and hence the viscosity plays an insignificant part.In mixtures of the two types of oil the results depend on the relative proportions in which the active fatty oil and the comparatively inactive mineral oil are mixed. W. G. High Pressure Due to Adsorption. WILLIAM D. HARKINS and D. T. EWING (Chem. News 1922 124 23-24 31-35).-Cf. this vol. ii 123. J. P. S. Electso-adsorption as a Purely Chemical Process. I. M. KOLTROFF (KoZZoid Z. 1922 30 3544).-The author discusses electro-adsorption (adsorption of ions) and from the experi- mental results of Freundlich OdBn and others shows that the process is strictly a chemical one. The adsorption of copper lead morphine codeine papaverine atropine ferricyanide oxalate chromate and iodate ions by norit carbon confirms this view. It is shown that the adsorption isotherm can be deduced directly from the stoicheiometric relationships if it is assumed that the electro-adsorption is a process in which a sparingly soluble sub- stance contained in the adsorbent is converted by the adsorbed ion into another sparingly soluble substance.The coefficient 1 /n of the adsorption isotherm bears a direct relationship to the valency of the reacting substances. If l / n is equal to a for a univalent ion then it has the value a12 for a bivalent ion and a/3 for a tervalent ion. This relationship is confirmed by the present experiments and by the earlier work of Preundlich and Od6n. The significance of the quantity of the adsorbent is explained by the characteristic constitution of its surface layer of particles. The active ion which determines the charge in the surface layer and in adsorption forms the insoluble salt is present in this layer in far larger concen- tration than in the liquid.When equilibrium has been set up on the surface of a particle then the concentration of the active ion in contact with the excess of reacting ions is small. In such a case if fresh adsorbent is placed in the liquid then the reacting ionsii. 198 ABSTRACTS OF CHEMICAL PAPERS. are again in contact with large concentrations of active ions and the reaction commences anew. The general chemical theory in its relationships to colloid chemistry is shortly discussed. Origin of the Charge of a Colloidal Particle and its Neutral- isation by Electrolytes. JNANENDRA NATH MUKRERJEE (Trans. Faraday SOC. 1821 16 Appendix 103-115).-The charge of a number of suspensoids has been shown to be due to the adsorption of a common ion and the nature of the chemical forces which cause this adsorption has been defined.The effect of the electrical charge of a surface (due to the disorption of ions) on ions of opposite sign has been theoretically investigated for the case when chemical action does not take place between the surface and the ion. It has been shown that the electrical forces are sufficiently strong tlo account for adsorption. The stabili1;y of the adsorption of an ion of opposite sign by electrical forces has been given a quantitative form assuming that the charge of the surface consists of ions which can be treated as point charges widely separated from each other. Actual calculations justify this assumption.The reversal of the charge by electrical adsorption has been discussed. The following series of the adsorbability of kations by a negatively charged surface has been deduced from the theory Th"" >Al**' > Ba" > Sr" > Ca" >Mg" > H' > Cs' > Rb' > K* > Na' > Li'. This order is the same as that of the precipitating power of these ions €or a number of suspensoids of widely differing chemical properties. Equations deduced from the theory agree satisfactorily with the experimental observations of Elissafoff (A. 1912 ii 419) on electro-endosmosis. The chemical affinity of the surface atoms is not always negligible and for this reason the series given above cannot be expected to hold in all cases. Electrical Theory of Adsorption.W. HARRISON (Trans. Faruday Soc. 1921 16 Appendix 116-118).-A criticism of Mukherjee's theory of adsorption (cf. preceding abstract). The author is of the opinion that the double layer consists of a surface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions any particular point on the rigid surface becoming in turn negative neutral and positive these conditions arising in any order. The observed contact difference is the average effect of these conditions. When several kinds of atoms are present in the solution the average number of any one of them a t the surface will depend on their concentration valency and mobility. The variation of contact difference from negative t o neutral and positive was observed with cotton and aluminium sulphate near the neutral point ( J .Xoc. Dyers and Col. 1911 27 279; 1918 34 91). These variations occurred during the same experiment the readings being direct measurements of E. M .P. developed by filtration under pressure. Diffusion of Hydrogen through Iron and Plahum. GERHARD C. SCHMIDT and TR. LUCKE (2. Physik 1921 8 152- 169) .-The diffusion of hydrogen through iron and platinlxm has J. F. S. J. F. S. J. P. S.GENERAL AND PITYSICAL CHEMISTRY. ii. 199 been investigated. A sheet of the metal was fixed between two glass vessels hydrogen was electrolytically generated on one side of the sheet and the potential on the other side measured over a period of time up to about twenty-four hours. The metal sheets were of various thicknesses. It is shown in the case of iron that the passage of the hydrogen through the metal is always indicated by a fall of potential.I n the case of thin sheets the fall of potential is observed as soon as the electrolysis commences; the fall of potential is rapid at first and gradually becomes slower until when the liberation of hydrogen has proceeded for some time it becomes constant. With sheets of medium thickness (0.5-1.0 mm.) the fall of potential is gradual and with sheets thicker than 1.0 mm. there is no fall of potential. On breaking the polarising current the potential increases thc more quickly the thinner the metal. From this fact' it is deduced that the hydrogen diffuses into the liquid. With thicker sheets the increase of potential is slower which is explained by the longer time required for the relativcly large volume of hydrogen to diffuse into the liquid.Similar results are obtained in the case of platinum. The results show that the passage of hydrogen across platinum plates is a diffusion and not as stated by Nernst and Lessing (Gottinger Nachr. 1902 146) due to small p r e s in the metal. The Nernst-Lessing rule was showri by them to hold for palladium and thin sheets of platinum but not €or thicker sheets of platinum. It is shown that the reason for the rule holding with palladium is that on account of the great power of palladium for absorbing hydrogen practically none is liberated from the other side and consequently the condition of the rule is obtained. J. F. S. Dispersoid Analysis of Non-aqueous Systems.WOLFGANG OSTWALD (Trans. Faraday Xoc. 1921 16 Sppendix 89-93).- The author describes the preparation of membranes and jellies suitable for dispersoid analysis of solutions in alcohol of 97% for both dialysis and dieusion experiments. The mercury sulphide alcosol the preparation of which is explained is an especially stable sol suitable for these tests. Solutions of dyes resins neutral salts fatty acids and soaps its far as at present examined produced by the spontaneous solution of these substances in 97% alcohol are all molecular-dispersed or contain a t any rate molecular- dispersed particles in considerable proportions. Zein the protein of maize which is soluble in alcohol is also found to be dialysable. J. F. S . Solubility. 111. Solubility of Metal Ammonia Salts in Salt Solutions.J. W. BRONSTED and AGNES PETERSEN ( J . Arner. Chem. Xoc. 1921 43 2265-2292; cf. A. 1920 ii 536).-A long list of the solubilities of eighty-six cobalt chromium and rhodium complex ammine salts in water a t 0" and 20" is given in the paper. The solubilities of a large number of complex ammine salts of cobalt and chromium in solutions of potassium chloride f ormate clilorate trichloroacetate dichloroacetate monochloroacetate thio-ii. 200 ABSTRACTS OF CHEMICAL PAPERS. cyanate hydroxide nitrate and phthalate ; sodium chloride sulphate chlorate nitrate formate oxalate and benzenesulphon- ate ; magnesium sulphate and chloride ; calcium formate acetic acid; and mono- di- and trichloro-acetic acids of various concen- trations have been determined a t 0".In the preceding papers (Zoc. cit.) it was shown that the expression log S/80=a(Ct1/3-S013) represents approximately the solubility changes of salts in hetero- ionic solvents up to about 0-1N-solutions when a is a constant which for uni-univalent salt systems has the value 1/3 C is the concentration of the solvent salt So the solubility in water and X that in the salt solution a t the same temperature. The experi- mental data furnished for salts of the same type in the present paper agree approximately with the formula and an equation of the same type is found for bivalent salts. The individual nature of the salts employed is more pronounced in the larger amount of material now presented and tends to obscure any numerical regularity in salt systems of promiscuous types.The experiments lead to the following rules. The influence of the solvent increases with increasing valency of the ion of the solvent salt which in the case of ter- bivalent salts leads to an enormous increase of solubility even on the addition of solvents of very low concentration. When both the dissolved and dissolving ions are of higher valency the effect of the sign of the electric charge is very marked producing the highest solubility values when the multivalent ions of solvent and solute are of different sign. The reason for the appearance of individuality in the solubility curves is to be sought partly in the hydration of the solvent and the solute and partly in the fact that in these ions the mass is not to be regarded as a point but as a particle of varying size bearing a number of electric charges of opposite signs the algebraic sum of which gives the valency of the ion.It is probable that the size of the ion in the present cases will have an influence of considerable magnitude. Probability of Spontaneous Crystallisation of Supercooled Liquids. C. N. HINSHELWOOD and HAROLD HARTLEY (Phil!. Mag. 1922 [vi] 43 78-94).-The statistical investigation of the spon- taneous crystallisation of supercooled salol phenol p-toluidine and o-nitrophenol leads to the following conclusions In all these cases crystallisation is provoked by colloidal organic dust particles the activity of which diminishes in general as the result of heating or ageing. The effectiveness of the dust particles depends on their radius.If this is equal to the radius of a small particle of the solid which should thermodynamically be in equilibrium with the supercooled liquid then crystallisation occurs a t once. If the radius is less than this the supercooled liquid has an average life depending on the discrepancy between the equilibrium radius and the radius of the particles present. The magnitudes of these quantities are discussed. The results of crystallisation experiments are given 16 sets of 70 tubes of salol were kept a t 32.3" in a thermostat and the number which had crystallised a t various times noted; similar results are recorded for 12 sets of 41 tubes of phenol a t 18-25'; J. F. S.QENERAL AND PHYSICAL CHEMISTRY. ii. 201 8 sets of 122 tubes of p-toluidine a t 33-36-17-48" and 5 sets of 130 tubes of o-nitrophenol a t 38.72-31.1'.J. F. s. Structure of [Hanging] Drops of Mixed Liquid Crystals. 0. LEHMANN (Ann. Physik 1921 [iv] 66,323-343).-The structure of hanging drops of liquid crystals of p-hydroxyphenetole and cholesteryl benzoate has been examined between parallel Nicols by means of the dichroic effects produced. A number of diagrams and descriptions of the structure observed are included in the paper. J. F. S. Submicrons Visible in the Tyndall Cone to the Naked Eye. J. TRAUBE and P. KLEIN (KoZEoid Z. 1922 30 19--20).-When 30 C.C. of 1/30000 N-lead nitrate solution are treated with 2 drops of N/2-sodium carbonate solution in a rectangular vessel stirred and illuminated by a Tyndall cone it is found that in forty to sixty seconds an extremely large number of small particles are visible by means of a hand lens.The particles are in violent and irregiilar motion. As the time of the existence of these particles increases more and more light is reflected from them so that in about two minutes they are visible to the naked eye a t a distance of 2 metres. It is held that the particles are crystals and are visible on account of the2 rotation which causes an intermittent reflexion of light from the crystal faces. The phenomenon is not produced by all concentrations of lead nitrate N/10000 is too concentrated and N/70000 is too dilute; the best concentration is that given above. The same phenomenon may be observed with very dilute solutions of calcium sulphate calcium ammonium phosphate barium sulphate mercurous chloride and lead chloride.J. F. S. Fibrous Structure of Hard Drawn Metal Wires. M. ETTISCH M. POLANYI and K. WEISSENBERG (2. physikal. Chem. 1921 99 332-337) .-From the X-ray examination of hard and soft wires of copper tungsten iron molybdenum palladium aluminium silver and zinc it is shown that the crystallite in soft wires is arranged irregularly whilst in hard wires it is arranged regularly. In the case of the metals with a space centred cubic lattice (tungsten iron molybdenum) it is found that only a single lattice plane lies in the section of the wire namely the plane (1 lo) whilst in the case of the metals with a face centred cubic lattice (copper palladium and aluminium) two lattice planes lie in the section of the wire namely the planes (111) and (100).The crystallite arrangement in hard wires is termed a fibrous structure because this arrangement was first observed in natural fibres such as ramie and silk. J. F. S. Molecular Structure of Amorphous Solids. C. V. RAMAN (Nature 1922 109 138-139).-I.n view of the fact that glass exhibits a very strong scattering of light its magnitude being of the order that might be expeoted if the arrangement of the moleculesii. 202 ABSTRACTS OP CHEMICAL PAPERS. was irregular it is assumed that such is the case. If thc arrange- ment of the molecules approximated to the crystalline state the scattering of light would be merely that due to the thermal move- ments of the molecules and would be much smaller. Careful microscopic examination failed to disclose any inclusions to which the effect has previously been ascribed (Strutt Proc.Roy. XOC. 1919 [ A ] 95 476). A. A. E. Action of ]Penetrating Radium Radiation on Inorganic and Bio-colloids. 111. A. FERNAU and Wo. PAULI (Kolloid Z. 1922,30,6-13 ; cf. A. 1915 ii 722 ; 1917 ii 189).-A continuation of previously published work (Zoc. cit.). I n the present paper the influence of the radiation from a radium preparation equivalent to 78.6 mg. of radium on gelatin albumin casein acid albumin and lecithin has been investigated. Of thc radiation emitted by the radium preparation only 25% of the hardest P-radiation and 99% of the y-radiation came in contact with the colloids. It is shown that the viscosity of a 0.99% solution of glutin from bone glue a t 35" falls rapidly a t first under the influence of the radiation and then successively less rapidly but in the presence of 0-1N-sodium chloride the fall in viscosity is much slower. The addition of O*OlN-hydrochloric acid to @5y0 glutin solution causes a t first a rapid fall in the viscosity which becomes less rapid as the time increases. Under the action of the radiation the rate of fall of the viscosity is still more rapid.The action of the radiation is analogous to the action of heat on glutin. Glutin jellies when exposed t o the radiation liquefy but the portion nearest the tube containing the radium sets to a solid opaque mass which sticks to the tube and is insoluble in water although soluble in alkali hydr- oxide. The coagulation of serum-albumin which had been freed from globulin by the radiation is found less rapid in the presence of sodium chloride the retardation being greater the greater the concentration of the salt.The time required for coagulation of albumin depends on the concentration of the albumin; it decreases a t f i s t with increasing Concentration passes through a minimum a t 0*5-1*0% of albumin and then increases. The action of the radiation on solutions of the sodium salts of acid albumin and casein is to displace the equilibrium toward the acid side that is to decrease the concentration of the hydroxyl ion. Thus an acid albuminate prepared from serum-albumin had a hydroxyl-ion concentration 1-66 x lO-5N; after subjection to the radiatlion for a week the value was 1-57 x 10-6N and after three weeks 3.62 X lO-*N whilst sodium caseinate solution had the value 8-64 x which became 1.19 x after treatment with the radiation for a week.A solution of 3 grams of lecithin in 200 grams of water exhibited a t 25" under the action of the radiation a gradual fall in viscosity but scarcely any change in the hydrogen-ion concentra- tion or in the specific conductivity. Similar results are also found with a 0.2% emulsion of cholesterol. The results show that whilst albumins undergo considerable change under the action of radium radiation this is not the case with l i p i d emulsions. J. F. S.CtENEUL AND PBYSICAL CHEMISTRY. ii. 203 Protective Colloids. XI. Carragheen as a Protective Colloid. I. General Colloid-chemical Investigation of the Extract of Irish Moss. A. GUTBIER and J.HUBER (KoZEoid Z. 1922,30,20-31; cf. A. 1921 ii 537).-The method of preparation and properties of colloidal solutions prepared from Irish mosm 0 are described. Purified carragheen (30 grams) is placed in a litre of water at the ordinary temperature and kept until the swelling process is complete then it is vigorously shaken for five hours. The mucilage is separated by pressing through linen. Several other preparations are described; the amount of dry colloid varies between 0.4400 gram and 0.2100 gram per 100 C.C. of mucilage and the ash between 0.0246 and 0.0600. Dialysis reduces the amount of ash and removes the turbidity and the foul odour and raises the degrec of dispersion. Carragheen solutions do not produce fungoid growths when kept and it is therefore unnecessary to add stabilising agents. On keeping the viscosity of a S-55% mucilage fell from 15.29 to an approximately constant value of 7.19 in thirty-three days.The rate of decrease in viscosity is rapid a t first and subsequently much slower. The change in viscosity with ageing indicates the change of the mucilage to a more stable system. Boiling the mucilage reduces the viscosity by an amount which increases with the length of time of boiling. This indicates a change in the chemical con- stitution of the mucilage but after filtration no further change occurs on prolonged keeping. Heating therefore may be regarded as a hastened ageing and gives rise to stable colloidal solutions. The viscosity increases with increasing concentration but the amount of increase is greater the higher the temperature employed in the preparation.Electrolytes have no unfavourable action on the mucilage no coagulatior or visible change being brought about except in the case of sodium hydroxide where it becomes light brown in colour. Increasing concentration o€ hydrochloric acid sodium hydroxide and sodium chloride decreases the viscosity to values which approach a constant value as the concentration of the electrolyte increases. J. P. S. Protective Colloids. XI. Carragheen as Protective Colloid. 11. Colloidal Silver. A. GUTBIER A. WOLF and A. KIESS (Kolloid Z. 1922 30 31-35; cf. preceding abstract).- Extract of Irish moss prepared as indicated previously (Eoc. cit.) has been investigated as to its efficacy as a protecting colloid in the case of colloidal silver.Before use the mucilage is aged for a considerable time and thereby stabiliaed. Colloidal silver prepared in the presence of carragheen by hydrazine hydrate has colours varying from dark reddish-brown to brownish-yellow in transmitted light depending on the concentration of the silver nitrate used. It is exceedingly stable and remains unchanged for two months and may be evaporated to dryness on a water-bath to an almost black residue which is completely reversible. On the other hand evaporation in a vacuum over sulphuric acid yields a viscous paste which is not completely reversible but yields a secondary system with water which is only stable in dilute solutions. Colloidalii. 204 ABSTRACTS OF CHEMICAL PAPERS. solutions of silver have been prepared in the presence of carragheen with a concentration of 17% of silver but they were not very stable.Carragheen itself has a reducing action on silver nitrate and produces colloidal silver. This action is not complete but the percentage of reduced silver increases with the dilution of the silver nitrate ; thus N/lO-silver nitrate gives 8.98% of reduced silver whilst N/640-silver nitrate gives 58.54% of reduced silver the amount of carragheen being the same in all cases. J. F. S. IUltra-violet Spectroscopical Studies on the Antagonistic Action of Salts in Organic Colloidal Solution. TETSUTARO TADOKORO ( J . COX Agric. Hoklcaido Imp. Univ. 1921,10 3 7 4 9 ; cf. A. 1918 ii 432).-The effect of different salts on the degree of dispersion of organic colloidal solutions (egg-albumin taka-diastase blood-serum and lettuce juice) was studied by observing the changes induced in their absorption spectra in the ultra-violet.Certain pairs of salts were shown to have antagonistic effects on dispersion. Ultramicroscopic observations confirmed the conclusions drawn from the spectroscopical observations. The Importance of Imbibition for some Biochemical Problems. M. RICHTER-QUITTNER (Biochem. Z. 1921 121 273-292) .-By means of the Zsigmondy-Haen ultra-filtration apparatus the author has examined the influence of electrolytes and non-electrolytes on the velocity of. ultra-filtration of various dispersoid systems for example sera for substances which inhibit imbibition will accelerate filtration. All potassium salts heavy metal salts urea and sugar inhibit whilst other kations favour imbibition. For anions the Hofmeister series holds good.H. K. [Reversal of Phases in Emulsions and Precipitation of Suspensoids by Electrolytes. SHANTI SWARUPA BHATNAGAR (Trans. Faraday Xoc. 1921 16 Appendix 27-31).-A study of the reversa,l of phase in oil-water emulsions in the presence of pure soaps by electrolytes (cf. T. 1920 117 542) and the precipitation of arsenic sulphide sols by lithium chloride (Mukherjee J . Amer. Chem. Xoc. 1915 37 2030). It is shown that the power of ions in reversing the phases in oil-water emulsions in the presence of soap follows the order Al'" 7 Cr"' > Ni" > Pb" > Ba" > Sr" 7 Ca". The amount of electrolyte required varies with different soaps but the order of the different electrolytes remains the same.The greater the dilution that is the distance between the oil particles in an emulsion the larger the amount of a multivalent ion required to bring about reversal of the phases. Some measurements are given of the effect of diluting milk on the rate of coagulation by dilute sulphuric acid. It is shown that the greater the dilution the larger is the concentration of acid required to bring about an immediate coagulation. Soaps are regarded as exerting a protective action on oil-water emulsions and i t is shown that the protective action follows the order potassium stearate 7 sodium stearate >sodium and potassium oleate >potassium oleate > sodium oleate. G. W. R. J. F. S.GENERAL AND PHYSICAL CHEMISTRY.ii. 206 Peptisation and Precipitation. N. G . CHATTERJI and N. R. DHAR (Trans. Faraday SOC. 1921,16 Appendix 122-127).-Silvcr chloride silver chromate calcium silioate cupric fluoride and barium sulphate when precipitated in the presence of glycerol or concentrated sucrose solutions are not peptised. The hydroxides of iron nickel cobalt thorium and mercury may be peptised by adding an alkaline hydroxide to the solutions of saltls of these metals in the presence of glycerol or concentrated sucrose solution. In the case of gold or uranium salts ammonium hydroxide should be used instead of sodium hydroxide. In these cases peptisation can only be brought about if the alkali is added to the mixture of the salt and glycerol but precipitation takes place if the solution of the salt is added to the mixture of glycerol and alkali These results are supported by conductivity measurements.The major portion of the hydroxides of aluminium chromium lead mercury and copper when dissolved in sodium or potassium hydroxide exists as a colloid whilst zinc hydroxide mainly forms a zincoxide as shown by con- ductivity experiments. Similarly the hydroxides of aluminium iron and chromium form colloidal solutions in acetic acid whilst zinc hydroxide forms zinc acetate. The transformation of the blue hydroxide of copper to the black variety and that of the blue hydroxide of cobalt to the pink form are changes of the same type and are almost equally effected by different catalysts. The hydr- oxides of aluminium chromium and zinc respectively are adsorbed by ferric hydroxide when the latter is precipitated in the presence of solutions of the hydroxides of t-hese metals in potassium hydroxidc.A Kinetic Precipitation Measurer. Wo. OSTWALD and l!'.-l'. VON HAHN (Kolloid Z. 1922 30 62-?'0).-Two new preci- pitation measures arc described which permit of the precipitation process and the peptisation of colloidal solutions being studied kinetically. The one instrument the two-limbed measurer is based on the principle of level difference in communicating tubes and the change of this difference due to decrease of density of one liquid by the sedimentation of the disperse phase contained in it. The second apparatus the single-limbed measurer depends on the rise of the seal liquid column of an enclosed gaseous volume through change in the density of the seal liquid in consequence of the precipitation of the disperse phase which it contains.A number of examples of the use of these instruments in the kinetic measurement of the precipitation processes of typical sols are given. Distribution of certain Drugs between Immiscible Solvents. w. 0. EnrERY and c. D. WRIGHT ( J . Amer. Chem. s'oc. 1921 43 2323-2335) .-Distribution experiments between water and chloro- form have been carried out with caffeine antipyrine and p-acetoxy- acetanilide. It is shown that the most suitable temperature for the extraction of caffeine from water by chloroform is the ordinary temperature alt.hough a change of temperature from 12" to 40" only reduces the amount recovered from wat'er by a single extraction from 96.3% to 93.2%.The distribution is the more favourable to J. F. S. J. F. S. VOL. XXII. ii. 8ii. 206 ABSTBACTS OF CHEMICAL PAYERS. the chloroform the more dilute the aqueous solution. The effect of small concentrations of sodium hydroxide sodium acetate sulphuric acid sodium salicylate sucrose alcohol and citric acid on the distribution of caffeine between water and chloroform has been examined a t 25". The presence of sulphuric acid leads to a less efficient extraction of the caffeine whilst sodium salicylate reduces the amount extracted from 96% to 20-7y0 due in all probability to the formation of a molecular compound between caffeine and sodium salicylate. The solubility of caffeine in water and aqueous solutions of sulphuric acid (A;) citric acid ( I ! ) potassium bromide ( N ) and (2*5N) sodium salicylate ( N ) and (0*1N) sodium benzoate ( N ) and (0.1N) has been determined at 25".The solubility in grams per 100 C.C. of solvent is 2.071 in water 3.365 in sulphuric acid 6.411 in citric acid 2.136 and 2.035 respectively in potassium bromide 22-22 and 4.921 respectively in sodium salicylate and 15.27 and 3-422 respectively in sodium benzoate. The solubility determinations and cryoscopic measurements of mixtures of caffeine with sodium salicylate and sodium benzoate respectively confirm the complex salt f orniation with these salts. Distribution experi- ments of caffeine between absolute chloroform and water N- sulphuric acid N-potassium bromide O . 1N-sodium salicylate and 0-1N-sodium benzoate have been made a t 25".It is shown that potassium bromide has but little effect on the partition whilst sodium salicylate reduces the amount of caffeine recovered from the water solutions by the greatest amount. The distribution of antipyrine shows that there is no tendency to the formation of double salts with sodium salicylate but on the other hand there is a far greater depression in the percent'age of antipyrine extracted from N-sulphuric acid when compared with that from pure water solution due presumably to difference in basicity. In the case of p-acetoxyacetanilide somewhat lower distribution ratios are obtained than for either caffeine or antipyrine. The solubility of p-acetoxyacetanilide in water a t 25" is found to be 0.239 gram per 100 C.C. of water and in chloroform at the same temperature 3.250 grams in 100 C.C.of chloroform. MARTIN H. FISCHER and GEORG D. MCLAUGIILIN (Kolloid Z. 1922 30 13-16).-1t is shown that Liesegang rings are only observed when a liquid phase is present; they may be formed when two dissolvcd substances which react with one another are brought together in the presence of a third insoluble substance; the formation of the rings occurs on the side of the solution of lower concentration the rings tend to increase in thickness from the commencementl of their formation and during the growth hend to pass from the originally liquid and amorph- ous condition to the solid and crystalline form. All substances which give satisfactory Liesegang rings are impermeable toward molecularly dissolved substances and consequently it would seem unlikely that after the formation of the first ring a second and third ring could be formed.The view is put forward that true semi- permeable media are solvated and when these become less solvated J. F. S. Theory of the Liesegang Rings.GENERAL AND PHYSICAL CHEMISTRY. ii. 207 holes appear through which the dissolved substance can diffuse and so go to form a second ring. Thermodynamical Theory of Explosions. I and 11. SIR J. B. HENDERSON and H. R. HASS~ (Proc. Roy. Soc. 1922 [A] 100 461-482) .-A theoretical paper in which calculations are made of the maximum temperature and pressure of an explosion in a closed vessel also the calculation of the curve of reversible adiabatic expansion of the products and incidentally the ideal indicator diagram.The calculations are applied to a gun in which the varia- tion with time of the volume of the chamber of the composition of the products and the temperature and pressure of explosion are worked out and the value of the maximum pressure determined. The maximum temperature obtained with Mark I cordite is 3210° and with MD cordite 2870° whilst the maximum pressure of Mark I cordite is 8370 atmospheres or 55.1 tons/sq. in. Equation for the Velocity of Reaction of Hydrogen Peroxide and Potassium Permanganate. JAN ZAWIDZKI (Roczniki Chemji l921,1,135-139).-From the measurements of Baeyer and Villiger (A. 1900 ii 719) on the course of the reaction between hydrogen peroxide and potassium permanganate the author calculates that the time law of this reaction is expressed by the differential equation dx'/dt=k,( 1 -x')/&/Z The velocity coefficient k ' = k l l / a is calculated for -16" and +15" and the values 0.119 and 0.379 respectively are obtained.From these the temperature coefficient of the velocity constant is found to be 1 -452. J. F. S. The Velocity of Reaction in Mixed Solvents. 11. The Velocity of Saponification of the Ethyl Esters of some Mono- substituted Benzoic Acids. ALBERT ERIC CASHMORE HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH (T. 1922,121 Influence of Temperature on the Velocity of Interpene- tration of Solids. H . WEISS and P. HENRY (Compt. rend. 1922 174 292-294; cf. A. 1920 ii 545; 1921 ii 551).-From a study of the velocity of solution of silver antimonide Ag,Sb in solid silver a t different temperatures in the case of a silver-antimony alloy containing 14% of antimony it is shown that the velocity is pro- portional to the temperature being expressed by the equation v=KaT where T is the absolute temperature and in this case K=4.17 x and a= 1.0324.W. G. The Mechanism of Catalytic Hydrogenation. A. SKITA (Ber. 1922 55 [B] 139-143).-1n a recent communication Willstiitter and Waldschmidt-Leitz (A. 1921 ii 185) have pointed out the necessity of priming the platinum catalyst with oxygen during the course of hydrogenations and have advanced the hypo- thesis that a platinum peroxide or oxide is intermediately formed. This suggestion is quite consonant with the author's repeated observation that the activity of the catalyst produced in situ is J.E'. S. J. F. S. 243-253). 8*ii. 208 ABSTRACTS OF CHEMICAL PAP~RS. superior to that of the pre-formed agent since the experimental conditions do not guarantee the complete absence of oxygen. Comparative experiments with a platinum catalyst produced in situ do not show any difference in the rate of hydrogenation of pulegone or us-p-xylidine when every trace of oxygen is excluded and when special precautions to this end are not observed; the formation of a peroxide as catalyst cannot therefore be assumed in these cases. Further if the platinum catalyst is in reality a peroxide? its oxygen must liberate iodine from potassium iodide and hydrogenation must be impossible in the presence of the salt. It is found however that phenol is reduced smoothly t o cyclo- hexanol a t 40" in the presence of potassium iodide.On the other hand the addition of potassium iodide completely inhibits the reduction of phenol or us-p-xylenol a t the atmospheric temperature whereas in its absence they are transformed readily into cyclo- hexanol and 1 4-dimethyZcyclohexan-2-oZ b. p. 179" respectively. Reduction occurs quantitatively but slowly if the mixtures are heated a t 50". At the higher temperature it appears therefore impossible that hydrogenation should depend on the formation of a platinum peroxide. It has not yet been elucidated whether the failure of the action a t the atmospheric temperature is due to the inactivation of a platinum peroxide or to poisoning of the catalyst. H. W. The Mechanism of Catalytic Action in the Hydrolysis of Fats.E. BRINER and (MLLE) A. TRAMPLER (HeEv. Chim. Actct 1922 5 18-20).-The product obtained by the sulphonation of phenylacetic acid is inferior to hydrochloric or sulphuric acid as a catalyst in the hydrolysis of ethyl acetate in homogeneous solution. It thus appears that the presence of a common group in catalyst and substrate does not confer any supplementary chemical activity on the former. In Twitchell's and similar catalysts the activity of the sulphonic group is diminished by the presence of the aliphatic radicle but this effect is more than compensated by the greater mutual solubility caused by the two similar groups. Coiiclusions from the Spherical Form of the Simplest Atom. L. ZEHNDER (Physikal. Z. 1922 23 53-55).-A theoretical paper of a highly speculative character? in which on the basis of a spherical primordial atom an atomic ether the atoms of which have a mass of about one-millionth that of hydrogen elasticity and gravitational forces the author draws a number of conclusions respecting the atomic weight of helium the structure of the carbon atom and the subdivision of organic compounds into three classes aliphatic aromatic and carbohydrates.A New Model of the Nucleus. MAXIMILIAX Cmruo NEU- BURGER (2. phy,sikaZ. Chem. 1921 99 454-473).-l?revious speculatiom (cf. A. 1921 ii 479) are extended by the consideration of isohydrogen particles of maw 1. The disintegration series of thorium uranium and actinium are considered on the basis of this hypo thesis H. W. J. F. S. J. R. P.GENERAL AND PHYSICAL CHEMfSTRY.ii. 209 Structure of the Atomic Nucleus. 0. CHWOLSON (2. Physik 1921 7 268-284).-A theoretical paper in which an attempt is made to deduce the structure of the atomic nucleus. It is main- tained that any hypothesis of the structure of t’he at,omic nucleus must conform to the following (1) t’he mass of the atomic nucleus is practically the same as that of the atom ( 2 ) the positive charge E of the nucleus is e N where -e is the charge of the electron and N the atomic number of the corresponding element (3) the atomic weight is roughly M=2N (4) in the case of hydrogen M=2N is not true and (5) the hypothesis must not be in conflict with Bohr’s hypothesis. As the basis of the present hypothesis the author assumes that the volume density 8 of electricity of both signs is a constant and that a given charge E irrespective of its sign has the same volume v=8/E.From this i t is shown that the atomic nucleus cannot easily be represented as a sphere built up of spherical particles and the assumption is made that it is cylindrical and is built up of disks. This conception is strictly in keeping with the relatively large volume of the nucleus in com- parison with that of the electron. It is further assumed that the positive elementary disk is identical with the helium nucleus and the cc-particle. The elementary positive disk is termed the “ penta- lon.” Negative electricity consists of spherical electrons and positive electricity of disk-shaped pentalons. If -e is the charge of an electron e’ the charge of the pentalon is e‘=2e; the mass of the pentalon is m’=4.The order number of the pentalon N’ is N ’ = N + l where N is the atomic number of the element. The atomic nucleus is a disk or cylinder made up of pentalons between each pair of which is a disk of negative electricity of charge -e equal to that of an electron. The disk of negative electricity is termed a “ piezo-electron ” and its order number is N”=N-2. The atomic nucleus of an element of atomic number N consists of N - 1 pentalons and N - 2 piezo-electrons ; these 2N-3 disks form a cylinder which has no interstices. The charge of the nucleus is E= ( N - 1)2e-(N-2)e= Ne. Calculating from the above it is shown that the radius of the pentalon is 69.98 where s is the radius of the electron and the thickness D is 0.0005450s; the radius of the piezo-electron is also 69-98 and the thickness is half that of the pentalon.The pentalon has a mass which is 7340 times that of the electron. The thickness D(N) of the nucleus of an element of atomic number N is D(N)= ( N - 1)D+ ( N - 2 ) 0 / 2 = (3N-4)D/2 and the mass M1=4(N - 1) + 2 ( N - 2) = 2N. The hypothesis is compared with the Bohr hypothesis and found not to conflict with it. The hydrogen nucleus on the basis of the hypothesis is shown to be built up of one pentalon and one piezo-electron both of double thickness and of reduced radii in the ratio 1 42. That is the hydrogen nucleus is three times as thick as the helium nucleus and has a radius 49-59 and a thickness 0.00 1635s. J. F. S. Attempt [to Find] a Physical Basis for Atomic Radiation.E. GEHRCKE (2. Physik 1921 6,400-402).-The author imagines 8’-2ii. 210 ABSTRACTS OF CHEMICAL PAPERS. the electrons surrounding an atomic nucleus as rings round the nucleus and not as spheres rotating in an orbit round the nucleus. The ring form of the electron has the same mass volume and surface as the spherical electron and is to be regarded as a spacial isotope of the spherical electron. If for any reason the ring electron changes its diameter a change in the ether must also occur and this change in the ether gives rise to emission or adsorption; emission when the ring reduces its diameter and absorption whcn the diameter increases. The change in the diameter of the ring consists in the displacement of the ether over the space between the initial and final positions of the ring.The mechanism of this process is visualised as follows. An atomic ether E the atoms of which are arranged in a space lattice is assumed. The space lattice has spherical symmetry in the neighbourhood of a positivc atomic nucleus. Between the atoms of E a magnetic ether M is assumed which in comparison with E can be regarded as a con- tinuum. The atomic ether E is the carrier of electric forces and is named the electric ether. The magnetic ether can spread out in stream lines (magnetic field lines) whilst the electric ether cannot spread out in the same way but may change the shape of its space lattice. The sudden change of the space lattice due to a change in diameter of the ring electron occasions vibrations in the ether atoms which are transmitted to neighbouring ether atoms and when the transmission of the vibration extends outside the ring emission of radiation results.Absorption results when incoming vibrations increase the kinetic energy of the ring electron that is increase its velocity and so increase its diameter. It is therefore not the ring electron which makes the spring a t each energy step but the E ether which is displaced by the thickness of a ring electron. The generator of light and Rontgen radiation in the material atom is therefore not a vibrating electron but the whole system of ether atoms between two radii R and r swinging in a pendulum-like manner. The frequency V of the vibrations of the ether atoms is given by the ether between the radii R and r and is proportional t o the thickness and inversely proportional to the square of the length that is v - B-r/Rr=l/r-l/R.J. BOESEKEN CHR. VAN LOON DERX and P. HERMANS (Proc. K . AEad. Wetensch. Amsterdam 1922 24 198-204).-A theoretical paper in which it is shown that atoms which are not directly bound to one another exercise a mutual action on other atoms in the same molecule. Saturated non-cyclic molecules execute among others movements in which the parts of the molecule revolve in opposite directions or with different velocities round the single bonds as axes. In the case of non-uniformly loaded molecules that is practically all molecules except those of hydrogen nitrogen oxygen ethane hexachloroethane and similar molecules the movements are irregular because the most stable position of the atoms will be passed most frequently. In the saturated cyclic molecules with six or seven atoms the ring-forming atoms are not fixed in one J. F. S. Condition of Motion of Molecules in Space.GENERAL AND PHYSICAL CHEMISTRY. ii. 211 plane but lie in a curved surface which travels through space in undulatory movements; the atoms in this surface are under no tension. J. F. S. Transition Elements and the Octet Theory A New Arrangement of the Rare Earth Elements in the Periodic Classification. R. G. W. NORRISH (Chern. News 1922 124 1&22).-A theoretical paper in which the author considers the fourth postulate of Langmuir’s octet hypothesis from the point of view of valency and colour of the ions produced in solutions of salts of the metals. A new arrangement of the periodic system is drawn up which has as its basis that the transition elements and the rare earth metals have a variable electronic structure as far as the outermost shell of electrons is concerned. It is shown that the elements which yield coloured kations can all be grouped together in a rectangle which extends from groups 4A to 1B and from series IV to VI. These elements are assumed to possess the variable electronic structure. The rare earth metals which give coloured kations are sharply cut off from those which give colour- less kations by this rectangle. The existing data concerning the characteristic infra-red frequency the latent heat of vaporisation the compressibility and the magnetic susceptibility are tabulated with the periodic arrangement and i t is shown that these properties maintain a more or less high value inside the rectangle but fall off sharply on either side of it. The elements inside the rectangle (excluding copper silver gold and zirconium) are paramagnetic whilst to the right of the rectangle all the elements except tin which is feebly paramagnetic are diamagnetic and those to the left of the rectangle are either feebly paramagnetic or diamagnetic. It appears that the magnetic susceptibility and colour are de- pendent on the presence of an incomplete subsidiary ring in the atom. J. F. S. Radii of the Alkali Metals and the Alkali Metal Ions. RICHARD LORENZ (2. Physilc 1921 6 271-275).-A theoretical paper in which the author has discussed the values previously obtained for the atomic radii (A. 1921 ii 191) and the space filling of the atoms concerned. A new table of the atomic radii ionic radii and the space filling of the alkali metals and alkali metal ions has been drawn up which is based on the present discussion and recent work of other investigators. A Lecture Experiment for Demonstrating the Dependence of the Antiseptic Action of Mercury Compounds on the Degree of Ionisation. G. JOACHIMOGLU (Biochem. Z 1921 121 259-261) .-The fermentation of dextrose by yeast with the visible production of carbon dioxide in fermentation tubes affords a means of demonstrating the antiseptic influence of mercuric ions. Addition of mercuric chloride inhibits fermentation completely but repression of the ionisation by addition of sodium chloride gives a moderate evolution of carbon dioxide. Mercuric cyanide has practically no inhibiting influence. J. F. S. H. K.

ISSN:0368-1769    

DOI:10.1039/CA9222205173

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

i. 190 ABSTRACTS OF CHEMICAL PAPERS. P h y si 01 o gi eal Chemistry . The Excretion of Acetone from the Lungs. A. P. BRIGGS and PHILIP A. SHAFFER ( J . Biol. Chem. 1921 48 4 1 3 4 2 8 ) . - Experiments on human diabetics normal fasting subjects and dogs after injection of large doses of acetone show (1) that acetone is distributed between blood and alveolar air in approximately the same ratio as between water and air (2) that the concentration of acetone in urine is approximately the same as in blood. These results confirm Widmark’s conclusion (Biochem. J. 1920 14 379) t)hat acetone is excreted from the lungs and kidneys by the physical process of diffusion. E. s. Physical Chemistry of Cell. Respiration. OTTO WARBURG (Biochem. Z. 1921 119 134-166).-The adsorption and oxidation of cystine by blood charcoal was investigated in the presence of various narcotics.There is an inhibition of both properties due to a displacement of the amino-acid and of oxygen from the charcoal surhce by the narcotic. Hydrocyanic acid also inhibits adsorption and oxidation but the same explanation does not hold good. A comparison was made of blood charcoal and charcoal prepared from benzoic acid. I n composition and qualities of adsorption they differ markedly. From analogy with the charcoal experi- ments cell respiration is considered to be essentially associated with the solid constituents of the cells. H. K.PHYSIOLOGICAL CHEMISTRY. i. I91 Blood-gas Analysis. IX. Narcosis and Charge on the Colloids. KLOTHILDE MEIER and W. KROXIG (Biochem. Z. 1921 119 1-15).-By following the curve of combination of carbon dioxide with corpuscles as used in previous papers (A.1920 i 200) the authors show that addition of narcotics favours the neutralisation of the charge on the surface colloids of the erythrocytes. Corpuscles suspended in saline solution are dis- charged at P 6-67 but a t the optimum concentration in the saline of methylurethane ethylurethane and ethyl alcohol the discharge takes place a t P 6.95 6.90 and 6.85 respectively. H. K. The Dextrose Concentration in the Arterial Blood and in the Venous Blood from the Muscles. V. HENRIQUES and R. EGE (Biochem. Z. 1921 119 121-133).-No great difference of dextrose content between arterial and venous blood is to be expected. The process is complicated by a reservoir of carbohydrate in the muscles Under special conditions a difference can be observed. In a condition of hyperglyczmia there is a large disappearance of dextrose during passage through the muscles and when the dextrose concentration in the blood has again fallen the venous blood may contain more than the arterial.H. I<. The Ammonia Content of the Blood and its Bearing on the Mechanism of Acid Neutralisation in the Animal Organ- ism. THOMAS P. NASR jun. and STAXLEY R. RENEDICT (J. Biol. Chem. 1921 48 463-488).-The work of previous investigators on the ammonia content of the blood is discussed and an improved technique for its estimation is described. The ammonia is removed from the blood by aeration collected in acidified water and estimated by means of Nessler’s reagent.By means of this method the authors find concentrations of ammonia nitrogen varying from 0.03 to 0.20 mg. per 100 C.C. The concentration of ammonia in the blood is unaffected by the adminis- tration of phloridzin the removal of the kidneys and the injection of acid or alkali; the concentration in the renal venous blood is about twice as great as that in the systemic arterial blood. From these results the authors conclude that the kidney is the seat of formation of ammonia and on this basis they offer an explanation of the different types of acidosis met with in various clinical conditions. C. R. H. Inorganic Blood Phosphate. EDWIN P. LEHMAN ( J . Biol. Chem. l921,48,293-303).-A number of estimations of inorganic phosphate in the whole blood of normal rabbits by the method of Bell and Doisy (A.1920 ii 769) show that this consti- tuent is practically constant and amounts to between 4 and 6 mg. per 100 C.C. When the concentration of phbsphate is increased by the injection of large amounts of di-sodium hydrogen phosphate (sufficient in some cases to cause tetany) a normal concentration is reached again in four hours. C. R. H.i. 192 ABSTRACTS OF CHEMICAL PAPERS. The Blood Calcium Content in Normal Children and in Tetany. I. 13. DE V i t i ~ s RORT~ES (Nederl. Tijdschr. Geneesk. 1919 63 [i] 1663).-Dcspite statements to the contrary there appears to be no abnormality in the content of calcium of tho blood of children with tetany. The Blood-sugar in Narcosis and Diseases of the Nervous System. H. CITANTRAINE (Zen.fr.inn. Med. 1920 41 521- 529).-During ether narcosis the blood-sugar is increased the increase ranging from 30 to 50%. During narcosis with ethyl chloride in patients with nervous diseases and in rabbits with experimentally produced concussion of the brain the proportion of blood-sugar remains normal. CHEMICAL ABSTRACTS. Acetone Substances in the Blood in Diabetes. R. FITZ (Trans. Assoc. Amer. Physicians 1917 32 154-158).-Simul- taneous estimation of the total acetone substances in the blood plasma and the degree of acidosis revealed no quantitative relation- ship between increased concentration of acetone and lowering of blood bicarbonate although in general the proportion of the acetone rose as that of the bicarbonate fell. The total acetone was increased by large amounts of fat the maximum occurring several hours after ingestion and after visible lipaeemia had disappeared. Small amounts of fat depressed blood acetone.Pasting and pure carbo- hydrate diet diminished a high acetone value. Sodium hydrogen carbonate increased the output of acetone but its effect on blood acetone was uncertain. I n three fatal cases of coma a rapid pre- mortal rise of blood acetone occurred; in one case this was independent of acidosis. CHEMICAL ABSTRACTS. Effect of Subcutaneous Injections of Solutions of Potassium Cyanide on the Catalase Content of the Blood. WIT~LIAM H. WELKER and J. L. BOLLMAN ( J . BioZ. Chem. 1921,48,445-451).- The subcutaneous injection in dogs of lethal doses of potassium cyanide has little if any effect on the catalase content of tho blood.E. s. A Direct Demonstration of the Impermeability of the Corpuscles of Man and of the Rabbit €or Dextrose. 8. VAN CREVELD and R. BRINKMAN (Biochem. Z. 1921 119 65-72).- Corpuscles obtained by the jugular method froin rabbits or by the paraffined tube method froin man are always free from dextrosc. JTaulty technique is the bask of the discrcpant resuItls of other workers. H. K. Colloidal Structure of Wed Blood Corpuscles and Hzerno- lysis. 111. Ultramicroscopic Investigation of Lipoids. KENZO HATTORI (Biochem. Z. 1921 119 45-64).-The colloidal balance of an optically homogeneous cholesterol-lecithin mixture is altered by water owing to swelling of the lecithin and separation of the cholesterol. By saline solution however the degree of swelling of lecithin is hmited and there is no separation of cholesterol.Reagents which affect the colloidal balance are haemolytic but the parallelism is only approximate. CTIEMICAT ABSTEACTS . H. K.PHYSIOLOGICAL CXEMXSTRY. i. 193 The Combinations of Haennoglobin with Oxygen and Carbon Monoxide and the EfEects of Acid axdl Carbon Dioxide. ARCHIBALD VIVIAN HILL (Biochem'. J. 1921 15 577-586).-A theoretical paper which suggests an explanation for the S-shaped dissociation curves of oxy-hzemoglobin and of carboxy-hzemoglobin and the identical effects of carbon dioxide on these curves. The chief assumptions made are (1) that hzmoglobin dissociates slightly into protein molecules and molecules containing iron and (2) that in the presence of salts the osmotic pressure of the complex hzemo- globin and of the simpler protein is reduced to l l n of its value calculated on the basis of one atom of iron per molecule of hzemo- globin.This reduction is not necessarily due to aggregation of molecules as was previously assumed ( J . Physiol. 1910,40 Proc. iv). It is shown that the effects of acid and of carbon dioxide on the dissociation curve of blood can be deduced from the hypothesis that the available alkali inside the corpuscle is competed for by oxy-hanoglobin reduced hemoglobin and the acid or carbon dioxide the first being a far stronger acid than the second. The rectangular hyperbola relating carbon monoxide saturation to carbon monoxide pressure or oxygen saturation to oxygen pressure in blood or hzmoglobin fully saturated with a mixture of these gases is also explained by the theory as are various other points.Acceleration of Blood-clotting by Euphylline. R. MEISSNER (Biochem. Z. 1921,120 197-202).-Euphylline (an additive pro- duct of theophylline and ethylenediamine) can accelerate blood- clotting even up to 50%. The components have individually a weak action. H. M. The Basal Metabolism and the Specific Dynamic Action of Protein in Liver Disease. JOSEPH C. ATTB and JAMES El. MEANS (Arch. Intern. X e d . 1921 28 173-191).-The basal metabolism in twelve cases of liver disease (gallstones cirrhosis carcinoma acute catarrhal jaundice) was essentially within normal limits. The liver is therefore either not an important regulator of the metabolic rate or it is adequate for this purpose even when severely diseased.The rate of absorption and utilisation of protein in large quantities was usually normal even in severe cirrhosis. In two cases of cirrhosis and one of gallstones the utilisation of the protein was delayed or absent. Marked portal obstruction caused no delay in the appearance of the specific dynamic action of protein. The cases of cirrhosis showed on the whole the highest metabolic response to protein katabolism. The conclusion seems justified that either the liver is not the main site of the specific dynamic action of protein or that it can adequately perform that function even in disease. The specific dynamic action of protein results from an increased combustion of protein and carbohydrate rather than of fat. The observations of Du Bois (ibid.1916 17 915) that in exophthalmic goitre a normal increase in heat pro- duction due to protein is superimposed on the high basal rate is confirmed. CHEMICAL ABSTRACTS. G. B.i. 194 BBSTRACTS O F CHEMICAL PAPERS The Influence of Food Ingestion 0n Endogenous Purine Metabolism. I and 11. WILLIAM C. ROSE ( J . Biol. Chem. 1921 48 563-573 and 575-590).-The uric acid output remains constant under constant dietetic conditions but is influenced by the quantity and nature of the food. In particular it is iiicreased by the amino-acids. The precursors of the purines are probably arginine and histidine; in the absence of these precursors varia- tions in the purine output rnay be brought about by the re-utilisa- tion for anabolic purposes of purines produced in catabolism.C. R. H. Mechanism of Reduction of Nitrates and Nitrites in Processes of Assimilation. OSKAR BAWDISCIE ( J . Bid. C'hem. 1921 48 489-502).-A summary of the author's previously published work on the subject. ' E. S. Quantitative Estimation of the Fat-sehble Factor. SYLVES- TER SOLONON ZILVA and MASATARO MIURA (Biochem. J. 1921,15 664-659).-Rats are used which have been kept 3-4 weeks on the basal diet without growing; their weight should not exceed 70 grams. The minimum dose of the active substance is then determined which jus'c induces a definite growth. For instance 1.7 mg. of the most active cod liver oil per day did this and 1.4 mg. did not. The minimum doses of various samples of cod liver oil varied from 1.7-5 mg. of butter from 200400 mg.G. E. Plnarmacological and Chemical Study of the Woes of the Barbel and Pike. FRANCIS H. MCCRUDDEN (Arch. a p t . Path. Pharin. 1921 91 46-80).-Fish poisoning produced by con- sumption of the barbel or pike is due to a toxic substance contained mainly if not exclusively in the hard roes of these fishes. For the investigation of its properties the globulin and albumin were extracted from the roes by salt solution. On separation of these by the usual methods the toxic action was found to be confined to the albumin fraction. Injected intravenously into rabbits i t produced paralysis of the central nervous system death finally resulting from paralysis- of respiration. The effects produced by extracts o€ the roes of either fish were similar but more marked in the case of the pike. A comparison is made of the globulins (ichthulins) from eggs of various fish and the difference between their chemical properties and those of vitellin from birds'-eggs emphasised.E. S. MEYER BODANSKY (J. Biol. Chem. 1921 48 361-364).-Analyses of one foetal and four adult brains indicate that zinc and copper are normal constituents of the human brain. Acetone in Cerebrospinal Fluid. J. KOOPMAN (Nederl. Tijdschr. Geneesk. 1920 64 1346-1350).-Acetone is present in the cerebrospinal fluid during diabetic coma diabetic acidosis and adrenal apoplexy ; in the first t1T-o cases it is accompanied by acetoacetic acid. CHlsnircaL ABSTRACTS. The toxicity is destroyed by heat. Zinc and Copper Content of the Human Brain. E. S.PHYSIOLOGICSL CHEXISTRY.i. 195 The Spacial Separation of Glycogen a i d Diastase in the Liver Cells. E. J. LIBSER (Biochem. Z. 1921 119 lOS-EO).- Perfusion of a frog's liver in the moiifhs August to January with hypertonic salt solutions leads to a fourfold excretion of dextrose over that produced by isotonic salt solutions. The dextrose production rises to a maximum after four hours. In the spring and summer months there is no great difference between the effect of isotonic and hypertonic salines. This effect is independent of the ions of the salts used and is only slightly affected by the hydrogen-ion concentration. The action appears to be purely osmotic. H. K. Sea-wolf Liver Oil. THOR LEXOW (Chem. Umschuu 1021 28 %13-214).-The livers were obtained from both male and female of the species Anarrhichas lupus L. ; the oil extracted separately was of a clear golden brown colour and had a curious odour unlike that of other liver oils.The oils from the male and female livers gave respectively the following characters dig 0,9162 0.9179 ; n!$ 1.4733 14702 ; acid number 13.11 14.37 ; saponification number 182.8 185.2 ; iodine number (Wijs) 131.2 118.1 ; unsaponifiable matter 5-23 3.86 ; fatty acids 92.4y0 92.2% ; m. p. of fatty acids 24*5" 34.7"; mean molecular weight of the fatty acids 276.8 279.9. The oil is used in Russia mixed with coal-fish liver oil in taming and can easily be distinguished from the sea-wolf liver oil by its low iodine number and high content of unsaponifiable matter. H. C. R. Variations in the hylolytic Activity of the Panicreas and Liver in Avian Polyneuritis. R.TIGER and H. SIMONNET (Bull. Soc. Chim. Biol. 1921 3 580-582).-The amylolytic activity of the panere& in pigeons wit'h polyneuritis is slightly less than in normal birds. Experiments with the liver did not yield concordant result's. E. S. The Function of the Pancreas. LEO ADLER (Arch. expt. Path. Pharnz. 1921 91 110-124).-The author has previously shown that hibernating hedgehogs are roused and the body temperature brought to summer level by subcutaneous injection of extracts of thyroid or thymus adrenaline or certain amines derived from proteins. In the present paper it is shown that a simultaneous injection of pancreas extract made from the pancreas of hiber- nating hedgehogs more or less completely suppresses the action of these substances.The suppression is less complete in the case of adrenaline than in the other cases. E. S. Heterogenetic Antigen and Hapten. XV. KARL LAND- STEINER (Biochem. Z. 1921 119 294-306).-The soluble hetero- genetic antigens obtained from horse kidney by alcohol extraction are as active in vitro as the unchanged materials but when injected into animals do not' produce hEmolysin. H. K.i. 196 ABSTRACTS OF CHEMICAL PAPERS. The Enzymes of the Abdominal Adipose Tissue of the Common Turkey Meleagris gallipawo. JOSEPH SAMUEL HEPBURN ( J . Arner. Chem. SOC. 1921 43 1963-1965).-Using the method previously applied to chicken fat (cf. Pennington and Hepburn A. 1912 ii 275) but taking tributyrin as the substrate for lipase and ethyl butyrate for esterase catalase lipase and esterase were always found in the adipose tissue.Simple reductase and oxydase acting on phenolphthalein were usually present. Tests for oxydases acting on rx-naphthol and tricresol and fbr protease gave negative results. Aldehyde reductase and peroxy- dases were found in several of the samples. The Selective Absorption of Potassium by Animal Cells. 11. The Cause of Potassium Selection as Indicated by the Absorption of Rubidium and Caesipxm. P a m ~ H. MITCHELL J. WALTER WILSON and RALPH E. STANTON (J. gen. Physiol. 1921 4 141-148).-Frog muscles perfused with Ringer solution in which potassium has been replaced by czesium (or rubidium) in equivalent amount and stimulated electrically during the per- fusion absorb the caesium (or rubidium) in such a way as to be retained during a subsequent perfusion with potassium-free Ringer solution.The substitution of cssium (or rubidium) for potassium in the diet of rats leads to a replacement of potassium by that metal in the tissues. Rubidium and czesium are toxic and in the presence or absence of potassium cause death. The physiological peculiarities of these metals may be related to their electronic structure and Physiological Significance of the Change in the Condition of Permeability in the Limiting Mendwane of the Muscle Fibres. GUSTAV EMBDEN and ERICH ADLER (2. physioE. Chern. 1922 118 1-49).-The permeability of. the limiting sheath of the muscle fibres of the gastrocnemius of the frog was studied under different physiological conditions. The diffusion of phos- phoric acid from the muscle into Ringer’s solution was adopted as the method for the estimation of the permeability.Investigations on Potassium Paralysis. HANS V O G ~ (Z. physiol. Chern. 1922,118 50-95).-The speed with which potass- ium paralysis intervenes in the gastrocnemius of the frog runs parallel with the permeability of the limiting membrane of the muscle fibres as determined by the diffusion of phosphoric acid out of the muscle (see preceding abstract). This of course depends on the physiological condition of the muscle. The onset of the potassium paralysis of the muscle can therefore be utilised as a standard for the permeability of the limiting membrane of the niusele fibres. The author utilises the above observation t o explain the different conclusions drawn by himself and Overton in an earlier investigation. s.s. z. The Influence of Asphyxiation on the Permeability of the Limiting Membrane of the Muscle Fibres. MAX SIMON (2. physiol. Chem. 1922 118 96-122).-Asphyxiation increases W. G. hence to their comparative migration velocities. w. 0. I<. S. S. Z.PHYSIOLOGICAL CHERTISTRY. i. I97 the permeability of the limiting membrane of the muscle fibres in the gastrocnemius of the frog. This can be demonstrated by replacing oxygen by hydrogen. The change is reversible. The permeability was determined both by the diffusion of phosphoric acid and by the production of paralysis by the potassium ion (see The Influence of the Chemical Composition and the Physico-chemical Structure on the Function of Frog Muscles.HANS BEHRENDT (2. physiol. Chem. 1922 118 123-167).- The lactacidogen content of the gastrocnemius and the adductor muscles of the frog is the same. The adductor muscles however contain sometimes more free phosphoric acid than the gastro- cnemius. The " residual phosphoric acid " (restphosphorsaiire) and the glycogen content is higher in the gastrocnemius than in the adductors. The nhvsico-chemical uronerties of the two muscles preceding abstracts). s. s. z. as obfained by ph;..Gological methodis ;re also compared. s. s. z. Chemistry of the Formation and Ripening of Honey. E. SARIN (Biochem. Z. 1921 120 250-258).-Bees mere fed with sucrose syrup the honey collected and re-fed to the bees. This process was repeated three times. Examinat'ion of the honey at each stage indicated that invertase and diastase are specific products of the Fees but catalase n.hich only occurs in natural honey is of plant origin. Influence of Organic Acids on the Formation and Ripening of Sugar-honey.E. SARIX (Biochena. Z. 1921 120 259- 264).-The addition of acids to the sugar syrups used for feeding bees exerts a harmful effect on the biochemical processes of the formation and ripening of honey. Citric Acid Content of Milk and Milk Prod-wts. G. CJ. SUPPLEE and B. BELLIS (J. Biol. C'hem. 1921 48 453-461).- From a series of estimations it is shown (1) that the citric acid content of milk from different cows on the same ration shows n marked variation (2) that there is no loss of citric acid during the process of drying or concentrating milk (3) that the citric acid content decreases during ageing in the presence of highly developed acidity (cf.Sommer and Hart A. 1918 i 465). Day and Night Urine during Complete Rest Laboratory Routine Light Muscular Work and Oxygen Administration. JAMES ARGYLL CAMPBELL and THOMAS ARTHUR WEESTER (Biochem. J. 1921 15 660-664).-The night urine contained always less total nitrogen more ammonia less creatinine urea uric acid and amino-acids and was more acid than during the day. The phos- phate tide is considered to be due to the increased acidity which in its turn is attributed to delayed excretion of certain fixed acids formed in the cells during the day. The sulphur was evenly distributed between the day and the night. Administration of 35-40% oxygen did not affect the composition of the urine.H. K. H. K. E. S. G. B. VOLb OXXII. i. ir,i. 198 ABSTRACTS O F CHEMICAL PAPERS. Viscometric and Stalagmometric Measurements of Urine. ERNST JOEL (Biochem. Z. 1921 119 93-107).-The viscosity of normal urine is 1.0 to 1-05. The presence of collojdal materials has a considerable influence on this value. Which Carbohydrates are excreted in the Urine of Sucklings when the Sucrose in the Food Exceeds the Assimilation Limit? A Method for the Quantitative Estimation of several Carbohydrates simultaneously in the Urine. HANS MURSCH- HAUSES (Biochem. Z. 1921 119 328-338).-Experiments with babes under one year of age showed that sucrose administered in excess of the assimilation value appeared in the urine partly unchanged and partly as dextrose and laevulose. The three sugars are estimated by determining the rotation and reducing power before and after inversion.Alkapton Ghromogen. G. KATSCH and G$ZA N~MET (Biochem. Z. 1921 120 212-217).-The ethereal extract of an alkapton urine poured on to unburnt lime acquires an evanescent vivid blue colour. The urine of many individuals after administration of homogentisic acid slowly darkens but hornogentisic acid is not detectable. The supposed derivatives of this acid which give rise to this reaction are called alkapton chromogens. AL. IONESCU (Bul. SOC. Chim. RomZnia 1921 3 97-104) .-A theoretical paper suggesting that glycosuria is due to a disturbance of the normal equilibrium between the diastatic reactions occurring in the blood.Thus excessive hydrolytic action would result in the formation of con- siderable quantities of acids ketones and aldehydes in the disposal of which the alkalinity of the blood would assist but these would probably be chiefly converted into dextrose in quantities greater than could be dealt with by the liver. The blood would be affected in regard to the distribution of electrolytes between the white corpusclcs and thc serum and as a consequence the act'ivity of the liver in converting dextrose into glycogen would be diminished. The Types 01 Reaction of the Bile Pigments and the Quaiititat ive Relation of Bilirubin to Cholesterol in the Blood during different Forms of Jaundice. F. ROSENTHAL and M. MEIER (Arch. ex@. Path. Pharm. 1921 91 246-271).- The forms of jaundice investigated were mainly experimental.In each case the type of diazoiiium reaction (cf. van den Bergh and Muller A. 1917 ii 58) given by the serum was determined and the cholesterol content of the latter estimated. The readiness with which bilirubin appears in the urine in each case was also noted. E. S. I. TRAUEE and I?. KLEIN (Biochem. Z. 1921,120 lll-l2i).-The authors have examined the Tyndall effect and the ultramicroscopic behaviour of aqueous solutions H. K. H. K. The reaction is very sensitive. H. K. Chemistry of Diabetic Glycosuria. J. K. The Theory of Narcosis.PIIYSIOLOQICAL CHEMISTRY. i. 199 of a number of organic substances of slight or moderate solubility and find that some substances show two widely differing degrees of dispersity. Stalagmometric experiments on these show that the higher the dispersity the greater the effect on the surface tension of water.The results show that other factors besides those postulated in Traube's theory of narcosis must play a part for the hydrocarbons and alkyl haloids have little effect on the surface tension and yet are powerful narcotics. The Effective Strengths of Narcotics. I. Experiments on the Isolated Frog's Heart. H. FUHNER (Biochenz. Z . 1921 120 143-163) .-The isonarcotic concentration of 40 narcotics has been determined on the isolated frog's heart and the drop numbers have been compared by means of Traube's stalagmometer. Alcohols and their derivatives paracetaldehyde acetone and ethyl ether have a marked effect on the surface tension. Esters are less active but benzene and many alkyl haloids are inactive even in saturated solution.Apart from the alcohols and related derivatives there is no correspondence between narcotic action and depression of surface activity as postulated by Traube's theory. The narcotic concentrations however show a parallelism with the aqueous solubility in salt solutions. The Action of some Derivatives of Chloroform with Special Reference to Traube's Theory of the Action of Narcotics 01 the Aliphatic Series. GEORG JOACHIMOGLU (Biochern. Z. 1921 120 203-21 1 ) .-Traube's theory of narcosis is untenable. Among the chloro-derivatives of methane and etha.ne or ethylene the narcotic action and surface activity are by no means parallel. H. K. F Barium Chloride Poisoning. AL. IONESCU (BuZ.SOC. Chim. Romdnia 1921 3 94--97).-Investigation of a number of recent fatal cases of poisoning due to barium chloride confirms the observa- tions of Ogier and others that a very small proportion of the fatal dose is discoverable in the organs positive results being only obtained by the Flandin-Danger method and not by a combination of dialysis with the Fresenius-Babo process. It is suggested that i t will be advisable in such cases to examine the bones since these appear to take up the overwhelming proportion of the poison. The action of this is attributed in agreement with previous workers to irritation of the neuro-motor system. Toad Venom. HEINRICH WIELAND (Sitxber. buyer. Akad. Wiss. 1920 329-343).-The formula? given to bufotalin and some of its derivatives by Wieland and Weil (A 1913 i 1343) must be changed since it is found that bufotalin retains organic solvents of crystallisation most energetically.Bufotalin crystallised from alcohol is not C1,H2,04 but C26H3606,C2H,0 (which has the game percentage composition). Crystals from ethyl acetate melt at 154" and have the composition 2C2,H,,0,,C4H,0,. The solvent is given off slowly in a high vacuum a t 150" and on careful heating in a high vacuum at 225-230" bufobalh sublimes. Of the six h 2 H. K. H. K. J. K.i. SO0 ABSTRACTS Oh' CHEMICAL PAPERS. oxygen atoms two are present as a lactone group two as an acetyl group and two are hydroxylic. Of the latter groups one is capable of acetylation which yields acetyl bufotazin C,,H,,O m. p. 254" and the other can be oxidised to a ketone group present in bufo- talone C,,H,O m.p. 261". Bufotalin is reduced by palladium black and hydrogen to tetrahydrobufotalin C2,Hg006 m. p. 204- 205". Bufotalien formed by the action of concentrated hydro- chloric acid on bufotalin is C2gH& (not C,,H,,O as previously supposed). I n its formation one molecular proportion of acetic acid and one of water are removed from bufotalin. Bufotalien melts at 222-223" and is yellow in colour. It is reduced cata- lytically by palladium to colourless bufotalun C,H,,O m. p. 198- 199" and hence contains four double bonds. Unhke its precursors bufotalan does not give Liebermann's cholesterol reaction with acetic anhydride and sulphuric acid. The carbon skeleton of bufotalin (apart from the acetyl group) is derived from a saturated hydrocarbon C24H42 with eight hydrogen atoms less than the corresponding aliphatic one.Hence bufotaliii contains four carbon rings. Now the bile acids are also derived from a complex C24 with four rings and as was shown by Windaus and Neukirchen (A. 1920 i 4l) cholesterol differs from the bile acids by an additional isopropyl group a t the end of a side-chain CHMe2*CH,*CH,*CH,*CHMe- which in cholic acid is represented by CO,H*CH,*CH,*CHMe-. Wieland considers it very probable that in bufotalin this side-chain is further oxidised to a y-lactone (?H2.CMe>0 and the chief problem a t preseiit is to convert CH,-CO buf otalan C24H3,03~ into cholanic acid C,,H,O the parent ~ u b - stance of the bile acids. R second crystalline toxic substance from the skin of the toad previously called bufotalein by Wieland aiid Weil is now iiamed Gufotalidin C,,H,,O probably oxybufotalin. With alcohol of crystallisation it melts a t 175" and after heating in a high vacuum a t 228-230". Bufagin the venom of the tropical toad Bufo agua isolated by Abel and Macht (A. 1912 ii 1193) is certainly not identical with bufotalin and according to Faust has only one-tenth of the physio- logical action of the latter. Wieland is not convinced that the molecular weight of bufagin has been correctly determined aiid considers that Abel and Macht's formula C18H2404 may require alteration to C,,H3,0 which is that of a methyl etcher of buf o talin. [The above toad venoms are heart poisons and pharmacologically similar to digitalis and strophanthus. Digitoxigenin is according to Cloetta (A 1921 i 39) C2,H,,04 and strophanthidin (cymari- genin A. 1915 i 704) has 23 or possibly also 24 carbon atoms. All these heart poisons from various animal and vegetable sources seem to be related to cholesterol and the bile acids.] G. B.

ISSN:0368-1769    

DOI:10.1039/CA9222200190

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AQRTCULTURE. i. 201 Chemistry of Vegetable Physiology and Agriculture. The Effect of Hydrogen-ion Concentration on the Pro- duction of Carbon Dioxide by Bacillus butyricus and Bacillus subtilis. MATILDA MOLDENHAUER BROOKS ( J . Gen. Physiol. 1921 4 177-186).-The rate of production of carbon dioxide by Bacillus butyricus and Bacillus subtilis is a maximum a t P 7 and 6% respectively. If alkali be added to the culture a t its optimum P recovery in the rate of production takes place; if acid be added recovery takes place only if the amount added be small and if Bacteria as a Source of the Water-Soluble B-Vitamin. SAMUEL R. DAMON ( J . Eiol. Chem. 1921 48 379-384).-Feeding experiments on rat's indicate that B. paratyplwsus B. B. coli and B. subtilis do not produce vitamin-B (cf.Pacini and Russell A. Characteristics of certain Pentose-destroying Bacteria especially as Concern6 their Action on Arabinose and Xylose. E. B. FRED W. H. PETERSON and J. A. ANDERSON ( J . BioZ. Chern. 1921 48 3 8 5 4 1 1 ; cf. A. 1920 i 406 513 911).-Pure cultures of twelve strains of lactic acid bacteria were isolated from corn silage and sauerkraut. They are classified in two main divisions according as they ferment lxvulose with or without the production of mannitol further subdivision depending on their fermentative ability towards various sugars. The fermentation of arabinose and xylose by these bacteria results in the formation of acetic acid lactic acid and carbon dioxide. The two acids are formed in approximately equimolecular proportions the main line of ferment- ation being apparently simple cleavage into acetic and lactic acids.The mannitol-forming bacteria also slowly ferment lact>ic acid to acetic acid and carbon dioxide. The Attack of Dextrose and Laevulose by the Pyocyanic Bacillus. IC. AUBEL (Gompt. rend. 1921 173 1493-1495).- Amongst the products of the decomposition of dextrose and lawulosc by the pyocyanic bacillus alcohol acetic acid and formic acid have invariably been found. I ~ ~ c t i c acid has also been found as a by- product from laevulose. The degradation of the two hexoses under thew conditions is consiclcrcd to proceed as €allows. Hcxuose -+ incthylglyoxnl -+ pyriivic acid +acetaldehyde acetic acid +forinaldehyclc -f f orinic acid Action of Acids on Fermentation by Yeast. i t be neutralised by an equivalent amount of acid.w. 0. K. 1918 i 339). E. s. E. 8. alcohol 4 lacetic acid W. G . R. SOMOGYI (Biochem. Z. 1921 120 100-102).-Acids exert a harmful effect on fermentation by yeast. This is proved by the examination ofi. 202 ABSTRACTS OF CHEMICAL PAPERS. tJhe action of thirteen acids organic and inorganic a t concen- tirations between N/G and N/1500. The inhibitory action does not appear to be solely dependent on the hydrogen-ion concen- The Change undergone by Nitrogenous Substances in the Final Phases of Yeast Autolysis. Nrco~sus N. IVANOV (Biochem. Z. 1921 120 1-24; cf. A. 1918 i 365).-If after yeast autolysis has proceeded for some time the solution be made alkaline the ensuing autolysis is accompanied by an increase of protein nitrogen (as estimated by Stutzer’s method) a t the expense of the original protein decomposition products which are pre- cipitable by lead acetate and phosphotungstic acid.The amino- nitrogen however as determined by Van Slyke’s method is unchanged. If the autolysis in alkaline solution is allowed to continue a t a higher temperature for example 60° there is a loss of amino-nitrogen unaccompanied by any increase of protein- nitrogen. This is interpreted as being due to the formation of humin-like substances a t the expense of the amino-acids of tlhe au t ol y sa t e and carbohydrates . The Influence of Fermentation Products on tho Decomposi- tion of Proteins in Yeast. NICOLAUS N. IVANOV (Biochem. Z. 1921 120 6240).-During the process of fermentation sub- stances are formed which inhibit the decomposition of protein.It is shown experimentally that the inhibition is the result of two factors (1) production of alcohol during fermentation (2) develop- ment of acidity ; the former plays the greater r6le. Protein Decomposition in Yeast during Fermentation. NICOLAUS N. IVANOV (Biochem. Z. 1921,120 25-61).-Stutzer7s method ( J . Lundw. 1580 28 103) for the estimation of proteins in solutions by precipitation with cupric hydroxide does not different)iate between proteins and humins. During the fer- mentation of sugar by yeast there is decomposition of protein earlier statements to the contrary being based on results obtained by Stutzer’s method the humins formed being stable to the proten- lytic enzymes present and compensating for the loss of protein.Meyer’s “ excrements of fermentation ” are probahly humin-like substances. H. IT<. Effect of certain Stimulating Substances on the Invwtase Activity of Yeast. ELIZABETH W. MILLER ( J . 13ioZ. Chem. 1921 48 329-346).-The addition of an alcoholic or aqueous yeast extract to growing yeast is known to stimulate both growth atnil formation of invertase. It is now shown that these two effectls are produced by different substances a partial separation of which may be effected by removal of the growth stimulant by extraction with benzene adsorption with Puller’s earth or precipitation with phosphotungstic acid. The substance accelerating invertase forma- tion is also contained in high concentration in a gummy precipitate which separates from alcoholic extracts of yeast.Its action is not of the nature of a co-enzyme since it is without influence on tration but on other physical properties as well. H. K. H. K. H. K.YEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 303 invertase itself ; moreover although Abderhalden and Schaumann (A. 1919 i 108) found that yeast extract increased the invertase activity of both dried yeast and maceration juice the increase was so small as to fall within the limits of experimental error. Extracts of wheat germ also stimulate growth but do not increase the invertase concentration in yeast. E. S. The Lactase Content and the Fermenting Power of Lactose- fermenting Yeasts. RICHARD \VIrJLsT;iTTER and GERTRUD OPPENHEIMER (2. physiol. Chem. 1922 118 168-188).- Lactase can be obtained from fresh yeast without previously destroying the cell providing that the acidity is neutralised. The lactose-splitting activity of yeasts sometimes even of the same strain varies within very wide limits.In some cases lactose is fermented more quickly than an equivalent mixture of dextrose and galactose. It is also shown that in certain cases the fermen- tation of lactose proceeds almost as quickly as or perhaps more quickly than the hydrolysis of the disaccharide. When the fer- mentation is interrupted in such cases no monosaccharides are found in the fermenting medium. This differs from the mechanism of the fermentation of sucrose when hydrolysis takes place almost immediately. It is concluded that lactose-fermenting yeasts can ferment that sugar without hydrolysing it and therefore contain a lactose-zymase.S. s. z. Vitamin Requirements of certain Yeasts and Bacteria. CASIMIR FUNK and HARRY E. DUBIN ( J . Biol. Chem. 1921 48 437-443).By shaking autolysed yeast with either Fuller's earth or '' norit " vitamin-B is completely removed ; the filtrate however still promotes the growth of yeast. The authors conclude that n hitherto unknown vitamin for which the name vitamin-D is suggested is present in yeast. E. 8. The R6le of Acetaldehyde in Alcoholic Fermentation. A. FERNBACH and &I. SCHOEN (Bull. inst. Pastcur 1930 18 385- 406).-A review of the present state of knowledge of the subject with special reference to the work already published of Neuhauer and Fromherz Neuberg and others nlllnz6 and Lintner Lichig J.B. Dumas Connstcin Leucleke and the authors. CHEMICAL ABSTRACTS. The Lipase of Aspcryillus niger (van Tiegh). ROBERT SCHENKER (Biochem. Z. 1921 120 164-196).-A pure culture of Aspergillus niger (identical with Brenner's p-strain) showed growth on various glycerides especially triacetin but no growth on ethyl esters. The lipase present can be extracted with water or glycerol in the form of a press-juice or as a stable acetone-treated prepara- tion. Fatty media favour the development of the enzyme more than media containing glycerol or sucrose. The optimum tem- perature for the enzyme is 40° and the optimum reaction of the solution for its activity neutral or weakly acid. H. K.i . 204 ABSTRACTS OF CHEMICAL PAPERS. The Toxicity of Biff went Nitrophenols towards Rspevgilbes niger.L. PLANTEFOL (Cornpt. rend. 1922 174 123-12G).- Phenol and its nitro-derivatives are toxic towards Aspergillus niger the nitro-derivatives being more toxic than phenol itself. Of the three mononitrophenols the ortho is the least and the para the most toxic. 2 4-Dinitrophenol is one hundred times more toxic than phenol and ten times more t,oxic than the most toxic mono- nitrophcnol. 2 4 6-Trinitrophenol is about as toxic as m-nitro- phenol. W. G. Bactericidal Action of the Quinones and Allied Compounds. GILBERT THOMAS MORGAN and EVELYN ASHLEY COOPER (Biochem. J. 1921 15 587-694).-When proteins are added to solut’ions of p-benzoquinone the latter slowly disappears and quinol can be detected; the quinone seems to react as a peroxide 2nd differs fundamentally from phenols which are merely protein precipitants.p-Benzoquinone is 80-190 times as effective in destroying B. typhosus as quinol or phenol. I n ascending a homologous series the quinones become less the phenols more bactericidal ; thymo- quinone is less effective than thymol. The authors incline to the view that the high bactericidal power of benzoquinonc is con- nected with the interaction of nascent peroxide molecules with the bacterial protoplasm. G . B. I. TRAUBE and R. SOMOGYI (Biochem. Z. 1921 120 90-99).-Experiments with Staphylococcus and Bacillus coli show that apart from disinfectants of the type of potassium permanganate and hydrogen peroxide which act chemi- cally physical forces are the deciding factor such as surface activity adsorption; flocculation and other properties.I. TRAUBE (Riochem. Z. 1922 120 108-llO).- The author’s contention is that Prr is too much in the fore- ground t o the exclusion of other factors. I. EUGEN PETRI- (Bioclzem. Z. 1921 119 23-44).-The inhibitory action of Rontgcn rays on the growth of seeds could not be influenced by temperature changes. lack of oxygen or by the presence of potnmium cyanide. The action is therefore not connected with the respiratory processes. The small tempemtiire coefficient points io the action being phoiochemic:il. The Action of Bases and Salts on Biocolloids and Cell Masses. D. T. MACDOUGALL (Proc. Aqner. Phil. Xoc. 1921,60,15- 30) .-A study of the swelling of biocolloids in dilute salt solutions in contiexion with the suggestion that the chief effect of salts in nutrient solutions is in restricting limiting or defining the hydration of the cell colloids.Hydroxides of the metallic bases were found to decrease the swelling of plates of agar in the order calcium potassium sodium in concentrations of 0.01 molar. The chlorides show the same relative action. Hydration of agar is increased by Theory of Disinfection. H. K. PH Again. H. K. Conditions for the Biological Action of Rentgen Rays. H. U.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 205 the hydroxides of these metals a t O.OOlN but no well-defined differences between the metals could be observed. Similar effects were produced by chlorides of calcium magnesium potassium and sodium at O.OOOlfM and potassium and sodium at 0.001M.The purified agar used in the experiments has a value of 6.5 and swells more in hydrochloric acid of p 4.2 than in pure water. The pIi range over which large swelling of the agar occurs is from 4.2 to 11. It also swells largely in O*OOOlM sodium and potassium nitrates but not in thc sulphates. Similar measurements were also made on the swelling of gelatin. The gelatin used had a pII value of 6.2 and it was noted that both hydrogen and hydroxyl ions caused increasing swelling with reference to the isoelectric point a t which minimum swelling occurred. The swelling in 0.0001M potassium chloride (p,=5*7) was not much greater than in water ; the swelling in potassium chloride 0-001M (pII=5*8) is about double that in water. Calcium chloride solutions induce maximurn swell- ing a t O*OOlM but depress hydration as the concentration increases or decreases from 0.001M.The interest of these results lies in the fact that a mixture of a vegetable mucilage (pentosan) type of colloid with a protein colloid exemplifies many of the reactions of living or dead cell masses. Experiments were therefore continued with plates of gelatin 3 agar 2 parts and gelatin 2 agar 3 parts. I n the latter sensitiveness to hydrogen ions was more marked than in the case of agar alone but the effect of potassium chloride is about the same as that upon agar alone. The mixkure in which gelatin predominated showed increase of swelling as p13 was increased to 2.01 whilst potassium chloride showed an effect similar to its effect on agar. The work was then extended to living and dead cell masses such as sections from the roots of Zea mais (dominantly pentosan) which were closely parallel to those of the agar 3 gelatin 2 mixture. Roots of strawberry showed different hydration reactions depending on whether they were grown in saline soils or in sand the latter showing greater hydration. Joints of Opuntia (dominantly pentosan) showed maximum swelling in 0.0 1 N-potassium hydroxide hydrogen chloride at 0*001N and potassium chloride a t 0*0001M all in excess of the swelling in water.The changes in volume of living cell masses in hydrating solutions include osmotic-plasmolytic effects in the alteration of the volume of the included cells. The hydration of dead cell rnasqes includes possible osmotic action of cell-wnlls.CIIEMTCAT ABSTRACTS. Action of Neutral Salts on Plant Plasma. 11. HUGO KAHHO (Eiochem. Z. 1922 120 125-142).-The coagulating action of neutral salts on plant plasma (sections of Tradescantiu zebrina) depends on both ions the anions playing a greater part than the kations. The coagulating property of anions falls off in the order CN8 > 17 Br > NO > Acetate > C1 >Tartrate > Citrate > SO and of the kations K>NH,>Na>Sr,Mg,Ba,Ca. The order of the ions is substantially the lyotrope series but in the reverse order of their action on protein. The possible reasons for this are discussed. H. K.i. 206 ABSTRACTS OF CHEMICAL PAPERS. The Occurrence and Action of Saccharophosphatase in the Organism of the Plant. ANTONIN K ~ ~ T E C and FRANTI~EK DUCHO~ (Biochem.Z. 1921 119 73-80).-The sodium and calcium salts of artificially prepared saccharophosphoric acid are bydrolysed with formation of free phosphoric acid by the resting seeds of the higher cultivated plants as well as by the leaves of Solanum tuberosum. Aqueous extracts of the seeds have the same power but to a lesser degree. Alkali is inimical to the action of the enzyme the optimum acidity being 0.03N for saccharophosphatase and 0-004N for the autolytic phosphatase of the seeds. H. K. Pectic Substances of Plants. II. Preliminary Investiga- tion of the Chemistry of the Cell-walls of Plants. DONALD HERBERT PRANK CLAYSON FREDERICK WALTER NORRIS and SAMUEL BARNETT SCHRYVER (Biochem. J. 1921 15 643-653 ; cf. A. 1917 i 245).-The authors call cytopentans substances related to Schulze’s hemicelluloses which are extracted by cold N-sodium hydroxide and then precipitated by addition of alcohol.They are coloured blue by iodine and do not reduce Fehling’s solution until after hydrolysis by acids when they give 40-S5y0 of pento- sans. Cytopentans form a relatively small part of crude pectin and the name cytopectic acid is suggested for the rest. The samples of this acid from six species of plants contained 41.22- 42.88% C 5.31-5-71% H and O-15-O*S5~o ash. [a]’g+26O0 to +2S0°. The percentage of methyl alcohol set free by sodium hydroxide was 0*16-0*42~0 (cf. von Fellenberg A. 1918 i 215 and Tutin A. 1921 i 751). Incrustive Substances of Plants. 11. ERICH SCHMIDT and FRANZ DUYSEN (Ber. 1921 54 [B] 3241-3244; cf.A. 1921 i 912).-The removal of incrustive substances is effected more conveniently by means of a solution of chlorine dioxide in acetic acid (50 yo) than by alternate treatment with chlorine perosiclc and sodium sulphite; the method has tjhe advantage that the attacked incrustations remain dissolved in the ncid. Subsequently the presence of polysaccharides which give a blue coloration in the tissues can be dernonstratcd readily by means of zinc chloride- iodine solution which gives tintrustwort hy results in the pre- sence of the incrustations. The simple manipulation required and the stability of the solutions render tlic chlorine dioxide- acetic ncid valuable for micro-chemical investigations. The reagent causes the cell-walls to swell slightly hut this action OCCUI’S so uniformly that t h e auatomical fcaturcs of the plant me not altered thereby.H. W. The Detection of the Pseudo-bases of Anthocyanidins in Plant-tissues. RAOUL COMBES (Compt. rend. 192 1 174 68- 61).-The substances characterised by Noack in the amyl alcohol extracts of leaves of Polygonurn compactum and Ampebpsis hederacea and the pericarps of Aesculus hippocastanum as antho- cyanidin pseudo-bases (cf. 2. Botanik 1918,10 561) were probably G. B.VEGETABLE PHYSIOLOGY AND AQRTCULTFRE. i. 207 phlobatannins and the red substaiices he obtained by the action of acids which he considered as anthocyanidins were probably phlobaphens. The author does not consider that Willstatter's method for the separation of anthocyanidins and anthocyanins by means of amyl alcohol can be applied to the detection of pseudo- bases of anthocyanidin in plant-tissues.It is necessary to extract the pigments and characterise them by examining the pure products to obtain conclusive results. Effect of Temperature and of the Concentration of Hydrogen Ions on the Rate of Destruction of Antiscorbutic Vitamin (Vitamin-C). H. C. SHERMAN V. K. LA MER and H. L. CAMP- BELL (Proc. Nat. Amd. Sci. 1921 7 279-281).-Guinea pigs were used and both the survival period and post-mortem findings were taken into account in estimating activity of solutions. Boiling tomato juice (PH 4.3) for one hour destroyed 50% for four hours 68%; the curve is much flatter than for a unimolecular reaction. The temperature coefficient for 10" between 60" and 80" was 1.23 between 80" and loo" 1.12.Partial neutralisation or making alkaline causes the vitamin to be destroyed a t a some- what greater rate. Ninety to ninety-five yo is destroyed in five days even a t lo" a t an alkalinity of only Pw=9 (cf. Delf A. 1920 i 460). G B. Occurrence of a Crystalline Tannin in the Leaves of the Acer ginnuZa. ARTHUR GEORGE PERRIN and YOSHISUKE UYEDA (T. 1922,121 66-76). Barbassu Nuts. HENRI JUMELLE (Mat. grasses 1921 13 5878-5879).-The nuts (genus Orbignia) contain Water 4.21 yo oil 66.12y0 carbohydrates 14*47% protein 7*18y0 aellulose 5.99yo ash 2.03%. The oil has the following constants m. p. 26" solidification point 22*7" saponification number 247.7 ether number 242.9 iodine number 16.83 Reichert-Meissl number 6.2 Polenske number 11.3 glycerol 13.2%.The cake has the follow- ing composition Water 11-59 oil 6-50 proteins 19-81 carbo- hydrates 40 cellulose 16-50 ash 5*60y0. CHEMICAL ABSTRACTS. Application of Bourquelot 's Biochemical Method to some Members of the CaryophyZZucete and PupiZionucece. CIrmms VERGELOT (Bull. Roc. chim. Biol. 1921 3 513-519).-By the successive action of invertase and ~mulsin on plant extracts and observation of the rotation and reducing power the author con- cludes tlhat Stellaria holostea contains sucrose but Raponaria oflcinalis Genista sagittalis Ervum hirsutum and Anlhyllis vulneraria contain other unknown sugars. Glucosich arc indicated in most cases and their extraction might be attempted from Genisfa sagittalis Ervum tetraspermum and Saponaria oficinalis.YOSRIHIKO TOCHINAI (Ann. Phytopath. Xoc. Japan 1920,1 22-33).-The fungus utilises carbohydrates as sources of carbon in the following descending order inulin dextrose maltose arabin soluble starch lzevulose W. G. G. R. The Food Relations of Pusarium Zini.i. 208 ABSTRACTS OF CHEMICAL PAPERS. galactose sucrose and lactose. As indicated by the growth made organic acids as sources of carbon are unfavourable to the fungus; the descending order of utilisation is as follows succinic malic citric fumaric maleic and racemic acids. d-Tartaric acid is more readily assimilated than I-tartaric acid. Mannitol but not glycerol is a favourable source of carbon. Phenol derivatives prevent growth. Organic nitrogen compounds particularly amides are far better sources of nitrogen tha'n inorga,nic compounds.CHEMICAL ABSTRACTS. Hazel-nut oil and the Estimation of Arachidic acid. J. PRITZKER and R. JUNGKUNZ (2. Unters. Nahr. Genussm. 1921 42 232-241).-The following characters were given by two samples of hazel-nut oil prepared in thc laboratory d15 0.9152 0.9156 ; n 54.2 54.4 ; acid number 0.8 1.7 ; saponification number 191.8 189.1 ; iodine number (Hanus) 83.5 85.4 ; Reichert-Meissl number 1.54 ; Polenske number 0.5 ; unsaponifiable matter 0.58 yo. Thorough investigation showed that there was no arachidic acid present. The following acetone method was used for the estimation of arachidic acid 20 grams of the oil were saponified with 40 C.C. of 2074 potassium hydroxide and the clear solution was diluted with 50 C.C. of hot water and 20 C.C.of 25% hydrochloric acid were added. After fifteen minutes the fatty acids were separated and dissolved in 180 C.C. of boiling acetone. Twenty c .c. of N-aqueous potassium hydroxide were added and the solution was allowed to cool and kept at 15" for half an hour. The crystals obtained were washed several times with small quantities of acetone dissolved in water the fatty acids liberated with hydrochloric acid and dissolved by warming with'50 C.C. of 90% alcohol. The solution was slowly cooled and left for three hours at 15". If arachidic acid is present the precipitate consists of fine lamina. It is filtered washed three times with 10 C.C. of 90% alcohol and transferred to a weighed flask by dissolving in boiling alcohol. The alcohol is evaporated and &he residue dried at 100" and weighed. Crude nrachidic acid has m.p. 72-75". If the m. p. is below 70" the residue must be again recrystallised from 90 yo alcohol and reweighed. The,quantity obtained is corrected for its solubility in 90% alcohol. This method does not requirc large quantities of alcohol and ether and the troublesome manipulation of tlhe lead soap is avoided. Rehiidlers and Knorr's colour rcsctions for hazel-nut oil are found to be untrustworthy. The Chemical Constituents of some Lorunthcew. D. H. WESTER (Rec. trav. chim. 1921,40 707-723).-Leaves of Loranthus pentandrus L. globosus L. atropurpureus and Viseurn album were examined with respect to their chemical constituents. The ash of the leaves was determined and also the percentage of manganese in the ash figures for the latter being rather high.From the first two species a glucoside identical with quercitrin mas isolated although its properties were not in all respects identical with those €1. C. R.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 209 previously described. The author states that a previous specimen of quercitrin prepared by him showed similar discrepancies m. p. being 174-176" not 183-185" and the benzoate has m. p. 187- 189" not 839" whilst the author's specimens recombine with water of crystallisation which is lost on heating and the solubility in 95% alcohol is 1 part in 70.5 parts not 1 in 229. The m. p. of quercitrin from Loranthus is lowered as the substaiice is purified. Its solubility in various solvents is described qualita- tively and in some cases quantitatively.Three reactions are given which serve to distinguish quercitrin from quercetin with ferric chloride and ether the latter gives characteristic colours the former no reaction ; with zinc and hydrochloric acid in presence of amyl alcohol the former gives a red coloration after some hours the latter a yellow tint ; with a soluble silver salt the former gives no reaction the latter a red coloration which turns blue and finally gives a black precipitate of metallic silver. The last test is stated to confirm the formula for quercitrin suggested by Perkin and Everest (" The Natural Colouring Matters," 191s). The brown coloration given by both substances on boiling with ferric chloride is due to separation of colloidal ferric hydroxide.Quercetin has d 1.6; that of quercitriii is lower. The glucoside sugar consists entirely of rhamnose. Wax from Loranthus species is complex ; the only constituent definitely identified is melissic alcohol but this was not found in L. atro- purpureus neither was quercitrin obtained from this species. Viscuin album does not contain invertase reductase amylase emulsin tannin nor glucoside ; however xanthophyllin and a volatile alkaloid were obtained but the experience of previous workers that it is difficult to extract pure substances from this species is confirmed. H. J. E. The Presence of Sucrose and Aucubin in the Seeds of Mekmpyrum awense L. *;MARC BRIDEL and (MLLE) MARIE BRAECKE (Conqt. rend. 1921 173 1403-1405; cf. A 1931 i 840).-The presence of a glucoside in the seeds of 1MeZamnpyrunz arvense decomposable by emulsin giving a black product has previously been indicated (Zoc.cit.). Aucubiii has now been extracted in definite crystalline form from these seeds and sucrose has also been isolated. Ludwig and Muller have isolated a glucoside from these seeds (cf. Rrchiv Phurm. 1872 199 S) which they considered to be identical with rhinanthin obtained from the seeds of Rhinanthus Crista-Galli L. (Archiv Pharm. 1870 192 199) but the authors consider further work is necessary to establish the identity or otherwise of aucubin and rhinanthin. W. G. The Changes which Oranges Undergo on Keeping. G. ANDR$ (Compt. rend. 1921 173 1399-1401).-When oranges cut in halves are kept under sterile conditions they undergo a slight loss in weight which is accompanied by a marked loss in acidity and a slighter diminution in sugar content together with inversion of some of the sucrose. These changes are not entirelyi.210 ABSTRACTS OF CHEMICAL PAPERS. due to oxidation as they proceed to a less extent in a vacuum. It is probable that there is also some diastatic action. W. G. Presence in Several Indigenous Orchids of Glucosides yielding Cownarin on Hydrolysk. H. H~RISSEY and P. DELAUNEY (Bull. SOC. Chim. Biol. 1921,3 573-579).-A glucoside yielding coumarin on hydrolysis by dilute sulphuric acid or by emulsin is contained in the following three species of orchids Orchis purpurea Huds. 0. Simia Lam. 0. militaris L. (cf. Bourquelot and HBrissey A. 1920 i 586). This glucoside is not identical with loroglossin (Bourquelot and Bridel A.1919 i 243; Delauney A 1920 i 801 and A. 1921 i 296) which does not yield coumarin on hydrolysis E. S. Occurrence of Ellagic Acid in Rubus Idaeus. The Cause of the Clouding of Raspberry Juice. HERMANN KTJNZ-KRAUSE (Arch. Pharm. 1921 259 193-206).-Raspberry juice on keeping becomes cloudy owing to the deposition of a small quantity of a microcrystalline substance the formation of which is accelerated by the addition of small quantities of a mineral acid. This deposit was collected and decolorised and purified by warming in sodium hydroxide solution with hydrogen peroxide and reprecipitating with acetic acid and was identified as ellagic acid by analysis of its pyridine compound (C,,H,0,,H,0),2C5H5N and by characteristic reactions with alkah hydroxides ferric chloride nitrous acid etc.The ellagic acid does not apparently exist as such in the fruit itself or initially in the fruit juice but originates from a molecular complex of a higher order such as a tannoid or possibly even from th; red colourkg matter of the fruit. G. F. M. Water-soluble Colouring Matters of the Sehixophgcece. KARL BORESCH (Biochem. Z. 1921 119 166-214).-The aqueous extracts of the water-soluble colowring matters of pure cultures of numerous species of Schixophycecc? were examined spectrophoto- metrically. Phycocyan a blue colouring matter with a maximum absorption between the C and B lines occurred alone in some species in others mixed with phycoerythiin a red colouring matter with an orange-yellow fluoresceiice and an absorption maximum in the green between the lines D and E.The latter pigment also occurred singly in certain species. When mixed the two pigments were separable by capillary analysis. H. K. Sakoa Oil from Madagascar. HENRI JUMELLE (Mat. grasses 1921 13 5854-5855).-Sakoa is the name given to Sclerocarpa caflra. The fruits are drupes and have an acid pulp owing to the presence of citric acid. The seeds contain 56% of oil having the following constanis d15 0.9167 do 1.460 saponification number 193.5 iodine number 76.6 Reichert-Meissl number 0.1 Polenske number 0.45 unsaponifiable matter 0*6% m. p. of fatty acids 25". The oil is non-drying. CHEMICAL ABSTRACTS.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 211 Alcohol-soluble Protein of the Caryopsis of Sorghum vulgure.I. Extraction and Identification. SABATO VISCO (Arch. Farm. sperim. Xci. aff. 1921 31 173-176).-Hot 70% aqueous alcohol extracts from the ground caryopsis of Sorghum vulgare about 3.5% 01 a nitrogenous substance which is named sorgein and is classified with the prolamines. It gives the principal colour reactions of the proteins but not the Adamkiewicz or the Liebermann reaction. In the isolation of the compound two fractions were obtaincd which contain respectively 11 -19 yo and 13'61y0 of nitrogen and may be different compounds. T. H. P. The Biochemistry of Tobacco. 11. Tobacco Seeds. G. PARIS (Bot. tec. [R. ist. sci. sper. tabacco Scafati] 1920 17 101-115; cf. A. 1917 ii 227).-The entire seed contains water 9.17% ; crude protein 21.87% ; fat 37.68% ; amides and sugar 6*05740 ; pentosans 2.9% ; cellulose 7*15y0 and ash 3.84%.The ash contains SO 1-97y0; P20 22.12%; Na,O 3.48%; K20 28.5%; CaO 9.54y0; MgO 14.63%. A sample of oil from Kentucky tobacco seed had d15 0-9408 ; temperature of solidifi- cation 12"; acid number 4 ; saponification number 196; iodine number 132.8; ether number 192. The oil consisted of about 52.4% of olein 22.1% of linolein and 23.9% of palmitin. No nicotine was found in tobacco seed except in slight quantities in the germinating seed. The dry fat-free seed contained 6.5% of total nitrogen 3.76% of protein nitrogen 2.39740 of nuclein nitrogen and O.%yO of non-protein nitrogen. The presence of arginine was established. CHEMICAL ABSTRACTS. Hesperidine-like Substances in the Umbelliferm.HAROLD NILSSON (Svensk Farm. Tidskr. 1921 25 233-23S).-The paper gives a brief resume of the chemistry properties and tests for hesperidine. Microscopic sections are best made after fixing with lactic acid and freezing. Microscopically the alkaloid is detected as spherocrysts and sheaves. These are soluble in pyridine and quinoline. Seventy specimens were examined ; either the sphero- crysts or sheaves were noted in the leaves and stems of the follow- ing Aiagelica archangelica A . atropurpurea A . decurrens A . litoralis A. silvestris Acthusa cynapium Bubon galbanuna Conium maculatuna Ferula co?nmunis F . neapolitana F . scorodosma Inz- pratorin ostruthium I . hispanica Libanotis siberica Ligusticunh scoticum Sesili glaucxm S. tenuifoliunz Trinia aulgaris.The presence of the alkaloid was also confirmed by chemical tests. In the fourth sixth and cighth there was also a positive test for the fruit. CHEMICAL ABSTRACTS. Action of Coal Gas on Plants. C. WEHIKER (Bied. Zentr. 1921 50 423-428).-The author has examined the effect of coal gas.on three- to seven-year old trees grown in pots. In winter the trees are scarcely affected but in spring they wither and gradually die. Fir and elm trees are especially sensitive then come maple whilst lime trees are least sensitive. The trees survivei. 212 ABSTRACTS OF CHEMICAL PAPERS. the act’ion of coal gas in the autumn. From these experiments and further experiments on twigs immersed in water saturated with coal gas it is concluded that the harmful effect of coal gas is most pronounced when the root system commences its activity after winter and is not due to action on the foliage.The harmful effect is due to certain constituents in the gas particularly those which impart an odour to the gas. Hydrocyanic acid is particularly harmful. W. G. C. S. ROBINSON 0. B. WINTER and E. J. MILLER ( J . l n d . Eng. Chem. 1921,13,933-936).-1t is probable that all amino-nitrogen present in soil in the form of a-amino-acids and a portion of that nitrogen present as acid amides may be added to the class of substances constituting the source of immediately available nitrogen the chief members of this class being inorganic compounds of ammonia and nitric acid. Pcptides may form a class of potentially available compounds; in some cases the peptides in fertilisers are readily hydrclysed to amino-acids and primary and secondary amines.Availability of Organic Nitrogenous Compounds. w. P. s. Effect of Alum on Silicate Colloids. C. S. SCOFIELD (J. TVccshin,gton Acud. Sci. 1921 11 438-439).-The removal of soluble salts from certain soils of the western United States by irrigation and drainage leads to serious trouble through the effect of colloidal silicates principally sodium silicate on soil texture. By the addition of alum as a dressing insoluble aluminium silicates are formed and sodium sulphate thereby formed is removable in drainage. Analyses of the drainage from soils to which aluminium sulphate had been applied showed that practically all the aluminium had been precipitated by the soil and that equivalent amounts of sodium calcium and magnesium had been liberated combined with the sulphate radicle. The Flocculation of Soils. IT. NORMAN M. COMBER ( J . Ayric. Sci. 1921,11 450-471).-“ Direct ” flocculation of the clay soils by salts of iron and aluminium occurs in a manner precisely similar to the coagulation of electro-negative suspensoids by electrolytes. ’. Indirect ” flocculation by neutral salts and some acids results from interaction with the constituents of the clay particle whereby normal flocculating agents are produced. The “ abnormal ” flocculation of clay by calcium hydroxide is a result of the reaction of lime with the emulsoid surface layer of the clay particle and does not depend on the formation of calcium carbonate. The difference in the action of flocculating agents on clay and silt particles depends entirely on the relative proportions of emulsoid surface layer to core in the particle. (See also J . SOC. Chem. I d 1922 69a.) G. W. R. A. G . P.

ISSN:0368-1769    

DOI:10.1039/CA9222200201

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 212 ABSTRACTS OF CHEMICAL PAPERS. In o r gani c Chemistry. The Steric Formula of the Molecule of Water. JEAN PICCARD (Heh. Chim. Acta 1922 5 72-74).-1t is only possible to explain certain physical properties of water if it is assumed that the centre of gravity of the positive charges of the molecule does not coincide with that of the negative charges. This asymmetry of the charges might result from the inequality in the distances of the two hydrogen atoms from the oxygen atom or by such a dis- position of the hydrogen atoms that the valencies uniting them to the oxygen atom are disposed a t an angle other than 180". There is however no evidence in favour of the first supposition. A consideration of oxonium salts on the other hand shows that in them the co-ordinative valency of oxygen is three and that the oxygen atom may be regarded as placed in the centre of an equi- lateral triangle with its valencies directed towards the apexes and therefore inclined to one another at an angle of 120".An explan- ation is thus given for the observation that only those carbon- oxygen heterocyclic rings are stable in which the total number of atoms is five or six. Thus for example if the valencies of carbon form an angle of 109" 28' with one another and those of oxygen an angle of 120" the mean deviation in a cyclic system composed of three carbon and three oxygen atoms is only 2" 38' whereas in cyclohexane the mean deviation is 5" 16'. Electrolytic Concentration of Aqueous Solutions of Nitric Acid. I. HENRY JERMAIN MAUDE CREIGHTON ( J . Franklin Inst.1922 193 89-95).-When a solution of nitric acid is electro- lysed in a cell in which the anode and cathode are separated by a porous diaphragm concentration of the acid occurs through electro- lytic decomposition of water and a t the same time the concentration of the acid in the anolyte is increased a t the expense of that in the catholyte on account of the different migration velocities of the hydrogen and nitrate ions. The acid in the catholyte is further reduced by reduction to nitrogen oxides hydroxylamine or ammonia according to the nature of the cathode metal. Experiments were made in which 7Q-71% nitric acid was electrolysed in a diaphragm cell using platinum electrodes and provision was made for returning the gaseous nitrogen oxides formed in the anolyte chamber back to the catholyte chamber.The current used was 6-8 amperes and the E.M.P. 3.0-6.5 volts It was found possible thus to increase the concentration of acid in the anolyte chamber t o 99.65% HNO,. The porous cylinder used underwent considerable disintegration in the process. H. W. [See further J . Soc. Chem. Ind. 1922 172A.I E. H. R. Preparation of Silicic Acid and Tungsten Hydroxide Sols by means of Hildebrand Cells. M. KROGER (Kolloid Z. 1922 30 16-18) .-By the electrolysis of a 1.5% solution of sodium silicateINORGANIC CHEMISTRY. ii. 213 between a mercury cathode and a platinum anode in a Hildebrand cell sols of silicic acid are obtained which do not gelatinise until they have been kept for four weeks. A 6% solution gelatinises as soon as the solution becomes neutral.The electrolysis is started with a current of 0.55 ampere but this steadily falls as the process proceeds and in ninety minutes has reached the value 0.12 ampere. After one hundred and ten minutes’ electrolysis the solution has a neutral reaction toward litmus. In the case of the 6% solution the gelatinisation proceeds so rapidly that the waves occasioned by stirring are often reproduced in the gel which is usually as clear as glass. Electrolysis of a 30% solution of water glass causes silica to separate on the anode. Electrolysis of a 2% solution of sodium tungstate using the apparatus named above with a silver anode rapidly produces the hydrosol of tungsten hydroxide. The removal of alkali may be hastened by the cautious addition from time to time of a little hydrochloric acid but in no circumstances may the neutral point be passed.Should the solution become acid blue tungsten compounds are produced. The tungsten hydroxide hydrosols are clear and transparent but of a deep brown colour which in dilute solutions is yellowish-brown. They arc coagulated by potassium chloride to form a black powder which resembles the lower oxides of tungsten. J. I?. S. Influence of Tungstic Acid on the Gelatinisation of Silicic Acid in Concentrated Hydrochloric Acid Solutions. M. KROGER (KoZEoid Z. 1922 30 18-19).-The time required for the gelatinisation of silicic acid in the presence of tungstic acid by hydrochloric acid has been investigated. The solution consisted in each case of 7 C.C. of a solution of sodium silicate containing 33.7% of silica to which had been added volumes of a 10% solution of sodium tungstate varying from 0.5 C.C.to 15 c.c. the total volume in each case being made up to 22 C.C. Nine C.C. of 9-77N-hydro- chloric acid were added in each case and the time required for complete gelatinisation was noted. The time-tungstic acid con- centration curve passes through a minimum a t 1 C.C. of tungstic acid and a maximum a t 2.6 C.C. of tungstic acid and then falls continuously . J. F. S. LAURENCE ST. c. BROUGHALL (Phil. Nag. 1922 [vi] 43 339-344).-A mathematical paper in which the frequency angular velocity and linear velocity of the electrons in the neon atom have been calculated on the assumption that the electrons do not radiate energy under normal conditions.The following numerical results are recorded Frequency of the electrons about the axis XX‘ n3=0.73 x 10l6 ; frequency about Y Y‘ and ZZ’ n’=1-00 x 10l6 ; angular velocity about X X ’ 0,=4.58 x l0ls rad./sec. ; angular velocity about Y Y’ and ZZ’ ~’=6.28 x 10l6 rad./sec. ; instantaneous linear velocity of the outer electrons about X X ‘ v,=2.98 x lo8 cm./sec. ; instantaneous linear velocity of the outer electrons about Y Y‘ and ZZ’ v’=4.08 x los cm./sec. ; instantaneous linear velocity of the inner electrons about YY‘ and ZZ’’=3-83x2Os cm./sec. Frequency of the Electrons in the Neon Atom.ii. 214 ABSTRACTS OF CIIEMICAL PAPERS. The value of v is small when compared with the velocity of light in consequence of which it follows that no appreciable error is committed in not'correcting for the variation of mass with velocity according to the equation w&=m,(-l -v2/c2)lI2 where c is the velociti of light.J. F. S. Crystal Structures of the Alkali Haloids. I. RALPH W. G. WYCKOFF ( J . Washington Acad. Sci. 1921 11 429434).- From data as to the crystalline structure of the alkali haloids obtained from powder photographs and on the assumption that the unit cell consists of four molecules it is held by the author that there are only two possible arrangements of the molecules within the unit cell namely the sodium chloride arrangement and the zinc sulphide arrangement. The geometrical considerations involved and the method of calculating the nature of the diffrac- tion effects to be expected are given elsewhere (Wyckoff and Posnjak following abstract).A closer accord of the normal decline of intensity of reflection with the spacing of the reflecting planes as observed in experiments on sodium chloride and similar crystals is obtained by assuming the intensity to be proportional to the 2.35 power of the spacing instead of the simple square. Experi- mental determinations of the intensity for a few of the principal lines of the spectrum were compared with the intensities calculated with alternative assumption of the two groupings above mentioned. The results agreed with the assumption of the sodium chloride grouping in the case of sodium bromide sodium iodide potassium bromide potassium iodide and rubidium chloride. Czesium bromide and caesium iodide have a similar structure to cmium chloride which has been shown to be body-centred (Davey and Wick Physical Rev.1921 17 403). RALPH W. G. WYCKOFF and EUGEN POSNJAK ( J . Amer. Chem. SOC. 1921 30 2292-2309) .-The crystal structure of ammonium platini- chloride has been determined by a general method which is based on the theory of space groups. It is shown that crystals of am- monium platinichloride have a structure which is analogous to that commonly assumed for fluorspar in which the PtCl groups occupy the positions of the calcium in fluorspar or crystals and the NH groups the positions of the fluorine. The unit crystal cell has a side 9.843 x 10-8 em. The only assumption made which is not required in the ordinary determination of the wave-length of X-rays from a reflection spectrum is that the four hydrogen atoms of the ammonium radicle are exactly alike with this exception that in attempting to place the chlorine atoms with accuracy it was assumed that atoms scatter X-rays in an amount which is roughly proportional to their atomic numbers and that in a lattice arrangement of atoms the intensities of reflection follow quanti- tatively the order of l/(h2+k2+Z2).J. F. S . Analysis of Glucinum Chloride. 0. HONIGSCHMID and L. BIRCKENBACH (Ber. 1922 55 [B] 4-l2).-The ratios BeC1, 2Ag and G. W. R. Crystal Structure of Ammonium Platinichloride. Revision of the Atomic Weight of Glucinum.INORGANIC CHEMISTRY. ii. 215 BeC1 2AgC1 have been determined in the same manner as used previously in the determination of the atomic weight of bismuth (Honigschmid and Birckenbach A.1921 ii 646). As mean result of all analyses the value G1=9.018 is adopted this figure being about 1 yo lower than that assigned by the International Commission. Technical glucinum carbonate is converted into the basic acetate and purified from iron compounds by repeated crystallisation from glacial acetic acid. The purified acetate is sublimed and converted into the nitrate. The solution of the latter in water is treated with an excess of ammonium carbonate and filtered from any undissolved aluminium compounds ; the glucinum carbonate is subsequently precipitated by boiling the filtrate and is finally converted into the oxide by calcination in a platinum dish in an electrically heated furnace. The pure oxide is transformed into the chloride by ignition with carbon in a current of chlorine.The apparatus used is identical with that described previously (Zoc. cit.). Great caution is needed in the quantitative decomposition of glucinum chloride by water. Glucinum chloride has d:5 1.8995. H. W. Inorganic Luminescence Phenomena. IV. Preparation of Pure Magnesium Sulphide and its Phosphorescence. 11. Phosphorescent Magnesium Sulphides. ERICH TIEDE and FRIEDRICH RICHTER (Ber. 1922 55 [B] 69-74).-The specimens of magnesium sulphide described previously (A. 1916 ii 619) were not sufficiently pure to allow definite conclusions to be drawn with respect to the capacity of the-substance to phos- phoresce. Pure magnesium sulphide has now been prepared by the ignition of magnesium oxide or preferably of anhydrous magnesium sulphate in a current of nitrogen laden with carbon disulphide vapour.The compound is not phosphorescent but becomes so by suitable additions of manganese bismuth or anti- mony the optimal amount of metal for 1 gram of sulphide being 0.001-0.002 gram of manganese as sulphate or chloride 0.0024 gram of bismuth as the basic nitrate and 0.0013 gram of antimony as potassium antimony1 tartrate. The main band of emission of phosphorescent light in the case of magnesium sulphide containing manganese lies in the red approximately between 615 and 765 pp with a maximum a t 720 pp. The intensity a t the atmospheric temperature for metal content from 0~00023-0~004 gram is almost constant and not markedly dependent on wide variations of tem- perature and duration of ignition.The duration of the phos- phorescence is small. Magnesium sulphide containing bismuth exhibits an intensely blue phosphorescence which is excited by daylight or arc or mercury-vapour light. The band lies between 430 and 550 pp with a maximum a t 465 pp. Specimens of mag- nesium sulphide containing antimony have a delicate yellow colour and a persistent intensely yellowish-green phosphorescence after excitation by daylight or arc or mercury-vapour light or particu- larly by exposure to cathode rays. The band lies between 570 and 610 pp with a maximum a t 545 pp. H. W. S**ii. 216 ABSTRACTS OF CHEMICAL PAPERS. Lead in the Uranium Minerals of Madagascar. MUCUET (Cmpt. rend. 1922 174 172-173).-The industrial treatment of several tons of betafite from Madagascar resulted in the isolation of lead to the extent of 0.6% of the mineral treated. The mineral being perfectly crystalline and practically free from impurities the lead apparently occurs in the same chemical form as the uranium and is a disintegration product of uranium.The radioactivity of this lead has increased regularly for six months. Abnormal Crystallisation of Lead Azide by Protective Colloids. A. G. LOWNDES (Trans. Faraday Soc. 1921 16 Appendix 128-129).-Lead azide when formed in large crystals is liable to explode and is therefore not entirely suitable for detonators. It is generally held that the explosions are caused by the fracture of large crystals. It is shown in preparing lead azide that if instead of running sodium azide and lead acetate solutions into water the solutions are run into a 0.5% solution of gelatin or dextrin small crystals which are not liable to fracture are pro- duced.The presence of ferric chloride also causes the formation of small crystals but these are useless for the filling of detonators. A number of photomicrographs of lead azide prepared by the various methods are included in the paper. Preparation of Catalytic Copper. JEAN PICCARD (Helv. Chim. Actu 1922 5 147-148).-The following modified method (cf. Piccard and Larsen A. 1917 i 644) yields catalytic copper which is superior in its activity to Kahlbaum’s ‘ I copper-bronze ” or “ naturkupfer C.:’ Granulated zinc (600 grams) is mixed with finely-powdered potassium dichromate (190 grams) or preferably with an equal weight of hydrated sodium dichromate in a three-litre flask and concentrated hydrochloric acid (1300 c.c.) is added within five to ten minutes.A vigorous action ensues which leads to the forma- tion of a clear blue solution. The lat’ter is filtered through glass wool into a flask filled with carbon dioxide a current of the gas being passed over the filter during the process. The solution is treated with brisk agitation with copper sulphate (120 grams) dissolved in ice-cold water (700 c.c.). Reduction is instantaneous. The precipitated copper is washed five times by decantation with water then filtered and washed successively with ordinary and absolute alcohol and benzene. If the product is to be dried the final washing should be effected with benzene containing a little vaselin.After desiccation in a vacuum the copper is relatively stable towards air but is preferably preserved in evacuated sealed tubes. C. PAAL and HERMANN STEYER (Kolloid Z. 1922 30 l-5).-The preparation of solid colloidal copper hydroxide is described. To 50 C.C. of 2% sodium prot- albinate solution which acts as protective colloid 20 C.C. of N - sodium hydroxide and 20 C.C. of 1% copper sulphate solution are added alternately in small quantities a t a time. A light blue W. G. J. F. S. It may also be stored as a paste beneath alcohol. H. W. Colloidal Copper Hydroxide.INORGANIC CHEMISTRY. ii. 217 turbid sol is produced which is dialysed for four days treated with 3 drops of N-sodium hydroxide and evaporated to dryness a t 60" in a vacuum.A blackish-blue brittle substance is obtained in the form of lamellae which dissolve in water to form the original sol. The solid colloid contains 14.02% of copper and 1.34% of sodium. By using sodium lysalbinate as protective colloid and varying the quantities of the other reagents? solid colloids similar in appearance and properties to the above but varying in com- position may be obtained. The colloid richest in copper contains 35.47y0 of copper and 5.31% of sodium. If solutions of the sols are heated for some time on a water-bath black lamella are deposited which dissolve in water to give a dark brown turbid hydrosol. This does not change in colour when treated with 4N-ammonia solution even after keeping for four days. The product is regarded as colloidal cupric oxide and has been obtained containing 28.58% of copper and 4.37% of sodium.The Peroxidic Compounds of Copper. (MISS) JOAN ALDRIDGE and MALCOLM PERCIVAL APPLEBEY (T. 1922,121,238- 243). Reduction of Solutions of Ferric Salts with Mercury. LEROY W. MCCAY and WILLIAM T. ANDERSON jun. (J. Amer. Chem. Roc. 1921 43 2372-2378).-Neutral and acid solutions of ferric chloride are completely and rapidly reduced when shaken with a little mercury. I n the case of ferric sulphate the reduction proceeds to an equilibrium which a t 20" lies a t about 53% of ferrous iron but if a little free hydrochloric acid or sodium chloride is added the reduction becomes complete. Under similar conditions solutions of titanic acid are not reduced. If the mercurous salt is filtered off the ferrous iron in the solution may be estimated by titration with either potassium permanganate or dichromate.Experiments on the estimation of iron in ferric alum and other ferric compounds shorn that this constitutes a rapid accurate and convenient method. Solutions of potassium ferricyanide potassium chromate ammonium molybdate sodium vanadate and potassium antimonate when acidified with hydrochloric acid are all reduced when shaken with mercury. Strengths of Cobaltammine Bases and Werner's Theory of Bases. ARTHUR B. LAMB and VICTOR YNGVE (J. Amer. Chem. Xoc. 1921,43 2352-2366).-The relative strengths of the following cobaltammine bases hexamminecobaltic dibromide dihydroxide hexamminecobaltic hydroxide aquopentamminecobaltic hydroxide. diaquotetramminecobaltic hydroxide triethylenediaminecobaltic hydroxide diaquodiethylenediaminecobaltic hydroxide carbonato- tetramminecobaltic hydroxide 1 2-dinitrotetramminecobaltic hydr- oxide 1 6-dinitrotetramminecobaltic hydroxide and dinitroaquo- triamminecobaltic hydroxide have been determined by measuring the electrical conductivity over a range of concentrations a t 25" and comparing these with the conductivities a t zero concentration its calculated from conductivity measurements of salts derived J.F. S. J. F. S. 8**-2ii. 218 ABSTRACTS OF CHEMICAL PAPERS. from these bases. The determinations shorn that these bases are very strong some of them being as highly ionised as potassium hydroxide ; the replacement of ammonia by ethylenediamine has no effect on the strength of the base.The replacement of ammonia by water molecules produces a marked and progressive decrease in the strength; the substitution of acid-groups has no marked effect on the strength the electrostatic effect of a decrease in valency probably counteracting the chemical effect of the acid radicle ; the stronger acid radicle produces the weaker base. There is no marked difference in the ionisation of the successive hydroxyl groups in hexamminecobalt hydroxide. The improbability of the distinctive features of Werner's theory of bases is pointed out and a more probable interpretation suggested. Equations have been derived giving an important correction of the con- ductivity of solutions of bases for the conductivity of the carbon dioxide dissolved in the water.These equations have been applied in the present work. Sub-salts of Bismuth. HENRY GEORGE DENHAM ( J . Amer. Chem. SOC. 1921 43 2367-2371).-Making use of the method and apparatus formerly employed in the preparation of the sub- salts of lead (T. 1917 111 29; 1918 113 249; 1919 115 log) the author has prepared sub-salts of bismuth from bismuth sub- oxide. The products obtained are a sub-oxyiodide 2Bi12,3Bi0 the sub-iodide Bi& and bismuth dimethyl. The sub-oxyiodide is a non-volatile brick-red substance which is stable in dry air; it commences to decompose at 360". A saturated solution gives a faint darkening with hydrogen sulphide and a faint turbidity with silver nitrate. It is decomposed into the metal and a soluble tervalent bismuth salt by sulphuric hydrochloric and acetic acids. It is insoluble in alcohol and in aqueous potassium iodide solutions and reduces acid solutions of potassium permanganate. Bismuth sub-iodide is a volatile substance which crystallises in red ortho- rhombic needles. In aqueous solution it gives stronger reactions for bismuth and iodine than the oxyiodide ; it dissolves freely in potassium iodide solution giving solutions of the colour of di- chromate solutions. It speedily reduces aqueous solutions of iodine and acid permanganate and is decomposed a t 400" into bismuth tri-iodide and metallic bismuth The distillate of excess methyl iodide from the preparation of the above compounds was yellow in colour but on exposure to air it became colourless and a white solid which turned yellow on keeping separated. This white compound is probably bismuth dimethyl and is insoluble in alcohol ; it is a strong reducing agent and on oxidation is converted into bismuth dimethoxide Bi( 0CHJ2. J. F. S. J. F. S.

ISSN:0368-1769    

DOI:10.1039/CA9222205212

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

i. 213 Organic Chemistry. The Chemical Nature of Mineral Lubricating Oils. A. E. DUNSTAN and F. B. THOLE ( J . Inst. Petroleum Y’ech. 1921 7 417421).-Mineral lubricating oils appear to contain but a small percentage of paraffin hydrocarbons of the CnHZn+2 series and consist chiefly of compounds the formula? of which range from C,H to CnH2n-8. The olefine contents cannot be determined by extraction with sulphuric acid as they are thereby converted into condensation products insoluble in the acid. A partial separation of unsaturated hydrocarbons can be achieved by extraction with liquid sulphur dioxide an oil with an iodine value 46 giving for example a residue with iodine value 33 and an extract witlh iodine value 73. The reaction of mineral oils towards iodine differs profoundly from that of fatty oils as no constant iodine value can be obtained an increase in the proportion of reagent to oil invariably augmenting the value. This fact coupled with the reluctance exhibited to hydrogenation seems to lead to the con- clusion that the unsaturated hydrocarbons in mineral oils consist only to a small degree of true olefines.The saturated compounds are principally naphthenic and probably polynuclear. Solid resinous components containing oxygen are present to the extent of a few parts per cent. and are probably an important cause of “ gumming.” Removal of these substances and the more readily oxidisable unsaturated hydrocarbons reduces the gumming tendency but in oil refining care should be taken not to destroy the more stable unsaturated hydrocarbons to which the viscosity of the oil is largely due it having been shown that an increase in viscosity occurs concurrently with a decrease in the hydrogen content.G. F. 111. The Hydrogenation of Ethylene in Contact with Nickel. ERIC KEIGHTLEY RIDEAL (T. 1922 121 309-318). Bivalent Carbon. ALFRED GILLET (Bull. Soc. chim. Belg. 1921 30 329-336).-A theoretical paper in which some evidence is adduced to show the existence of certain bivalent carbon compounds either as unstable intermediate substances or as isomerides of differing degrees of stability. The Exchange of Halogen in Unsaturated Aliphatic Halo- genated Hydrocarbons. I. H. P. KAUFMABN (Ber. 2922 55 [B] 249-267).-1t is shown in a variety of ways that the iodine atoms of the stereoisomeric s.-di-iodoethylenes are removed with much greater difficulty than those of similar saturated aliphatic iodo-compounds. The most probable explanation is that the unsaturated hydrocarbon residue in the immediate vicinity of the halogen atom makes such a complete demand on t,he affinity H. J. E. VOL. CXXII. i. ii. 214 ABSTRACTS OF CHEMICAL PAPERS. of the latter that but little remains for the attraction of a new atom whereas the saturated hydrocarbon residue saturates the affinity-of the halogen atom less completely and's0 leaves it more disposed to react with reagents in general. Solid ccp-di-iodoethylene m. p. 7S0 is conveniently prepared by allowing a solution of iodine in absolute alcohol to remain in contact with acetylene gas under slightly increased pressure and a t the atmospheric temperature; the liquid isomeride has b.p. 185". A solution oi the solid di-iodde in anhydrous ether reacts quantitatively with activated magnesium in accordance with the equation C2H212+Mg=C2H2+Ig~2 ; in all probability an unstable organo-metalhc compound is formed primarily. Metallic potassium 1s slowly attacked by a boiling solution of solid di- iodoethylene in anhydrous ether with ultimate production of acetylene and potassium iodide ; the formation of acc-di-iodoethylene (see below) during the reaction is established. The latter is pre- pared more conveniently by allowing the ethereal solution of the solid &-iodide (or more rapidly from the liquid isomeride) to remain in contact with metallic sodmm a t the atmospheric temperature.It forms colourless crystals which sublime with great ease m. p. 56" ; the vapours have an extremely unpleasant odour and attack the eyes with great violence. When chssolved in carbon tetrachloride and treated with bromine in direct s d g h t it is transformed into aa-hbromoethylene yellow leaflets m. p. go" which is thus pre- pared in the dimeric form (CgH2IBr2),. If an excess of bromine is used aaap-tetrabromoethane is produced which is formed also by the further action of bromine on the solid dimeric dibromide. Similar acc-di-iodoethylene is converted by 'an excess of chlorine in the presence of bright sunlight into asap-tetrachloroethane b. p. 135" and iodine trichloride. cta-Di-iodoethylene is decom- posed by potassium or activated magnesium in the presence of anhydrous ether with quantitative formation of acetylene.trans- and cis-ap-Di-iodoethylene and aa-di-iodoethylene are decomposed with liberation of iodine when their ethereal solutions are exposed to ultra-violet light the velocity of the reaction in the case of the compound f i s t named being approximately twice as great as that in the remaining two cases. L With E'. SCHWEITZER.1-A solution of solid up-di-iodoethylene in anhydrous ether is attacked slowly by zinc ethyl when the mixture is heated until it becomes slightly turbid and subsequently exposed to direct sunlight during several weeks; the main product is cc-iodo-Aa-butylene CHKCHEt a pale yellow liquid which decom- poses gradually when exposed to light b. p. 127-128"/atmospheric pressure or 57"/30 mm.The same product is mainly obtained in a similar manner from the liquid ap-&-iodoethylene but in this case an isomeride (probably the cis-modification) b. p. 168" is produced in minor amount. It is converted by an excess of bromine m the presence of carbon tetrachloride into aaP-tribromobutane CHBr2*CHBr-CH2*CH a pale yellow liquid b. p. 158" (partial decomp.)/normal pressure or 98"/25 mm. The chief evidence with regard to the constitution of the iodobutylene rests on the observationORGANIC CHEWSTRY. i. 215 that it is converted by sodium into the hydrocarbon Lhv~-octadiene] C8Hl1! a colourless slightly refractive liquid b. p. 138-140". The latter is transformed by ozone into the explosive oxonide a yellowish- red viscous liquid which is decomposed by boiling water into glyoxal propaldehyde and hydrogen peroxide.The transformation of the liquid (cis) ccp-di-iodoethylene into the solid (trans-) modification has been observed repeatedly. The reverse change occurs to the extent of 45" in six hours when the solid isomeride is heated carefully a t 190" ; slight decompositioii with elimination of iodine occurs simultaneously. The System Water-Ethyl Alcohol-Chloroform Misci- bility of the Three Components in Different Proportions and some Practical Applications. N. SCHOORL and (MLLE) A. REGENBOGEN (Rec. trav. chim. 1922 41 l-l4).-The ternary system has been examined and a diagram is given showing the limits of homogeneous mixtures a t temperatures of 0" lo" 20" and 66'. The results obtained by Bancroft (A 1895 ii 157) are criticised on the ground of incomplete drying of the alcohol used.The authors suggest that their data may be of use in the examination of spirits of wine €or water content and of chloroform for the detection of impurities. Details of some typical estima- tions carried out in this manner are given. The System Ethyl Alcohol-Water-Aromatic Hydrocarbons from 30" to -30". W. R. ORMANDY and E. C. CRAVEN (J. Inst. Petroleum Tech. 1921 7 422439).-The freezing-point curves of binary mixtures of benzene with ethyl alcohol toluene and xylene and of ternary mixtures of benzene alcohol and water and of " benzole " (benzene 3 toluene l ) alcohol and water were deter- mined and also t,he liquid separation points of ternary mixtures of benzene toluene and xylene with alcohol and water a t tem- peratures ranging from -30' to 3-30".The method adopted was to add from a burette dilute aqueous alcohol to known mixtures of absolute alcohol and the hydrocarbon maintained a t a constant temperature until separation occurred. The full numerical results are given in numerous tables and results obtained by graphical interpolation are also given showing the strengths of ethyl alcohol necessary to dissolve various proportions of benzene and toluene a t 15" and xylene a t 0". For these the original paper should be consulted. I n regard to the binary mixtures of benzene and toluene the depression of the freezing point of benzene follows the cryoscopic law over a considerable range. The results of the liquid separation point determinations on the ternary mixtures showed that a t any temperature above the melting point of benzene the solubilities of the three hydrocarbons in an alcohol of given strength are in the order benzene-toluene-xylene.At tempera- tures below this separation of solid phase occurs and the solubility of benzene falls below that of its homologues. G. F. M. J. LEROIDE (Ann. Chim. 1921 [ix] 16 354-410).-acc-Disubstituted ketones react with magnesium alkyl haloids in which the alkyl group has H. W. H. J. E. Some Properties of aa-Disubstituted Esters. i 2i. 216 ABSTRACTS OF CHEMICAL PAPERS. a normal chain and not more than four carbon atoms to give excellent yields of the corresponding secondary alcohols. Thus pinacolin reacts with magnesium propyI chloride to give p P-dimethyl- butan-7-01.Under similar conditions camphenylone gives cam- phenylol. With magnesium propyl bromide f enchone gives fenchyl alcohol and camphor gives a mixture of borneol and isoborneol. The esters of aa-disubstituted monobasic acids react with the same magnesium alkyl haloids to give principally secondary and not tertiary alcohols. This action is more marked with the mag- nesium alkyl iodides than with the bromides or chlorides. In all cases it is very slow and the yields are by no means quantitative. This is probably due to the fact that the first part of the change consists in the formation of the ketone CR3*C02R'+C3H7MgX=R'*OMgX+CR3*CB*C,H7 which only takes place very slowly. Ethyl pivalate reacts with magnesium ethyl iodide to give PP-dimethylpentan-y-ol CMe,*CHEt*OH b.p. 140-148" giving a phenylurethane m. p. 83" ; with magnesium propyl iodide bromide or chloride the products are pp-dimethylhelL.an-y-oE CMe,*CHPr*OH b. p. 153-156"/755 mm. ; ng 1.4280; dI7 0-830 giving a phenyl- urethane m. p. 68-69" ; and PP-dimethyl-y-propylhexan-7-01 CMe,-CPr,*OH b. p. 90°/20 mm.; 122" 1.4455; dLY 0.853. The ratio of the yield of secondary alcohol to that of the tertiary alcohol is greatest with magnesium propyl iodide and least with malgnesium propyl chloride. On oxidation with chromic acid in acetic acid solution pp-dimethylhexan-y-o1 gives tert.-butyl propyE ketone CMe,*COPr b. p. 145-148" ; ng 1.4148 ; dl' 0.8225. Ethyl pivalate reacts with magnesium butyl iodide to give PP-dimethylheptan-y-ol CMe,*CH(OH)*C,H b. p.76-79"/16 mm. giving a phenylurethane m. p. 65". To examine the effect of heavier groups in the a-position in the disubstituted esters ethyl a-methyl- a-propylvalerate has been pre- pared as follows and used. a-Propylvaleric acid yields with thionyl chloride the acid chloride b. p. 77-79"/20 mm. which with benzene in the presence of aluminium chloride gives phenyl m-propylbutyl ketone CHPr,-COPh b. p. 157-159"/25 mm. ; ng 1.5064 ; d18 0.9492 which with sodamide followed by methyl iodide gives some im- pure phenyl a-methyl- a-propylbutyl ketone. The latter ketone is better prepared by propylating propiophenone which gives phenyl a-methylbutyl ketone CIIMePr-COPh b. p. 122-125"/14 mm. ; ni 1.5109; dl' 0.964 and this on further propylation yields phenyl a-methyl-a-propylbutyl ketone CMePr,*COPh b.p. 149-152"/13 mm. ; ng 1.5063; d'* 0.9502. The latter ketone on treatment with sod- amide and subsequent hydrolysis with hydrochloric acid yields a-methyl-a-propylvaleric acid CMePr,*CO,H m. p. 4 3 4 4 " ; b. p. 124-128"/18 mm. giving an amide and an ethyl ester b. p. 90- 92"/18 mm. which with magnesium propyl bromide yields &methyl- 6-prop yloctan- E - ol CH,Me*CH,-CMePr CHPr *OH b . p . 109- ll2'/18 mm. ; ng'5 1.4421 ; d1'j2j 0.8455 ; giving a phenylurethccne m. p. 96" and its hydrate m. p. 89-91'.ORGANIC CHEMISTRY. i. 217 Ethyl campholate gives with magnesium propyl chloride or bromide 1 2 2 3-tetramethylcyclopentylpropylcarbinol flHMe*CMe ,/CMe*CHPr*OH m. p. 58"; b. p. 126-129'/15 mm. CH,-CH Using a straight chain ester of high molecular weight namely ethyl palmitate a secondary alcohol was also obtained with mag- nesium propyl bromide the product being nonadecan-6-ol C1,H,,*CKPr*QH m.p. 19"; b. p. 221-224'/15 mm. giving a phenylurethane m. p. 50-51". The behaviour of the esters of aa-disubstituted dibasic acids towards magnesium alkyl haloids is variable. Ethyl dimethyl- malonate gives with magnesium propyl chloride a number of derivatives including a small amount of a bisecondary glycol ethyl isobutyrate dipropyl ketone propyl isopropyl ketone tri- propylcarbinol and dipropylcarbinol. There are thus apparently two reactions; one in which the molecule is split up giving tripropylcarbinol and the hydrocarbon resulting from its dehydr- ation and the other in which hydrogenation occurs.The new compounds isolated are cc-dimethylnonan-8;-dioE C,EI,*CH( OH)*CMe,*CHPr*OH m. p. 73" ; b. p. 150-152"/18 mm. ; tripropylcarbinol phenylurethane m. p. 74-75' ; dipropylisopropylcarbinol phenylurethane m. p. 71-72'. To confirm the formation of dipropyl and propyl iso- propyl ketones a similar condensation of magnesium isobutyl chloride and ethyl dimethylmalonate was carried out and from the products diisobutyl ketone semicarbaxone m. p. 119" and isopropyl isobutyl ketone semicarbaxone m. p. 139-140' were isolated. To prove the constitution of the nonandiol described above the follow- ing preparations were made. Ethyl butyrate was condensed with methyl propyl ketone in the presence of sodium ethoxide to give dibutyrylmethane C,H,*CO*CH,*CQ*C,H b.p. 96-98"/21 mm. ; ng'3 1.46125; d16'j 0.9218 giving a copper derivative m. p. 157- 158'. On methylation it yielded cxa-dibutyrylethane CH,*CH(COPr) b. p. 124-126'121 mm. giving a copper derivative m. p. 140- 141" and on further methylation pp-dibutyrylpropane CMe,(COPr) b. p. 129-130"/18 mm. which gave a disemicarbaxone m. p. 216" identical with that obtained from the nonandiol. With a view to elucidating the course of the reaction of the dimethylmalonic ester and magnesium propyl chloride dipropyl ketone was condensed with ethyl bromoisobutyrate in dry benzene in the presence of zinc giving ethyl p-hydroxy-cca-dimethyl-p-propyl- hexoate HO*CPr,*CMe2*C0,Et b. p. 135-1 36'/26 mm. which when treated with magnesium propyl bromide has its molecule ruptured in such a way as to give tripropylcarbinol and a magnesium additive compound.Ethyl aa-dimethylsuccinate and magnesium propyl chloride yield yH,-CPr 3 3-dimethyl-2 5 5-tripropyltetral~ydrofuran~ CMe2.CHPr >o b. p. 114-118"/15 mm.; ni; 1.4531 ; dL8 0.8629. Ethyl aa-dimethylglutarate and magnesium propyl bromide givei. 218 ABSTRACTS OF CHEMICAL PAPERS. (?H2*CMe2*Co>0 be p. 153- ax-dimethyl- 66-diprop ylvalerolactone CH--CPr 157/16 mm. ng 1.4585 dl* 0.9311 giving a bar&; salt. Similarly ethyl camphorate yields dipropylcampholactone m. p. 58" ; b. p. 177-180"/18 mm. giving a copper salt. The presence of an alkyloxy-group in the ester results in the general reaction pursuing its normal course giving a tertiary alcohol. Thus ethyl ethoxy- cx-methylpropionate and magnesium propyl chlor- ide give p- ethoxy - p-meth y 1 - y -propfjlhexan- y -01 OEt *CMe,*CPr,*OH b.p. 118-122"/35 mm.; n; 1.4392; d" 0.8864. Under similar conditions ethyl p - hydroxy- cxcx p-trimeth yl butyrate gives p y y-trimeth yl- 6-propylheptan- pa-diol lHO~CMe,*C~e,*CPr,*OH m. p. 91 ". W. G. Symmetrical Dichlorodimethyl Sulphide. IGNAZ BLOCH and FRITZ HOHN (Ber. 1922 55 [B] 53-57).-Dich~rodimethyZ sulphide is prepared by cautious admixture of trithioformaldehyde and sulphur chloride and subsequent heating of the mixture under reflux after the initial violent action has subsided. It is an almost colourless liquid b. p. 156-156.5"/765 mm. or 51°/11 mm. Its formation appears to take place in accordance with the equation (CH2S)3+2S2C12=C2H,ClzS+CSz+ZHC1+4S. It is converted by hot water into trithioformaldehyde and amorphous polyoxy- methylene and by methyl-alcoholic potassium hydroxide or ammonia solution into ( ?) polyoxymethylene and s-dimethoxy- dimethyl sulphide b.p. 152"/760 mm. (cf. de Lattre A. 1912 i 745). The formation of s-dichlorodimethyl sulphide from trithio- formaldehyde brings additional confirmation of the constitution - S<g2:E>CHz generally assigned to this compound. H. W. Production of Alcohols Ketones and the Like [Lithium Formate Methyl Alcohol Acetone etc.]. BADISCHE ANILIN- & SODA-FABRIK (Brit. Pat. 173097).-Carbon monoxide may be utilised for the production of alcohols ketones etc. through the intermediate formation of lithium formate which when heated at 380420" preferably in a current of moist hydrogen under dimin- ished pressure is decomposed with the formatisn of methyl alcohol acetone formaldehyde etc.in addition to oily and empyreumatic substances. Lithium formate is obtained by the action of carbon monoxide on lithium hydroxide or carbonate in presence of water a t a temperature of 120-250" and a pressure of 20-70 atm. When absorption is complete the solution is evaporated and the dry salt powdered and transferred to the decomposition plant which may consist of a tube-shaped vessel with a conveyor worm or of shallow pans or revolving drums heated in a bath of fused potassium nitrate. The residue after decomposition consisting of lithium carbonate and carbon may be utilised again for the production of formate but provision must be made by washing the gases or otherwise for the removal of the carbon dioxide pro-ORGANIC CHEMISTRY.i. 219 duced during absorption of the monoxide Li,C03+H,0+2CO= 2HC0,Li + CO,. The Mode of Sudden Pyrogenic Decomposition of Acetic Acid at High Temperature. (MLLE) ~GLANTME PEYTRAL (Bull. SOC. chim. 1922 riv] 31 113-118; cf. A. 1918 i 1 ; 1920 i 217; 1921 i 156 166).-The sudden decomposit'ion of acetic acid vapour a t 1150' takes place in such a way that the mole- cule is deformed as little as possible. There are three reactions of the first order namely (1) 2CH,*CO,H= (CH,*CO),O+H,O ; (2) CH,*CO,H=CO,+CH ; (3) 2CH,*CO2H=2H,O+2CO+C,H ; and two reactions of the second order namely (4) CO,+CH,=CO+ H,+H,O+C ; (5) C,H,=C,H,+H,. (1) is greater as the velocity of flow of the acetic acid vapour is greater.I n reaction (4) instead of the formation of free carbon very condensed hydrocarbons are probably formed. The Mode of Pyrogenic Decomposition of Methyl Acetate at High Temperature. (MLLE) ~GLANTME PEYTRAL (Bull. Soc. chim. 1922 [iv] 31 118-122 ; cf. preceding abstract).-In the pyrogenic decomposition of methyl acetate a t high temperatures the two principal changes are (1) CH,*CO,Me=CH,*CHO+H-CHO ; (2) 2CH,*CO,Me= 2CH,*CO,H+ C,H,. The acetaldehyde formed in reaction (1) tends to decompose giving methane and carbon monoxide and the formaldehyde gives hydrogen and carb.on monoxide. The acetic acid formed in re- action (2) which is less important than reaction (l) tends to decompose in the manner already described (Zoc.cit.). Carboxylic Esters as Amphoteric Electrolytes. H. v. EULER and OLOF SVANBERG (2. physiol. Chem. 1921 115 139-146).- Ethyl acetate acts as an amphoteric electrolyte the constant K KIKUNAE IKEDA and SHINTARO KODAMA (Jap. Pat. 37211).-By the action of sodium nitrite solid or in concentrated solution on amino-acid hydrochlorides or their ester hydrochlorides in the presence of hydrogen chloride chloro- acids or their esters are easily produced. For example 1 part of leucine or its hydrochloride is dissolved in 1-2 parts of the water layer obtained in the previous manufacture of the chloro-acid from leucine and saturated with hydrogen chloride; the corre- sponding quantity of 30% sodium nitrite solution is gradually added a t the ordinary temperature. Chlorohexoic acid separates as 'an oil.It is separated from the water layer dried with sodium sulphate and distilled in a vacuum. The method is applied to crude leucine phenylalanine valine alanine etc. Reactions between the Higher Fatty Acids and Salts of the Lower Fatty Acids. ARTHUR W. KNAPP and RAYMOND V. WADS- WORTH (Chem. News 1922,124,44-45).-1f finely-powdered sodium acetate is added to oils or melted fats a gelatinous precipitate is G. F. M. The importance of reaction ' W. G. W. G. being about and Kb about 10-*0. s. s. z. Manufacture of Chloro-acids. CHEMICAL ABSTRACTS.i . 220 ABSTRACTS OF CHEMICAL PAPERS. generally produced. Sodium propionate and sodium butyrate give similar results. Castor oil does not give a jelly. Pure glycerides do not give this reaction which is due to the free fatty acids present The jelly consists of soaps formed by the interaction of the salt and the free fatty acids.Sodium acetate is soluble in oleic acid forming a viscous solution. When cooled this becomes a thick jelly. If the fatty acid is dissolved in absolute alcohol and the acetate added a gelatinous precipitate of soap is formed almost immediately. The reaction is reversed by adding water. H. C. R. The Preparation of Acrylic Acid and some of its Derivatives. J. H. N. VAN DER BURG (Rec. tmv. chim. 1922 41 21-23; cf. Gaspary and Tollens A 1872 814 and Moureu A. 1893 i 548).- The methods of preparation used hitherto are inconvenient when large quantities are required or give poor yields. The acid itself and some of its derivatives tend to polymerise on keeping and must therefore be freshly ,prepared.The sodium salt will keep in- definitely and may be used as a starting-point. It is prepared from ethylene glycol which gives a 70-80% yield of chlorohydrin. The latter is treated with sodium cyanide the resulting nitrile being transformed into hydracrylic acid. The sodium salt of the latter carefully dried gives on distillation with sulphuric acid very pure acrylic acid and on treatment with phosphorus oxy- chloride the chloride of the acid. Two New Ammonium Molybdomalates. E DARMOIS (Compt. rend. 1922 174 294-296; cf. A. 1920 ii 575; 1921 i 539).-From a study of the optical activity of solutions of different proportions of molybdic acid malic acid and ammonia the exist- ence of two lzevorotatory compounds having the compositions Mo 0,,2C,H60 2NK and MoO3,2C,H 6O ,4NH respectively has been proved and these two compounds and the corresponding sodium and patassiunz salts have been isolated.Equilibrium in Solution of the Desmotropic-Isomeric Diacetylsuccinic Esters and its Colorimetric Estimation. L. KNORR and H. P. KAUFMANN (Ber. 1922 55 [B] 232-248).- Ethyl diacetylsuccinatc has been isolated in two diketonic forms namely (3-ester m. p. 89" y-ester (formerly cc,-ester) m. p. 30° one dienolic form wester (formerly a,-ester) and two keto-enolic forms +ester (formerly El-ester) a liquid and rx,p-ester (formerly a,-ester) m. p. 20". The equilibrium in solution in various solvents and the rate of transformation of the isomerides have been measured a t 30" with the aid of the deeply-coloured enolic iron salts according t o the method of Wislicenus (cf.also Knorr and Schubert A. 1911 i 948). I n methyl and ethyl alcohols acetone and chloro- form the rate of enolisation of the p-ester a t 30" diminishes with decreasing dielectric constant of the solvent; in hexane ether or benzene the change takes place too slowly to permit its measure- ment. The influence of temperature on the velocity of transform- ation and the relative proportions in the equilibrium mixtures has It is a reversible colloid. H. J. E. W. G.ORGANIC CHEMISTRY. i. 221 been examined mainly by comparison of thc data obtained a t 30" and at the boiling points of the solutions. The velocity of enolisation is found to increase with increasing temperature but the composition of the equilibrium mixture is approximately constant.I n N / 5 i V / l O and N/20 solu'tion the concentration of the p-ester is without influence on the velocity of transformation or the composition of the equilibrium mixture. The influence of the dielectric constant of the solvent on the composition of the equilibrium mixture could not be elucidated definitely. Examination of the equilibrium in hexane and ether led to the observation of an unexpectedly high enolic content indicating the possible presence of the dienol m. p. 45". This is shown by mechanical separation of the products t o be actually the case. The presence of this ester in molten mixtures or in dissolved equilibrium mixtures has not been established previously. The iron salt of ethyl a-diacetylsuccinate is obtained when a solution of the p-ester in absolute alcohol is treated successively with an alcoholic solution of sodium ethoxide and an ethereal solution of ferric chloride; it is a brown powder.The analysed product however appears to be basic in character. The salt FeCl,*O*CMe:C( CO,Et)*C( CO,Et):CMe*O*FeCl a voluminous un- stable violet-black powder is prepared by agitating the brown salt with a solution of ferric chloride in anhydrous ether. H. W. New Method of Preparing Gluconic Acid. ARTHUR R. LING and DINSHAW RATTONJI NANJI ( J . Xoc. Chem. Ind. 1922 41 28-29~; cf. Herzfeld and Lenart A. 1920 i 143).-A slow well-regulated current of chlorine (about one bubble per second) is passed through a solution of dextrose (20 yo) containing 0.025 yo of cobalt nitrate as catalyst and a quantity of calcium bromide corresponding in potential bromine content with 26% of the bromine used by Herzfeld and Lenart (Zoc.cit.). The temperature is main- tained at 45-50" and care is taken that this limit is not exceeded otherwise the hypobromous acid may be converted into bromate. As the reaction proceeds there is a constant accumulation of halogen acids and to avoid their retarding action calcium carbonate is added from time to time. The reaction is complete in about four hours. The final solution when reaction has proceeded normally contains calcium gluconate calcium chloride and calcium bromide and when concentrated appropriately deposits the former in the course of a few days the yield being about 90% of that theoretically possible.The use of calcium bromide and chlorine is preferable to that of bromine since the latter acts more efficiently in the nascent state and there is no loss of bromine by volatilisation under the correct experiment a1 conditions . Colophenic Acid. OSSIAN ASCHAN (Be?. 1922 55 [B] 1-3; cf. A. 1921 i 512).-The author is unable to share Fahrion's view of the identity of colophenic acid with oxyabietic acid prepared by the autoxidation of colophony (A. 1907 i 329; 1921 i 792) H. W. i"i. 222 ABSTRACTS OF CHEMICAL PAPERS. and points out that it is not possible for Pahrion's product to be homogeneous. Colophenic acid is an excellent material for the preparation of varnishes. H. W. Sulphiformin (Methanalsulphurous Acid). PHILIPPE MAL- VEZIN (Ind.chimique 1921 8 311-314; from Chem. Zentr. 1921 iii 11 18).-Sulphiformin obtained by the distillation of form- aldehyde in the presence of sulphur dioxide has the formula OH*CH,*Q*SQ*OH. It reduces Millon's reagent and gives a violet coloration and precipitate with magenta solution. It decomposes readily giving sulphur dioxide and formic acid. 'CT7it h aniline alone a yellow dye is formed; in the presence of hydro- chloric acid a red caoutchouc-like mass is formed; in the presence of acetic acid a dye is obtained which is yellowish-green in. the cold and orange-red on warming. Sulphiformin has antiseptic proper ties. G. W. R. Laboratory Preparation of Acetaldehyde. CHESTER E. ADAMS and ROGER J. WILLIAMS ( J . Amer. Chem. Xoc. 1921 43 2420-2421) .-In the preparation of acetaldehyde by the oxidation of ethyl alcohol with sodium dichromate the yield is practically doubled if the mixture is stirred vigorously to disengage the acet- aldehyde as fast as it is formed.The best proportions to use are 200 grams of sodium dichromate for 100 grams of alcohol. W. G. Production of Butaldehyde and Butyric Acid therefrom. MATTHEW ATKINSON ADAM and DAVID ALLISTON LEGG (Brit. Pat. 173004) .-Butaldehyde is obtained by the dehydrogenation of n-butyl alcohol by passing it in a state of vapour over a fused copper oxide catalyst heated a t 280-320" and fractionally dis- tilling the product. About 75% conversion is obtainable by one passage over the catalyst at a good speed; for example 240 C.C. per hour using a &inch copper tube packed for 26 inches of its length with the catalyst.Butyric acid is prepared from the liquid aldehyde by adding a small proportion of an oxygen-carrying catalyst for example manganese butyrate and introducing air or oxygen at either ordinary or higher pressures with suitable cooling to maintain the liquid below the boiling point cf the aldehyde. G. P. M. The Mode of Pyrogeni? Decomposition of Acetone at High Temperature. (MZLE) EGLANTINE PEYTRAL (Bull. Xoc. chim. 1922 [iv] 31 122-124; cf. this vol. i 219).-The sudden pyro- genic decomposition of acetone at high temperatures consists almost exclusively of a simple scission of the molecule into keten CH,:CO and methane The keten then decomposes giving carbon monoxide and ethylene. W. G. Monosulphates of Dextrose and Sucrose. 111.CARL NEU- BERG and LUDWIG LIEBERMANN (Biochem. Z. 1921 121 326- 332).-By the action of chlorosulphonic acid in pure chloroformORGANIC CHEMISTRY. i. 223 at -10" on a pyridine solution of dextrose or ancrose the mono- sulphates of these carbohydrates are ohained and can be isolated as the calcium salts which are amorphous. The calcium salt from sucrose sulphate has [a],+48.0 that from dextrose sulphate [a],+44.43. Lactose reacts similarly but no details are given. H. K. The Action of Ozone on Pure Solutions of Dextrose Laevu- lose and Sucrose. C. w. SCHONEBAUAI (Rec. trav. chim. 1922 41 4445).-Various workers in this field have obtained results which are mutually contradictory. The author finds that dextrose lawulose and sucrose in alkaline solution are decomposed quanti- tatively when ozonised the products being carbon dioxide and water.Formic acid is obtained as an intermediate product. The reaction takes a considerable time and for this reason various technical applications are suggested. 11. H. KILIANI (Ber. 1922 55 [B] 75-101; cf. A. 1921 i 304).- Further experience of the oxidation of sugars and polyhydroxy- acids by nitric acid a t the atmospheric temperature has emphasised the necessity of excluding air during the process. This is effected conveniently by performing the operation in Erlenmeyer flasks provided with ground-glass stoppers and inserting a t one point between the neck and the stopper a small plug of long-fibred glass wool. It is now recognised that the Oxidation may lead to the production of a-keto-acids the predominance of aldehydic or ketonic product appearing to depend on the configuration of the original material.Attempts to replace the use of bromine and sodium hydroxide by that of a filtered solution of bleaching powder in the oxidation of the primary alcoholic to the aldehydic group in the sugars have not been quite satisfactory possibly owing to deficient alkalinity of the solution. Action of Nitric Acid on Dextrose and d-Gluconic Acid.-The product of the oxidation is in all probability a-ketogluconic acid OH*CH,*[CH( OH)],*CQ*CO,H ; the acid is unstable when preserved at the atmospheric temperature and evolves carbon dioxide when its aqueous solution is boiled. After successive addition of hydro- cyanic acid and hydrolysis a dibasic acid is produced which evolves carbon dioxide more freely than the parent acid; inability to effect the completion of the latter change has prevented its definite characterisation as a substituted malonic acid.Preparation of Rhnrnnonic Acid.-The acid is prepared more conveniently by the older bromine method than by the new oxidation process. It is emphasised that the oxidation of aldoses b'y bromine is never quantitative and that with freely soluble acids and lactones it is advisable to boil the solution of the acid (which has been freed from hydrobromic acid) with challc for a t least three-quarters of an hour; the solution is evaporated to small bulk and the calcium salt is precipitated with alcohol and H. J. E. New Observations on the Chemistry of the Sugars.i* 2i. 224 ABSTRACTS OF CHEMICAL PAPERS. decomposed subsequently with oxalic acid. Contrary to the statements of the literature pure rhamnolactone does not reduce alkaline copper solutions. Action of Nitric Acid on Rhamnonic Acid and Rhamnose.-The oxidation of either substance a t the atmospheric temperature gives the lactone of a-ketorkamno?zic acid in good yield. The product has m. p. (indefinite) 188" (decomp.) after becoming discoloured a t 168" [.ID -25-2". The solubility in water is about 1. part in 20 parts at 20". It gives a p-nifrophenylhydraxone C,,H,,O,N,,H,O long yellow needles m. p. 150" after softening and darkening above 130". It retains the terminal methyl group of rhamnonic acid since it is not oxidised by bromine water and yields acetic acid when treated with an aqueous suspension of silver oxide.The presence of the ketonic group in the a-position is deduced from the ability of the keto-lactone to evolve carbon dioxide from its boiling aqueous solution and the greater readiness with which the gas is evolved from the hydrolysed cyanohydrin of the keto- lac t one. Oxidation of a-Galaheptonic Acid by Nitric Acid.-I-Manno- hepturonic lactone (from d-galactose) m. p. 205-206" (decornp.) after becoming discoloured a t about 190" is obtained in good yield from a-galaheptonic acid ; the aldehydic nature of the product has been established. Conjigurntion of Digitoxone and Digitoxosecarboxylic Acid.-Digit- HO.~:O oxose CH,*[CH( OH)],*CH,*CHO is oxidised by nitric acid to a dihydroxyglutaric acid and meso-tartaric acid y H 2 thus showing that the hydroxyl groups 3 and 4 are HO*F*H in the meso-position to one another.Since the lactone HO*F*H of digitoxoiiic acid has been shown previously to be v ~ . ~ ~ lzevorotatory the annexed configuration can be assigned to digitoxonic acid on the basis of Hudson's rule. CH3 On the other hand the proof of the meso-position of the 3- and 4-hydroxyl groups of digitoxonic acid can now be M~.~H.OH extended. The well-crystallised lactone of digitoxose- carboxylic acid is lzevorotatory ([XI -13*67") as is also the phenylhydraxide of digitoxosecarboxylic acid (groups of needles m. p. 145-148" [a]= -37.7"). In consequence the newly-formed hydroxyl group in the production of cyanohydrin must be to the left and digitoxosecarboxylic acid receives the annexed configuration in which the configuration of the 6-CH.OH remains unelucidated.Formation of Digilalonic Acid from Digitalose (cf. A 1916 i 493). -Digitalonic acid gives a well-crystallised kevorotatory lactone and must therefore contain a hydroxyl group attached to carbon atom 4. The methoxyl group cannot be in lyosition 5 since the acid does not give pure trihydroxyglutaric acid when oxidised by nitric acid. It must therefore have the latter group in position 3 or 2. The former possibility is discounted by the apparent inability of digitalose to yield an osazone. Since the phenyl- hydrazide of digitalonic acid is lzevorotatory ([.ID about -16") H*F*OH YHz H.C.OH CO,HORGANIC CHEMISTRY. i. 225 YH ?Me H H the configuration CH,*CH( OH)*@ *CH( OH)* $! *CO,H may be assigned to the parent acid.Salts of Trihydroxyadipic Acid (from Metasaccharin) .-The following salts are described generally with particular reference to their solubility in water calcium strontium (+4H20) m a g - nesium ( +3H20) barium potassium C,H,0,M2,H20 silver cadmium ( +2H20) quinine. The behaviour of the calcium and quinine salts of 1-trihydroxyglutaric acid is described in detail. The cadmium barium and calcium salts of E-galaheptanepentol- dicarboxylic acid have been further investigated. The crystallisation of d-galactonic acid is readily effected by evaporation of solutions of the acid (from the calcium salt and oxalic acid) in an open dish and subsequent treatment of the paste obtained in this manner with alcohol under conditions which are specified in detail in the original.The preparation of the gnlaheptonic acid from d-galactone is described in detail the process depending on a modification of Fisc her's p henylh ydrazide met hod. The production of I-mannonic and 1-gluconic acids from arabinose has been investigated further. Under conditions which are fully described the cyanohydrin synthesis leads to the crystallisation of 1-mannonamide which is smoothly converted into 1-mannonic acid by boiling barium hydroxide solution. The isolation of I-gluconic acid from the mother-liquors is conveniently effected by means of the brucine salt. The Partial Replacement of the Acid Groups in p-Penta- acetylglucose. PERCY BRIGL (2. physiol. Chem. 1921 116 1-52).-The following compounds have been prepared a-Chloro-y~~-triacetyl-~-trichloroacetylglucose from p-penta-acetyl- glucose and phosphorus pentachloride forms long white needles m. p.142" [a]" +2.95" in benzene. The position of the chlorine atoms was ascertained by various forms of saponification. P y c - Tetracet yl- a- trichloroacet ylglucose from p-pent a- acet ylglucose tri- chloroacetyl chloride and phosphorus oxychloride forms dense needles m. p. 131" [a] +94%". ay€%-Tetracetyl-P-trichZoroacetyZ- glucose by treating the tetrachloro-substance with anhydrous zinc chloride and acetic anhydride. A mixture of two isomerides obtained has m. p. 110-112". The m-isomeride forms long fine needles m. p. 120" [a] +101*5"; the p-isomeride forms needles m. p. 167" [4]13~15 +28.85". a-ChZoro-ye(-triacetyZ-p-monochloro- acetylglucose by reduction of tetrachlorine compound needles m.p. 81". u-C~loro-y€%-triacetyZgZ?icose from the tetrachloro- compound with an ethereal solution of ammonia crystallises in needles m. p. 158"; it exhibits rnultirotation the initial [a] + 25.0 " rising to + 15 1 -5 ". a- Chloro- y E l - triacetylglucose- p-chloro- suzphinite OAC~CH,*CH ( OA~)*CN< CH(OAc)*FH*O*SOCl by treat- ing the last compound with thionyl chloride has m. p. 103' (approx.). H. W. 0- CHCli. 226 ABSTRACTS OF CHEMICAL PAPERS. ap-DichZoro-y€~-triacetyZgZucose from triacetylchloroglucose with phosphorus pentachloride crystallises in platelets m. p. 83" [a] + 65.6". Triacetylglucal from triacetyldichloroglucose by treatment with zinc dust. Acetobromoglucose was also converted into acetochloroglucose with mercuric chloride.s. s. z. The Synthesis of Disaccharides containing Sulphur and Selenium by combining two Dextrose Residues in the Cc- position. Some New Derivatives of [-Bromoglucose. FRITZ WREDE (2. physiol. Chern. 1921 115 284-304).-The following compounds have been prepared Acetodibromoglucose from penta- acetyl glucose [XI + 184.1" in ethyl acetate. Methylglucoside- [-bromohydrin triacetate [ c x ] ~ ? -7.78" in ethyl acetate from the last compound. Triacetyl-ethylglucoside-[-bromohydrin from aceto- dibromoglucose and ethyl alcohol in the presence of dry silver carbonate crystallises from methyl alcohol in compact needles m. p. 154" (uncorr.) ; [a]: -11.78" in ethyl acetate. P-Tetra-acetyl- [-bromoglucose by heating acetodibromoglucose with acetic anhydride and sodium acetate a t loo" melts a t 127" (corr.). The a-form produced a t the same time crystallises from methyl alcohol in fine white needles m.p. 171" [a]" +107-2" in ethyl acetate. Dimethylglucoside of bisglucosyl [-sulphide hexa-acetate from triacetylmethylglucoside-[-bromohydrin and alcoholic potassium sulphide by heating in a sealed tube crystallises in white needles m. p. 168") [a]% -10.51" in ethyl acetate. Dimethylglucoside of bisglucosyl [-sulphide from the hexa-acetate by treating it with absolute methyl alcohol and ammonia in the cold crystallises in dense masses m. p. 188" [XI: +6*53" in water. Bisglucosyl 4-sulphide by heating the last compound with 5% sulphuric acid in a sealed tube sinters a t approximately 135" and liquefies a t approximately 150" [.I:? +80*9" in water.Octa-acetyl-bis- glucosyl [-sulphide by acetylating the last compound crystallises in nodules m. p. 163" [CX]; +5G.2" in ethyl acetate. Dimethyl- glucoside of bisglucosyl <-selenide hexa-acetate prepared in the same way as the sulphide crystallises in long white needles m. p. 179-180". Dimethylglucoside of bisglucosyl [-selenide prepared in the same way as the sulphide crystallises from 90% alcohol in dense aggregates m. p. 138" [a]" +14.59" in water. BisglucosyZ 5-selenide by hydrolysis from the glucoside sinters a t approximately 160" decomposes a t approximately 200") [a]: + 69.5" in water. Octa-acetyl-bisglucosyl [-selenide by acetylating the seleiiide with acetic anhydride crystallises from ether and light petroleum in nodules m.p. 150-155" ctD +4O" (approx.). Dimethylglucoside of bisglucosyl 5-diselenide hexa- acetate by treatment of acetyl-methylglucoside-[-bromohydrin with an alcoholic solution of potassium diselenide has m. p. 148" [a]'; +49-74" in ethyl acetate. Dimethylglucoside of bis- glucosyl [-diselenide by treatment with methyl alcohol solution and gaseous ammonia crystallises from 98% alcohol in dense needles m. p. 96-97" [a12 +75*65" in water. Bisglucosyl [-diselenide by hydrolysis of the methyl glucoside decomposes atORGANIC CHEMISTRY. i. 227 approximately 125" [a] + 145.6" in water. Octa-acetyl-bis- glucos yl c-diselenide by acetylation of the last compound with acetic anhydride forms small crystals which sintered a t 175-179'.Unsaturated Reduction Products of the Sugars and their Transformations. 111. 2-Deoxyglucose (Glucodesose) . MAX BERGMANN HERBERT SCHOTTE and WOLFGANG LECHINSKY (Ber. 1922 55 [B] 158-172; cf. A. 1921 i 307 648).-With the object of obtaining a derivative of dextrose so modified that a hydroxyl group is not present in position 2 glucal (A. 1913 i 445 ; 1914 i 252; 1920 i 420) has been converted by dilute acid into 2-deoxyglucose OH*yH*CH,*CH( OH)*FH*CH( OH)*CH,*OH which has only been isolated previously in the form of its phenylbenzyl- hydrazone. In connexion with this substance it is proposed to define a simple sugar as an aldehyde-alcohol or keto-alcohol with an open carbon chain and one or more hydroxyl groups of which a t least one is in the direct neighbourhood of the carbonyl radicle; deoxyglucose and Kiliani's digitoxose are therefore not within the class.It is also proposed to establish a nomenclature for the 2-deoxy-sugars by inserting the syllable " des '' between the name of the sugar from which they are derived and the characteristic ending of all sugars " ose " ; thus 2-deoxyglucose is termed " glucodesose." 2- Deoxyglucose is prepared by hydrolysing triacetylglucal by means of methyl-alcoholic ammonia to glucal and treatment of the latter with 2N-sulphuric acid a t 0". Alternatively triacetyl- glucal is treated directly with 2N-sulphuric acid a t 10-15" and the deoxyglucose is converted into its phenylbenzylhydrazone m. p. 158-159" from which it is regenerated by treatment with benzaldehyde containing 10% of benzoic acid.The first method is preferred. 2-Deoxyglucose is a white anhydrous powder m. p. 148" (corr.) to a turbid liquid which decomposes a t about 155" [a] +46*59" in water +17.56" in pyridine. It does not appear to be mutarotatory in aqueous solution although it has been isolated in two forms with differing specific rotation (details will be given later). It behaves in the same manner as dextrose towards Fehling's solution alkaline silver solution and magenta- sulphurous acid. It gives a yellow coloration with warm alkali hydroxides. It is very readily decomposed by not too dilute acid with separation of greyish-green or darker amorphous sub- stances; the reaction may he used for the detection of deoxy- glucose and for distinguishing it from the true sugars.A pine shaving dipped into a solution of deoxyglucose and then exposed to hydrogen chloride becomes intensely green (these reactions are also shown by Kiliani's digitoxose). DeoxyglucosephenyZmethyZ- hydrazone crystallises in colourless needles or prisms m. p. 157- 158" (corr.) decomp. about 195" ; the corresponding p-nitrophenyl- hydrazone forms small canary-yellow prisms m. 1). 190-191" (corr. decomp.). Deoxyglucose could not be ferment'ed by a number of varieties of yeast. s. s. z. ~ -o-i. 228 ABSTRACTS OF CHEMICAL PAPEES. Deoxyglucose is distinguished by the extreme ease with which it is converted into glucosido-derivatives by acids in the presence of alcohols. Small amounts of acetic acid cause the production of glucoside in a short time at loo' whilst with methyl alcohol containing 0.25-1 yo of hydrogen chloride the formation of the methylglucoside is complete in less than fifteen minutes a t the atmospheric temperature.The product has m. p. 91-92' after softening at 87' [XI +137-8" in aqueous solution whereas the isomeride described previously has ni. p. 122-123" [pIln -48.2'. The difference in the specific rotation (186") is approximately the same as that between cc- and F-methylglucosides (189"). Since in all probability the two rnethyldeoxyglucosides are similarly related to one another and contain the oxygen bridge between the 1 and 4 carbon atoms it is proposed to designate the first- named substance a-2-deoxymethylglucoside [ a-methylglucodesoside] and the latter p-2-deoxymethylglucoside. The sensitiveness of the two substances towards acidic hydrolysing agents is similar and closely resembles that of 7-methylglucoside.Fission of the glucoside appears to be facilitated by the absence of the ,hydroxyl group from position 2. a-2-Deoxymethylglucoside like the p-isomeride is not affected by yeast or emulsin. Glucodesose tetrabenzoate is prepared by the action of benzoyl chloride on glucodesose in the presence of pyridine and chloroform ; it crvstallises in rectangular dates or short. broad prisms. The prepiration m. p. 13&145" ippears to be a mixture i f isomerides. H. W. The Constitution and Configuration of the Anhydro-sugars. P. KARRER and ALEX. P. SMIRNOV (Helv. Chim. Acta 1922 5 124-128).-Triacetyl-lzvoglucosan is converted by liquid hydrogen bromide a t the atmospheric temperature in the course of a few days into acetodibromoglucose (A.a1912 i 239) thus confirming the constitution assigned to lzvoglucosan by Pictet (A. 1920 i 819). The reaction is effected more advantageously by the use of phosphorus pentabromide and in this form is the readiest and best method of preparing acetodibromoghcose. Assuming that a displacement of the oxygen bridge and of an acetyl residue does not occur during the change (which is very improbable by reason of the relative stability of lzvoglucosan and the non-convertibility of penta-acetylglucose into acetodibromoglucose by means of phosphorus pentabromide) the annexed configuration can be assigned to h v o - @- y - 7 \ glucosan. Anhydroglucose has the con- 0 OH)CH figuration I in which the disposition of the hydrogen and hydroxyl attached to the a-carbon atom is undecided.The formula accounts for the unusual stability of the compound since it is composed of two five-membered rings and shows further that anhydro-compounds are only to be expected from sugars which have the y- and 8-hydroxy-groups on opposite sides of the carbon chain. ?H 1,I ~L?!&o/ OH HORGANIC CIIEMTSTRY. i. 229 0 0 /\ H i,B I wo I / \ ,H /OH C- C CH-0-H*C C -IC 0 H*C*H /'IH C T-H H0C.H C'- 7-H !,H 1 Ho I C-C HO*C*H( ? ) ~ H H \ / 0 (1.1 Diglucan and isodiglucm (A. 0 0 " \ / (11.) 0 1921 i 765) are revresented bv formula If in which the coi- figuration a t the a-carbon atoms remains undetermined. The dilactones of the saccharic acids must have a configuration similar to that of anhydroglucose.The dilactone of mannosaccharic acid and the diacetyl derivative of saceharic acid dilactone are therefore represented by the formulz I11 and IV. Polysaccharides. XIII. Inulin and the Alkali Hydroxide Compounds of the Anhydro-sugars. P. KARRER MAX STAUB and A. WUTI (Helv. Chim. Acta 1922 5 129-139; cf. this vol. i 11).-It has been shown previously (A. 1921 i 765) that poly- meric anhydro-sugars form additive compounds with sodium hydroxide of the type (C,,H,,O ,,NaOM) which are dissociated more or less readily by water. It is now shown that these com- pounds can be prepared conveniently by precipitating them from their solutions in sodium hydroxide (&-lo%) by alcohol and wash- ing the precipitates thoroughly with alcohol (96%).The use of absolute alcohol does not generally effeet the complete removal of absorbed sodium hydroxide. The compounds of a-diamylose a-tetra-amylose P-hexa-amylose and ct-octa-amylose with potass- ium hydroxide have been prepared in a similar manner and con- form to the type (C,,H,,O,,,KOH),. Inulin sodium hydroxide (C,H,,O,,NaOH) is prepared by dissolving inulin in sodium hydroxide solution (8 yo) and adding the product to a large volume of alcohol and is purified by re-solution in a little water and re-pre- cipitation by alcohol. Inulin potassium hydroxide (C,H,,O,,KOH) is more readily dissociated than the corresponding sodium compound and is prepared from solution containing 15% or more of potassium hydroxide. The isolation of these compounds brings additional evidence in favour of the view that inulin is a polymeric form of anhydro-fructose.Further confirmation is found in the behaviour of inulin towards fission with acetyl bromide under conditions which cause only slight disintegration of disaccharides such as maltose; the only compound obtained was fructose although the action was carried out a t 0" to +5" and for only such time as was necessary to effect the solution of the inulin. H. W. H. W.i. 230 ABSTRACTS OF CHEMICAL PAPERS. Speed of Reaction in Concentrated Solutions and the Mechanism of the Inversion of Sucrose. GEORGE SCATCHARD (J. Amer. Chem. Xoc. 1921 43 2387-2406).-A theoretical paper in which a method is outlined for calculating the activity of water in sucrose solutions of any concentration a t temperatures near the ordinary temperature.The method is also extended to solu- tions containing a small amount of another solute such as sulphuric acid. A formula for the speed of the reaction in solution in terms of the activities of the reacting substances is developed and it is suggested as the most logical formula for solutions. By the application of this formula to the inversion of sucrose it is shown that the available data indicate that the reaction is of the sixth order with respect to water. The results are interpreted as indi- cating the existence of a hexahydrate of sucrose. The effect of the addition of sucrose in increasing the activity of the hydrogen ion is explained as being very largely due to an increase in the molar fraction of hydrogen ions without any large change in the actual degree of ionisation.Precautions necessary in calculating the catalytic effect of the non-ionised portion of the acid by the customary method are pointed out. Hydration of Sucrose in Water Solution as Calculated from Vapour Pressure Measurements. GEORGE SCATCHARD (J. dmer. Chem. Xoc. 1921 43 2406-2418 ; cf. preceding abstract).- The average degree of hydration of sucrose in water solution a t 0" and 30" is calculated from the vapour pressures of sucrose solu- tions. The hypothesis is advanced that sucrose solutions are equilibrium mixtures of water unhydrated sucrose and a single hydrate of sucrose and that the relative quantities of these sub- stances are determined by the law of mass action.This hypothesis is tested by comparison of the experimental results with those calculated from the law of mass action. The agreement is fair for either a hexahydrate or a heptahydrate. The hypothesis is further tested by a comparison of the activity of the sucrose calculated from its degree of hydration and that calculated by the Duhem- Margules equation. The results confirm those obtained by the use of the law of mass action mebhod. The present results are in J. F. S. keeping with those obtained from the inversion of sucrose (Eoc. c i t . ) . J. F. S. Preservation of Starch Solution. NAOTSUNA KANG (J. Chem. Xoc. Japan 1921 42 974-975).-Starch solution (50 c.c.) for use as an indicator in iodometry can be preserved for more than eight months by the addition of 0-5 C.C.of 2N-hydrochloric acid or of a drop of carbon disulphide. J. J. LYNST ZWIKKER (Rec. tmv. chim. 1922 41 49-53).-0n the assumption that the polysaccharide molecule may be regarded as formed from a small number of hexose molecules each of which consists of a straight chain of carbon atoms the author shows that a regular tetrahedron and a triangular prism each bounded by such a straight chain K. K. The Constitution of Polysaccharides.ORGANIC CHEMISTRY. i. 231 lying along the junction of each pair of sides gives a structural formula which is in accordance with the properties of cellulose and starch respectively. Such a structure involves the homo- geneous filling of space and is consistent with the opinion that the polysaccharide molecule is not built up of long chains of sugar molecules.H. J. E. M. SAMEC and V. SSAJEVIE) (Compt. rend. l921,173,14741475).-Evidence is given in support of the view that agar is a sulphuric ester of gelose in much the same way as amylopectin is a phosphoric ester of the amyloses. A gram-atom of sulphur in the gelose ester corresponds with 9320 grams of organic matter. The great viscosity of agar is prob- ably due to its relatively high content of the SO,” ion. W. G. Alkali-cellulose and the Structure of Cellulose. P. KARRER (CeZluZosechemie 1921 2 125-128).-The experimental results of Gladstone are confxmed namely that the product of the action of strong sodium hydroxide solution on cellulose after complete washing with alcohol has a constant composition corresponding with the formula C,,H,oO,o,NaOH.This is regarded as a definite additive compound which is hydrolysed by water so that the products obtained with dilute sodium hydroxide are the results of equilibria. Alkali-cellulose therefore falls into line with analogous compounds obt’ained with starch inulin and the various poly- merides of anhydro-maltose classed as amyloses. All these com- bine with sodium hydroxide in the same proportions regardless of the degree of polymerisation. Cellulose is a polymeride of cellobiose anhydride and it is probable from analogies based on the heats of combustion and the Rontgen spectrum (cf. A. 1921 i 310 397 771) that the degree of polymerisation is not high. It is suggested that the cellulose formula may be written (C12H2,-,010)2 and that the polymerisation of the anhydro-sugar takes place through subsidiary valencies without the rupture of the oxygen bridges.The cellulose fibre-substance has a configuration analogous to a crystal structure with nuclei of these dimeride molecules in co-ordinated arrangements. The molecules are held together in the crystal by other valency forces of unusual strength and this strong cohesion accounts for the properties hitherto attributed to a highly polymerised molecule. The tendency is for the cellulose matter to concentrate its mass into the smallest possible volume and to assume a co-ordinated arrangement of its molecules. The Composition of Agar. J. F. B. A New Degradation of Cellulose ; Conversion of Cellulose into a Biose Anhydride. P. KARRER (Ber. 1922 55 [B] 153-156).-A reply to the criticisms of Hess (this vol.i 12). The conversion of amylose by acetyl bromide into acetylbromo- maltose is “ quantitative ” in the sense that the same yield of this substance is obtained from maltose amylose or starch. The process of the depolymerisation of starch does not appear to be involved in this matter. H. W.i . 232 ABSTRACTS OF CHEMICAL PAPERS. Saccharification of Cellulose. A. WOHL and H. KRULL (Cellulosechemie 1921 2 1-7).-When cellulose is moistened with 3 parts of water cooled with ice saturated with hydrogen chloride kept for five hours a t 20° the acid removed by evaporation in a vacuum a t temperatures up to 70° the residue dissolved in water to form a 10% solution containing 1:h of hydrogen chloride and boiled for eight hours 970/ of the theoretical quantity of reducing sugars is obtained and can be estimated by cupric reduction.The process may be applied to the eatiiuation of cellulose. In view of discrepancies in the yields of alcohol obtained by fermentation of the reducing sugars from pine wood and from pure cellulose respec- tively it is probable that the hydrolysis of the cellulose in the former is impeded by incrusting substances which cannot be removed by preliminary treatment whilst prolonged action of the acid leads to the formation of non-fermentable reversion products in relatively large quantity. CHEMICAL ABSTRACTS. Viscosity of some Cellulose Acetate Solutions. GUY BARR and L. L. BIRCUMSHAW (Trans. Paradcry S ~ O C . 1921 16 Appendix 72-75) .-The viscosity and density of 6 yo solutions of cellulose acetate have been determined in acetone and mixtures of acetone and water benzene and ethyl alcohol respectively.The second solvent was added in all concentrations up to the point where cellulose acetate \t as precipitated. The viscosity-concentration (of second solvent) curves are markedly diff erent. Benzene causes a progressive increase in the viscosity with increase in the concen- tration whereas water and ethyl alcohol give an initial rapid fall in viscosity which in the case of water reaches a minimum and then rises fairly rapidly but with alcohol remains fairly constant a t the minimum value. W. LEIGH BARNETT (J. SOC. Chem. Pnd. 1921 40 286; cf. A. 1921 i 847).-Examina- tion of the gases evolved during the reaction between chloroacetyl chloride and cellulose showed that hydrogen chloride alone is formed in the absence of water but on treating the acetic acid solution of the cellulose esters with water large quantities of formic acid are produced.The author concludes that the reaction proceeds in four distinct stages and has succeeded in preparing compounds corresponding with all these stages in the case of The Elimination of Furfuraldehyde from Oxycelluloses. The Solubility in Alkali and the Reduction Capacity of Oxycelluloses. CARL G. SCHWALBE and ERNST BECKER (Zellstoff u. Papier 1921 1 100-103; 135-139).-The yield of furfur- aldehyde on treatment with barium hydroxide is not a characteristic property of oxycelluloses and there are marked differences in their copper number acidity and resistance to alkali.The values obtained indicate the existence of two classes of oxycelluloses in which the predominating character is acidic and aldehydic respec- tively whilst the former character is almost completely lacking J. F. S. Syntheses with Chloroacetyl Chloride. glycerol. W. P. s.ORGAB IC CHEMISTRY. i. 233 in the hydrocelluloses. Denitrated wood pulp and denitrated nitro-silk (Chardonnet silk) have the chemical character of the oxycelluloses and the hydrocelluloses respectively. CHEMICAL ABSTRACTS. Physico-chemical Characterisation of Lignin from Winter Rye Straw. ERNST BECKMANN OTTO LIESCHE and FRITZ LEH- MANN (Biochem. Z. 1921,1211,293-310 ; cf. A. 1921 i 546).-The formula C,,H,,O for ljgnin has been confirmed in a number of ways.There are four inethoxyl groups present and on benzoylation four bcnzoyl groups enter the molecule. The sodium salt of lignin contains slightly less than two sodium atoms. The molecular weight in phenol and in boiling acetic acid and that of the sodium salt in water agrees with the above formula. Conductivity measure- ments show that lignin obeys the Ostwald valency rule. The Lignin-like Resins and Tannins of Spruce Needles. A. CLINE VON EULER (CeZZuZosechemie 1921 2 125-135; 1922 3 1-7; cf. A . 1921 i 769 849; 1922 i 100).-Powdered spruce needles were exhaustively extracted with 93 yo commercial methyl alcohol and the concentrated extract was divided into three fractions by means of ether. There were thus obtained “crude fat,’’ soluble in ether “ molasses,’’ the brown aqueous bottom layer and “crude resin,” an intermediate layer soluble in alcohol but not in ether.The crude fat contained besides true resins and fats about 29% of humus-like substances classified under the name of abiephyllic acids consisting of allied derivatives of coniferyl aldehyde more or less condensed and partly hydrogenised. The crude resin which amounted to not less than 10% of the weight of the needles might be described as a hydrated form partly hydrogenised of lignin; that is to say it is an allied substance at a lower stage of condensation than the ordinary lignin of wood. Its composition C=60.6 H=7.12y0 has no relation to that of a true resin; it is moreover extremely susceptible t o change either spontaneously or by solution in alkali and reprecipitation by acid giving a brownish-red product not unlike the phlobaphens derived from tannic acid.The alcoholic solution of the crude resin has the property of precipitating gelatin. A study of the constituents of the ‘ I molasses ” soluble in water yielded a whole series of definitely pronounced tannins which have been fractionated and classified into components soluble and insoluble in ethyl acetate some yielding uncoloured iead salts and others lemon-yellow lead salts. A comparison of this series of needle tannins with the series of bark tannins studied by Etti and Bottinger (Ber. 22 753 ; 23 647) revealed many analogies. The spruce-needle tannins are ketonic acids most of them hydroaromatic related t o p-cumarylferulic acid or feruylferulic acid a t various degrees of hydrogenation ; derivatives related to caffeic acid are also represented.Those giving colourless lead salts and insoluble in ethyl acetate are richest in hydrogen and those giving yellow lead salts are poorest. According to Klason’s hypothesis (A 1920 i SZl) p-lignin is a ketonic acid not hydroaromatic but otherwise very closely related H. K.i. 234 ABSTRACTS OF CHEMICAL PAPERS. to this series of water-soluble spruce-needle tannins. The author formulates p-lignin as a dihydroxyhydrocaff eylferulic acid. All these tannins and P-lignin are built up from more or less hydro- genised hydroxycinnamic acids. The author does not accept Klason's flavone constitution for cc-lignin; he regards it as being verysimilar to p-lignin but built up from more or less hydrogenised hydroxycinnamic acids and aldehydes ; the abiephyllic acids are built up of similar aldehydes and the tannins of the crude resin of similar aldehydes and alcohols The following formula might represent cx-lignin except that it includes two hydroxyls instead of one as determined by mason OMe*C,H,( OI-I)*CH,*CH,*CO*C,H,( OH) (OMe)*CH:CH*CHO and the tannins of the crude resin and abiephyllic acids would be derived from this by various additions of H,O and H,.Preparation of Amines from Alcohols and Ammonia. EUGENIE SMOLENSKI and KAZIMIR SMOLENSKI (Roczniki Chemji 1921 1 232-243).-When the vapours of methyl ethyl or amyl alcohol react with ammonia in the presence of a dehydrating catalyst such as alumina or kaolin a t about 300" a satisfactory yield of primary secondary and tertiary amines is obtained.I n the case of ethyl alcohol secondary products consisting of ethylene and ethyl ether are also obtained. If the ratio of the quantities of alcohol to ammonia is about 2 mols 1 mol when the temperature is kept between 300" and 330" a good yield of diethylamine is obtained. The total yield after accounting for the alcohol which is regained is 53% of amine 25% of ether and 20% of ethylene. Under the same conditions ethyl ether and ammonia also give ethylamine. Good results are obtained with aromatic compounds ; thus aniline and methyl alcohol a t 350" in the proportion of 1 mol. 4 mols. give toluidines and xylidines but if the temperature is kept below 330" and lO-20% of a salt of aniline is added the yield of the homologues of aniline is practically zero.Action of some Acylic Halogenated Derivatives on Hexa- methylenetetramine. MARCEL DEL~PINE and (11'Piu~ ) PIERRE JAFFEUX (Bull. SOC. chim. 1922 [iv] 31 108-112).-With the exception of isopropyl iodide secondary and tertiary albyl haloids do not form quaternary ammonium salts with hexamethylene- tetramine. Primary alkyl haloids do but the ease of the action diminishes as the molecular weight increases. Alkyl haloids having the same molecular weight but differing in the branching of the chain differ in their reactivity. Condensation Products from Acid Haloids. IX. Ketenium Compounds. E. WEDEKIND and CL. WEINAND (Ber. 1922,55 [B] 60-68 ; cf. Wedekind and LMiller A. 1909 i 459).-It has been shown previously that isobutyryl chloride and phenylchloroacetyl chloride are converted by triethylamine into dimethylketentriethylium CMe,:CO,NEt and phenylchloroketentriethylium CPhC1:C0,NEt3.The similar reactions with chloroacetyl chloride bromoacetyl chloride and dichloroacetyl chloride are now described. For this J. E'. B. J. F. S. W. G.ORGANIC CHEMISTRY. i. 235 type of compound the constitutions NEt3<?"2 and NEt3<? co CCR have been advanced tentatively. The first of these however is excluded by the observation that dimethylketentriethylium is smoothly hydrogenated in the presence of platinum black to isobutaldehyde and triethylamine NEt3<X:CMen + Ll (NEt<Y ) -3 CHMe,*CHO+NEt3. The incapability of existence of the assumed intermediate compound combined with the improbability of the direct addition of a saturated tertiary amine a t a C=O group cause the authors to prefer the subsidiary valency formula CR,:C:O .. . NAB,. An explanation is thereby afforded of the inability of the pre-formed keten t o combine with triethylamine since it is probable that in i t the subsidiary valencies have to some extent compensated one another. [With M. MILLER.]-~O~U~~O~S of the requisite acid chloride and triethylamine are gradually mixed when a violent reaction occurs ; the product is filtered and the residue extracted with benzene whereby triethylamine hydrochloride remains undissolved. The ketenium compound is isolated by distillation of the residue left after removal of the solvent from the filtrate under diminished pressure. The yields are small.ChZoroEetentriethylium CHCKCO,NEt is an almost colourless liquid b. p. 120-125"/10 mm. Bromol%etentriethyEium a pale yellow liquid b. p. 128-129.5"/18 mm. is transformed by hydro- chloric acid a t 135" into triethylamine hydrochloride and bromo- acetic acid. It cannot be hydrogenated in the presence of palladium towards which it behaves as a poison. DichEoroEetentriethylium is a golden-yellow liquid b. p. 142-145"/18 mm. It is decomposed by alcoholic potassium hydroxide solution with quantitative pro- duction of potassium chloride ; carbon monoxide is not however evolved. H. W. L. GRUNHUT and J. WEBER (Biochem. Z. 1921 121 109-119).-The interaction between various amino-acids and sugars with special reference t o melanoidin formation has been followed by a study of the formol titration the optical activity and reducing power.The reaction is in general very complex and varies from case to case. H. K. Alkylation of the Anhydrides of Amino-acids. P. MARRER CH. GRANACHER and A. SCHLOSSER (HeZv. Chim. Acta 1922 5 139-141 ; cf. Sasaki and Hashimoto this vol. i 56).-Sarcosine anhydride is obtained in more than 50% yield by the protracted action of methyl iodide on the silver salt of glycine anhydride. An attempt to prepare the silver salt of leucine anhydride by the method used for the corresponding glycine compound was un- successful. In general very marked differences are found in the behaviour of the anhydrides of various amino-acids for which a t present a CHOCHMe The Action of Amino-acids on Sugars.i.236 ABSTRACTS OF CHEMICAL PAPERS. satisfactory explanation cannot be given. Thus for example glycine anhydride and phenylalanine anhydride give sparingly soluble additive compounds with solutions of calcium chloride in alcohol but this behaviour is not exhibited by leucine anhydride. H. W. Monochlorocarbamide. Preparation of Chlorohydrins by its Action on Ethylenic Hydrocarbons. A N D B ~ DETGUF (Bull. SOC. chim. 1922 [iv] 31 102-108).-Monochlorocarbamide may be obtained by the action of chlorine on carbamide in the presence of a small amount of water at 0". By this method a certain amount of carbamide hydrochloride is also formed. The chlorocarbamide may be obtained in approximately 20% solution by passing chlorine through a solution of 620 grams of carbamide in 60 grams of water at O" in which 60 grams of powdered marble is suspended until the theoretical amount of chlorine is taken up.The solution is then filtered. Such a solution after the addition of 5% of acetic acid readily reacts with ethylenic hydrocarbons giving the corre- sponding chlorohydrins. For the latter action to take place the solution of chlorocarbamide must be acid either from the addition of acetic acid or from the presence of carbamide hydrochloride. W. G. Preparation of Thiocarbamides. THE GOODYEAR TIRE AND RUBBER Co. (Brit. Pat. 164326).-In the preparation of sub- stituted thiocarbamides by the action of carbon disulphide on a primary amine the speed of the reaction is greatly increased and a product of greater purity is obtained if the reaction is carried out at a temperature above the boiling point of carbon disulphide but below that of the amine by passing for example the super- heated vapours of carbon disulphide into the amine previously heated to the desired temperature.Isomeric Citraconyl Hydrazides. FREDERICK DANIEL CHATTAWAY and DERIC WILLIAM PARKES (T. 1922,121,283-288). Simultaneous Reduction and Oxidation. 111. Trans- formation of Halogenaldehydes into Aldehydes and Acids through Ketenes. ARTHUR KOTZ and H. RATHERT ( J . pr. Chem. 1921 [ii] 103 227-240; cf. A. 1913 i 1309; 1915 i 208).- Pp-Dichloro-cc-acetoxyacrylonitrile when hydrolysed with strong sulphuric acid in the cold gives p p-dichloro-a-acetoxyacrylctmide CCl,:C(OAc)*CO*NH needles m. p. 122-123". The nitrile on boiling with water gives dichloroacetic acid acetic acid and hydrogen cyanide and when heated with ethyl alcohol at 150" it gives dichloroacetic acid acetic ester and hydrogen cyanide.It also reacts readily with aniline to give the corresponding anilides and hydrogen cyanide and not dichloroketen. Ethyl p-dichloro- a-ethoxyacrylate on the other hand gives on boiling with water dichloroacetaldehyde alcohol and carbon dioxide. Dichloro- acetoxyacrylonitrile on reduction with hydrogen in presence of colloidal palladium or platinum black gives pp-dichloro-a-acetoxy propionitrile CHCl,*CH( OAc).CN b. p. 4 2 4 3 " / 6 mm. and with G. F. M.ORGANIC CHEMISTRY. i. 237 dry hydrogen chloride i t gives up p-trichloro- or-acetoxypropionitde CHCl,*CCl(OAc)*CN b. p. 202" which on hydrolysis gives di- chloroacetic acid hydrogen chloride and hydrogen cyanide thus proving its structure.Dichloroncetoxyacrylonitrile with alcoholic hydrogen chloride gives the hydrochloride of the iminoether of a p p -trichZoro- a-acetoxyacetic acid CCl,H*CCl( OAc) *C ( OEt ) :NH HC1 m. p. 93-94". Bromoacetaldehyde when heated in a sealed tube with triethylamine gives diketocyclobutane b. p. 125-126". Chloral does not under similar conditions eliminate hydrogen chloride and give dichloroketen. Aliphatic Diazo-compounds. XXIV. Organic Phosphorus Compounds. VI. Preparation and Rea6tions of Phos- phazines. H. STAUDINGER and G . LUSCHER (HeZv. Chim. Acta 1922 5 75-86).-A continuation of the work of Staudinger and Meyer (A. 1920 i 105). The aliphatic diazo-compounds do not exhibit great differences in the readiness with which they combine with tertiary phosphines to give phosphazines.The latter are hydrolysed with greater or less readiness by water into hydrazones and phosphine oxides. They all decompose with evolution of nitrogen when heated but the formation of phosphinemethylenes thereby is not observed except in the case of triphenylphosphine- benzophenoneazine (Zoc. cit.). Clear proof is adduced that the initial change consists of a dissociation of the compound into its constituents since volatile diazo-compounds can be distilled un- changed from the difficultly volatile triphenylphosphine when the compounds are heated carefully in a vacuum. TriphenylphosphinebenxiEaxine PPh,:N-N:CPhBz a yellow crystal- line powder m. p. 115-117" (decomp.) is obtained in 83%.yield by mixing benzoylphenyldiazomethane and triphepylphosphine in ethereal solution.It is hydrolysed readily by alcohol (90%) to triphenylphosphine oxide and benzilhydrazone. It is decomposed by heat in a complicated manner giving nitrogen t>riphenylphos- phine triphenylphosphine oxide possibly benzonitrile and a dark brown resin. E t h y 1 trip hen y lp ho sp hinegl y ox y la t e - az in e [from trip hen y lp ho s - phine and ethyl diazoacetate (cf. Staudinger and Meyer Zoc. cit.)] is hydrolysed with great readiness to triphenylphosphine oxide and ethyl anti-glyoxylatehydrazone m. p. 38" thus indicating for the phosphazine. It the anti-configuration decomposes at 200" with liberation of about half the total quantity of nitrogen; when distilled a t 140" in a vacuum it yields ethyl diazoacetate and triphenylphosphine. Triphenylphosphine and methyl benzoyldiazoacetate react with- out development of heat to give the phosphaxine PPh,:N*N:C(COPh)*CO,Me a pale yellow crystalline powder m.p. 132.5-133" (decornp.). It is converted by alcohol (90%) into the substance C,,H,,O,N,P m. p. 95.5-96.5". It gives nitrogen triphenylphosphine triphenyl- phosphine oxide and resinous matter when heated. 17. 0. K. CO,Et*I=;H ru'*N:PPh,'i. 238 ABSTRACTS OF CHEMICAL PAPERS. Triphenylphosphine and methyl cinnamoyldiazoacetate yield the phosphaxine PPh3:N*N:C(C0,Me)*CO*CH:CHPh a pale yellow solid m. p. 174". Ethyl triphenylphosphineacet ylglyoxglate-axine PPh,:N*N:CAc*CO,Et yellow crystals m. p. 9Q" is hydrolysed readily by atmospheric moisture.It decomposes completely when heated under atmo- spheric pressure; it regenerates its components when heated in a vacuum. Triphenylphosphine and ethyl diazomalonate react comparatively slowly to give the phosphazine PPh,:N*N:C(C0,Et)2 almost colour- less crystals m. p. 128" (decomp.). It is very sensitive towards moisture and is hydrolysed readily t o ethyl mesoxalatehydrazone and triphenylphosphine oxide. Towards heat it behaves in the same manner as the preceding compound. The corresponding phosphaxine PPh,:N*N:C( CO,Me) a pale yellow crystalline mass m. p. about 92") crystallises more readily than the ethyl compound but like the latter is extremely sensitive to moisture. It dis- sociates into its components when heated in an absolute vacuum.Triphenylphosphine and benzoylacetyldiazomethane give the phosphaxine PPh,:N*N:CAcBz dark yellow crystals m. p. 128" which is hydrolysed by boiling dilute alcohol with the formation of benxoylacetyllcetonehydrazone NH,*N:CAcBz colourless crystals m. p. 111-112"; it decomposes completely when heated. Triphenylphosphinedinitroquinoneuzine (annexed formula) bril- C:N.N:PPh3 liant red crystals decomp. about 194" is pre- pared from its components in chloroform solu- / b o tion. Relatively it is an extremely stable N02!@02 substance possibly owing to its sparing solu- bility ; protracted heating with aqueous alcohol converts i t into triphenylphosphine oxide and smeary products. Further investigation of the decomposition of triphenylphos- phinefluorenoneazine by heat has shown that the main product is the ketazine m.p. 264" ; triphenylphosphinediphenylenemethylene m. p. 274" is produced in minor amount but the method is unsuit- able for its preparation for this reason and also because of the difficulty of separating i t from the ketazine by crystallisation. - H. W. Aliphatic Diazo-compounds . XXV. Ketens . XXXVIII. Aliphatic Diazo-compounds and Ketens. H. STAUDINGER (Helv. Chim. Acta 1922,5,87-103).-A theoretical paper. Further investigation has led the author to modify his view of the consti- tution of the aliphatic diazo-compounds (A. 1916 i 847) which are now formulated in accordance with the manner proposed by Angeli and Thiele. Compounds with the group X N which are derived from the unsaturated nitrogen molecule are termed azens.This class of compound shows a great variety of chemical actions some of which are common to all members of the class whereas others are limited to particular members. The observations may be explained by the assumption that the azens contain two re-ORGANIC CHEMISTRY. i. 239 active points as indicated by the schemes A:NiN< and A:N!F respectively. Reactions occurring a t the terminal nitrogen’ atom (first scheme) such as the addition of phosphines reduction of aliphatic diazo-compounds and azides and addition of Grignard’s reagents are common to a,ll azens since an alteration in the nature or substitution of the first atom has relatively little influence on the third atom. Great differences in the reactivity of the different azens are observed on the other hand in many reactions which are considered to be based on compounds formulated in accord- ance with the second scheme; instances are afforded by (I) the addition of unsaturated compounds which is presumed to occur R2yAN=Y + R2C<$ ; (2) the action thus,R,C=K=N+A=B -+ I A-- B of compounds HR (acids water alcohols and amines) proceeding R27-N=NH - according to the scheme R,C=N=N+HCl-+ I c1 R,CHCl+N ; (3) the addition of halogen acid chloride or nitrogen dioxide.Reduction may occur in accordance with either scheme the course of the changes being dependent on the particular azen and the reducing agent employed. A number of reactions cannot be explained by either scheme; in all of these the azens react with salts. Carbonylen compounds resemble the azens closely in their general reactions which may be referred to the two schemes R,C=C=O R*N=C=O or R,C=C=O<::’ R*N=C=O.::: and R,C=C=O R*T=C=O.Those occurring in accordance with the first ’ scheme are but ‘ little affected by substituents at the third atom and are exemplified by the action with phosphineimines CH2=F=Q+PR3=NPh -+ CH,:C:NPh+PR,O the addition of tertiary phosphines CPh,=C= O<:::+PEt + CPh,=C=O=PEt and the action of compounds of the type HR such as water alcohol acids and primary and secondary amines. Reactions occurring in accordance with the second scheme are affected greatly by the presence of substituents a t atom 3 ; typical insta,nces are afforded by the behaviour towards oxygen and unsaturated compounds such as ethylene derivatives Schiff ’s bases carbonyl -compounds thioketones and nitroso-compounds by the polymerisation of ketens and by the decomposition of carbonylens by heat.The similarity of azens and carbonylens extends to colour and to absorption spectrum. Further consideration of unsaturated substances leads to the recognition of the existence of two distinct groups which are influenced differently by substituents frequently in a reversed direction; one class includes the ketens and diazo- Compounds whereas the other comprises the carbonyl compounds and their nitrogenous derivatives such as the hydrazones Schiff’s bases ketazines and phosphazines. These differences are most readily explained in accordance with Thiele’s theory of partial valencies. In the cases of the highly reactive o-diketones and 3 2 1 8 1 I ,i.240 ABSTRACTS OF CHEMICAL PAPERS. unsaturated ketones there is a strengthened partial valency a t the end of the conjugated system O=C-C=O which accounts for both the increase in the colour and enhanckd activity. I n the less reactive carbonyl substituted ketens and carbonyl substituted and unsaturated diazo-compounds conjugation influences the second atom which has but little effect on the reactivity whereas the third atom is weakened in its action by the neutralisation of the partial valencies thus O=C-C=C=O and O=C-C=EF in- stead of R,C=C=Q I an R,C=N-N respectively. Ketens. XXXIX. Aliphatic Diazo-compounds. XXVI. Behaviour of Ring Systems. H. STAUDINGER (Helv. Chim. Acta 1922 5 103-108).-A general review of the stability of cyclic compounds formed from carbonylens and azens and unsaturated substances.The four-membered rings obtained in large number from di- phenylketen and unsaturated compounds are shown in tabular form; a general conception of the dependence of stability of these structures on the members of the ring cannot be given but the effect of substitueiits is very marked. Five-membered rings are formed from azens and unsaturated compounds which in general are exceedingly unstable and immediately lose nitrogen with the production of three-membered rings. The five-atom rings contain- ing one double bond are less stable than similar rings with two double bonds. Heterocyclic rings containing three atoms are less stable than the trimethylene derivatives ; the influence of substi- tuents is very marked and requires further investigation. -.-- I i i '..-*' ! H.W. ______.__.__.. L ___ _________._ M. w. A New Process €or the Preparation of Cadmium Dimethyl. E. DE M~HLER (Bull. Xoc. chim. 1922 [iv] 31 125).-Cadmium iodide and magnesium methyl iodide readily react in ethereal solution at the ordinary temperature giving cadmium dimethyl and magnesium iodide. The cadmium dimethyl b. p. 105"/760 mm. is readily separated by fractional distillation. A. SKITA and A. SCHENCK (Ber. 1922 55 [B] 144-152).-1f Auwer's hypothesis (A. 1920 i; 721) that the reduction of aromatic hydrocarbons by Sabatier's method and in the presence of platinum leads to the formation of trans- and &-derivatives respectively is correct it must be possible to prepare a large number of previously unknown cyclic hexamethylenes by the latter process.For this purpose a modification of the catalyst is however necessary since the addition of water which is necessary for the solution of the catalyst protected by gum arabic causes the separation of the hydrocarbon. A glacial acetic acid reversible platinum colloid in which the metal is deposited on pure gelatin has therefore been introduced (the details of the preparation will be described later) with which it is possible to secure the smooth reduction of benzenoid hydrocarbons to hexamethylenes. W. G. Stereoisomerism of Cyclic Hydrocarbons.ORGANIC CHEMISTRY. i. 241 Iteduction of the three xylenes is effected by dwolving the hydrocarbon in glacial acetic acid and adding successively solutions of chloroplatinic acid and gelatin in glacial acetic acid and colloidal platinum solution ; hydrogenation is completed rapidly a t 80" under an excess pressure of three atmospheres.I n each case a mixture is obtained which is separated by repeated fractional distillation into its components the purity of which is controlled by observation of the molecular coefficient of refraction. The following constants are recorded 1" 2c-dimethyZcyclohexane b. p. 126.5"' Go 0-786 n$ 1.43114; lC 2WimethylcycZohexane; b. p. 124" djo 0-780 n 1.43037; 1" 3~-dimethylcyclohexane b. p. 121.5" dy 0.775 n$ 1.42609; lc 3t-dimethylcyclohexane b. p. 119" d 0.772 n; 1.42470; lC 4C-dimethylcyclohexane b. p. 121.5 diO 0.773 nz 1.42300; lC 4t-dimethylcycZohexane b..p. 119.5" diO 0-769 1.42095. The constants of the trans-series are identical with those of the products obtained by von Auwers by Sabatier's method. p-Cymene is reduced exclusively to 1~-methyl-4~-isopropylcyclohexane b. p. 168.5" d'" 0.816 n; 1.45149. 1 c 2c 4~-TetramethylcycZohexane b. p. 146" d'io 0.790 n'fP 1.43314 is obtained a sole product of the reduction of $-cumene by the new process; it is identical with the substance obtained recently (A. 1919 i 578) by the catalytic reduction of $-cumen01 in acid solution and differs markedly from the lc 2c 4l-isorneride obtained by von Auwers by Sabatier's method. The lC 2t 4-isomeride b. p. 140" dfJ 0.774 nz 1.42916 is prepared by the reduction of tetra- hydro-$-cumene (from cis-1-hydroxy-cis-2 4 5-trimethylcyclo- hexane) with sodium and alcohol.The differences observed with the cyclohexenes are similar to those with the saturated cyclic hydrocarbons. Thus the 1 2 4- trimethylcyclohexene derived from cis- 1 -hydroxy-cis-2 4 5-tri- methylcydohexane in contrast to the stereoisomeric hydrocarbon obtained by von Auwers (Zoc. cit.) by Sabatier's method has a pronounced cis-form the constants being b. p. 147" d'io 0.814 ng1.44905 for the former and b. p. 145" diO 0.805 n 1-44820 for the latter. cis- 1 -Hydroxy-cis-2 4 5-trimethylcycZohexane is converted into the corresponding ketone which is converted by magnesium methyl iodide into the tertiary alcohol; the latter is transformed by phos- phorus pentachloride into a tetrahydrodurene b. p. 169" d' 0.828 nz 1,46053.In all probability it is the lC 2c 4 5-compound whereas the isomeride b. p. 166" d'' 0.817 n$ 1.45722 obtained by von Auwers by Sabatier's method has the 1 c 2t 4 5-con- figuration. H. W. SEYEWETZ and VIGNAT (Compt. rend. 1922 174 296-299).-When nitro- benzene in suspension is boiled with a 10-20~0 solution of sodium sulphite it gradually disappears the solution becoming orange- coloured and ammonia being evolved. Prom the solution a compound can be isolated which is apparently identical with 4-aminophenol-3-sulphonic acid (cf. Schultz and Stable A. 1904 Action of Sodium Sulphite on Nitrobenzene.i. 242 ABSTRACTS OF CHEMICAL PAPERS. i 597). Phenylhydroxylamiiiesulphonic acid is probably formed as an intermediate product and being unstable is transformed into the aminophenolsulphonic acid.The coloration is probably due to the formation of an azoxybemene and may be suppressed by adding sodium hydrogen carbonate to the sulphite solution. W. G. The Products of Nitration of Toluene. WILLIAM HOWIESON GIBSON REBECCA DUCKHAM and RUTH FAIRBAIRN (T. 1922 121 270-283). Reductions with Titanium Trichloride. HANS RATHSBURG (Ber. 1921 54 [B] 3183-3184).-The following nitro-compounds are completely reduced by titanium trichloride according to the method of Knecht and Hibbert in boiling concentrated hydro- chloric acid solution in a current of carbon dioxide s-chloro- trinitrobenzene trinitroresorcinol trinitrophenylhydroxylamine picramide m-dinitro-o-dinitrosobenzene picramic acid tetra- nitrophenol ( +4H,O) trinitrophloroglucinol (+ +H,O).Over- reduction is observed with hexanitrotetrahydroxydiphenyl. If account is taken of the partial reduction of other groups which are present in addition to the nitro-radicles trinitrophenyldliazo- imide dinitrodiazophenol anhydride and the substance C,H606N from hexamethylenetetramine can be reduced smoothly in accord- ance with the schemes (i) C&,(NO,),N,+ 20TiC1 -+ C6H,( NH,),*N(NH) ; (ii) C6H,O(N02)2’N,+ 13TiC1 + C,H,O(NH,),*N*NH ; (iii) c3H6N3(NO2),+ 12TiC1 + C3H6N6. Complete reduction occurs also with the following salts and salt- like compounds a disturbing influence due to ;he metallic ion not being observed lead styphnate (+lH,O) lead picrate and the potassium compounds of dinitrodinitrosobenzene ( +0-25H2O) and tetranitrophenol (+ lH,O).The Electrochemical Oxidation of o-Toluenesulphonamide. FR. FIGHTER and HANS LOWE (Heh. Chinz. Acta 1922 5 60- 69) .-An examination of the possibility of converting o-toluene- sulphonamide into “ saccharin ” by electrochemical oxidation. Electrolysis of solutions of o-toluenesulphonamide in an excess of aqueous sodium hydroxide a t platinum nickel or copper anodes (cf. D.R.-P. 85491) does not lead to the formation of more than slight traces of “ saccharin ”; the sulphonamide appears to be completely decomposed with the formation of sodium sulphate as the sole isolable product. Electrolysis of 0- toluenesulphonamide partly suspended and partly dissolved in 0*5N-sulphuric acid a t 60” with anodes of platinum gauze graphite or lead coated with lead peroxide in a divided cell in which the cathode is formed of a lead cylinder im- mersed in 2N-sulphuric acid causes the separation of ammonia which is not due to hydrolysis and the production of small quantities of “saccharin.” It is thus shown to be possible to oxidise the H.W.01U3ANIC CHEiVlISTRY. i. 243 methyl to the carboxy-group. For the successful production of " saccharin," however it is necessary to secure the smooth oxidation of the methyl radicle and to protect the sulphonamide group during the process so as to secure the ultimate formation of the sulphon- imide ring. The first point is investigated by examining the oxidation of o-toluenesulphonic acid in 0.5N-sulphuric acid solution a t a rotating anode of lead covered with lead peroxide.It is found that the substance is not transformed smoothly into o-sulpho- benzoic acid. A portion of it is oxidised to phenolic substances which still contain the sulphonic group; according to analyses of the barium salts the phenolic substances and the products which are not precipitable with lead acetate are sulphocarboxylic acids. The electrolytic oxidation of 0- toluenesulphonic acid proceeds therefore beyond the o-sulphobenzoic acid stage and for the preparation of " saccharin," it is necessary to protect the oxidised product by ring closure immediately the methyl is converted into carboxyl. Electrolysis of benzenesulphonamide o-toluenesulphon- amide and " saccharin '' in 0-dN-sulphuric acid solution a t a platinum gauze anode proves that neither the sulphonamide nor the sulphonimide group is stable under these conditions.These groups however can be considerably protected by the use of ammoniacal solutions in which the ammonia functions as " relative depolariser " ; thus o-toluenesulphonamide is converted in 4N-ammoniacal solu- tion in the presence of ammonium sulphate at 40" and a t a platinum gauze anode into " saccharin," the material yield being 43.7% and the current yield 9.2%. The most favourable results however (material yield 75.4% current yield 42-6y0) are obtained by the electrolysis of o-toluenesulphonamide dissolved and suspended in 2N-sodmm carbonate solution a t about 80" with a platinum gauze anode and rotating lead cathode which secures efhcient agitation of the mixture; a porous cell is unnecessary.The success of the method does not depend on the intermediate formation of potassium perc ar b ona t e . H. W. Theory of the cis-tram-Isomerism of Decahydronaph- thalene. ERNST MOHR (Ber.. 1922. 55 [B] 230-231 ).-Will- statter and Waldschmid<Leit,z in 'a H H H CH2-CH 1' H H recent dmussion of the theoretically possible number of isomerides in completely hydrogenated naphthalene derivatives have expressed the opinion that only the cis-form (I) is capable of existence (A. 1921 i 667). Since how- ever the author has been able to construct a model for both cis- and -trms-tetrahydronaph- thalene (11) which is completely free from strain (cf. A. 1919 ii 229) he considers that the ultimate experimental realisation of the tram-isomeride is possible. H. w.i.244 ABSTRACTS OB CHEMICAL PAPERS. Certaiii CWloronaphthalene Derivatives. P. FRIEDL~~NDER S. QRAMESSINIS and 0. SCHENK (Ber. 1922 55 [B] 45-52).- The chlorination of nitronaphthalenesulphonic acids leads to the elimination of the sulphonic group which is,replaced by chlorine. The reaction is not quite quantitative since even with the calcu- lated quantity of the reagents a certain amount of oxidation occurs leading apparently to the production of chloroquinones which however are readily separated from the chloronitronaphthalenes by means of alkali. Gradual addition of an aqueous solution of sodium chlorate a t 90-95" t o a solution of sodium 1 -nitronaphthalene-5-sulphonate in aqueous hydrochloric acid yields 5-chloro-1 -nitronaphthalene almost colourless needles m.p. 111" ; it is preferable to remove the chloronitronaphthalene from the mixture as it is formed by means of di-(tri-)chlorobenzene. 5-C'hloro-a-naphthylamine crystallises in long colourless needles m. p. 85" whilst its ucetyl derivative forms hexagonal prisms m. p. 128". The crude chloronitronaphthalene contains small amounts of 1 4 5-trichloronaphthalene m. p. 133". 1-Nitronaphthalene-8-sulphonic acid is transformed similarly into 8-chloro- 1 -nitronaphthalene. 2-Nitronaphthalene-4 8-disulphonic acid is the main produ,ct of the nitration of naphthalene-1 5-disulphonic acid (the sodium salt lustrous needles and the sparingly soluble barium salt C,oH,O,NS,Ba are described) ; it is converted by chlorination into 4 8-dichloro-2-nitronaphthalene long yellow needles m.p. 132". The latter is reduced by stannous chloride or iron and hydrochloric acid to 4 8-dichloro- p-naphthylamine colourless needles m. p. 132-133" (the hydrochloride and the acetyl derivative colour- less needles m. p. 266" are described). The base can be diazotised in concentrated sulphuric acid solution from which the diaxonium sulphte is precipitated by addition of water in small pale yellow needles. The lstter couples normally with phenols and naphthols ; it is transformed by boiling dilute sulphuric acid into 4 8-dichloro- p-naphtlwl colourless needles m. p. 158-159" (methyl ether needles m. p. 93") and by hydrochloric acid and cuprous chloride into 2 4 8-trichloronaphthalene yellow needles m. p. 94". 4 8-Dichloro-l-nitronczphthalene pale yellow needles m.p. 142" is prepared by the chlorination of 1 -nitronaphthalene-4 8-disul- phonic acid or o€ 4-chloro-1-nitronaphthalene-8-sulphonic acid (the latter appears to be the sole product of the nitration of 1-chloro- naphthalene-5-sulphonic acid ; the sodium salt is described. It is reduced to 4- chloro- u-naphthylamine- 8 -sulphonic acid rhombic crystals the sodium salt of which is sparingly soluble in water). 4 8-Dichloro-u-naphthylumine crystallises in bong slender needles m. p. 113" and yields an acetyl derivative m. p. 163". 5 8-Dichloro-l-nitronaphthalene m. p. 93" (5 8-dichloro-a- naphthylamine y . &p. 104" and its acetyl derivative hexagonal prisms m. p. 202 ) ID prepared by the chlorination of the product of the nitration of 1 -chloronaphthalene-4-sulphonic acid.The production of two isomeric nitro-acids during the latter process is most conclusively demonstrated by their reduction to theORGANIC CIEEMISTRY i. 245 readily soluble 8-chloro- 1 -aminonaphthalene-5-sulphonic acid (the constitution of which follows from its conversion by sodium amalgam into 8-chloro-a-naphthylamine) and /\/\ the sparingly soluble 5-chloro- 1 -aminonaphthalene-8-sul- I I I phonic acid which is converted by boiling-its diazotised \d\/ solution into the suZphone (annexed formula) colourless 4-Chloro-1 8-dinitronaphthalene m. p. 180" is prepared from 1 8-dinitronaphthalene-4-sulphonic acid (the sodium salt and the corresponding s u l p h n y l chloride pale yellow needles m. p. 152.5" of the latter are described).When similarly chlorinated 1 8-dinitronaphthalene-3 6-di- sulphonic acid and 1 5-dinitronaphthalene-3 7-disulphonic acid do not yield precipitates. Vapour Pressure Determinations on Naphthalene Anthra- cene Phenanthrene and hthraquinone between their Melting and Boiling Points. 0. A. NELSON and C. E. SENSEMAK ( J . l n d . Eng. Chem. 1922 14 58-62).-Pew determinations of vapour pressure have been carried out with most of the solid hydrocarbons between the temperatures of their melting and boiling points or above. Vapour-pressure determinations over a range of temperatures have now been carried out on naphthalene anthracene phenanthrene and anthraquinone using Smith and Menzies's dynamic isoteniscope (A. 1910 ii 1037) and tables and curves of observed vapour pressures of these compounds are recorded.Boiling-point determinations on anthracene phenan- threne and anthraquinone gave anthracene b. p. 342"; phenan- threne b. p. 340-2"; anthraquinone b. p. 379.8". Perylene. F. HANSGIRG (US. Pat. 1384615; cf. A. 1920 i 54l).-A high yield of perylene is obtained by treating 2-derivatives of naphthalene or of 1 l'-dina,phthyl with halogenating agents such as the halogen compounds of phosphorus antimony arsenic or aluminium to obtain 2-substituted halogen derivatives and then transforming the latter into perylene by the action of ring-closing reagents such as aluminium chloride or by the " pyrogene synthesis." A reducing flux such as phosphorous acid is preferably used in the process and it may be carried out as a single operation with isolation of the intermediate halogen derivatives or if desired the latter may be separately obtained and used as starting materials for the last stage of the process.Among the starting materials which may be used are 2 2'-hydroxy-1 1'-dinaphthyl and 2 Y-dichloro- 1 1'-dinaphthyl. CXIEMICAL ABSTRACTS. Condensations of Acetylene. I. Elucidation of the Con- stitution of Cuprene. H. P. KAUFMANN and M. SCHNEIDER (Ber. 1922 55 [B] 267-282).-Cuprene has been obtained previously by several observers by the decomposition of acetylene in the presence of reduced copper or oxides of copper but the elucidation of its constitution has been rendered difficult by the poverty of the yield the insolubility of the product and the "2. * needles m. p. 184". H.W. F. M. R. VOL. CXXII. i. ki. 246 ABSTRACTS OF CHEMICAL PAPERS. difficulty with which it is attacked by reagents. A more potent catalyst has now been found in the residue obtained by heating anhydrous copper ferrocyanide in a current of air a t 250" during fifteen minutes which is approximately three times as active as reduced copper. The optimal temperatures for reduced copper cupric oxide cuprous oxide and copper ferrocyanide residue are 240-250" 230-240" 230-240" and 240-250" respectively. The product of the reaction has a differing colour dependent on the duration of heating and the particular contact agent. The residue obtained with decomposed copper ferrocyanide is yellow to pale brown whereas that prepared with other catalysts is darker in shade the portions richer in copper being dark brown to black.The latter are converted into paler products poorer in copper by further treatment with acetylene. With a short period of heating the product is loose and voluminous but becomes more compact when the heating is protracted. It is frequently spon- taneously inflammable a t 100-150" but this property is not due to cuprene itself but to finely-divided pyrophoric metal. A liquid condensation product is deposited in green oily drops on the cooler portions of the tube; the further investigation has been prevented by the small quantity available. Copper can only be removed from the solid product with great difficulty by treatment with hydrochloric acid (20y0) and it is necessary to use aqua regia to obtain specimens the copper content of which is so small that if can be neglected in the analysis.The composition of cuprene is not uniform varying between (Cl~Hl,,)z and (CISHIO)z. The main factor in the formation of the hfferent types of cuprene is the uncontrollable oxidative action of the oxygen. The formation of cuprene cannot a t present be completely explained but it appears most probable that a copper acetylide is formed intermediately which decomposes into cuprene without explosion ; the uniform distribution of the metal throughout the product is otherwise difficult t o account for. Cuprene is attacked violently by very concentrated nitric acid. It dissolves very slowly in boiling 50% nitric acid and the clear yellow solution when neutralised with ammonia and concentrated yields ammonium mellitate.If the acid solution is diluted largely with water a brown mellogen-like precipitate is obtained which is transformed into mellitic acid by nitric acid (80%) and into benzoic acid by dry distillation. The filtrate from the brown precipitate is neutralised by barium hydroxide whereby an in- separable mixture of barium salts is obtained from which naph- thalene is produced by dry distillation. Cuprene is not attacked by dilute solutions of bromine in w-ater or organic media whereas the action of elementary bromine causes carbonisation with elimination of hydrogen bromide. It may however be brominated by heating a paste of it with water and bromine at 100-130" in the presence of iron bromide. Since cuprene itself is not homo- geneous it is not surprising that the composition of the brominated product depends on the experimental conditions adopted.One such substance prepared by extracting the crude product withORGANIC CHEMISTRY. i. 247 alcohol and subsequent treatment of the residue from the alcoholic solution with ether forms a pale yellow amorphous powder analyses and determinations of the molecular weight of which agree with the formula C,8.H,2Br,. It is converted by nitric acid into mektic acid. formula) in which the position of the bromine atoms is not established. All attempts to isolate the parent hydrocarbon by removal of the bromine atoms were unsuccessful since the residue (immediately after loss of bromine) became polymerised to a hydrocarbon resembling cuprene. Br It appears therefore to be a hexabromohexahydrotriphenylene (annexed Br H.W. The System Acetanilide-Water. N. SCHOORL and F. N. B. DE WEERD (Rec. trav. chim. 1922 41 15-20).-The acetanilide- water system exhibits a region of heterogeneous equilibrium which is situated above the ordinary temperature and connects the solu- bility and depression of freezing-point curves. The temperature limits of this region are 83.2" and lU' and the composition limits from 5.2% to 87% of acetanilide. At 144" the highest temperature a t which the system is heterogeneous the composition is 40% acetanilide 60% water. H. J. E. Aniline Glucoside (Glucose Anilide ) . TH. SABALITSCHKA (Ber. deut. Pharm. Ges. 1921 31 439-445).-Acetobromoglucose reacts with aniline at ordinary temperatures and after twenty- four hours the initially clear solution sets to a solid mass from which aniline tetracetyl-d-glucoside was isolated in long needles m.p. 95-96' [a]" -59.5 (after twenty-four hours). On hydrolysis in methyl alcoholic solution with barium hydroxide it was con- verted into aniline-d-glucoside which accordingly has the y-oxidic structure OH*C€I,*CH( OH)*QH-CH( OH)-CH( OH)*yH*NHPh. The substance was deposited from organic solvents as a gelatinous mass which dried to a white amorphous powder m. p. 147" [a] -52*4O (in methyl alcohol) constant after four days. Aniline-d-glucoside thus prepared was identical with glucose anilide obtained by the direct action of aniline on dextrose to which the structure of a Schiff's base had originally been ascribed and the correctness of Sorokin's (A.1888 807) and later of Irvine's views (T. 1908 93 95 1429) of the constitution of this substance as a glucoside is thus confirmed. G. F. M. 0 6-Amino-a-naphthol-5-sulphonic Acid (A-acid) and its Derivatives. HANS TH. BUCHERER and RUDOLF WAHL ( J . pr. Chem. 1921 [ii] 103 129-162).-2-Naphthylamine-1 5-disul- phonic acid which may be obtained by treating S-naphthylamine- 1-sulphonic acid with fuming sulphuric acid a t 30-40° is con- verted into its potassium salt and fused with potassium hydroxide to give 6-ami?ao-ol-na~hthol-5-sulphonic acid (A-acid). The yield k 3i. 248 ABSTRACTS OF CHEMICAL PAPERS. and nature of the by-products (6-amino-a-naphthol 1 6-dihydroxy- naphthalene and 1 6-dihydroxynaphthalene-5-sulphonic acid) vary with the exact conditions employed.A-acid forms a characteristic orange diazonium salt. 2-Naphthylamine-1 5- disulphonic acid on heating with 75% sulphuric acid gives P-naphthylamine and 2-naphthylamine-5-sulphonic acid and with sulphuric acid monohydrate 2-naphthylamine6 -6- and -7- sulphonic acids. A-acid with mineral acids gives 6-amino-a- naphthol. On sulphonation with concentrated sulphuric acid a mixture of 6-amino-a-naphthol-2 5-disulphonic acid and 6-amino- a-naphthol-4 5-disulphonic acid are obtained. With acetic an- hydride 6-acetylamino-a-naphthol-5-sulphonic acid is formed with benzo yl chloride 6 -di benxo y lamino- a-nap ht hol-5-sulphonic acid with toluenesulphonyl chloride it forms the expected product C1,Hl5O6NS and with carbonyl chloride the carbamide.w. 0. K. Rearrangements of some New Hydroxamic Acids Related to Heterocyclic Acids and to Diphenyl- and Triphenyl-acetic Acids. LAUDER W. JONES and CHARLES D. HURD (J. Amer. Chem. Soc. 1921 43 2422-2448).-An interpretation of the mechanism of the Beckmann rearrangement is proposed based on Langmuir’s theory of the atom. The stages in the rearrangement are pictured as follows in which Fig. 1 represents the intermediate (14 (11.) (111.) univalent nitrogen derivative and Pig. 111 the carbimide stage in the rearrangement. As a further hypothesis to explain why one radicle R will migrate more readily than another radicle R’ the authors suggest that the relative ease of arrangements of the Beckmann type is dependent on the tendency for the radicle R in the univalent nitrogen derivative such as [R*CO*N] to exist as it free radicle.This hypothesis finds support in the results obtained for the relative ease with which the sodium and potassium salts of the acyl esters of diphenylacethydroxamic acid and t riphenylacethydroxamic acid undergo rearrangement. The salts of the triphenyl derivative undergo rearrangement the more readily. Two new methods of preparing hydroxamic acids are described. In the first by the action of free hydroxylamine on a keten such as diphenylketen the corresponding hydroxamic acid is obtained CPh,:CO +NH,*OH= CHPh,*CO*NH*OH. The second method is a modification of the one usually employed namely the action of acid chlorides on hydroxylamine in aqueous solution. ‘If a neutral solvent such as benzene is used in place of water a quantitative yield of the monohydroxamic acid is obtained.ORGANIC CHEMISTRY.i. 249 Diphenylacethydroxamic acid CHPh,*CO*NH*OH m. p. 172' is prepared by the action of hydroxylamine on ethyl diphenylacetate in the presence of sodium methoxide or by either of the above methods. It gives a benxoyl ester m. p. 140-140.5' the sodium and potassium salts of which could not be obtained in the pure state. The silver salt showed chromoisomerism. The alcohol- ether solution of the sodium salt on evaporation leaves a mixture of the salt with its products of decomposition and rearrangement namely diphenylmethylcarbimide diphenylmethylurethane m. p. 122-133' and sodium benzoate. When this residue is extracted with cold water and the solution filtered and boiled s-bisdiphenyl- methylcarbamide CO(NH*CHPh,) m.p. 2696-270' is obtained. Diphenylacethydroxamic acid yields a monoacetyl derivative m. p. 113-1 13.5" ; giving potassium sodium and silver salts and a diacetyl derivative m. p. 95.5-97.5'. Diphenylmethyl urethane reacts with phosphorus pentachloride yielding diphenylmethylcarbamyl chloride CHPh,*NH*COCl which when left in contact with calcium oxide gives diphenylmethylcarbimide and this when treated with benzoyl- hydrylamine yields s- bisdiphenylmethylcarbamide. Triphenylacetyl chloride reacts with hydroxylamine to give triphenylacethydroxamic acid m. .p. 175-176' which yields a benxoyl ester giving sodium potassmm and silver salts. The silver salt showed chromoisomerism but the sodium and potassium salt's could not be obtained pure owing to the readiness with which they decomposed giving triphenylmethylcarbimide m.p. 85-87'. The acetyl ester m. p. 1334-134' gives potassium sodium and silver salts the two former of which are somewhat more stable than the corresponding salts of the benzoyl ester. In these rear- rangements none of the s-bistriphenylmethylcarbamide was formed. II*CO*NH*OH (cf. Pickard and Neville T. 1901 79 847) its ammonium salt m. p. 130-131" its benxoyl ester m. p. 140' and the potassium sodium and silver salts of the ester were prepared. When the potassium salt was warmed in aqueous solution some of the ester was first precipitated and when this was filtered off and the filtrate boiled a red resinous mass presumably of difurylcarbamide was obtained. The acetyl ester m.p. 95-96' of the hydroxamic acid gave potassium sodium and silver salts the rearrangement and hydrolysis of these salts being similar to those of the corresponding salts ofthe benzoyl ester. /I*CO*NH*OH m. p. 123-1246" was obtained either by the action of hydroxylamine on ethyl thiophen- carboxylate C,H,S*CO,Et or by the action of hydroxylamine on thienoyl chloride. It gave an ammonium salt m. p. 142-143" (decomp.); a benxoyl ester m. p. 143-144" giving potassium sodium and silver salts; an acetyl ester m. p. 96-5-97' giving potassium sodium and silver salts ; and a thienoyl ester [dithienoyl- Pyromucylhydroxamic acid 'I \/ 0 _- Thienoylhydroxamic acid \/ Si. 250 ABSTRACTS OF CHEMICAL PAPERS. hydroxamic acid C4H3S*CO*NH*O*CO*C,H,S] whiah ocourred in two forms and gave potassium sodium and silver salts.The salts of the esters of thienoylhydroxamic acid underwent slight hydrolysis in aqueous solution but the main change was one of rearrangement to sym-dithienylcarbamide. The thienoyl ester m. p. 133-1336" of benzhydroxamic acid which was isomeric with the benzoyl ester of thenhydroxamic acid was prepared and its potassium and silver salts were inves- tigated. The melting points of the esters and the decomposition temperatures of their salts and the ease of rearrangement of the latter were almost identical in the two cases. W. G. Metallic Derivatives of Nitsophenolic Compounds. IV. Some Complex Nitrophenoxides of Magnesium Silver and Lead. ARCHIBALD EDWIN GODDARD and JAMES BERTRAM WARD (T.1922,121,262-266). Auto-oxidation the Anti-oxygens. CHARLES MOUREU and CHARLES DUFRAISSE (Compt. rend. 1922 174 258-264).-The auto-oxidation of a large number of substances may he checked by the presence of traces of certain compounds to which the authors give the name " anti-oxygens." Most of the substances which have been found to show this inhibiting action belong to the phenol group and of these quinol catechol and pyrogallol are particularly active. This protecting action may be prolonged for two years a t least providing the substance capable of auto-oxidation does not sublime from the anti-oxygen. The secondary reactions which often accompany auto-oxidation are also inhibited by the presence of the anti-oxygens. The action of the anti-oxygens is apparently catalytic and it is of interest to note that traces of pyrogallol a substance commonly used as an absorbent of oxygen oppose the action of this gas.The bearing of these observations on the phenomena of life in the animal and the vegetable kingdom is discussed. It is suggested that the toxic properties of phenols are connected with their activities as anti-oxygens. W. G . H. WUYTS and A. VANCINDERTAELEN (Bull. SOC. chim. BeZg. 1921 30 323- 32S).-Stannic mercaptides can be prepared (a) by the action of tin and hydrochloric acid on organic disulphides with subs'equent neutralisation ( b ) from a thionlcohol and stannous chloride in presence of air or (c) from a thioalcohol and stannic chloride. Attempts to prepare stannous mercaptides did not succeed and the behaviour of tin in this respect is compared with that of its sulphides towards alkali sulphide solutions.The mercaptide Sn( S-C,H,*NMe,) prepared from dimethylaniline- disulphide is a red crystalline substance m. p. 159" ; with benzoyl chloride in benzene solution it forms the benzoate of the corre- sponding thioalcohol m. p. about 136'; with methyl iodide two reactions take place one with the rupture of the sulphur-tin linking The Quadrivalence of Tin in its Mercaptides.ORGANIC CI-PEMISTRY. i. 251 and the combination of methyl and iodine with the elements res- pectively the other with formation of the iodide of the quaternary ammonium base ~e,I*C,H,*SMe. Similarly from di-p-amino- phenyl disulphide the mercaptide Sn( S*C,H,*NH,) red leafy crystals m. p.about 166" was obtained. Sulphobenzide [Diphenylsulphone]. EUG. GRANDMOUGIN (Compt. rend. 1922 174 168-170).-3 3'-Diaminodiphenyl- sulphone gives a bis-diazo-derivative which couples normally with the naphthols and their sulphonic derivatives. The dyes obtained have almost the same shades as the corresponding dyes from aniline itself the chromophoric influence of the sulphone group in t'he meta-position to the two amino-groups being thus practically negligible. New compounds mentioned are 3 3'-dichZorodiphenyZsulphone m. p. 108" ; 3 3'-dibrornodiphenylsulphone m. p. 119" ; and 3 3'-di-iododiphenylsulphone m. p. 158". I n view of the erroneous statements occurring in the literature the correct melting points of certain of the 3 3'- and 4 4'-deriv- atives of diphenylsulphone are tabulated a9 follows H.J. E. The dyes obtained dye only wool and not cotton. (NO,),. (NH,)? (NHAc),. (OH),. Cl,. Br,. I,. 3 :3' ............ 201" 16s" 211" 186-187' 108" 119' 158' 4 4' ............ 282 174 280 239 147 1'72 197 w. G. Cholesterol Dibromide. I. LIFSCHUTZ (Zeitsch. physiol. Chem. 1921 114 286-289).-Cholesterol dibromide prepared by the ether method has m. p. 93-94" whilst when the glacial acetic acid method is used i t has m. p. 110-111". The author brings forward evidence which suggests that a compound of the dibromide and acetic acid has been formed in the second case. The author considers that the cholesterol dibromide m. p. 122" obtained by Windatus a'nd Luders is possibly an isomeride of the The Replacement of Halogen in 4-Chloro-3-nitrobenzo- nitrile and in 4-Bromo-3-nitrobenzonitrile. TH.J. 3'. MATTAAR (Rec. trav. chim. 1922 41 24-37).-The reactions between 4-c hloro- 3-nitro benzonit'rile and /or 4- bromo- 3-nitrobenzonitrile and sodium methoxide sodium ethoxide sodium phenoxide methyl- amine ethylamine dimethylamine aniline o-toluidine m-tolu- idine p-toluidine methylaniline p-phenylenediamine hydrazine phenylhydrazine and phenylmethylhydrazine have been investi- gated. The following new substances have been prepared 3-n7itro- 4-methoxybenzonitrile pale brown needles m. p. 151" ; 3-nitro- 4-ethoxybenzonitrile white needles m. p. 121 " ; 3-nitro-4-phenoxy- benxonitrile colourless prisms m. p. 138" ; 3-nitro-4-methylamino- benxonitrile yellow needles m. p. 169" ; 3-nitro-4-ethylaminobenxo- nitrile yellow needles m.p. 132" ; 3 5-dinitro-4-ethylnitroamino- benzonitrile lustrous plates m. p. 142.5" ; 3-nitro-4-dimethylamino- benzonitrile yellow plates m. p. 114" ; 3-nitro-4-o-toluidinoDer~xo- nitrile browniah-yellon7 plates m. p. 116" ; 3-nitro-4-m-toZuidino- dibromide obtained by himself. s. s. z.i. 252 ABSTRACTS OF CHRMTCAL PAPERS. benzonitrile orange needles m. p. 149" ; 3-nitro-4-p-toluidinobenxo- nitrile orange needles m. p. 128" ; 3-nitro-4-methylanilinobenxo- nitrile yellow irregular plates m. p. 144" ; 3-nitro-4-p-amino- anilinobenzonitrile deep violet crystals m. p. 158" ; benxaldehyde- 2-nitro-4-cyanophenylhydraxone red plates which turn colourless on drying m. p. 225" ; acetophenone-2-nitro-4-cyanophenylhydr- azone lustrous red needles m.p. 232" ; 3-nitro-4-phenylrnethyl- hydraxinobenzonitrile red crystals m. p. 132". The reaction between phenylhydrazine and 4-chloro-3-nitrobenzonitrile (cf. Borsche Stackmann and Makaroff-Semljansky A. 1917 i 15) yields a substance which is considered to be converted on oxidation into 3-nitro-4-phenylhydrazinobenzonitrile colourless needles m. p. 181". H. J. E. Preparation of Phenylglycine Compounds. BRITISH DYE- STUFFS CORPORATION LTD. HERBERT LEVINSTEIN and GEORGES IMBERT (Brit. Pat. 173540).-Phenylglycine compounds are obtained in one operation from trichloroethylene by heating it in aqueous suspension with aniline and an alkali preferably calcium hydroxide ' in an autoclaves at 140-19Qo the treatment being continued until the intermediate products for example ethylenetriphenyltriamine are completely transformed into phenylglycine compounds.For example 132 parts of trichloroethylene 100 parts of lime 800 parts of water and 280 parts of aniline are heated in an autoclave with constant agitation for twenty-four hours at 180". The excess of aniline is distilled off the calcium phenylglycine and excess of lime separated from the mother liquors and converted into sodium phenylglycine by boiling with -the requisite quantity of sodium carbonate . G . 3'. M. The Hydrolytic Decomposition of the Bismuth Salts of Phenolcarboxylic Acids. A. PERLING (Ber. Deut. Pharm. Ges. 1921 31 433-438).-The hydrolysis by water of the neutral and basic bismuth salts of benzoic salicylic protocatechuic gallic and cinnamic acids proceeds to a definite limit which is attained when they are heated a t 100" with four consecutive quantities of water for a total of ten hours.Both the neutral and basic salts of the various acids eventually attain the same composition the only salt remaining unchanged being the basic benzoate having the composition (PhC02*BiO)6,Bi20,. The experimentally-determined composition of the final hydrolytic product of all the other bismuth salts above mentioned was found to be in close agreement with the theoretical figure required for a salt of the composition (R*CO,*BiO),,Bi,O analogous to the basic benzoate (H,=phenol residue) and it is therefore evident that hydrolysis proceeds to precisely the same point with all the salts. When shaken at 37" with 0.25% hydro- chloric acid conditions resembling those existing in the stomach a slightly greater degree of hydrolysis was observed.Substituted Salicylic Acids. I. H. P. KAUFMANN and W. KAUFMANN (Ber. 1922 55 [B] 282-2SS).-A number of G. P. M.ORGANIC CHEMISTRY. i. 253 substances are described which were obtained during an investi- gation of the influence of different substituents on the physiological action of salicylic acid. [With H. GOTTING .]-Acetylglycollylsalicylic acid C,H,( C0,H) 0 *CO *CH,* 0 Ac small colourless needles m. p. 103-104" is prepared by tlhe action of acetylglycollyl chloride on sodium salicylate in the presence of benzene a t the atmospheric temperature. It is readily hydrolysed by warm water to acetylglycollic and salicylic acids. The action of s-o-phthalyl chloride on sodium or disodium salicylate in the presence of boiling YO-? C6H,<-c->0 dry benzene leads to the formation of a substance (annexed formu18 I or ('0 11) colourless needles m.p. 158.5". C,H4-bo It is slowly hydrolysed by alco- co*o*co holic sodium hydroxide solution to (1.) (I1*) phthalic and salicylic acids. It is reduced by zinc dust and glacial acetic acid to phthalide and salicylic acid; the latter reaction appears to indicate the un- symmetrical constitution of the parent substance but this point cannot yet be regarded as established with certainty. $!6H4 ?sH4 . H. W. Glucosides. X. The Action of dZ-Acetobrornoglucose on the Silver Salt of dl-Mandelic Acid. P. KARRER C. NAGELI and ALEX. P. SMIRNOV (Helv. Chim. Acta 1922 5 141-146).- It has been shown previously (Karrer and Nageli A.1919 i 594) that acetobromoglucose reacts with silver dl-mandelate in the presence of toluene to form d-tetra-acetylglucosido-dZ-mandelic acid C0,H*CHPh*O*C6H,05Ac4 d-tetra-acetylglucose dl-mande- late and d-tetra-acetylglucose d-tetra-acetylglucosido-Z-mandelate from which I-mandelic acid was isolated by hydrolysis. The similar action between dl-acetobromoglucose and silver dl-mande- late has been found to give products of the same three types all of which are optically inactive. Since d-acetobromoglucose only combines with I-.mandelic acid to form a corresponding compound (loc. cit.) it follows that the inactive tetra-acetylglucose tetra- acetylglucosidomandelate must be a racemate combined from d-tetra-acetylglucose d-tetra-acetylglucosido-I-mandelate and I- tetra- acetylglucose I-tetra-acetylglucosido-d-mandelate. Reaction thus appears to be unusually selective the d-glucose derivative com- bining only with the Z-acid in this manner whereas the I-glucose compound unites with the d-acid.A satisfactory explanation of the unusually marked effect of configuration on the reaction cannot a t present be given. - 192.7" in ethereal solution is prepared by the action of acetyl bromide and glacial acetic acid on I-glucose. When mixed in ethereal solution with an equal quantity. of d-acetobromoglucose it gives dl-acetobrornoglucose colourless needles m. p. 85". dl-Tetra-acetyl- glucose dl-mndelate and dl-tetra-acetylglucose dlatetra-acetylglucosido- dl-mandelate have m.p. 146" and 227" respectively. 1-Acetobrornoglucose colourless needles m. p. 88" [ H. W. E"i. 254 ABSTRACTS OF CHEMICAL PAPERS. b New Synthesis of ' Hydroxylated Benzoylformic [Phenyl- glyoxylic] Acids. H. FINGER and LINA EIRICH ( J . pr. Chem. 1921 [ii] 103 249-252).-Ethyl cyanoformate can be used instead of hydrocyanic acid in the Gattermann aldehyde synthesis and hydroxylated phenylglyoxylic acids are produced. Pyrogallol and methyl cyanoformate dissolved in ether give with zinc chloride and gaseous hydrogen chloride 2 3 4-trihydroxyphe~ylglyoxylic acid C,H,( OH),*CO*CO,H m. p. 171 " which dyes chrome-mordanted wool. It gives a sodium salt C,H5Q,Na; a normal aniline salt m. p. 138"; whilst on heating with aniline a t 135" 2 3 4-tri- hydroxybenzylidineaniline C,H,( QH),-CH:NPh is formed thus proving the constitution of the acid.The following derivatives of 2 3 4-trihydroxyphenylglyoxylic acid are also described nitrophenylhydraxme yellowish-red needles m. p. 230-240° (decomp.) ; semicurbaxone decomp. 230". With oxythionaphthen dissolved in acetic anhydride trihydroxyphenyl- glyoxylic acid forms a compound C,H,(OAc),*C(CO,H):C<~~) C,H and it couples with benzenediazonium chloride to give an azo-dye. The Preparation of Chloro- and Bromo-tyrosine and the Analogous Tyrasnines. R. ZEYNEK (2. physiol. Chem. 1921 114 275-285) .-3 5-Dibromotyrosine and 3 5-dichlorotyrosine are best prepared by the action of the respective halogens on I-tyrosine suspended in glacial acetic acid. 1-3 5Dichlorotyrosine has m.p. 256-260" (decomp.) crystallises in rhombic platelets and the anhydrous hydrochloride gives in 5% aqueous solution [ m ] i r -7.S"; in 4% hydrochloric acid [Q]? -2.9". A 5% solution of dichlorotyrosine containing 2H,O dis- solved in 4% hydrochloric acid gave [ a g -2.8". p-Hydroxy- phenylethylamine when suspended in glacial acetic acid and brominated yields dibromotyramine hydrobromide crystallking in monoclinic platelets m. p. 270". The free base crystallises in white flat rhombic rods m. p. 210". Dichlorotyramine hydro- chloride prepared similarly crystallises in monoclinic plates m. p. Preparation of Soluble Derivatives of Camphoric Acid. SOCIETY OF CHEMICAL INDUSTRY IN BASLE (Brit. Pat. 173063).- Soluble derivatives of camphor which retain the therapeutic properties of that substance but give stable solutions in water sterilisable by heat and therefore suitable for subcutaneous injec- tion are exemplified by certain N-substituted derivatives of camphorimide of the type CsH,,<CO>N*R*N<R, where R is an alkyl or alkylene group and R' and R" are hydrogen alkyl or alkylene groups.These compounds are obtainable from camphor- imide by the usual methods as for example by causing its isolated dry salt or a solution to react with polyhalogenised saturated or unsaturated aliphatic hydrocarbons or with halogen hydrins and W. 0. K. 284-286"; the base has m. p. 219-222". s. s. z. CO R'ORGANIC CHEMISTRY. i. 265 the N-halogen alkyl or N-halogen alkylene camphorimide thus obtained (after substituting halogen for hydroxyl if a halogen- hydrin has been used) is treated with ammonia or an alkylamine.Or alternatively camphoric acid or its anhydride may be caused to react with a diamine of the type NH,*R*NR'R". The following substances are described Camphor- p-hydroxyethplimide a thick colourless oil b. p. 19Oo/l5 mm. is prepared by the action of ethylene iodohydrin on sodiocamphorimide in absolute alcoholic solution. Camphor- p-chloroethylimide prepared by the action of phosphorus pentachloride on the above is st pale yellow oil b. p. 168"/10.5 mm. By heating with ammonia a t 100" under pressure it is converted into camphor-p-aminoethylimide C,H,,<~~>N*CH,*CH2*NH2 which can be isolated as its hydrobromide as an incompletely solidi- fying syrup which decomposes a t 135-140". The chloroethyl- imide when similarly heated with 33 yo dimethylamine solution a t 120-125" gives camphor- p-dimethylaminoethylimide b.p. 163'1 14 mm. It forms a crystalline hydrobromide m. p. 207" soluble in both water and alcohol. Camphor- p-bromoethylimide is obt'ained by heating potassiocamphorirnide with an excess of ethylene dibromide on an oil-bath. It boils a t 186"/13 mm. When heated a t 100" with diethylamine it is converted into camphor- p-diethyl- aminoethylimide a viscid oil b. p. 183-185"/12 mm. which gives a crystalline hydrobromide m. p. 167". Camphor-P-allyl- amirwethylimide is similarly prepared from allylamine and the halogenethylimide. It boils at 187"/12 mm. and gives a hgdro- bromide crystallising in fine leaflets m. p. 144". Illustrative of the second general method of preparation the above-mentioned P-diethylaminoetlhylimide may also be obta.ined by heating at 180-200" camphoric acid and as-diethylethylenediamine. The latter substance obtained by the reduction of diethylaminoaceto- nitrile with sodium and alcohol forms an oil b.p. 140-145" with strongly basic properties. I n a similar way from the reduc- tion product of piperidine acetonitrile by heating with camphoric acid the corresponding imide camphor- p-~iperidylethy~imide is obtained. Its hydrobromide crystallises in fine felted needles m. p. 193.5". G. F. M. The Bile Acids. 111. Biloidanic Acid [Letsche's Acid]. W. BORSOHE 0. WEICKERT and ROBERT MEYER (Ber. 1921 54 [B] 3177-3182).-Biloidanic acid has been prepared by Letsche (A. 1909 i 697) by the action of a mixture of nitric a'nd sulphuric acids on cholic acid and examined subsequently by Schenck (A 1920 i 847; 1921 i 179) who concurs in ascribing to it the formula C#2@,().Specimens of the purified acid examined by the authors did not give analytical results in agree- ment with this formula. The acid was therefore esterified with methyl alcohol and hydrogen chloride but the product mainly a dimethyl trihydrogen ester was not quite uniform. It was there- fore converted by diazomethene into the pentamethyl ester (which E" 2i. 256 ABSTRACTS OF CHEMICAL PAPERS. has also I)eeij prepared by Schenck from the silvcr salt and methyl iodide). The latter caiinot be satisfactorily purified by crystallis- ation but after being distilled under diminished pressure gives analytical results in agreement with the formula C23H36010 thus indicating the formula C,,H2,01 for the parent acid.The penta- methyl ester has m. p. 91-92" after softening a t 87" b. p. 321- 322"/18 mm. [.ID about + Z O O in absolute alcoholic solution. Direct analysis of the acid regenerated from the hydrogen ester leads to the same result. The pentamethyl ester has not yet been smoothly re-converted into the acid. A modification of Letsche's method of preparing the acid is described which permits the isolation of biloidanic acid in the pure condition after a single crystallisation. A Critical Examination of the Aromatic Aldehydes occur- ring in certain Eucalyptus Oils. ARTHUR RAMON PENFOLD The Reduction of Naphtholcarboxylic Acids to Aldehydes.HUGO WEIL and WALTER HEERDT (Ber. 1922 55 [B] 224- 830) .-A continuation of previous work (Weil and Ostermaier this vol. i 139). Tetrahydronaphthaldehyde has been obtained previously (Zoc. cit.) by the reduction of p-naphthol-3-carboxylic acid by sodium amalgam in boric acid solution with the addition of a neutral mixture of sodium sulphite and sodium hydrogen sulphite. Tho same result is obtained when the action is effected a t a temperature not exceeding -5". The aldehyde is also obtained by the reduction of 2-acetoxynaphthalene-3-carboxylic acid 1-amino-p-naphthol 3-carboxylic acid and 1-bromo-p-naphthol-3-carboxylic acid ammonia or hydrogen bromide respectively being eliminated from the compounds last named. Tetrahydronaphthaldehyde hydrazone after being crystallised from alcohol containing a little glacial acetic acid has m.p. 106.5" instead of 96.5" as previously recorded (Zoc. cit.). l-Amino-~-naphthol-3-carboxylic acid is pre- pared conveniently by coupling p-naphthol-3-carboxylic acid with diazotised sulphanilic acid and reduction of the dye so formed with zinc dust and glacial acetic acid. a-Naphthol-2-carboxylic acid does not appear to be reduced beyond the 1 -hydroxynaphthal-%aldehyde stage even by energetic treatment a t 25" 40" or 55". 4-Amino- 1 -hydroxynaphthalene-2-carboxylic acid is so feebly acidic that it is precipitated from solutions of its salts by boric acid and thus escapes reduction. 4-Sulpho-1-hydroxynaphthalene-2-carboxylic acid is reduced to a-naphthol-2-aldehyde the sulphonic group being eliminated.On the other hand the cautious reduction of 4-bromo-1-hydroxy- naphthalene-Zcarboxylic acid leads to the formation of 4-bromo- 1 - hydroxynap hthdene-2 -aldeh yde which however could not be obtained in the homogeneous state. It gives the normal corn- pounds with phenylhydrazine (yellow leaflets m. p. 15Q") aniline (orange-yellow needles m. p. 161") o-toluidine (yellowish-red H. W . (T. 1922,121 266-269).ORGANIC CHEMISTRY. i. 257 needles m. p. 188O) p-toluidine (yellowish-red needles m. p. 171") benzidine (C,,H1,ON,Br red leaflets m. p. 218") a-naphthylamine (red needles m. p. 196") o-phenylenediamine (C,,H,,ON,Br m. p. 225") m-phenylenediamine (m. p. ZOl") p-phenylenediamine (m. p. 198") ; with ammonia it gives the compound C,,H,,O,N,Br yellow crystals m.p. 126". 4-Chloro-l-hydroxy~p~t~lene-2-carboleyl~c acid m. p. 228" pre- pared by the passage of chlorine into a solution of a-naphthol- 2-carboxylic acid in glacial acetic acid is reduced similarly to 4-chloro- 1 -hydroxyruzphthuEene-2-aldehyde. The latter gives the usual derivatives with hydroxylamine (colourless needles m. . p. 184") hydrazine (yellow needles m. p. 179") phenylhydrazinc (yellow leaflets m. p. 153") aniline (yellow needles m. p. 157") o-toluidine (orange-yellow crystals m. p. 183") p-toluidine (orange- yellow crystals m. p. 164") a-naphthylamine (reddish-yellow leaflets m. p. 188O) benzidine (C,,H,,ON,Cl red crystals m. p. 214") o-phenylenediamine (C1,H,,ON,C1 leaflets m p. 221°) m-phenylenediamine (m. p. 250") p-phenylenediamine (m.p. 244") ; with ammonia it gives the compound C,,H1,03N,C1,. The sodium compound of 4-chloro- 1 - hydroxynaphthalene-2-alde- hyde crystallises in yellow leaflets. Preparation of Hydroxyaldehydes and their Derivatives. SOCI~TB CHIMIQUE DES USINES DU R H ~ N E (Brit. Pat. 164715).- I n the manufacture of aromatic hydroxyaldehydes by the process described in Brit. Pat. 161679 (A. 1921 i 420) equally good results are obtained without the use of an organic solvent. Thus vanillin is obtained by adding a concentrated solution of 5.3 kilos. of sodium nitrite and after some time 4 kilos. of guaiacol and 8 kilos. of 40% formaldehyde solution to a solution of 8 kilos. of dimethyl- aniline in 33 kilos. of hydrochloric acid in presence of 33 kilos. of ice. A low temperature is maintained for some hours and the reaction is completed on a water-bath.The Melting Points of certain Fatty-aromatic Ketones. RIKO MAJIMA KWANTO NAGAOKA and KEISTJKE TAMADA (Ber. 1922 55 [B] 215-217).-A number of ketones of the types C,H,( OMe),*CO*R C,H,( OMe)*CO*R and C,H,*CO-R have been prepared. The melting points of a compound with an even number of carbon atoms in the side-chain is invariably higher than that of either of its immediate neighbours with an odd number of carbon atoms as shown by the annexed table. H. W. G . P. M. M. p. of the compounds. Side-chain. __ __ - ._ C 0 . C loHz 49" .CO-CIlHz3 68-69' 62.5 45O 'C0.C 13H2 7 74-75 67 54-56 vC0-R C,H,(OiM&cO .R C,H,( 0Me)CO.R C,H;-CO -R -CO*C12H2 59-5-60 59 41-42 .CO -C 14H29 64-65 65-66 50-5 1 .CO.Cl 5H31 79-80 72-73 59-60 C0.C,6H33 67-68 70.5 56-56.5 sC0.C 17H3 82-83 77-77.5 H.W.i. 258 ABSTRACTS OF CHEMICAL PAPERS. Elimination of Hydrogen from Aromatic Nuclei and Union of the Latter by means of Aluminium Chloride. ROLAND SCROLL and CHRISTIAN SEER (Ber. 1922 55 [B] 109- 117; cf. A. 1913 i 56 734).-Previous attempts to convert o-chlorophenyl oc-naphthyl ketone into 5-chloro- 1 9-benzanthrone were unsuccessful; this does not however appear to be a general characteristic of chlorophenyl ketones since the corresponding meta- and para-compounds give substituted benzanthrones in rather poor yield. [With JOSEF D~IMER.]-~-ChEoropF~nyl-u-~~hthyl ketone crystal- lises in colourless needles m. p. 82". izl-Chlorophenyl-cc-naphthyl ketone small pale yellow prisms m.p 77-79" is obtained by the action of m-chlorobenzoyl chlonde on naphthalene in the presence of carbon disulphide and aluminium chloride. It is converted by aluminium chloride a t 145" into 6-chloro-1 9-benxanthrone golden-yellow needles m. p. 186-187". The constitution of the latter follows from the obser- vation that it is oxidised by chromic acid to 6-chloroanthraquinone 1-carboxylic acid lustrous golden needles m. p. 295" which loses carbon dioxide a t 310-320" and yields 2-~hloroanthraquinone slender yellow needles m. p. 203-204". p-Chlorophenyl a-naphthyl ketone colourless rods m. p. 126- 128" is converted by aluminium chloride into 7-chloro-1 9-benx- anthrone yellow microscopic crystals m. p. 187-188". Anthraquinone- 1 -carboxylyl chloride pale yellow needles m.p. 203-204" (cf. Schaarschmidt A. 1915 i 566) is conveniently prepared by boiling a solution of the carboxylic acid in phosphoryl chloride with a slight excess of phosphorus pentachloride. It is converted by naphthalene and aluminium chloride in the presence of nitrobenzene into oc-naphthyl 1-anthraquinonyl ketone m. p. 231-232". Attempts to prepare a benzanthrone derivative from the latter were unsuccessful. H. W. Syntheses by means of Sodamide. IX. The Preparation of pp-Dialkyl-a-hydrindones or 2 2-Dialkylindan-l-ones. ALBIN HALLER and EDOUARD BAUER (Ann. Chim. 1921 [ix] 16 340-354).-The chlorides of p-phenyl-cccc-dialkylpropionic acids CH2Ph*CR2*C02H behave like p-phenylpropionyl chloride (cf . Kipping T. 1894 65 480) in the presence of aluminium chloride giving 2 2-dialkylindan-l-ones which themselves react with sodamide to give the amide corresponding with the original acid chloride .p - Phenyl- cc E- dime th ylpr opionic acid reacts with t hionyl chloride giving the acid chloride m. p. 5"; b. p. 125-126"/15 mm. which when treated in the cold with aluminium chloride gives 2 2- - CH dimethylindan-1-one C,H,<C0_2>CMe m. p. 44-45' ; b. p. 118- 119"/15 mm. giving a semicarbaxone m. p. 209-210". The indanone is decomposed by sodamide giving (3-phenyl-&a-dimethyl- propionamide and since the alkylated indanone may be prepared from indanone itself by the action of methyl iodide on its sodiumORGANIC CHEMISTRY. i. 259 derivative this furnishes a new method for preparing p-phenyl- aa-dialkylpropionamides .Phenyl n-propyl ketone when treated first with sodamide in anhydrous ether and subsequently with benzyl chloride gives a mixture of phenyl cc- benxylpropyl ketone COPh*CHEt*CH,Ph b. p. 183-184"/13 mm. giving an oxime m. p. 78"; and phenyl cia-dibenzyZpropy2 ketone COPh*CEt(CH,Ph) m. p. 67-68' ; b. p. 258"/13 mm. The former when treated with sodamide in benzene and then with ethyl iodide yields phenyl a-benzyl-a-ethyl- propyl ketone COPh*CEt,*CH,Ph m. p. 80-80*5"; b. p. 190- 202"/12-13 mm. which can also be prepared by the benzylation of phenyl a -ethylpropyl ketone. Phenyl a- benz yl- a-ethylpropyl ketone reacts with sodamide to give a-benzyl-a-ethylbutyramide which was not isolated in the free state but was converted into a-benzyl-a-ethyZbut?r~c acid CH,Ph*CEt,*CO,H b.p. 197- 199"/17 mm. giving an acid chloride b. p. 148"/13 mm. The acid chloride in the presence of aluminium chloride in the cold yielded 2 2-diethylindccn-l-oneY C,H4<gE!>CEt m. p. 9" ; b. p. 138"/13 mm. W. G. Position of the Double Linking in Piperitone. I. A. R. PENFOLD (Perf. Essent. Oil Rec. 1922 13 19-20).-Piperitone gave on oxidation with cold permanganate a product from which diosphenol was isolated and identified by its reaction as a keto- phenol and by the preparation of the oxime and the phenyl- urethane. It is probable therefore that the double bond occupies the same position in piperitone as in diosphenol and the former substance would accordingly be Al-menthen-3-one. Constitution of Quinonoid Organic Onium Salts.F. KEHRMANN (Heh. Chim. Acta 1922 5 69-71).-The recent criticisms of Hantzsch (this vol. i 24) has led the author to state specifically that his formulze (cf. A. 1918 i 312; 1921 ii 476) are applicable to carbonium salts. Further consideration how- ever shows that i t is unnecessary to indicate the particular union of the dissociable ion with the nitrogen atom or more generally the basic point of attachment of the molecule by means of the dotted line as previously proposed. Nevertheless it is advisable in writing the formu18 that the connexion between the dissociable ion and the basic group should be rendered sufficiently obvious either by placing them in close proximity or by marking the central atom in some particular manner for example by Preparation of Intermediates [3-Chloro-2-aminoanthra- quinone and 3-Chloro-l-b~omo-2-ainoanthraquinone] and a Dyestuff of the Anthraquinone Series.FREDERICK WILLIAM ATACK and CHARLES WILLIAM SOUTAR (Brit. Pat. 172682).- 3-Chloro-2-aminoanthraquinone is obtained by the regulated chlorin- ation at ordinary temperatures of 2-aminoanthraquinone in a suitable solvent such as glacial acetic acid or nitrobenzene until G. F. M. thickened type. H. w.i. 260 ABSTRACTS OF CHEMICAL PAPERS. the requisite increase in weight has taken place. It crystallises from acetic acid in orange-yellow needles m. p. 221". When 20 parts of the chloro-compound suspended with 10 parts of sodium carbonate in nitrobenzene are brominated a t ordinary temperatures with 21 parts of bromine in 60 parts of nitrobenzene 3-chloro- 1 -bromo-2-aminoanthraquinone is obtained as orange-coloured needles m.p. 235". This compound undergoes condensation on boiling in nitrobenzene solution with sodium and copper acetates with formation of a dyestuff having probably the constitution 3 3'-dichloroanthraquinone-l 2 1' 2'-dihydroazine but possibly the azine as distinguished from the hydroazine may be present. J t dyes cotton bright blue shades from a hyposulphite vat. All the above reactions may be performed consecutively in the same 1 iquid medium for example nitrobenzene without isolation of the intermediate products. Production of Dyestuff Intermediates [Aminoanthraquin- ones]. JOHN THOMAS ARTHUR HUGH DAVIES and S c o T m m DYES LTD. (Brit. Pat. 173006).-Higher yields of the corresponding aminosnthraquinones and products of better quality are obtained by heating 1-chloroanthraquinone or dichloroanthraquinones with aqueous ammonia in an autoclave than by the usual process nith the sulphonic acids.The presence of small amounts of copper salts has a favourable influence on the course o€ the reaction. For example a nearly theoretical yield of 1 -aminoanthraquinone is obtained by heating 100 parts of 1 -chloroanthraquinone with 700 parts of 26% ammonia a t 170" for twelve hours in prescncc of 0.1 part of copper sulphate. Preparation of l-Chloro-Z-amino~thra~~~ne. ALEXAN - DER WALKER PYFE and BRITISH DYESTUFFS CORPORATION LTD. (Brit. Pat. 173166).-1-Chloro-2-aminoanthraquinone is prepared without previously protecting the amino-group by acetylation by the direct chlorination a t 15" of 2-aminoanthraquinone suspended in ten times its weight of nitrobenzene or other suitable solvent such as acetic acid or chlorobenzene until the requisite increase in weight has taken place.The yield amounts to 88% of the theoretical. G. F. M. G. F. M. G. li'. M. Some Products of the Reduction of 2-Hydroxyanthraquin- ARTHUR GEORGE PERKIN and THOMAS WILLIAM WHATTAM one. (T. 1922 121 289-300). Derivatives of P-Methylanthraquinone. I. Syntheses of Chrysophanic Acid [l 8-Dihydroxy-3-methylanthraqyinone] and of 1 5-Dihydroxy-3-methylanthraquinone. R. EDER and C. WIDMER (HeEv. Chim. Acta 1922 5 3-17).-The course of the reaction between a-nitrophthalic anhydride and m-cresol depends considerably on the condensing agent employed.In the presence of boric acid at 170-180" %-(or 6')-nitro-3 6-dimethyl- fluoran colourless lustrous plates m. p. 240-241" a substance,ORGANIC CHEMISTRY. i. 261 C22H1506 colourless needles m. p. 210-21 1" (the constitution of which has not been elucidated) 6-nitro-o-2'-hydroxytoluoyl- benxoic acid OH*C6H,Me*CO*C6H,(N0,).C0,H coarse pale green prisms m. p. 227" and 3-nitro-o-2'-hydroxy-p-toZuoylbenzoic acid prisms and needles m. p. 239-240" are formed. Attempts to convert the nitro-acids smoothly into anthraquinone derivatives by means of concentrated sulphuric acid were unsuccessful. In the presence of aluminium chloride a-nitrophthalic anhydride and m-cresol give 3-nitro-o-2'-hydroxytoluoylbenzoic acid as the sole isolable product. The isomeric nitro-acids are reduced by ferrous hydroxide in boiling ammoniacal solution to 6-amino-o-2'-p- hydroxytoluoylbenzoic acid almost colourless leaflets m.p. 227- 228" and 3-amino-o-2'-hydroxytoluoylbenxoic acid leaflets m. p. 333-234" respectively which are converted in the usual manner into 6-hydroxy -0-2 ' - hydrox y-p -toluo yEbenzoic acid colourless slender needles m. p. 175-176" and 3-hydroxy-o-2'-hydroxy-p-toluoyE- benxoic acid coarse colourless needles m. p. 229-230". The 6-hydroxy-acid is transformed by concentrated sulphuric acid a t 160-170" into 1 5-dihydroxy-3-methylanthraquinone golden- yellow leaflets m. p. 190-191" whereas the 3-hydroxy-acid is converted by a mixture of boric and sulphuric acids into 1 8-di- hydroxy-3-methylanthraquinone yellow leaflets m.p. 193-194" which is identical in all respects witlh natural chrysophanic acid. H. W. Elimination of Hydrogen from Aromatic Nuclei and Union of the Latter by means of Alum- 0 inium Chloride. IV. Ring Closure with Doubly Benzoylated Naphthalenes. Ro- LAND SCROLL and HEINRICH NEUMANN (Ber. 1922 55 [B] 118-126; cf. A. 1913 i 56 Il4 1 '1. 734 and this vol. i 258).-1 4-Dibenz- \IF/\/\ oylnaphthalene is convertible into dibenz- Il2 pyrene-5 8-quinone (annexed formula) but \I/ the corresponding compound from 1 5-di- benzoylnaphthalene could not be prepared. 1 4-Dicyanonaphthalene long pale yellow needles m. p. 206" is prepared by distilling sodium naphthalene- 1 4-disulphonate with potassium cyanide and is hydrolysed by boiling moderately concentrated sulphuric 'acid to naphthalene- 1 4-dicarboxylic acid m.p. 309". The latter is converted by phosphorus pentachloride into naphdhalene-1 4-dicarboxyl chloride slender needles m. p. SO" which is transformed by benzene and aluminium chloride in the presence of carbon disulphide into 1 4-dibenzoylnaphthaZene colourless needles m. p. 106". The ketone yields after treatment with aluminium chloride a t 230" a small amount of dibenzpyrene- 5 8-quinone broad reddish-brown needles m. p. 365" which is purified preferably by sublimation. The corresponding dibenz- pyrene greenish-yellow leaflets or prisms m. p. 281.5-282" is formed by reduction of the quinone with zinc dust in an atmo- sphere of hydrogen. The quinone is oxidised by chromic acid /4\2\P\ I; I I 71i . 262 ABSTRACTS OF CHEMICAL PAPERS.0 to 1 2-phthalylanthraquinone yellow leaflets m. p. 325" which is transformed by hydrazine ')')') hydrate into the azine (annexed formula) orange-red needles decornp. about 440° after '/'"''):darkening at 430" in an atmosphere of hydrogen. N\N!)') 1 6-Dicyanonaphtlhalene m. p. 260" is converted successively into the corresponding " dicarboxylic acid in. p. 315-320" (decornp.) and its chloride ; 1 5-dibenxoyZnuphthaZene colourless crystals m. p. 185-186O is obtained from the latter. H. W. Phenolcamphorein. SRI KRISHNA (T. 1922 121 253-255). Preparation of Terpineol. ROBERT MARCHAND (Brit. Pat. 153605) .-Terpineol is obtained from terpin hydrate in nearly theoretical yield by distilling it with water and an organic sulphonic acid preferably quinoline-8-sulphonic acid.The process may if desired be rendered continuous by adding further quantities of terpin hydrate as the terpineol distils over. The Main Constituent of Japanese Lac. VIII. Position of the Double Bonds in the Side Chain of Urushiol and Demonstration that Urushiol is not Homogeneous. RIKO MAJIMA (Ber. 1922 55 [B] 172-191; cf. A. 1920 i 837 and previous abstracts) .-Hydrourushiol is present to the extent of 10% in urushiol the main constituent of Japanese lac. I n addition the following compounds are probably present C6H3(0H),*[CH,]7*CH:CH*[CH2]5CH which on oxidation gives rise to heptaldehyde and the acid C6H,(OH),*[CH,],*C0,H or its homologues and C,H,(OH),*[CH,]7*CH:CH*[CH,l,.CH:CH which yields on oxidation formic acid and the same aromatic substances as the preceding compound.The results of the analyses of the bromide and ozonide of the dimethyl ether and the volume of hydrogen absorbed during reduction indicate that it contains two double bonds in the molecule. Urushiol is a mixture of compounds which differ from one another in the number and position of the double bonds present in the long normal carbon chain. I n this respect i t exhibits a close similarity to the drying oils. It is difficult or almost impossible by the available methods to separate urushiol quantitatively into its components. Since however all the latter are converted by reduction into the same hydrourushiol it appears desirable to retain the name urushiol for the original mixture which is regarded as having a mean molecular formula C,,H,,O or C,H,( OH),*CI5H,,.The isolation of veratrol-o-carboxylic acid from the products of the oxidation of urushiol dimethyl ether by potassium permanganate affords valuable confirmation of the constitution of urushiol as deduced by other methods. [With YOSHIHIDE T~~~~~.]-Diacetylurushiol is conveniently prepared by acetylating crude urushiol and distilling the product in a high vacuum (b. p. 212-220"/0*3 mm.). It is ozonised in G. F. M.ORGANIC CREMISTRY. i. 263 chloroform solution and the crude ozonide is decomposed with steam. The volatile products contain acetaldehyde heptaldehyde and n-heptoic acid ; the non-volatile portions consist of diacetyl- hydrourushiol 2 3-diacetoxy~henyZ-n-octuZdehy~e a pale yellow liquid b. p. 205-207"/1 mm and azelaic acid.[With GITARO T~K~~~~~.]-Acetylmefhylurushiol is converted into its diomnide and the latter is decomposed with steam. The products isolated in the usual manner are heptaldehyde 2-acetoxy- 3-methoxy~he~zyZ-n-octaldehyde C6H5( OMe) (Oh)*[ CH,J,*CHO b. p. 190-210"/0~8 mm. and the corresponding acid whlch could not be caused to crystallise and is characterised by conversion into 2-hydroxy-3-rnethoxyphenyZoctoic acid colourless needles m. p. 49-50'. The presence of acetylhydrournshiol monomethyl ether is also established. [With WAT~N,~BE .]-Urushiol dimethyl ether is emulsified with water by the aid of a little palmitic acid and sodium hydroxide and oxidised with aqueous potassium permanganate solution initially at the atmospheric temperature and finally a t 6Q0 whereby a mixture of salts and an oil is obtained.The latter contains hydrourushiol dimethyl ether. The mixture of salts is decomposed by sulphuric acid yielding carbon dioxide formic acid oxalic acid adipic acid sebacic acid veratrol-o-carboxylic acid 2 3- dimethoxyphenyl-n-octoic acid and its higher homologues. [With W ~ ~ a ~ ~ ~ ~ . ] - A c e t a l d e h y d e has been isolated from the products of the decomposition of the ozonides of dimethylurushiol and diacetylurushiol but not from that of urushiol monomethyl ether. The difference in behaviour is probably due to the more careful fractional distillation of the latter. A series of experi- ments with various fractions obtained from urushiol dimethyl ether indicates that the parent substance of the acetaldehyde accumulates in the fractions of lower boiling point and demon- strates that urushiol is a mixture of closely allied substances which can only be separated from one another with difficulty by fractional distillation.[With TAIZAYAMA.]-T~~ distillation of large quantities of urushiol monomethyl and dimethyl ethers has disclosed the presence of small amounts of an unsaturated volatile hydrocarbon to which the name urusene is applied; analyses indicate that it is probably a mixture of Cl5HZ8 and C15H,,. [With OKAZAKI.]-~~US~~O~ dimethyl ether absorbs approxim- ately four atomic proportions of bromine in carbon disulphide solution; the product obtained is not homogeneous. H. W. The Chief Constituent of Japanese Lac. IX. Chemical Investigation of the different naturally-occurring Species of Lac which are closely allied to Japanese Lac.RIKO MAJIMA (Bey. 1922 55 [B] 191-214; cf. preceding abstract).- A Burmese lac (from the stems of MeZunorrhcza usitata Wall) to which the name "Thitsi" is applied is shown to contain thitsiol a homologue of isohydrourushiol with an unsaturated side ohain. As judged by the amount of hyclrothitsiol formed byi. 264 ABSTRACTS OF CHEMICAL PAPERS. reduction however this substance cannot comprise more than the third part of the material investigated. I n this respect the Burmese variety differs markedly from the Japanese and Indo- Chinese products since in the latter cases the crude material con- sists of substances which are reducible to hydrourushiol or hydro- laccol to an extent of at least 90%.Indo-Chinese lac probably tapped from Rhus succedanea L. contains mainly laccol which is reduced readily t o hydrolaccol; the latter is isomeric with hydrothitsiol and is a higher homologue of hydrourushiol. Formosa lac from Xemeocarpus vernicifera and a product from Rhus amhigua Lav. or Rhus orientalis Schn are shown t o contain laccol as main constituent whereas two specimens of Chinese lac (probably from Rhus vernicifera or a closely allied species) contained mainly iirushiol. A Siamese lac was found t o be impure and to consist in all probability of a mixture of Indo-Chinese and Burmese lac. [With CHOZO CHIBA.]-The Indo-Chinese lac is purified by solution in alcohol filtration and evaporation of the filtrate treat- ment of the residue with saturated aqueous sodium chloride solu- tion and finally with light petroleum. It is thus obtained as a pale- brown viscous liquid which resembles urushiol closely in appearance and in chemical behaviour.When treated with methyl iodide and sodium ethoxide i t is transformed into laccol dimethyl ether C8H3( OMe),*C,,H, b. p. 206-208'/0.25 mm. dr 0.92964. It is reduced by hydrogen in the presence of platinum black t o hydrolaccol C6H3( OH),*C1,H, m. p. 63-64" which is oxidised by potassium permanganate in the presence of acetone to stearic acid. Hydrolaccol dimethyl ether obtained by the catalytic hydro- genation of laccol dimethyl ether crystallises in long prisms ni. p. 4 3 4 4 " ; with nitric acid it yields 6-nitrohydrolaccol dimethyl ether m. p. 75-76' and 5 6-dinitrohydrolaccol dimethyl ether m.p. 86-87". [With YOSHIHIRO KuDo.]-A solution of laccol dimethyl ether in chloroform is converted by ozone into a mono-oxonide. The latter is decomposed by boiling water into heptaldehyde acetalde- hyde formic acid oxalic acid an impure aldehyde of the composition C6H,( OMe),*[CH,I9*CHO and nonane-w w'-dicarboxylic acid m. p. 109-111". Hydrolaccol is shown t o be contained in the crude laccol thus giving an analogy to the occurrence of hydrourushiol in urushiol (preceding abstract). [With CHOZO c ~ r s ~ . ] - T h e isolation of thitsiol from the black variety of " Thitsi " or Burmese lac is effected by means of alcohol and light petroleum. Thitsiol dimethyl ether C,,H,,O is a pale yellow viscous liquid b. p. 204-205'/0.2 mm.d 0.96390. Hydro- thitsiol C,H,( OH),*CI,H, has m. p. 94-96". Hydrothitsiol dimethyl ether crystallises in leaflets m. p. 66-57"; it is trans- formed by nitric acid in glacial acetic acid solution into 6-nitro- hydrothitsiol dimethyl ether pale yellow needles m. p. 75-76'. Hydrothitsiol is shown to be identical with heptadecylcatechol by the direct synthesis of the latter; for this purpose margaric acid is condensed with catechol in the presence of tin chloride and theORGANIC CHEMISTRY. i. 266 3 4-dihydroxyphnyl hxadecyl ketone m. p. 100-103" thus formed is reduced by Clemmensen's method to heptadecylcatechol. The proximity to fresh lac juice or even to the lac tree is known to produce a painful but not dangerous skin disease in susceptible persons; this is now shown to be caused by urushiol and is pro- duced in order of decreasing intensity by distilled urushiol ordinary urushiol and crude Japanese lac.Similar effects are produced by other urushiol derivatives and in this respect urushiol hydro- urushiol urushiol dimethyl ether and hydrourushiol dimethyl ether are placed in order of diminishing activity. The action of urushiol is attributed t o the conjoint effect of two contiguous hydroxyl groups and the unsaturated alkyl radicle. A series of experiments with catechol derivatives shows that the intensity of the action increases with increasing length of the alkyl chain but is not noticeably affected by its position. Laccol of Indo- Chinese Formosa and Tsutaurushi lac is approximately as toxic as thitsiol of Burmah lac but either substance attacks the skin much less violently than urushiol of Japanese or Chinese lac.H. W. Kawa-kawa Resin. YQSHIHARU MURAYAMA and KENJIRG MAYEDA ( J . Phurm. SOC. Japan) 1921 No. 477 959-968).- S. Murakami (ibid. 1916 393 and 1918 563) isolated three com- pounds demethoxy-yanogonine C14H1@3 m. p. 133-134" p-methyl- sticinic acid Cl4Hl4O3 m p. 175" and kawaic acid CllH,,O or C1,H1,06 m. p. 84-86' from the kawa-kawa resin. The authors investigated kawaic acid and found that it corresponds with the empirical formula Cl,Hl,O and contains one methoxyl group. When heated with alcoholic potash it gives benzaldehyde and a compound C14H1603 light yellow leaves m. p. 164" (decomp.) which contains one methoxyl group. By oxidation with 2% potassium permanganate it yields benzaldehyde and benzoic acid.From the mother-liquor from which kawaic acid was isolated a new acid p-kawaic ucid C14H18O4 colourless slender needles m. p. 101-103" was isolated; it is moderately soluble in boiling water and ether and very soluble in alcohol. It contains a methoxyl group and yields benzoic acid when oxidised with 5% potassium permanganate. K. K. The Tinctorial Properties of some Anthocyanins and certain Related Pigments. 11. ARTHUR E. EVEREST and ARCHIBALD JOHN HALL ( J . SOC. Dyers and Col. 1922 38 9-13; cf. A. 1921 i 485).-An account of experiments carried out with a view to study the influence on the tinctorial properties of the introduction of acidic and basic radicles in the benzene nucleus of synthetic pigments related to anthocyanins.Attempts to prepare amino-derivatives by nitration and reduc- tion failed for treatment of 2-phenylbenzopyroniumferrichloride with nitric acid or nitric acid and sulphuric acid resulted in oxidation but satisfactory results were obtained by an indirect method. Diazotised amines such as aniline 0- and p-toluidine,i. 266 ABSTRACTS OF CHEMICAL PAPERS. sulphanilic acid p-nitroaniline a- and p-naphthylamine couple with phenyl o-hydroxystyryl ketone probably in the p-position with respect to the hydroxyl group and on reduction yield an amino-derivative which is converted into the corresponding oxonium salt by alcoholic hydrochloric acid. The azo-compounds which were prepared from phenyl o-hydroxystyryl ketone possess an affinity for wool but owing to their sparing solubility in water their application is difficult except in the case of the compound derived from sulphanilic acid.The corresponding azo-pyrylium compounds are to be dealt with subsequently. N NIERENSTEIN ( J . Xoc. Chem. Ind. 1922 41 29-301.; cf. Nierenstein Spiers and Geake T. 1921 119 275).- A critical discussion of the attempts to elucidate the constitution of gallotannin is given. It is considered that it is probably a glucoside of the following polydigalloylleucodigallic anhydride I?. M. R. Gallotannin. The formula explains the high molecular weight the optical activity and the low electrical conductivity of gallotannin. It is in accord with the observation that gallotannin is more acidic than pyro- gallol towards diazoacetic ester.It accounts for the mut'arotation of gallotannin and explains the different phases observed in the formation of ellagic acid from gallotannin. It is in accordance with the formation of tetramethylglucose from methylogallotannin. None of the four points last mentioned is explicable on the basis of Pischer's conception of gallotannin as pentadigalloylglucose. H. W. Crystalline Synthetic Tannins. I. P. KAREER and HARRY R. SALOMON (Helv. Chim. Acta 1922 5 108-123).-A solution of laevoglucosan in chloroform is converted by triacetylgalloyl chloride and quinoline into tri-(triacetylgalloyl)l~voglucosan I m. p. (indefinite) 137" after softening at 126" [a]"D' -10.45" in acetone solution which has not been obtained in the crystalline condition. It is hydrolysed by an excess of sodium hydroxide in aqueous acetone solution a t 0" and the solution after neutraha- tion and removal of acetone in a vacuum deposits successively two gelatinous precipitates ( A and B) when preserved. The former dissolves freely in cold alcohol but by allowing the alcoholic solution to evaporate slowly a t the atmospheric temperature it gradually becomes crystalline and sparingly aoluble in alcohol.It is subsequently readily crystallised from this solvent and yields u-trigalloyll~voglucosan long six-sided crystals decomp. 250-320" [ZJZ -18.02" in alcoholic solution The ability of the substanoe (and others of this class) to give the typical tannin reaction8 cannot be investigated since it is insoluble in water but in 10% alcoholioORGANIC CHEMISTRY.i. 267 solutioii it readily causes gelatinisation with arsenic acid. It gives a potassium salt which is sparingly soluble in alcohol. The pre- cipitate B (see above) yields ~-trigaZZoyZZcevogZucosan broad needles and flat rectangular plates decomp. 270-320" [a32 -21*00" in alcoholic solution (the potassium salt is described). The a- and (3-compounds are &ff erentiated clearly by their behaviour towards ferric chloride in alcoholic solution since the former gives a bluish- black gelatinous precipitate whereas under similar conditions the latter gives only a bluish-violet solution without a precipitate. Digulloyllcevoglucosan colourless needles decomp. 220-270" [a]? -27.93" in alcoholic solution is prepared by extraction of the filtrate from the precipitates A and B with ethyl acetate removal of the solvent and treatment of the residue with aqueous acetone; the sparingly soluble potassium salt is described. The mother-liquors from the crystallisation of the digalloyl derivative contain gallic acid and monogaZZoyUcevogZucown decomp.240" after darkening at 220". It is remarkable that the trigalloyllamoglucosans when impure are freely soluble in acetone or alcohol in which they dissolve but sparingly after being recrystallised ; similarly crude digalloyl- lavoglucosan dissolves with great ease in water whereas the pure product is very sparingly soluble. It appears probable therefore that the natural and synthetic tannins which are freely soluble in water and alcohol are all mixtures the components of which in the pure condition are characterised by sparing solubility.The typical tannin reactions such as the gelatinisation of alcoholic arsenic acid solution are not exhibited by monogalloyllaevoglucosan which in this respect behaves similarly to Fischer's monogalloyl- glucose; the presence of at least two galloyl residues in the sugar molecule appears essential to the development of tannin char- adteristics. H. W. Synthesis of a-Benzopyrone Derivatives and the Rupture of the Pyrone Ring in these Compounds. J. TROGER and FR. BOLTE ( J . p r . Chem. 1921 [ii] 103 163-187; cf. Troger and Lux A. 1910 i 161).-Coumarin derivatives of the type ""H4<o-~o CH:L*So2R are obtained by the action of acetic anhydride a t water- bath temperature on a mixture of salicylaldehyde and the requisite arylsulphonylacetic acid.From benzenesulphonyl- acetic acid is obtained 3- benzenesulphonylcoumarin m. p. 217- 217-5" (Zoc. cit.) from p-toluenesulphonylacetic acid 3-p-toluene- sulphonylcoumarin colourless tabular crystals m. p. 222 " and from p-chlorobenzenesulphonylacetic acid 3-p-chlorobenzenesulph- onyicoumarin m. p. 242" (Zoc. cit.). 3-Benzenesulphonylcoumarin is changed by alcoholic sodium ethoxide a t water-bath temperature into phenyl-o-hydroxystyryhdphone OH*C,H,*CH:CH*SO,*C~H~ colourless plates m. p. 166" ; the correspondmg acetoxy-compound has m. p. 123" and the benxoyloxy-derivative m. p. 135". The following compounds were prepared in similar manner. p-ToZyE-o- h~drmy8tyrykuZpPhone OLL:*C,~CH:CEI.*S02*C,H,Me colourlessi. 268 ABSTRACTS OF CHEMICAL PAPERS. plates m.p. 154" ; the acetoxy-derivative m. p. 109" ; and benzoyl- oxy -derivative m . p . 98 O ; p-chlorophen yl- 0- hydroxyst yrylsulphone m. p. 168-169" ; acetoxy-derivative m. p. 126" ; and benxoyloxy- derivative m. p. 96". vJ# Benzenesulphonylacetic acid and resorcylaldehyde (CHO OH OH = 1 2 4) with acetic anhydride gives 7-acetoxy-3-benxenesulphonyl- coumarin colourless needles m. p. 237" but only if there be some sodium benzenesulphonylacetate in the free acid. With sulphuric acid 7-acetoxy-3-benzenesulphonecoumarin yields 7-hydroxy-3-benx- enesulphonylcoumarin. On alkaline hydrolysis the acetyl compound yieldsphenyl-2 4-dihydroxystyrylsulphone C,H,( OH),*CH:CH*SO,Ph yellow crystals m. p. 209-210" of which the following derivatives are described dimethyl ether a pale yellow powder m.p. 108"; diacetoxy-derivative leafy crystals m. p. 112" ; dibenxoyloxy-deriv- ative colourless needles m. p. 77". Similarly 7-acetoxy-3-p- toluenesulphonylcoumarin m . p .234" ; 7- hydroxy -3-p- toluenesulphone- coumarin m. p. 239" ; tolyl-2 4-dihydroxystyrylsulphone m. p. 184" and its dimethyl ester m. p. 108" ; diacetoxy-derivative m. p. 108" ; and dibenxo ylox y -derivative m. p . 132 O and 7-acetoxy-3-p-chloro- benxenesulphonylcoumarin rhombic crystals m. p. 224" ; 7-hydroxy- 3 - p -chloro benxenesulp hon ylcoumarin small transparent needles m . p . 22 6 " ; p - chlorophen yl-2 4 -di h ydrox yst yr ylsulp hone transparent crys- tals m. p. 193" and its dimethyl ether m. p. 77" diacetoxy-deriv- ative m.p. 112"; dibenzoyloxy-derivative m. p. 164" were pre- pared. No derivatives of coumarinic or coumaric acid could be isolated on attempting to rupture the pyrone ring but they are to be assumed as intermediate stages in some of the hydrolyses. W. 0. K. Sulphur as the Bridge Atom in the Middle Ring of a Derivative of Amthracene. A. BISTRZYCKI and B. BRENK~N (Helv. Chim. Acta 1922 5 20-28; cf. A 1915 i 245; 1920 i 629).-The action of concentrated sulphuric acid on 2 4 4- triphenyl-1 3-oxthiophan-5-oneY CPh,< '-VHPh has been ex- amined further and is shown to yield 9-phenyl- coo0 CPh 9 10-dihydromesothioanthracene. 2 4 4-Triphenyl-l 3-oxthiophan-5-one dissolves gradually in sulphuric acid (d 1.84) with brisk evolution of carbon monoxide and formation of a yellow solution which rapidly becomes dark violet-red.The solution is neutralised with aqueous ammonia and boiled until the precipitate becomes flocculent thus yielding 9 -@en y 1 - 9 10 - d i h y dromes ot hioant hracene slender yellow needles m. p. 117-118". The latter is converted by distillation with Z ~ C dust into 9-phenylanthracene m. p. 152" the production of which suggests the possibility that the parent substance is in reality the thioketone C6H4<CS>C6H4. This hypothesis however is negatived by its stability towards phenylhydrazh alcoholic sodium hydroxide solution and aniline as well as by CHPhORUANIC CHEMISTRY. i. 269 its reduction by zinc and hydrochloric acid in the presence of CHPh>S glacial acetic acid to 1 3-&iphenylthiophthahn C6H4<CHph colourless silky needles m. p.106.5-107-5" the constitution of which follows from its conversion by more drastic treatment with the same reagents into o-dibenzylbenzene m. p. 78". Oxidation of phenyldihydromesothioanthracene with hydrogen peroxide in glacial acetic acid solution gives o-dibenzoylbenzene m. p. 145- 146" which is shown by direct comparison to be identical with the product prepared by Simonis and Remmert (A. 1915 i 136). 4 4-Diphenyl-2-p-chlorophenyl-1 3-oxthiophan-&one (A. 1920 i 631) is similarly converted by sulphuric acid into 2-chloro-9- phercyl-9 10-dihydromesothioanthracene microscopic aggregates of yellow prisms m. p. 12A126" after softening a t 120". Constitution of Matrine. 11. HEIZABUR~ KONDG NIICHIRG KISHI and CH~RG ARAKI ( J .Pharm. Soc. Japan 1921 1047- 1069; cf. A. 1921 i 882).-By reducing matrine with sodium and amyl alcohol deoxymatrine (C,,H,,N,) rhombic prisms m. p 162" (aurichloride yellow amorphous precipitate ; plutini- chlorzde orange-yellow plates decomposes a t 284". The dimeth- iodide colourless needles m. p. 178" and its aurichloride yellow needles m. p. 180" ; platinichloride an orange-yellow crystalline precipitates decomposing a t 282" ; picrate yellow slender crystals m. p. 109"; mercurichloride white prisms m. p. 175-180") and desoxymutrine oxide (C,,H,,N,),O a yellow amorphous base were obtained. To reduce the products further deoxymatrine was heated with hydrogen iodide (d 1.7) and red phosphorus a t above 250" for five hours when dimutridine (C15H25N2)2 long colourless needles m.p. 160" (platinichloride orange-yellow needles decomposing a t 275" ; aurichloride yellow needles m. p. 215" ; dimethiodide an amorphous precipitate ; and its aurichloride a yellow crystalline powder decomposing at 193" ; phtinichloride a light reddish-yellow crystalline powder decomposing at 279" ; mercurichloride a white powder m. p. about 150"; picrate a yellow powder m. p. about 92") and a crystalline base m. p. 75-76" isomeric with the former were produced. Dimatridine was formed also by the catalytic reduction of deoxymatrine with hydrogen in the presence of platinum black. Deoxymatrine oxide when subjected to reduction with hydrogen iodide and red phosphorus yielded the base CIoHl9N described in the former paper. The electrolytic reduc- tion of matrine did not give a satisfactory result but a small quantity of an unsaponifiable crystalline base m.p. 72-76" was formed (platinichloride decomposing a t 254" and aurichloride m. p. 206-208"). K. K. Synthesis of p-Arylsulphonylqyinolines containing a Side Chain in the 2-Position. J. TROGER and W. MENZEL (J. ar. H. W. Chem. 192 1 [ii] 103 188-2 15) .-3-p- Toluenesulphonyl-2-meth&- quinoline c6H3<' ~(i*s02*C6H4eCH3~ obtained by heating an N. C*CH3i. 270 ABSTRACTS OF CHEMICAL PAPERS. alcoholic solution of o-aminobenzaldehyde with p-toluenesulphonyl- acetone and a small amount of sodium hydroxide forms lustrous broad needles m. p. 152" and on distillation with zinc dust yields 2-methylquinoline thus proving its constitution. The following derivatives are described hydrochloride Cl7H,,O2NS,HC1 m. p.150" ; nitrate m. p. 138" ; sulphate C1,H1,O2NS,H2SO4 ; oxalate Cl,H1,02NS,C,0,H decomp. 145" ; platinichloride m. p. 216" ; aurichloride C17H,,02NS,HAuC14 m. p. 194" ; mercuri- chloride m. p. 148" ; stannochloride (Cl7H1,O2NS),,H2SnCI m. p. 235" ; methiodide C,7Hl,NS0,,RfeI m. p. 146" * methochloride CH $' S 0,C7H7 m. p. 156"; the benzylidene derivative C,H,< N=C*CH:CH*C,H 5) yellowish-white needles m. p. 204" (hydrochloride m. p. 202") ; the corresponding ethylidene derivative m. p. 165" (hydrochloride m. p. 160") and p -p-toluenesulphon ylquinophthalone (C17H1,02NS),,H2PtC1 CH:F*S02*C,H7 c6H4<,,C*CH:( C0)2:C,H; small brittle prisms m. p. 147". In the same way from benzenesulphonylacetone and o-amino- benzaldehyde is obtained 3-benzenesulphonyl-~-methylquinoline yellowish-white thin needles m.p. 144" and the following deriv- atives hydrochloride C1,Hl30,N8,HCI m. p. 105" ; nitrate m. p. 126" ; sulphate decomp. 150" ; oxalate ; platinichloride ; aurichloride m. p. 186" (decomp.) ; mercurichloride m. p. 95" ; stannochloride m. p 245"; methiodide Cl6Hl3O2NS,CH3I m. p. 135". metho- chlorzde m. p. 149" ; the benzylidene derivative C23H170,NS slender needles m. p. 195" (hydrochloride m. p. 198") ; the ethylidene derivative C,,H,,NSO small nodular crystals m. p. 154" (hydro- chloride) ; and 3-benzenesulphonylginophthalone C,,H,,O,NS yellow needles m. p. 140". Similarly from p-chlorobenzene- sulphonylacetone is obtained 3-p-chlorobenzenesulphonyl-2-methyl- quinoline lustrous colourless long slender needles m.p. 155" and the following derivatives hydrochloride C,,H1,O2NSC1,HC~ m. p. 200" ; nitrate m. p. 132" ; sulphate oxalate platinichloride auri- chloride m. p. 180" ; mercurichloride m. p. 195-198" ; stannachloride m. p. 235"; methiodide C,,H,,02NSC1,CH,I m. p. 150"; metho- chloride m. p. 160" ; the benzylzdene derivative C2,Hl,0,NSC1 a yellowish-green microcrystalline powder m. p. 200" (hydrochloride) ; the ethylidene derivative C ,,O,NSCI slender yellowish -white needles m. p. 185" (hydrochlorzde) ; and 3-p-chlorobenzenesu~phonyl- quinophthulone C,,H,,O,NSCI small rhombic crystals m. p. 150". In no case could the Fenzylidene or ethylidene derivative be oxidised to the corresponding carhosylic acid. From p-naphthalenesulphonylacetone and o-aminobenzaldehyde 3-~-mphthulenesulphonyl-2-methylquinoline C,H4<N.CMe C Q*S O2*CloH is obtained as greyish-white prismatic needles m.p. 160" ; platini- chloride (C20H1,02Ns),,H,PtCI m. p. 228". By using benzene- sulphonylacetophenone derivatives corresponding phenylquholines are obtained and will be described later. Y W. 0. K,ORQANIC CHEMISTRY. i. 271 €ktension of the Kishner-WolfE Method of Reduction. I. ERNST THIELEPAPE (Ber. 1922 55 [B] 136-l38).-The replace- ment of the oxygen atom of ketones and aldehydes by hydrogen has been effected by Wolff (A. 1912 i 988) through the corre- sponding hydrazones. The extension of the reaction to carbonyl groups in general is now being investigated together with the decomposition of substituted hydrazine or hydrazone groups with the elimination of nitrogen in the cases of substances which are not derived from true ketones or aldehvdes.4-Methylquinoline-2-hydrazone C H < m. p. 148" NH-C:N*NH is prepared from 2-chloro-4-methylquinoline more lconveniently from 4-methylquinoline and hydrazine hydrate. The hydrazone is converted into 4-methylquinoline when heated during seventy- two hours at 150-180" with potassium hydroxide or by treat- ment of its solution in boiling water with copper sulphate or in cold water with iron chloride. The Quinoline Series. I. Synthesis of 4Substituted Qaxinolines and of Quinoline-4-carboxylic Acids. ERN ST THIELEPAPE (Ber. 1922 55 [B] 127-135).-Attempts are de- scribed t o synthesise 4-substituted quinolines or 2 4-&substituted quinolines in which the substituent in position 2 is easily removable.Aniline hydrochloride and sodium f ormylacetone yield the anil NPh:CII-CR,*CQ*CH colourless crystals m. p. 91.5" ; after being distilled in a high vacuum (b. p. 128-134"/2-5-5 mm.) the product has m. p. about 61" and then passes into the modification m. p. 91*5" which is also produced when attempts are made to crystallise the variety m. p. 61". The nature of the isomerism has not been elucidated. All attempts to cf'Eect ring closure with formation of a quinolyl derivative were unsuccessful. OMe*C,H,*N:C( C0,Et ) *CH,*COMe yellow crystals m. p. 68" which could not be converted into a substituted quinoline. a-Ethoxalyl-N-methylacetunilide NMePh-CO*CH,*CO*CQ,Et col- ourless crystals m.p. 84*5" is prepared by the condensation of N-methylacetanilide with ethyl oxalate in ethereal solution in the Presence of sodium ethoxide. It is converted bv concentrated H. W. p - Anisidine and ethyl acetoneoxalate give the and sulphuric acid at - 15" into ethyl 1-methyl- Z-quinolo~e-4-carbozylate m. p. 134-135" which is hydrolysed by c H <C(CO,Et):FH NMe-CO' boiling aqueoua sodium hydroxide to the corresponding acid m. p. 251-252". The ester is converted by phosphorus penta- chloride in the presence of phosphoryl chloride into ethyl 2-chloro- quirtoZisze-4-carboxy~te yellow crystals m. p. 64.5" (2-chloro- quinoline-4-carboxylic acid may be obtained similarly from 2-hydr- oxyquinoline-4-carbox ylic acid). 2 - Hydrazinoquinoline-4 - carbox yl ic acid unstable yellow crystals which do not melt below 305" is obtained from the chloro-acid and hydrazine; the corrmpondingi.272 ABSTRACTS OF CHEMICAL PAPERS. hydrazide colourless unstable crystals m p. 228-229" (decomp.) after darkening and softening above 190" is prepared from ethyl 2-chloroquinoline-4-carboxylate. Quinoline-4-carboxylic ester is converted similarly into quinoline-4-carboxyhydraxide colourless crystals m. p. 154.5". 2-lodoquinoline-4-carboxylic acid almost colourless crystals m. p. 195-196" after darkening at 180" and softening a t 190" is prepared from the 2-chloro-acid by the action of potassium iodide and red phosphorus in the presence of hydriodic acid (d 1.50). H. W. Arylated Pyridines. 111. Quinodihydropyridines. W. DILTHEY (Ber.1922 55 [B] 57-59; cf. A. 1920 i 448; 1921 i 735).-The pyridine analogues of the deeply coloured anhydro- bases obtabed by the action of dilute alkali on p-hydroxyaryl- pyrylium salts are readily prepared when the pyridine nitrogen atom is united to an aromatic residue. Thus 1 2 6-triphenyl-4- p-hydroxyphenylpyridinium chloride pale yellow crystals which do not melt below 340" (obtained from 2 6-diphenyl-4-p-hydroxy- phenylpyrylium chloride and aniline) is converted by ammonia in alcoholic solution into 1 2 6-triphenyl-4-quinopyridun O:C,H,:C,NH,Ph yellowish-red needles m. p. 302". . Solutions of the substance or its salts are not fluorescent. H. W. New Method for the Preparation of Alkamines. 11. JIRG TAKEDA and SAJ~~RG KURODA ( J . Pharrn. SOC. Japan 1921 1-76).-The authors have shown (A. 1920 i 228) that styrene dibromide anethole dibromide and the like reacting with carbamide produce substituted dihydro-oxazoles which are changed to the corre- sponding alkamines by the action of alkali hydroxides. By the decomposition of the methyl derivatives of these dihydro-oxazoles N-methvlalkamines are. however. obtained. so that the imino- oxazoliine formula ' R*YeNH>C:NH ' must replace the R H-0 constitution R*(?HeN>C*NH2 given earlier. By the action R'*CH-0 of acetic anhydride and sodium acet'ate these compounds are con- verted mainly into acetyl derivatives R*C'H"Ac>C:NH,CH3*C0,H R'CH -0 but to a small extent into the acetyloxazolidones R*YH*NAc>~~. R'CH-0 ' the hydrolysis of the former by alkali hydroxides produces the corresponding alkamine through the oxazolidone more easily than imino-oxazolidines themselves.I n these reactions an isomeric p-alkamine is produced in small quantity with the a-alkamine ; the isoadrenaline base of Mannich (A. 1910 i 411) corresponds with the former. The method was applied to dihydronaphthalene dibromide which with carbamide yields the corresponding imino- oxazolidine ; this is converted into the corresponding alkamine by.way of the acetyl derivative. The bases are not identical with those described by Bamberger and Lodter (A. 1893 i 591;OMANIC CHEMISTRY. i. 273 1896 i 99) but are stereoisomerides. The following substances were prepared. I. Anetholealkamine group. 4-p- Anisyl-5-methylomxolidone 0Me*c6H4*FH*NH>C0 rhombic plates m.p. 110-112" is' prepared by heating anethole-2-imino-oxazolidine with water at 140-150" in a sealed tube with a small auantitv of anethole- Me-CH-0 alkamine ; acetyl derivative hexagonal plat& m. " p. 11 1-112". OMe*C,H4*FH*Ny-,eSH 4 - p - Anis y 1 - 5-met h yl oxazoline mermp tan Me*CH-0 9 white plates m. p. 86-88" from anetholealkamine carbon disulphide and potassium hydroxide ; acetyl derivative colourless plates m . p . 79-8 1 ". a-p- H ydrox yphen yl- p- h ydroxyprop ylamine OH*C,H,*CH(NH,)*C~e*OH colourless hexagonal plates m. p. 173" from anetholealkamine and hydrogen iodide (hydrochloride m. p. 187" ; dibenxoate m. p. 173") which yields a-p-hydroxyphenyl- methyl-p-hydroxypropylamine with methyl iodide ; hydrochloride m. p. 184-186". p-Anetholealhmine thin plates m.p. 80" is prepared by heating anethole oxide with alcoholic ammonia at 130" (copper salt m. p. 161"). By acetylation of the bromo- anethole-2-imino-oxazolidine with acetic anhydride and sodium acetate its N-acetyl derivative plates m. p. 190-192" and the acetyloxazolidone m. p. 134" are prepared ; the former gives bromoanetholealkamzne (a- p-methoxybrornophenyl- p-hydroxypropyl- amine) thin plates m. p. 118" (hydrochloride m. p. 247"; copper derivative m. p. 168"). 11. isosafrolialkamhe group. 4- Methylenedioxypbnyl- 5-methyl - oxuzolidone CH,'02'C6H30~H'NH>C0 plates m. p. 170-171" Me* CH-- 0 is prepared by heating isosafrole-2-imino-oxazolidine with water at 140" in a sealed tube isosafrolealkamine and ammonia being simultaneously formed. By acetylation of isosafrole-2-imino- oxazolidine with acetic anhydride and sodium acetate the N-acetyl- acetate m.p. 208" and the acetyloxaxolidone colourless prisms m. p. 116-119" are formed the former when heated a t 205" is changed first into the latter and then into p-isosafrolealkumine (copper salt m. p. 171-173"). Benzoylation of isosafrole-2-imino- oxazolidine by Schotten-Baumann's method yields only the N-benzoyloxazolidone m. p. 180-182". When boiled with 30% sodium hydroxide the acetyl-acetate yields isosafrolealkamine CH,O,:C,H,*CH(NH,)*CHMe*OH slender needles m. p. 79" (hydro- chloride m. p. 210-215" ; platinichloride orange-yellow crystals m. p. 200-202" ; copper derivative ( CloH1,03N),Cu0 + 2H,O deep violet crystals m. p. 185-186") whilst with very dilute alkali the free N-acetyl derivative m.p. 153" is formed. By acetylation with acetic anhydride isosafrolealkamine gives the N-acetyl derivative prisms m. p. 156" which change to isosafrole- alkamine acetate (hydrochloride needles m. p. 198-2OO" when treated in benzene suspension with hydrogen chloride ; platini- chloride orange-yellow crystals in. p. 200"). In the same way,i. 274 ABSTRACTS OF CHEMICAL PAPERS. N-Denxoylisosafrolea~~amine needles m. p. 139" suffers rearrange- ment to isosafrolealkamine benzoate (hydrochloride m. p. 203" ; platinichloride m. p. 201"). By heating with carbon disulphide and potassium hydroxide isosafrolealkamine moduces the mer- captan CH202'C~H3'~H''~C*SH granules m. p. 160" ; the MeCH.0 acetyl-mercaptan forms white hexagonal plates m.p. 93". Methyl- isosafrole-2-imino-oxaxolidine CH 2 0 2 :C 6 H 3 *CH*NMe>C:NH I a fight Me*CH -0 yellow syrup is prepared from isosafrole-2-imino-oxazolidine and methyl iodide (hydrochloride m. p. 205") the hydrolysis of which by alcoholic sodium hydroxide produces N-methylisosafrolealkamine (u-methylenedioxyphenylmethyl- p-h ydroxyprop ylumine) CH,O,:C,H,*CH( NHMe)*CHMe-OH m. p. 89-90' (hydrochloride m. p. 142-144" ; phztinichloride m. p. 196"; copper derivative deep violet crystals m. p. 151"). Dimethylisosafrole-2-imino-oxaxolidine is prepared from the mono- methyl compound and methyl iodide (hydriodide thin plates m. p. 181") the hydrolysis of which by alcoholic sodium hydroxide produces N-methylisosafrolealkamine and methylamine.N-Acetyl- methylisosafroleulkamine white crystals m. p. I1 1-113" and the N-benxoyl compound prisms m. p. 145-148" are prepared from the methylalkamine. They are converted i3to 0-acetyl-N-methyl- isosafroleulkamine hydrochloride m. p. 182" (platinichloride m. p. 163-169") and the 0-benxoyl compound prisms m. p. 215" (platinichloride m. p. 170") by passing hydrogen chloride into their ethereal solutions. N- Dimethylisosafroleulkumine m. p. 7 1-73" is prepared from the monomethyl compound and methyl iodide (hydrochloride m. p. 173" ; platinichloride m. p. 190-200") ; benzoyl chloride produces 0-benxoyl-N-dimethylisosafroleulhmine hydrochloride m. p. 224-226" (platinichloride m. p. 140"). Brmo- isosafrole-2-imino-oxaxoEidine thin plates m. p. 197" is prepared by heating bromoisosafrole dibromide and carbamide at 150" (hydrochloride m.p. 197") ; on acetylation it yields N-acetylbrmo- isosafrole-2-imino-oxaxolidine acetate long needles m. p. 173- 176" which gives bromoisosafrolealkarnine prisms m. p. 126-128" by hydrolysis (hydrochloride m. p. 231"; copper derivative m. p. 158"). 111. Methylisoeugenolalkaminc group. Methylisoeugenol di- bromide and carbamide react to form methylisoeugenol-2-imino- oxaxolidine m. p. 153-155" (hydrochloride m. p. 166-168" ; platinichloride m. p. 195') which is converted into the N-acetyl- acetate m. p. 155-157" by heating with acetic anhydride; hydro- lysis of the acetyl compound with 30% sodium hydroxide produces a-3 ; 4- d imethox yphen yl- p - h ydrox yprop y lamine (meth ylisoeugenolulk- amine) (0Me)2C6H3*?H*NH2 thin plates m.p. 95-96' [hydro- MeCHaOH chloride m. p. 222"; phtinichloride m. p. 201"; copper compound (ba~e)~CuO +2H20 m. p. 166-167"J. 0-N-Dimet~ylisoezcgenoE-2- imino-oxaxolidine a pale yellow oil is prepared from the imino-ORGANIC CHEMISTRY. i. 275 oxazolidine and methyl iodide (hydrochloride m. p. 144") ; hydrolysis produces a-3 4-dimethoxyphenylmethyl-~-hydroxypropyl- amine (dimethylisoeugenolalkamine) hexagonal plates m. p. 90- 91" (hydrochloride m. p. 190-193" ; platinichloride m. p. 172- 174"; copper derivative m. p. 138") which gives the hydro- chloride of the O-benxoyl derivative m. p. 198"; the latter suffers rearrangement to the N-benxoyl derivative m.. p. 140". a-3 ; 4- Dirnethoxyphenyl- p-hydrox yprop yldimeth ylamine (trzmethyliso- eugenolalkamine) .is a light yellow oil ; the hydrochloride forms white nodular crystals m. p. 149-150". IV. Dihydronaphthalenealkamine group. Dihydronaphthalene dibromide and carbamide react at 140" to form dihydronaphthulene- 2-imino-oxazolidine thin plates m. p. 158-159" (hydrochloride prismatic plates m. p. 198"; platinichloride m. p. 224") which is converted to the N-acetyl-acetate plates m. p. 123-124" and then into p- h ydroxytetrah ydro- p-naphthylumine (dihydromphthulene- alkamine) thin plates m. p. 107-108" (hydrochloride m. p. 215"; platinichloride m. p. 220"; picrate yellow needles m. p. 191"; copper derivative (base),CuO + 2H,O violet-red needles m. p. 176"). Methyldih ydronaphthalene-2-imino-oxaxolidine prepared from the above compound and methyl iodide forms thin plates m.p. 66-68"; hydriodide m. p. 203" [hydrochloride (+lH,O) m. p. 254" anhydrous]. As by-product an oily isomeride is obtained; hydrochloride m. p. 235". P - H ydroxytetrahydro- p-naphth ylmethyl- amine needles m. p. 85" is prepared from the above imino- oxazolidine derivative by hydrolysis with 20 yo sodium hydroxide [hydrochloride m. p. 214" ; copper derivative (base),CuO light reddish-brown crystals m. p. 218'1 which by methyl iodide is converted into P-hydroxytetrahydro- p-naphthyldimethylumine an oil ; hydrochloride m. p. 224"; picrate yellow plates m. p. 160". K. K. Nitro-derivatives of Alkylated Benzidines. G. VAN ROM- BURGH (Rec. trav. chim. 1922 41 38-43; cf. Mertens A. 1877 6 0 5 ; A. 1886 1022; and van Romburgh A.1887 245).-0ne of the substances obtained by the action of dilute nitric acid on dimethylaniline at first known as isodinitrodimethylaniline was shown to be a tetranitrotetramethylbenzidine but the positions of the nitro-groups were not determined. The author considered it probable that the 3 3' 5 5'-positions were occupied by these groups and prepared the 3 3' 5 5'-tetranitrotetramethyl- benzidine. Tetranitro-4 4'-dirnethoxydiphenyl (cf. Hirsch A. 1889 i 511) was treated with dimethylamine nitrated and boiled with phenol the resulting product being found to be identical with the tetranitrotetramethylbenzidine first obtained. The reactions in- volved serve as a means for the preparation of alkylated tetranitro- benzidines. The following were prepared 3 3' 5 5'-tetranitro- diethylbenxidine m.p. 248" which on treatment with concentrated nitric acid yields 3 3' 5 5'-tetranitrodiphenyl-4 .Q'-diethyldirzitro- amine long needles m. p. 230" (decomp.); 3 3' 5 5'-tetranitro- dipropylbenzidine dark red needles m. p. 200" which with nitrici. 276 ABSTPACTS OF CHEMICAL PAPERS. acid (d 1.49) yields 3 3' 5 5'-tetranitrodiphenyl-4 4'-dipropyl- dinitroamine small yellow plates exploding a t 213"; 3 3' 5 5'- tetranitrodiisopropylbenzidine deep red needles decomp. 250" yielding with nitric acid 3 3' 5 5'-tetranitrodiphenyl-4 4'-di- isopropyldinitroamine colourless decomp. 209" ; 3 3' 5 5'-tetra- nitrodiisobutylbenxidine deep red crystals m. p. 194" yielding with concentrated nitric acid 3 3' 5 5'-tetranitrodiphenyl-4 4'- diisobutyldinitroamine colourless needles decomp.205" ; 3 3' 5 5'- tetranitrodiallylbenzidine orange-red needles m. p. 205" yielding on nitration 3 3' 5 5'-tetranitrodiphenyl-4 4'-diallyldinitroamine decomp. 100". All the above nitroamines are converted into the corresponding dialkylbenzidines on treatment with boiling phenol. H. J. E. The Iron Salts of Dipyrrylphenylmethane Dyes. Tri- phenylpyrrylmethane. I. HANS FISCHER and VIKTORIA LUCK- MANN (2. physiol. Chem. 1921 115 77-93).-p-Dimethylamino- p henyl- bis (3 -acet yl- 2 4-dimeth ylp yrryl )methane NMe,*C 6H4*CH (C,NHMe,Ac) is prepared by heating on the water-bath an alcoholic solution of 3-acetyl-2 4-dimethylpyrrole with p-dimethylaminobenzaldehyde in the presence of potassium hydrogen sulphate and precipitated with sodium carbonate.It crystallises from ethyl acetate in tufts of slender colourless needles m. p. 165-166". The ferri- chloride forms brown prisms m. p. 255" (decomp.). Dimethyluminophenyl- bis(- 3-carbethoxy - 2 4 - dimethylpyrry1)meth- ane NMe,*C,H,~CH(C,NHMe,~CO,Et) prepared from ethyl 2 4- dime thylpyrrole- 3- car boxylate and p - dimethylaminobenzalde- hyde in presence of potassium hydrogen sulphate forms colourless irregular leaflets m. p. 204-205". The ferrichloride crystallises in fine needles. p-Dimethylaminophenyl-bis( -3-carbethoxy-2 5-di- methyZpyrry1)methane prepared from ethyl 2 5-dimethylpyrrole- 3-carboxylate and p-dimethylaminobenzaldehyde in presence of concentrated sulphuric acid has m. p. 240" and its ferrichloride has m.p. 228". Triphenyl-3-acetyl-2 4-dimethylpyrrylmethne prepared from triphenylcarbinol and 3-acetyldimethylpyrrole by heating in glacial acetic acid forms slender colourless needles m . p . 156". Triphenyl- 3-carbethoxy-2 4-dimeth ylp yrrylmethane obtained from triphenylcarbinol and ethyl 2 4-dimethylpyrrole- 3-carboxylate crystallises in prisms m. p. 170". Triphenyl-p-di- methylaminophenylmethane prepared from triphenylcarbinol and dimethylaniline crystallises in slender needles m. p. 208". s. s. z. Preparation of a New Acridine Compound. LEOPOLU CASSELLA & Co. G.m.b.H. (Swiss Pat. 89241; from Chem. Zentr. ivy 1010).-Formaldehyde is allowed to react with a 3 6-diamino- 10-methylacridinium salt. For example 3 6-diamino- 10-methyl- acridinium chloride is dissolved in'water and mixed with N-hydro- chloric acid.On addition of 30% formaldehyde a bright orange- coloured suspension is obtained. After agitation the condens-ORQANIC CHEMISTRY. i. 277 ation product is separated washed with N-hydrochloric acid and water and dried ; it is a brick-red powder with antiseptic properties. G. W. R. Certain Triazoles. F. ARNDT [with E. MILDE F. TSCHEN- SCHER (FRL.) F. BRELICH and G. ECKERT] (Ber. 1922 55 [B] 12-18; cf. A 1921 i 813).-An arrangement has been reached between the author and Fromm (cf. this vol. i 62) concerning publication in this field. The present communication is due to the fact that in some respects certain triazoles prepared by the authors do not harmonise in their properties with those described by Fromm in his forthcoming paper in the Annalen.An alcoholic suspension of phenyldithiobiuret is converted by hydrazine hydrate and subsequent acidification with hydrochloric C(:NPh)*YH colourless lustrous NH' acid into anilothiouraxole NH< cs- leaflets m. p. 275" or somewhat higher when rapidly heated (Fromm m. p. 26S0) which is oxidised by potassium ferricyanide in alkaline solution t o the disulphide (NHPh*C<:*g>C)2S2 yellow crystals m. p. 233" (Fromm m. p. 225"). Anilothiouraxole methyl ether NH< C(:NPh)*yH a matt crystalline powder has C( SMe) -N m. p. 187-188"; the corresponding nitrate m. p. 110" (decomp.) is described. Iminoazt ilouraxole N H < ~ ( ~ ~ ~ ) * T colourless CCNHI-NH' leaflets m. p. 157" (the monohydrute is also 'described) is obtained by the addition of ammonia to the acidic mother-liquors from the preparation of anilothiourazole.The constitution of the compound is deduced from its analysis its mode of formation amphoteric nature convertibility into a sparingly soluble nitrate decomp. 118" and oxidisability to the uzo-compound C( :NPh)*z NH<C(:NH)-N' a pale brownish-red powder violent decomp. 138". The same constitution is assigned by Fromm to a substance m. p. 70° pre- pared by the action of hydrazine on phenylthiuret; this product however appears to be a salt containing anilothiourazole as acidic component and two basic components one of which m. p. 149" is possibly identical with aminoguanylphenylthiocarbamide whereas the other is iminoanilourazole. H.W. The Significance of the Second Dissociation Constant of Uric Acid in the Equilibrium of Monourate Solutions. ARISTIDES KANITZ (2. physiol. Chem. 1921 116 96-106).-A theoretical paper. Salts of uric acid formed by the action of monoacidic bases on the acid dissociate in accordance with its two stages of dissociation partly into the normal diurate salt and free uric acid as follows VOL. CXXII. i. Zi. 275 ABSTRACTS OF CHEMICAL PAPERS. Monourate - El Diurate x free uric acid-k (k = constant for first stage of dissociation of the acid k2 = constant for second stage of dissociation of the acid). Calculated from results previously obtained by various workers EJE2 = 775 or 2350. From which there is derived E = 2.6 x loA9 or 8.6 x 10-l0. s. s. z. The Azo-dyes of Bilirubin.I. HANS FISCHER and HER- MANN BARRENSCHEEN (2. physiol. Chem. 1921 115 94-104).- A monoazo- and a diazo-product were obtained by treating bili- rubin with benzenediazonium chloride. The two compounds were separated by crystallising the mixture from alcohol-the monoazo- derivative being soluble in this solvent. The monoaxo-compounds C,,H3,0,N,*NiNPh crystallised in small brownish-red prisms the diazo-compound C,,H,,O,N,( NZNPh) in monoclinic crystals. Colouring Matters of the Isatin-yellow Series. Jir. MARTINET (Rev. Gin. Mat. Col. 1921 26 177-179).-When a solution of a diazonium compound is added to a solution of isatin- 6-sulphonic acid in presence of sodium acetate a hydrazone is formed and not an azo-compound as is shown by the stability of these compounds towards reducing agents and by the fact that identical compounds are formed by the action of the corresponding hydrazine on isatin-6-sulphonic acid.The following hydrazones of sodium isatin-6-sulphonate in this series are described :- Phenylhydraxone slender lemon-yellow needles soluble in sulphuric acid with an orange-yellow colour isomeric with isatin-yellow (the p-sulphophenylhydrazone of isatin). p-Chlorophenylhydraxone forms yellow needles soluble in sulphuric acid with an orange- yellow colour. 0- Tolylhydraxone crystallises in orange-yellow needles soluble in sulphuric acid with a dark orange-yellow colour. m-Tolylhydraxone an orange-yellow crystalline powder soluble in sulphuric acid with an orange-yellow colour. p-Tolylhydraxone rosettes of golden-yellow needles coloured bright red by sulphuric acid and soluble with an orange-yellow colour .m-Xylylhydraxone forms an orange-red powder soluble in sulphuric acid with a dark brownish-red colour. t,b-Cumylhydraxone a reddish-brown powder soluble in sulphuric acid with a dark brownish-red colour. p-Ethoxyphenylhydraxone dark yellow felted needles soluble in sulphuric acid with a red colour. o-MethoxyphenyZh?/draxone dark yellow needles soluble in sulphuric acid with a red colour. p- Chloro- o-methoxyphenylhydraxone a dark yellow crystalline powder soluble in sulphuric acid with a scarlet-red colour. 0- Carboxyphenylhydraxone a lemon- yellow crystalline powder soluble in sulphuric acid with a golden-yellow colour ; the aqueous solution forms a brick-red precipitate with silver nitrate.Di- phenyl-4 4'-dihydraxone a brown crystalline powder with a brownish-red reflex soluble in perchloric acid with a violet-red colour. 3 3'-Dimethoxydiphenyl-4 4'-dihydraxone a brown powder 8. s. z.ORGANIC CHEMISTRY. i. 279 soluble in perchloric acid with a violet colour. All these hydrazones are soluble in water and acetic a'cid crystallise from alcohol and their aqueous solutions are darkened slightly by alkalis. They dye wool and silk in bright yellow orange or red shades and all possess a direct affinity for cotton from an alkaline bath the affinity increasing with the molecular weight'. The fastness is not great but these colouring matters possess an interest on account of their tinctorial power brightness and level-dyeing properties.In a parallel series of experiments some derivatives of isatin- 5-sulphonic acid were prepared by the action of various hydrazines. Potassium isatin-5-sulphonate phenylhydraxone lemon- yellow needles very soluble in water dyes wool and silk greenish-yellow shades of low fastness. Sodium isatin-5-sulphonate p-tolylhydraxone forms long golden-yellow needles. Isatin-5-sulphonic acid phenylmethyl hydrazone forms yellow felted needles. The Free Amino-groups of the Proteins. R. ENGELAND (2. physiol. Chem. 1921 116 226-227); S. EDLBACHER (ibid. 228 ; cf. A. 1921 i 199) .-Polemical. The Optical Rotatory Power of Crystalline Ovalbumin and Serum-albumin. ELRID GOREON YOUNG (Proc. Roy. SOC. 1922 [B] 93 15-35).-The specific rotation of crystalline ovalbumin is constant if recrystallisation is made at the isoelectric point but varies with changes in the hydrogen-ion concentration of the solution.The constant values obtained by the author are :-[a]:; -30-81" and [a]? -37.53". The variations produced by the addition of small quantities of acid or alkali are explained on the basis of a tautomeric change of the lactam-lactim type. Crystalline horse serum-albumin was prepared by two methods. I n each case the preparation had [a]': -62.8" and [a] -78.4". F. M. R. s. s. z. E. S. The Action of Nitrous Acid on Casein. MAX S. DUNN and HOWARD B. LEWIS (J. Biol. Chem. 1921 49 327-341).-The distribution of nitrogen in casein and deaminised casein was deter- mined. In agreement with the current view as to the nature of the free amino-groups in proteins lysine was found t o be absent from the hydrolysate of deaminised casein whilst the amount of monoamino-nitrogen was correspondingly increased. Some des- truction of tyrosine occurs during the deamination of casein. E.S. Yeast-nucleic Acid. 11. H. STEUDEL and E. PEISER (2. physiol. Chem. 1921 114 201-203; cf. A. 1921 i 66).-By utilising the method of precipitating sodium guanylate with a concentrated solution of sodium acetate it is found that a certain sample of yeast-nucleic acid contained 12-14% of this salt. s. s. z. The Influence of P-Naphthslenesulphonyl Chloride on the Proteins. S. EDLBACHER arid BERTIIOLD PUCHS (2. physiol. Chem. 1921 114 133-136).-Clupeine salmine sturine thymus- pi. 280 ABSTRACTS OF CHEMICAL PAPERS. histone gelatin casein and edestin were treated with P-naphthalene- sulphonyl chloride and the amount which combined with the respective proteins was ascertained.The basic protamines and the histone showed a relatively higher figure than the other proteins. The difference was however rather insignificant. The lysine content of the protein seems to have no influence on this reaction. s. s. z. The Titration Curve of Gelatin. DOROTHY JORDAN LLOYD and CHARLES MAYES (Proc. Roy. Xoc. 1922 [B] 93 69-85).- Determinations were made of the hydrogen-ion concentrations of solutions of gelatin in known concentrations of acid and alkali hydroxide and the amount of combined acid or alkali hydroxide was calculated in each case. It is concluded from the results that for concentrations of acid not exceeding 0.02N combination occurs a t the free amino-groups of the gelatin molecule ; for greater concentrations of acid however there is probably also combination a t the nitrogen of the peptide linkings.No conclusion was drawn as to the mode of attachment of alkalis. E. S. Equilibrium Gelatin-Hydrochloric Acid. 11. ROBERT WINTGEN and HEINZ VOCEL (KoZZoid Z. 1922 30 45-53; cf. A. 1921 ii 247).-The hydrogen-ion concentration of mixtures of gelatin and hydrochloric acid has been determined electrometrically a t 25" and the values have been compared with those calculated by means of the equilibrium formula previously published (Zoc. cit.). The acid concentration varied between 0.05N and 0.004N and the gelatin concentration between 0" and 7%. The two sets of results agree astonishingly well and indicate that dilute hydro- chloric acid and concentrated acid combine with the same number of basic groups in gelatin and if it is assumed that gelatin is a uniform substance only one amino-group reacts with hydrochloric acid.It behaves therefore as a monacid base toward hydro- chloric acid and has a molecular weight of 885 for the anhydrous material or 1070 for the air-dried material and an ionisation constant 5.74 x 10-ll. Turbidity and precipitation occur in the neigh- bourhood of the isoelectric point and a t this point solutions of 0.2% and 0.5% gelatin with N/3000- and N/1300-hydrochloric acid are seen in the ultramicroscope to contain numerous rapidly moving particles. The electrical conductivity of solutions of gelatin of concentrations up to 7 yo in 0.05N- and OaO25N-hydrochloric acid has been measured a t 25" and from the results it is shown that Am =88.5 for gelatin chloride a t 25" and that the ionic conductivity of the gelatin ion is 13.Comparative measurements with p-glutin show that the power of this substance to combine with hydro- chloric acid does not differ essentially from that of gelatin and that p-glutin has a molecular weight of about one-half that of gelatin. J. F. S. Vitamins from the Point of View of Structural Chemistry. R. R. WILLIAMS ( J . Ind. Eng. Chem. 1921,13 1107).-3-Hydroxy-ORGANXU CHEMZSTRY. i. 281 pyridine which exists in two crystalline modifications is shown by titration with bromine to be non-enolic in neutral solution like the 2- and 4-compounds.It forms a l-methyl ether which is a viscous oil miscible with water in all proportions and not volatile in steam. Its physiological action is not established. Three modifications of 4-phenylisocytosine were obtained two of which had identical melting points and crystallographic pro- perties but differed greatly in their solubility in alcohol. Two freshly prepared modifications which seemed to be Johnson and Hill's p- and 8-formsy were fed to pigeons and all the birds receiving the @-form lost weight less rapidly than those receiving the &form. After being kept for two months however the same two prepar- ations showed no physiological difference. The author considers that vitamin-B will eventually be found to be a cyclic nitrogen compound in some ways analogous to the above.H. C. R. Vitamins from the Point of View of Physical Chemistry. VICTOR LAMER ( J . Ind. Eng. Chem. 1922 13 1108-lllO).- The amount of vitamin-A in skim milk is roughly equal to that contained in the fat layer. The water-soluble vitamin-B is also somewhat soluble in fatty oils. Vitamin-B is absorbed by Fuller's earth and by dialysed iron and blood charcoal removes a measur- able amount of vitamin-C from orange juice; the extent of adsorp- tion is very sensitive to changes in the hydrogen-ion concentration. Vitamin-C is partly retained on filtration through Chamberland candles. The destruction of the antiscorbutic vitamin by heat is a chemical reaction the velocity of which is accelerated by increase of temperature according to the equation X=K$'< where X is the per cent.of destruction t the time in hours and values of K are 0.26 0.39 and 0.49 for 60° 80° and loo" respectively. These data exclude the possibility that vitamin-C is of a protein or enzyme-like nature. Heating a t a reduced hydrogen-ion con- centration results in an increased velocity of destruction. Bubbling oxygen through the solution a t 100" results in the complete destruction of the vitamin in one hour both in acid and weakly a,lkaline solution. Bubbling hydrogen through causes somewhat greater destruction than when no gas was used. H. C. R. Chloroform and Pepsic Digestion. A. ASTRUC and E. RENAUD ( J . Pharm. Chim. 1922 [vii] 25 81-87).-Chloroform has only a very slow destructive influence on the diastatic activity of pepsin whilst chloroform vapours have no appreciable action. Chloroform water is a suitable solvent for pharmaceutical pre- parations of pepsin and exerts a distinct preservative action although after two months a small decrease in the fermentative activity can be detected.Chloroform water is however a bad digestive medium and considerably retards digestion in vitro but it would not be correct to deduce therefrom that in the stomach it also exerts an opposing influence on digestion and the activity of the pepsin. G. E'. M. I" 2i. 282 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Reaction on the Action of Trypsin. I. W. E. RINGER (2. physiol. Chem. 1921 116 107-128).-The optimum H-ion concentration for the action of trypsin a t 37" was under certain conditions found to be P 11.3.It was also found that strongly acid solutions inactivated the enzyme. At a H-ion concentration of P 3.15 trypsin could be kept a t 37". As the H-ion concentration diminished the inactivation became more marked. At P,=12 the enzyme was almost instantaneously destroyed. The maximum imbibition of fibrin took place at a reaction which had an instantaneous inactivating action on trypsin. The Inactivation of Trypsin. I. II. The Equilibrium between Trypsin and the Inhibiting Substance formed by its Action on Proteins. 111. Spontaneous Inactivation. JOHN H. NORTHROP ( J . Gen. Physiol. 1921 4 227-244 245-260 261-274) .-The decomposition of gelatin by trypsin was investi- gated quantitatively by conductivity determinations and also by formal titration.Inactivation of trypsin is not effected by amino- acids or by the products of the hydrolysis of proteins by acid or alkali. The inhibiting substance occurs in the products of trypsin digestion and is dialysable. The equilibrium between the inhibitor and trypsin is found to agree with the scheme trypsin+inhibitor independent of the substrate concentration. On the assumption that hydrolysis is proportional to the concentration of free trypsin it is shown that the laws of mass action are applicable. There is no evidence for any appreciable combination of trypsin with gelatin. Spontaneous inactivation of trypsin is also shown to occur inde- pendently of the influence of hydrolytic products. The rate of this inactivation approximates closely t o that demanded by a unimolecular reaction.Trypsin digestion products in excess exert a protective effect by inhibiting spontaneous inactivation. s. s. z. A -- trypsin-inhibitor ; it is reached instantaneously and is G. W. R. Maltase. 111. The Non-identity of Maltase and oc-Glucos- idase. RICHARD WILLSTATTER and WERNER STEIBELT (2. physiol. Chem. 1921 115 199-210; cf. A. 1920 i 795; 1921 ii 72).- A number of preparations and yeasts have given quotients for the time value for glucosidate/time value for maltase of varying magni- tudes. Effect of certain Antiseptics on the Activity of Amylases. H. C. SHERMAN and MARGUERITE WAYMAN ( J . Amer. Chem. SOC. 1921 43 2454-2461) .-TOW concentrations of chloroform did not affect the activity of commercial pancreatin or malt extract but did affect the purified preparations of these amylases.Toluene had very little influence on $he activities of the amylases either in their commercial or purified condition. All the preparations studied either commercial or purified were injured by formaldehyde even in low concentrations and they were all very sensitive to copper sulphate. The percentage loss of enzyme action due to The two enzymes are therefore not identical. s. s. z.ORGANIC CHEMISTRY. i. 283 these two antiseptics did not depend on the ratio of antiseptic to enzyme or to substrate but on the concentration of the antiseptic in the system. The sensitiveness of the amylases to formaldehyde or cotmer suhhate as comDared with their sensitiveness to toluene is poiGbly cLnnected withtthe protein nature of the enzymes. .W. G . The Influence of certain Amino-acids on the Enzymic Hydrolyses of Starch. H. c. SImRirAN and FLOREKCE WALKER ( J . Amer. Chem. Soc. 1921 43 2461-2469).-Previous work (cf. this vol. i 66) has been extended to a study of glycine alanine tyrosine and phenylalanine using however Lintner’s soluble starch as the substrate. Addition of any of these amino-acids caused an increase in the rate of hydrolysis of starch by purified pancreatic amylase commercial pancreatin saliva or purified malt amylase but less marked results were obtained with malt extract taka-diastase or an aspergillus amylase. The addition of two of these amino-acids produced no greater effect than would result from the same concentration of one of them. The favourable effect of the added amino-acid was not due to any alteration in hydrogen-ion concentration of the medium or to the combination of the amino-acid with the product of the enzyme action. It is probably due in part at least to a protection of the enzyme from deterioration in the aqueous dispersion in which it acts.The addition of these amino-acids is a very effective means of pro- tecting the enzyme from the deleterious action of copper sulphate (cf. preceding abstract) and may even serve to restore to full activity an enzyme which has been partly inactivated by copper sulphate. W. G. The Influence of Arginine Histidine Tryptophan and Cystine on the Hydrolysis of Starch by Purified Pancreatic Amylase. H. C. SHERMAN and MARY L. CALDWELL (J. Amer. Chem. SOC. 1921 43 2469-2476).-The amyloclastic power of purified pancreatic amylase on soluble starch was measured in the presence of these amino-acids using glycine and phenylalanine as control amino-acids (cf. preceding abstract).Arginine and cystine favourably influence the digestion of starch but histidine and tryptophan do not. It is again shown (Zoc. cit.) that the results obtained were not due to any variation in the hydrogen-ion con- centration of the medium. There are thus apparently specific effects due to the amino-acids studied which may depend on the structure of these acids and thus discriminate their action from that of the monoamino-acids originally studied. Remarks on the Elution of Saccharase and Maltase from Adsorbed Substances. RICHARD WILLSTATTER and RICHARD KUHN (2.phzpiol. Chem. 1921 116 53-66).-Monosodium phosphate accelerates the elution of adsorbed saccharase from alumina with a solution of sucrose. A phosphate mixture of PH=7 has the same effect. This is not due either to the definite H-ion concentration or to the specific action of the phosphate W. G.i. 284 ABSTRACTS OF CHEMICAL PAPERS. as a citrate buffer of PH=4.5 produces a similar acceleration but not an acetate buffer of this H-ion concentration. Primary phos- phate has also an influence on the elution. Very low concentrations of glycerol sometimes raise the extracting power of primary phosphates. Maltase solutions do not remove adsorbed saccharase from alumina but they can do so in the presence of monosodium phosphate. Maltase is not extracted by maltose alone but is extracted by maltose in the presence of a buffer mixture.S. S. Z. The Specific Nature of Saccharase and Raffinase RICITARD WILLSTATTER and RICHARD KUHN (2. physiol. Chem. 1921,115 180-198).-The quotient for time value for raffinase/time value for saccharase for several preparations of inverting enzymes was found to be 11.3. Similar quotients were also worked out for a number of yeasts. It is therefore concluded that saccharase and raffinase are two different enzymes. From the constant quotient obtained with the various inverting preparations it may be assumed that the two enzymes show a great similarity in some of their physical properties and are therefore not amenable to fractionation. s. s. z. The Regeneration of Inactivated Saccharase by Dialysis. HANS v. EULER and OLOF SVANBERG (2. physiol. Chem. 1921 114 137-148).-Saccharase inactivated by silver nitrate mercuric chloride or aniline can be regenerated by dialysis. Whilst in the case of the metal salts the total regeneration of the enzyme cannot be accomplished saccharase inactivated by the action of aniline can have its entire activity restored by dialysis. The saccharase of an active dry preparation could not be extracted with aniline. s. s. z. Rennet Coagulation of Milk as a Stimulated Process. EMIL BAUR and EUGEN HERZFELD (2. physikal. Chem. 1921 98 460-473) .-The velocity of coagulation of milk by rennet of various concentrations has been determined a t 37" with the object of ascertaining whether the process is stimulated and whether the rennet concentration is augmented by rennet contained in the milk. The results show that the coagulation is accompanied by an autocatalytic formation of new rennet in the milk. Experi- ments have been made to ascertain the rate at which the reaction is transmitted through milk in which no rennet has been placed. The reactions were carried out in a capillary tube which was con- nected with a large tube containing milk and rennet. The rate of transmission of the reaction is found to be 0.8 cm./hour. A control experiment shows that diffusion would have occasioned only a transmission of 1.0k0.5 cm. in hours. A. W. VAN DER HAAR (Chem. WeeEbZad 1922,19 33-34).-The failure of Wester (ibid. 1921 18 700-703) to detect EL blue coloration with guaiacol in alcohol may be due to the presence of reducing saccharides ; after removal of these by dialysis the blue colour is readily obtained. Priority is claimed for the J. F. S. Oxydases.ORGANIC CHEMISTRY. i. 285 author (A. 1910 i 604; 1917 i 301) for observations as to the chemical nature of the oxydase molecule advanced by Willstatter and Stoll. s. I. L. Tannase. KARL FREUDENBERG and ERICH VOLLBRECHT (2. p?tysioZ. Chem. 1921 116 277-292).-For the preparation of tannase the mould (Aspergillus niger 1 ) was grown on a medium consisting of myrobalan extract &potassium phosphate ammonium sulphate and magnesium sulphate. After about four days' growth it was extracted with water care being taken that the acid was neutralised with barium hydroxide during the extraction. The extract was then concentrated in a vacuum and the enzyme pre- cipitated with absolute alcohol. The conditions under which tannase can be estimated quantitatively using methyl gallate as the substrate were also worked out. s. s. z. Reactions of the Phosphazines. WALTER THEODORE KARL BRAUNHOLTZ (T. 1922,121 300-305). Action of Arsenious Chloride on Aniline. JOHN H. SCHMIDT ( J . Amer. Chem. Xoc. 1921 43 2449-2454).-Aniline reacts with arsenious chloride in solution in n-heptane to give a yellow com- pound trianilinearsine hydrochloride As(NHPh,HCl) m. p. 148- 150" which is probably identical with the compound described by Schiff (Compt. rend. 1863 56 268 1095). This compound is readily transformed by heating it either alone or preferably with an excess of aniline into cyclic arsenic compounds. The first product is chlorophenarsazine which with alkalis gives phenarsaxine oxide O(As<E:2>NH) and this on oxidation with hydrogen peroxide in alkaline solution yields phenaxarsinic acid NH<C6H4>AsO*oH. From this acid on nitration dinitrophenaxarsinic acid was obtained giving a disodium salt. Aniline arsenate m. p. 147-148" and dianiEine arsenate m. p. 143" were obtained by the interaction of aniline and syrupy arsenic acid in alcoholic solution using excess of aniline or acid according to the salt required. A simple arrangement for sublimation in a vacuum using st Beckmann boiling apparatus is described. Organo-derivatives of Thallium. IV. Action of Thallium Chlorides on the Grignard Reagent and on Organo-derivatives of Tin Lead and Bismuth. DOROTHY GODDARD and ARCH~BALB EDWIN GODDARD (T. 1922,121 256-261). C H 2 6 4 W. G.

ISSN:0368-1769    

DOI:10.1039/CA9222200213

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

MINER-4LOQICAL CHEMISTRY. Mineralogical Chemistry. ii. 219 Chemical Aspects of Volcanism with a Collection of the Analyses of Volcanic Gases. E. T. ALLEN ( J . Franklin Irast. 1922 193 29-80).-The author has collected and tabulated all published aiialyses of volcanic gases of any import'ance for. the purpose primarily of determining whether any relation exists between the composition of the gases and the temperature at which they issue from the ground. The analyses are made tlrc basis of a critical inquiry into the nature of the original gases and into the extent to which they have become contaminated with atmospheric gases and water. Consideration of the gases contained in igneous rocks leads to the conclusion that these are the source of the original volcanic gases of which the most important is water.The original gases are probably changed in composition by the time they reach the point of collection; in some cases they probably lose a portion of the strong acid gases by interaction of these wit'h metallic oxides; in most cases they become diluted with steam from surface waters arid by atmospheric gases. In some volcanic gases the relations between the inert gases argon and nitrogen point to an atmospheric origin for these constituents ; in others they must either be of deep-seated origin or their original atmospheric relation has been changed by selective solubility in the magma. The composition of the original gases may also be changed by interaction with mineral substances by surface oxidation or by the shifting of chemical equilibrium due to change of tern- perature.Such equilibria as the following may be affected C02+H2 H20+CO; 3S2+4H20 4H2S+2S02; H2S+ 2H20 s 3H2+S0,; 2H2S G+= 2H2+S. These and other reac- tions are discussed from the thermal point of view. A more cr less abrupt evolution of gas from the magma may occur during crystallisation. Energy derived from shifting chemical equilibria may have a considerable influence in prolonging the life of an eruption but not in initiating volcanic activity. Surface combus- tion is sometimes an important factor in keeping up the tem- perature. Secondary explosions of great violence are undoubtedly produced by the access of surface water t'o hot volcanic ejecta. Primary explosions are probably the result of pressure from mag- matic gases not the result of chemical action.Absence of Cobalt in Cornetite. ALFRED SCHOEP (Min. Mag. 1922 19 301-302).-Cornetite from the original locality Star of the Congo mine in Katanga Belgian Congo (A. 1920 ii 441) is intimately mixed with minute black specks of heterogenite (A. 1921 ii 649). When freed from these the mineral shows no cobalt when tested microchemically with mercury thiocyanate. It thus agrees completely with the cornetite from Bwana Mkubwa in Northern Rhodesia (A. 1921 ii 701). E. H. R. L. J. S.ii. 220 ABSTRACTS OF CIIEMICAL PAPERS. Chemical Investigation of Japanese Minerals containing Rarer Elements. 11. Analysis of Columbite and Monazite Of Ishikawa Iwaki Province. Y ~ J I SHIBATA and KENJIR6 KIMURA ( J . Chern. Xoc. Japan 1921,42,957-964; cf.A. 1921 ii 269).-Columbite (d 5.59) from Ishikawa Iwaki Province gave on analysis Nb,O,,Ta,O,. SnO,. A1,0,. MnO. FeO. H,O. Total. 78.94 0.38 0.3G 3.56 15.99 0-90 100.13 with traces of SiO TiO WO and CaO. The amount of Ta20 was about 10%. The ratio (Fe,Mn)O (Nb,Ta),O,=l 1.03. Monazite (d 5-17) from the same locality gave on analysis P,O,. SiO,. UOs. Tho,. Al,O,. Fe20,. Ce,O,. (La,Nd),O etc. P,O,,etc. CaO. NgO. H,O. Total. 2752 2'98 0'42 11'08 0'80 0'66 21'08 31.27 3'53 0 5 2 0.27 0'56 100.69 Various samples differed; some contained traces of ZrO TiO and SnO whilst others did not contain UO and the quantities of Tho and SiO were very irregular. On spectroscopic examin- ation lines of praseodymium gadolinium dysprosium erbium ytterbium holmium and terbium were observed.K. K. Density Refractivity and Composition Relations of some Natural Glasses. C. E. TILLEY (Min. Hag. 2922 19 275- 294).-The natural glasses fall into two groups (a) tektites in- cluding moldavites and australites which are perhaps of meteoric origin and ( b ) volcanic glasses including rhyolitic trachytic and basaltic obsidians. The refractive index and density were deter- mined for a number of these and their specific refractivity (ra= (n- 1) Id) compared with that of artificial glasses of definite composition (silica felspars and CaSi0,-MgSiO,). When plotted on graphs the different glasses fall in well-defined areas according to their composition. Values for the specific refractivity of various rock-constituents in a state of glass are calculated.An analysis is given of tachylyte forming the selvage of a basic andesite at Kil- donan Eigg Western Isles of Scotland. An estimation of water in the pitchstone of Newry Ireland gave 7*04%. The presence of water has a marked influence on the specific refractivity as shown in the case of analysed rhyolite-obsidians from the Island of Lipari . L. J. S. Augite from Hawaii. HENRY S. WASHINGTON and H. E. MERWIN (Amer. J . Xci. 1922 [v] 3 117-122).-Loose jet-black crystals of augite from the volcano of Haleakala on the island of Maui were powdered and pure material separated by heavy solu- tions and the electromagnet d 3.358. In thin sections the material is pale grey with a darker surface film; extinction-angle 47" (red) to 49" (blue) a 1.700 p 1.706 y 1.724. A n analysis of the powder dried at 110" gave SiO,. no,. Al,O,. Orso,. Fe,08. FeO. MILO. CaO. MgO. NhO. G O . H.0. Total. 47.70 1.89 6.82 0.23 3-36 4.43 0.16 21.35 13-34 0.65 0.03 0.15 100.11ANALYTICAL CHEMISTRY. ii. 221 Tschermak’s (A 1921 ii 121) Boeke’s (A 1914 ii 283) and Zambonini’s (1914) views as to the constitution of aluminous augites are criticised; and the alumina and excess of ferric oxide are regarded as being in solid solution in the pyroxene constituents (diopside-hedenbergite acmite-jadeite and clinoenstatite). The present analysis is interpreted as CaMgSi,O 69.12 ; CaFeSi,O 15-13 ; NaFeSi,O 5.08 ; MgSiO 1.90 ; FeSiO 0.40 ; (Al,Fe),O 8.65%. Assuming with Zambonini that the alumina is present as spinel (12.23y0) there remains a residue of silica (4*2oyO) and CaSiO (6.61 yo). L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9222205219

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. ii. 221 An alyti eal Chemistry. A Microvolumenometer. A. BOLLAND (RoczniEi Chemji 1921 1 147-156).-A volumenometer is described which consists of a thick-walled capillary tube which is closed at its lower end; the tube is 50 mm. long and has a capacity of 0-02 c.c. it is accurately graduated into forty divisions each corresponding with 0*0005 C.C. and widens a t the top into the shape of a test-tube 40 mm. long. The method of weighing filling and emptying the apparatus is described. It is shown that it may be used for quantitative micro- analysis by measuring the volume of precipitates after centrifuging. J. F. S. Standard Dropping Pipette. HEDE HALPHEN (P7Larm. 2entr.-h. 1921 62 767-768).-A pipette which will deliver 20 drops of water per gram should have an orifice 3 mm.in diameter (external measurement); such a pipette can be made by drawing out a glass tube at one end and passing this narrow portion as far as it will go through a 3 mm. hole drilled in a brass plate. The tube is w. P. s. H. WOLFFRAM (Chern. Ztg. 1922 46 93).-A very simple apparatus to replace a Soxhlet extractor consists of a cylindrical part somewhat wider than the extraction thimble to be employed narrowing below to an outlet tube in the usual way. A small glass triangle prevents the thimble from closing up the way into the outlet tube and three or four indent- ations in the sides of the glass cylinder prevent the thimble from leaning over against the side of the glass. G. F. M. Proposed Standard Method of Colorimetry. HERBERT E. IVES ( J .Opt. Xoc. Amer. 1921 5 469-478).-3F'or the purpose of simplifying spectrometric measurements for colour specification the author has designed a method of colour measurement which consists essentially of the spectrophotometry of adjacent patches of the spectrum each patch of a width fixed by the hue scale and then cut exactly at the surface of the plate. Rapid Extraction FunneI.ii. 222 ABSTRACTS OF CHEMICAL PAPERS. narrow enough so that there is no colour difference in the spectro- photometer field at each setting. The number of patches is deter- mined by the kind of colour and the degree of a,ccuracy required. An instrument is described by which the measurements can be made and in which any colour may be reproduced for comparison. J. F. S. The Salt Error of Coloured Indicators.I. 31. KOLTHOE’F (Rec. truv. chim. 1922 41 54-67 ; cf. Ssrensen A. 1909 i 861 ; 1910 i 147).-The corrections that should be made for the presence of solutions of sodium chloride and potassium chloride of concen- trations ranging from decinormal to normal have been determined for a large number of indicators. The results are discussed in detail for each indicator and a table summarising the chief results is appended together with notes as to the suitability of the different indicators for varibus conditions. H. J. E. The Colorimetric Estimation sf Hydrogen-ion Concen- tration without Buffer Solutions. I. M. KOLTHOFF (Pharm. Weekblad 1922 59 104-1 18) .-Hydrogen-ion concentration may be estimated by comparing the colour given with standard indi- cators with the colours given by mixtures of coloured salts in specified proportions.For many indicators suitable comparison solutions may be made by mixing a solution of 11.262 grams FeC13,6H,0 in 250 C.C. of 1 yo hydrochloric acid solution with a solution of 18-2 grams of crystallised cobalt nitrate in 250 C.C. of 1% hydrochloric acid solution ; both these solutions may be employed after long keeping. Mixtures of these salt solutions in various proportions given in the tables show the same tints as the following Neutral-red in solutions with range pIi from 7.0 to 8.0; methyl-orange range 3-054.60; tropaeolin-00 range 1.80-3*00 ; methyl-red 5.2-6.0. For solutions having p H between 4.2 and 6.0 where methyl-red is used as indicator suitable comparison solutions may be made up with permanganate solution (0.004N) and dichromate solution (OSOlN-potassium di- chromate in 0*4N-HH,S0,) but these solutions are not stable in colour and must be prepared afresh as required.For the range 4.4-6.0 with this indicator the ferric chloride solution may be mixed with one obtained by mixing 10 C.C. of 0 - 0 2 5 ~ 0 pure methyl- red solution with 10 C.C. of 4N-acetic acid solution and diluting to 250 c.c.; the latter solution is stable for about a week. For the range of pH between 8.2 and 10.0 with phenolphthalein as indicator the comparison solutions are best prepared by adding to 10 C.C. of O5N-sodium carbonate solution given volumes of a 0*004% phenolphthalein solution. From the figures prepared for this table the dissociation constants of phenolphthalein have been calculated ; the values agree approximately with the figures deduced from theory (assuming the indicator is a bibasic acid) by Rosenstein (A.1912 ii 893). For the range of pH between 6.0 and 7.0 p-nitrophenol is a suit- able indicator the colour comparison solutions being prepared in this case also from an alkaline solution of the indicator. With thisANAT.YT1CAL CHJ~MISTRP. ii. 223 range completed it is possible to use the method for all values of pII between 2.0 and 10.0. The Titration of Moderately Strong Acids or Bases in the Presence of Very Weak Ones. I. M. KOLTHOFF (P7mrna. Week- blad 1922 59 129-142).-The observation of Tizard and Boeree (T. 1921 -~ ~~ 119 132) that the hydrogen-ion concentration is equal to ,/KlK2 in the case of two acids having the same concentration in the presence of sufficient alkali to neutralise the stronger one and where K and K are the dissociation constants of the two acids is confirmed theoretically and by experiment.To obtlain accurate results by titration it is necessary that the ratio .K K should bc not less than 1 x lo4 and the approximate concentrations must be determined before the final titration is made. For this purpose the approximate concentration of both acids is first determined by +,itration with N-sodium hydroxide solution in presence of tropzolin-0 and the concentration of the stronger acid by titration in presence of neutral-red or phenol-red. The value of p can then be calculated from the above and a com- parison solution made up from the sodium salt of the strong acid and the necessary proportion of the weak acid or a buffer solution of the same p H can be selected.With this comparison solution to give the colour required for the particular indicator employed the accurate titration may be made. Generally neutral-red or an indicator of the same transition range is most suitable. Formation of Nitrogen Oxides in the Slow Combustion and Explosion Methods in Gas Analysis. G. W. JONES and W. I,. PARKER ( J . I n d . Ens. Chem. 1921 13 1154-1155).- When the time of burning is not more than three minutes and the platinum wire is not heated above bright yello~ the formation of nitrogen oxides in the slow combustion method does not exceed 0-003 c.c. and nitrogen oxides are not produced in the explosion method when air is used as the oxygen supply.If a mixture of air and oxygen is employed in the explosion method appreciable quantlities of nitrogen oxides are formed and the error thus intro- duced may amount to 2%; their formation is due to increase in hhe flame temperature produced by the addition of oxygen. s. I. L. S. I. L. m7. P. s. Estimation of Water in Fuels. ANDRB M~RINOT (Ann. Chim. AvuZyt. 1922 [ii] 4 7-€I).-In the estimation of water in fuels or fuel oils errors may be introduced by the absorption of oxygen or the distillation of anthracene concurrently with the evaporation of the water even a t temperatures below 100". These errors are avoided by carrying out the operation in a current of dry hydrogen and an apparatus is described for the purpose consisting of two 100 C.C.flasks connected together and heated in a constant level water-bath. From 10-15 grams of the material are placed in each flask and a slow current of hydrogen dried in a calcium chloride-sulphuric acid tower is passed through for one and a half hours. The vapours from the flasks pass through aii. 224 ABSTRACTS OF CHEMICAL PAPERS. horizontal elongated bulb where any anthracene is deposited into a weighed U-tube containing calcium chloride the exit of which is protected from atmospheric moisture by a guard tube. G. F. M. Potassium Ferricyanide as a Reagent in Iodometry. I. M. KOLTHOFF (Pharm. Weekblad 1922 59 66-68).-The accuracy of the author’s method of standardising thiosulphate solutions by the use of potassium ferricyanide (ibid.1919 56 1618) having been questioned a further examination has been made. The method is found extremely accurate and very rapid. The ferricyanide must be pnre and dry and if the zinc sulphate and hydrochloric acid used are free from iron a perfectly white precipitate of zinc ferrocyanide is obtained and the end-point with starch is very sharp. s. I. L. High Percentage Hydrogen Peroxide (Perhydrol) for the Estimation of the Total Sulphur in Illuminating Gas. b o y s KLEMMER (Chem. Ztg. 1922 46 79).-The sulphur com- pounds including hydrogen sulphide carbon oxysulphide carbon disulphide and mercaptan are oxidised to sulphuric acid by pa,ssing $he gas through a strongly alkaline solution of hydrogen peroxide. Ten C.C. of perhydrol are mixed with 80 C.C.of fairly concentrated sodium hydroxide and the gas is led through the thick crystalline paste consisting of sodium peroxide Na,02,8H20 which is formed at a rate not exceeding 100 litres per hour. At the end of the operation the liquid is acidified with hydrochloric acid boiled to expel the excess of hydrogen peroxide and the sulphuric acid precipitated as barium sulphate. G. F. M. Estimation of Sulphur in Cast Irons and Steels. A N D R ~ ~ MARINOT (Ann. Chim. AnaEyt. 1922 [ii] 4 5-6).-E’ive grams of the metal are treated with a reagent consisting of 30 C.C. of 50% sulphuric acid and 60 C.C. of hydrochloric acid in an apparatus consisting of a conical reaction flask of 375 C.C. capacity sur- mounted by a vertical condenser into the top of which is ground a small pear-shaped gas washer from which a delivery tube leads into a flask containing 200 C.C.of a 2.5% solution of zinc acetate acidified with acetic acid. The gas washer consists of a vertical narrow tube surmounting the condenser and extending almost to touch the apex of a conical muff which surrounds it and is sealed to the tube a t the base where however it is perforated with five or six small holes which allow of the escape of the gas into the outer envelope of the pear and thence through the delivery tube into the zinc acetate flask. All the sulphur in the metal is evolved as hydrogen sulphide and a slow stream of carbon dioxide is passed through the whole apparatus to displace the gas and prevent the formation of colloidal sulphur or organic sulphur compounds.The sulphur is flnally estimated by oxidising the zinc sulphide formed in the flask by standard iodine solution and titrating back the excess. G. F. M.ANALYTICAL CHEMISTRY. ii. 225 Estimation of Available Sulphur in Golden Sulphide of Antimony. B. D. W. LUFF and B. D. PORRITT (J. Xoc. Chem. Ind. 1921 40 275-278~).-1t is suggested that the " available sulphur " be estimated by extraction with carbon disulphide after the pigment has been heated at 150" for five hours in an atmosphere rendered slightly alkaline with ammonia ; this heating converts any amorphous sulphur which may be present into a form which is soluble in the solvent. The carbon disulphide used should be Sulphates in Blood. W. DENIS ( J . Biol. Chem. 1921 49 31 1-317).-A nephelometric method for the estimation of in- organic sulphates in blood or plasma is described.Proteins are removed by means of mercuric chloride and the precipitate pro- duced by the addition of acidified barium chloride solution is com- pared with a standard in a nephelometer. No evidence was obtained of the existence in deproteinised blood of other compounds of sulphur. E. S. A Micro-method for Estimation of Nitrogen. D. A C ~ L (Biochem. Z. 1921,121,120-124).-After destruction of the organic matter with sulphuric acid in the usual manner the ammonia formed is not distilled off but is determined colorimetrically by Nessler's reagent. The control is treated with standard ammonium chloride solution until the colours match. The method is suitable for the estimation of nitrogen in as little as 0.001-0.003 C.C.of serum or urine if diluted for measurement. A Rapid Method for the Estimation of Ammoniacal Nitrogen. R. MEURICE (Ann. Chim. Analyt. 1922 [ii] 4 9-10> .-In the estimation of ammonium salts by converting them into hexamethylenetetramine and titrating the free acid thus produced errors are likely to occur if phenolphthalein is used as indicator in the preliminary exact neutralisation of the am- monium salt owing to the uncertainty of this indicator in presence of ammonia. This error is eliminated if rosolic acid is used as indicator for the preliminary neutralisation but as under ordinary conditions it is also sensitive to hexamethylenetetramine a special device is adopted to render it insensitive. After the mixture of ammonium salt and formaldehyde has been kept about thirty minutes an equal volume of ether is added and the whole is well shaken whereby the rosolic acid passes into the ether and becomes insensitive to the amine although still sensitive to a strong base such as sodium hydroxide.Titration of the free acid with standard alkali can now therefore be proceeded with until the appearance of a pale rose colour which persists on agitating the liquid with the ether. G. F. M. Precipitation of Arsenic Sulphide from Arsenates. J. H. REEDY ( J . dmer. Chem. Soc. 1921 43 2419).-The time required for precipitation of arsenic sulphide from solutions of arsenates may be greatly reduced by the addition of a small quantity of a solubleiodide such as ammonium iodide. The hastening of the purified previously by distillafion over sulphur.w. I?. s. H. K.ii. 226 ABSTRACTS OF CTIXMTCAL PAPERS. precipitation is due to the reduction of the arsenic acid to arsenious acid according to the equations H3As0,+2HI + H3As03+ H@ +I2 ; H,S+I Z ZHI+S. The reaction is applied by adding 1-2 C.C. of N-ammonium iodide solution to the hot solution which contains 4 C.C. of 6N-hydrochloric acid in 40 C.C. of solution just before the hydrogen sulphide is passed in. Precipitation begins immediately and is usually complete in four to five minutes. Com- plications arise in the precipitation of mercury and copper as iodides and in tlhe partial reduction of mercury to the mercurous condition. This difficulty is however removed during the digestion with yellow ammonium sulphide which oxidises both metals to the higher valency precipitating them as mercuric and cupric sulphides.J. F. S. Method for the Estimation of Free and Combined Carbon Dioxide. J. A. SHAW ( J . Ind. Eng. Chem. 1921 13 1151- 1152).-A definite quantity of the solution under examination (for example mine water) is drawn into a cylindrical bulb which is fitted at the top and bottom with threc-way taps; the tap a t the top connects with a small funnel for the introduction of the sample and with a measuring burette whilst the tap at the bottom connects with a smaller cylindrical bulb and with a mercury reservoir. At the commencement of the operation the whole apparatus is filled with mercury. Any gas liberated from the sample is passed over into the burette the upper tap is then closed and the mercury reservoir lowered so that the whole of the liquid is drawn into the lower cylinder a low pressure being thus pro- duced in the upper cylinder and above the surface of the liquid.The gas collecting in the upper cylinder is then forced over into the burette by raising the mercury reservoir the tap between the two cylinders being meanwhile closed and by repeating these operations several times the whole of the carbon dioxide may be collected and its volume measured in the burette. Concentrated sulphuric acid is added after the sample has been introduced into the cylinder when it is desired to estimate the total (free and combined) carbon dioxide. [Estimatio,n of Silica Phosphorus in Iron etc.]. ERNST MURMANN (&err. Chem.Zeit.,' 1921 24 142).-In the estimation of silica two evaporations with an inter- vening filtration are necessary in order to render the whole of the silica insoluble care being taken that the evaporation is carried to complete dryness of the residue. To estimate phosphorus in iron soil extracts etc. the sample is evaporated with hydrochloric and nitric acid and the residue heated in order to destroy any organic matter; by extracting the residue with nitric acid the phosphoric acid is obtained in solution and it is not necessary to dissolve the ferric oxide resulting from the decomposition of the ferric nitrate during the heating. The grinding of ores is facilitated if the powder is moistened with ether and graphitic carbon burns readily if it has been moistened previously with a small quantify of magnesium acetate solution.The use of chalk mineral phos- w. P. s. Laboratory Notes.ANALYTICAL CHEMISTRY. ii. 227 phate or bone-ash is recommended in place of sand in sand-baths since sand is liable to scratch glass vessels and cause them to break MACHELEIDT ( Woch. Brau. 1922 39 23-24).-A standard solution of sodium hydrogen tartrate is prepared by dissolving 60 grams of tartaric acid and 16 grams of sodium hydroxide in water and diluting to 1 litre. Six grams of potassium hydrogen tartrate are added and the solution is shaken for several hours. Thirty C.C. are filtered off and titrated with N/lO-barium hydroxide solution. A second 30 C.C. are shaken for one to two hours with 0.5-0.75 gram of the salt mixture to be tested the solution is filtered into a tared basin and without washing the filter titrated with the barium hydroxide solution.The solution is weighed before and after filtering and allowance is made for the loss. The difference between the two titrations ' is calculated to potassium oxide. [See further J. SOC. Chem. Ind. 1922 200.1 Estimation of the Calcium Content of Blood. R. WEISS (Deut. med. Woch. 1921 47 1298; from Physiol. Abstr. 1922 6 568).-A small measured quantity of serum is placed in a specially graduated tube ammonium oxalate is added and the precipitate washed on the centrifuge with water. It is dissolved in sulphuric acid and titrated with permanganate. The figures given are Normal 12 in tetany as low as 4 in rickets as high as 18 mg. per 100 C.C. E. s.when heated. w. P. s. Volumetric Estimation of Potassium. A. R. P. Micro-estimation of Calcium in Whole Blood Plasma and Serum by Direct Precipitation. GUY W. CLARK ( J . Biol. Chem. 1921 49 487-517).-The method described is practically identical with that of Halverson and Bergeim (A. 1916 ii 370). E. s. Sensitiveness and Applicability of Qualitative Reactions. 111. Strontium Ions. 0. LUTZ (2. anal. Chem. 1921 60 433-441; cf. A. 1921 ii 596).-The minimum quantities of strontium which can be detected by various reagents are as follows in each case 5 C.C. of the strontium salt solution were treated with 0-5 C.C. of the reagent in the cold and the observation made after five minutes. Sodium phosphate 1 9400; sodium sulphite 1 12000; ammonium oxalate 1 50000; ammonium carbonate and ammonia (at loo") 1 210000; sulphuric acid 1 125000.The addition of 5 C.C. of alcohol increases the sensitiveness of thc Estimation of Magnesium in Technical Nickel. K. CHALUPNY and K. BREISCH (Chem. Ztg. 1922 46 91).-For the estimation of small quantities of magnesium in technical nickel 10-15 grams of the metal must be used and the atration and washing of the voluminous precipitate of nickel sulphide are very laborious and a frequent source of error. The advantage of a sulphuric acid test to 1 1400000. w. P. s.ii. 228 ABSTRACTS OF CHEMICAL PAPERS. method whereby the magnesium could be precipitated whilst the nickel remained in solution is apparent and the non-precipitation of nickel phosphate from potassium nickelocyanide by sodium phosphate affords a means of attaining this object.The analysis is carried out as follows 15-20 grams of the metal are dissolved in nitric acid and the solution is twice evaporated to dryness with hydrochloric acid to precipitate silicic acid. To the filtered solution is then added 5-10 grams of ammonium chloride followed by bromine water and ammonia to precipitate iron manganese etc. The filtrate is approximately neutralised with hydrochloric acid and a concentrated solution of potassium cyanide is added until the precipitate of nickel cyanide is just redissolved followed by 20 C.C. of 10% disodium hydrogen phosphate solution and a third o f the volume of concentrated ammonia. After keeping over- night the crystalline precipitate of magnesium ammonium phos- phate is separated and washed free from nickel.It is dissolved in dilute hydrochloric acid and reprecipitated with sodium phosphate and ammonia (this step is necessary on account of the large excess of alkali cyanide present during the first Precipitation which causes somewhat too high results). The precipitate is collected in a Gooch crucible ignited and weighed as magnesium pyro- phosphate in the usual way. G . F. M. Estimation of Zinc as Zinc Pyrophosphate. D. BALAREFF (2. anal. Chem. 1921 60 442448).-The precipitation of the zinc phosphate should be made under the following conditions. The slightly acid solution containing ammonium chloride and ammonium phosphate is treated with ammonia until it is slightly alkaline in reaction towards litmus; the mixture is kept at the ordinary temperature for eighteen hours then heated on a water- bath for fifteen minutes and the precipitate is collected ignited and weighed.The amorphous precipitate which first forms when zinc is precipitated as phosphate from a solution containing ammonium salts is not zinc phosphate but ammonium zinc phos- phate; if the zinc is precipitated by treating the hot solution with ammonia ammonium zinc phosphate and zinc phosphate are precipitated together and the results obtained are too low (cf. Austin A. 1900 ii 49 and Dakin A. 1900 ii 624). W. P. S . The Separation of Aluminium from Glucinwn. 111. HUBERT T. S. BRITTON (AnaEpst 1922 47 50-60; cf. A. 1921 ii 657 712).-Rerzelius’s method consisting in boiling the pre- cipitated hydroxides with ammonium chloride solution whereby the glucinum hydroxide is dissolved is unsatisfactory as no means could be found by which the occlusion of glucinum hydroxide by aluminium hydroxide could be eliminated the results being accord- ingly low for glucinum and correspondingly high for aluminium.Wiinder and Wenger’a sodium carbonate fusion method (A. 1912 ii 687) is satisfactory but the time required for an analysis is long rn two fusions are necessary for a complete separation. The thiosulphate method in which the neutral salt solutions are boiledii. 229 ANALYTICAL CHEMISTRY. with ail excess of sodium thiosulphate until evolution of sulphur dioxide has ceased does not give quantitative separations owing to adsorption of glucina by the aluminium hydroxide which is precipitated.Haven’s ether-hydrochloric acid method (A. 1898 ii 142) is quantitative and is one of the most satisfactory and easily manipulated of all the methods investigated. Of the remain- ing methods none were investigated but it is probable that only Kling and Gelin’s basic acetate distillation method (A. 1914 ii 867) and Renz’s ethylamine method (A. 1903 ii 729) are quanti- tative and as the former requires considerable manipulation and time and the latter involves the use of a large quantity of an expensive reagent they have no particular feature -tlo recommend them. G. F. M. [Detection of Manganese with Benzidine and of Cobalt by means of the Tlsiocyanate Reaction. HUGO DITZ (Chem. Ztg. 1922 46 121-122).-The author claims priority for the method described by Feigl and Stern (A.1921 ii 278) of detecting traces of manganese by the blue coloration produced on adding an acetic acid solution of benzidine to the peroxidised manganese compound formed by autoxidation in an alkaline medium. As little as 0.000008 gram of manganese can be detected by this method. No interference with the reaction by iron salts occurs provided a considerable excess of acetic acid is present and it can therefore be used for the detection of manganese in iron ores and slags. Vogel’s thiocyanate reaction for cobalt (Ber. 1879 12 2314) is rendered more sensitive by using acetone instead of either amyl or ethyl alcohols and quantities of the order of 0.003 mg. of the metal can be detected by this means. G. F. M. Separation of Molybdenum and Tungsten by means of Selenium Oxychloride.HENRY BALDWIN MERRILL ( J . Amer. Chem. Soc. 1921 43 23834387) .-Mixtures of molybdenum trioxide and tungsten trioxide may be quantitatively separated by boiling 1 gram of the mixture with 30 C.C. of a 1 1 mixture of selenium oxychloride and concentrated sulphuric acid for sixty minutes. The solution is decanted through a weighed Gooch crucible and the residue washed several times with small quantities of selenium oxychloride and finally brought on to the filter with a hot 10% solution of ammonium nitrate. The crucible is ignited and weighed and gives the weight of tungsten trioxide the molyb- denum trioxide being obtained by difference. The above method which is effective for mixtures made by mixing the two oxides by hand does not work with mixtures of the two oxides precipitated together if the amount of tungsten trioxide is greater than 10%.In such cases it is impossible to dissolve all the molybdenum tri- oxide owing to the formation of solid solutions. This difficulty is overcome by dissolving the oxides in ammonia adding sufficient nitric acid to precipitate most of the tungsten evaporating to dryness and proceeding as described above. The method gives good results. J. F. S.ii. 230 ABSTRACTS OF CHEMICAL PAPERS. Technical Estimation of the Colloidal Part of Tungsten Powder. A. LOTTERMOSER (Kolloid Z. 1922 30 53-61).- Two methods are described for the estimation of the percentage of colloidal tungsten in commercial tungsten powders. The methods are (1) a sedimentation method and (2) an optical method both of which lead to approximately the same results.Sedimentation method the sample (20 grams) is shaken thoroughly with 100 C.C. of water in a tube and allowed to sediment for two days 75 C.C. of the supernatant liquid are removed and 75 C.C. of water added to the sediment. The mixture is shaken and allowed to sediment for a further two days. The process is repeated as long as a measurable quantity of tungsten remains in the supernatant liquid. The sediment is then dried and weighed and gives the non-colloidal portion. The addition of ammonia to the water shows that whilst most specimens of tungsten powder are very finely divided and give suspensions some only are truly colloidal inasmuch as they are peptised by ammonia. Optical metlhod this consists in estimating the quantity of tungsten in the solutions from which the powder has sedimented by means of its absorp- tion of light. The light from a quartz mercury lamp is allowed to pass through the solution on to a potassium photo-electric cell and the absorption determined from the galvanometer deflection.In this connexion it is shown that the de Beer-Pick law is applic- able. Five specimens of tungsten powder have been examined and found to contain respectively 7.574 54% 11*25% 39*75% and 7.0% of colloidal tungsten. The fourth and fifth samples are peptised by ammonia. J. F. S. Separation of Columbium and Tantalum by means of Selenium Oxychloride. HARRY BALDWIN MERRILL (J. Amer. Chem. Soc. 1921 43 2378-2383).-A method of analysis of mixtures of tantalum and columbium oxides and for the pre- paration of the pure oxides is described.The mixed oxides together with titanium oxide if such.be present are separated together from the mineral ignited and weighed. A sample (0-2-0.3 gram) of the mixed ignited oxides is boiled in an Erlenmeyer flask with 50 C.C. of a 1 1 mixture of selenium oxychloride and concentrated sulphuric acid for thirty minutes on a sand-bath care being taken that clouds of vapour are not evolved. The solution after cooling is decanted on to an asbestos pad in a Gooch crucible and filtered by suction. The filtrate is poured into a large volume of water and boiled when hydrated columbium pentoxide is precipitated. The residue is boiled with 20 C.C. of the 1 1 mixture for fifteen minutes decanted and treated as before and the process repeated until the filtrate on hydrolysis gives only a faint cloudiness due to traces of tantalum pentoxide.The residue from the flask is now washed into the Gooch crucible and without much wasliing the crucible is ignited and weighed; the gain in weight gives the amount of tantalum pentoxide whilst the loss of weight gives the columbium pentoxide with titanium if this is present. The method gives results which have a maximum error of 3% andANALYTICAL CHEMISTRY. ii. 231 is therefore better than the Marignac method whilst at the same time being more rapid. To prepare pure columbium oxide the mixed oxides are extracted with sufficient solvent to dissolve all the columbium but it should not be boiled until all the columbium is dissolved since this would mean the solution of much tantalum oxide.The dissolved oxide is precipitated with water and ammonia filtered and ignited. It still contains some tantalum oxide which by repeating the treatment can be removed and very pure columbium oxide obtained. Pure tantalum oxide is prepared by boiling the mixed oxides with the reagent until all the columbium oxide is dissolved; thus whilst sacrificing a little tantalum oxide a very pure product is obtained. The complete removal of the columbium oxide is hastened by adding a little more sulphuric acid to the 1 1 mixture of selenium oxychloride and sulphuric acid. The Estimation of Small Quantities of Antimony in Copper and Brass. B. S. EVANS (Analyst 1922 47 l-g).-Five grams of the sample are dissolved in 60 C.C.of nitric acid (d 1.2) and 10 C.C. of sulphuric acid and the solution evaporated until it fumes strongly. When cold the mass is dissolved in 100 C.C. of water 14 grams of sodium hypophosphite are added and the solution is heated nearly to boiling whereby the copper is precipitated. The solution is filtered and the precipitate washed with hot water. A further 2 grams of sodium hypophosphite and 100 C.C. of hydrochloric acid are added to the filtrate and the liquid is boiled for fifteen minutes to precipitate any arsenic present. After cooling slightly 10 C.C. of benzene are added to the filtrate and the liquid is well shaken so that the colloidal arsenic becomes suspended in the benzene layer. The liquid is filtered through a wet filter (to retain the benzene and arsenic) and the latter is washed twice with warm water.The filtrate is heated to boiling and a spiral roll of clean copper foil is dropped in and the boiling continued for one and a half to two hours the liquid is then poured off the copper washed rapidly with cold water covered with water and treated with 1 gram of sodium peroxide. The liquid is warmed until the deposited antimony has dissolved then decanted off and the strip washed with cold water. The solution is treated with 0.5 gram of zinc sulphide and after one and a half to two hours filtered. The filtrate is acidified with hydrochloric acid treated with sulphur dioxide and evaporated to 10 C.C. Five C.C. of standard antimony solution (1 c.c.=O.OOOl gram Sb) 80 C.C.of water and a few drops of hydrochloric acid are treated with sulphur dioxide and the solution is evaporated to 10 C.C. Both assay and standard solutions are treated with 5 C.C. of 1% gum arabic solution diluted to 100 c.c. treated with hydrogen sulphide for a few seconds and transferred to Nessler tubes. The liquid having the greater depth of colour is poured from the glass until the colours match; the depth of the two liquids is measured and the result calculated from these figures. The standard antimony solution is made by dissolving 0.2764 gram J. F. S.ii. 232 ABSTRACTS OF CHEMICAL PAPERS. of potassium antimony1 tartrate in 100 C.C. of hydrochloric acid and diluting to 1 litre. A. R. P. I. Estimation of Methyl Alcohol in Remains for Forensic Purposes.11. Occurrence of Methyl Alcohol in the Human Body. H. JANSCH (Vrttjschr. ger. Ned. offentl. Sanitatsw. 1921 62 1-18; from Chem. Zentr. 1921 ivy 983-984).-A weighed portion of the finely divided remains is acidified with tartaric acid and distilled in a current of steam. The distillate (500-1500 c.c.) is repeatedly redistilled recovering about goo/ each time until a distillate of 5 to 10 C.C. is obtained. Patty acids are removed by filtration. The later distillations are carried out with alkaline reaction. Acetaldehyde and glycerol which may be present are suitably oxidised. The density and refractive index of the end distillate are determined; from these the amount of methyl alcohol present is calculated using appropriate tables. For the detection of methyl alcohol the iodoform benzoyl chloride and morphine-sulphuric acid tests are used.Methyl alcohol is a normal constituent of human faeces and urine with mixed diets. It originates probably from pectins in the food. Apparatus €or the Estimation of Methoxyl Groups. WILLIAM M. CUMMINC ( J . Soc. Chem. Ind. 1922 41 20~).-An improved form of apparatus for the estimation of methoxyl groups by Hewitt and Jones's modification of the Zeisel method in which the methyl iodide is absorbed in pyridine consists of a round- bottomed flask of 250 C.C. capacity with a neck 10 inches long to which a delivery tube is attached by a ground glass joint. A thermometer is provided with its bulb opposite the delivery exit and a carbon dioxide inlet tube. The delivery tube leads to a narrow bored U-tube one arm of which contains four convolutions and each convolution a bulb.This absorber holds about 10-15 C.C. of pyridine and by passing a very slow current of carbon dioxide the whole of the methyl iodide is carried out of the flask and com- pletely absorbed. The thermometer should not register more than 40" (cf. T. 1919,115 1030). G. W. R. G. F. M. A Method for the Estimation of Trimethylene Glycol in Crude Glycerol. L. V. COCKS and A. H. SALWAY ( J . SOC. Chern. Ind. 1922 41 17-20~).-The method previously described (ibid. 1918 i 123 1 5 8 ~ ) consisting in the distillation of the crude glycerol and the determination of the specific gravity and acetin value of the distillate from which figures the trimethylene glycol content was calculated from the known specific gravity and acetin values of the pure substances gives only approximate results as no allowance is made for alterations in volume when glycerol water and trimethylene glycol are mixed.The specific gravity of a series of mixtures contlaining known proport.ions of these three substances has now been systematically determined and tables and curves have been constructed by means of which the trimethylene glycol content of any glycerol distillate of known gravity and apparentANALYTICAL CRENISTRY. ii. 233 glycerol content can be deduced. The pure trimethylene glycol prepared for the purpose boiled at 210-211"/760 mm. or 171"/174 mm. ; d$=1*0554. The reduction in specific gravity with increasing trimethylene glycol content was fairly regular and as a simple method for calculating the amount present apart from reference to the curves all that is necessary is to divide by the given factor the difference between the observed sp.gr. and the sp. gr. of pure glycerol of the strength indicated by the acetin figure of the mixture. The factor in question increases regularly with the acetin value from 0.00134 per 1% trimethylene glycol for 50% acetin to 0.00179 for 95% acetin value. An accuracy of &0.2 is claimcd. G. 3'. M. Test for Sucrose in the Presence of Dextrose. LEON A. CONGDON and CHARLES R. STEWART ( J . Indc Eng. Chem. 1921 13 1143-1144).-When a dry mixture of sucrose and dextrose is extracted with hot ethyl acetate the dextrose dissolves and the sucrose remains insoluble ; on cooling the ethyl acetate solution crystals of dextrose are obtained.w. P. s. Clarification of Urines by Zinc Ferrocyanide. C. CARREZ (Ann. Chim. Analyt. 1922 [vi] 4 ll-l2).-Polemical. The author points out that his method involving the use of potassium ferro- cya'nide and an excess of zinc acetate (A. 1908 ii 329) was never intended as a preliminary step for any estimation other than that of glucose in the urine and ThiBry's criticism (A. 1921 ii 527) therefore ha,s no point. G. F. M. Colsur Reaction of Sucrose. PERDINAND KRYZ (Oesterr. Chem. Ztq. 1921 24 141-142).-When a mixture of 1 C.C. of saturated anilvonium nickel sulphate Solution 1 C.C. of sucrose solution and a few drops of sulphuric acid or hydrochloric acid is boiled the green colour of the mixture changes to yellow and then to red; this red coloration persists even when the mixture is cooled.The reaction cannot be obtained with less than 0.005 gram of sucrose but other sugars do not interfere. The coloration is not obtained when nitric acid is used in place of the sulphuric w. P. s. acid or hydrochloric acid. Re-testing the 100O-point of the Saccharimeter. 11. Preparation of Chemically Pure Sucrose. ANTON KRATS Y (2. Ver. deut. Zuckerind. 1921 785-797).-A method of procedure for recrystallising refined sugar from alcohol for the preparation of pure sucrose for purposes of standardisation is described. The product obtained after several successive crystallisations is con- sidered to be free from invert-sugar. Such a product yielded 0~002-0~005~0 of ash and reduced 36-38 mg. of copper under the well-known Herzfeld conditions for estimating invert-sugar in sucrose and 1.5-14 mg.under the conditions of the method recently proposed by the author (ibid. 123). [See also J . SOC. Chem I d . 1922 151s.J J. H.-L.ii. 234 ABSTRACTS OF CHEMICAL PAPERS. Detection of Formic Acid in Wine. W. FRESENIUS and L. GRUNHUT (2. unal. Chem. 1921 60 457463).-The wine is acidified with sulphuric acid and extracted with ether ; the ethereal extract is then shaken with dilute sodium hydroxide solution the alkaline aqueous solution is separated evaporated to dryness and the residue heated at 130" for one hour to remove any traces of formaldehyde. The residue is dissolvcd in 10 C.C. of water and the solution treated with 5 C.C. of hydrochloric acid (d 1.12) and 0.4 gram of magnesium turnings.After two hours the mixture is distilled 5 C.C. of distillate being collected; this distillate is boiled for one minute with the addition of 2 C.C. of milk and 7 C.C. of hydrochloric acid (d 1.12) containing a trace of ferric chloride. If the wine contained formic acid or its salts a violet coloration Apparatus for Measuring the Hydrogen-ion Concentration of a Solution. Application to the Detection of Mineral Acids in Vinegar. ANDR~ KLING A. LASSIEUR and (MME) A. LASSIEUR (Compt. rend. 1922 174 165-168).-A compensation electro- metric method for measuring hydrogen-ion concentration is described in which a millivoltmeter capable of measuring 1200 millivolts with an accuracy of 1 millivolt is used. The hydrogen- ion concentration of vinegar measured with this apparatus or by the colorimetric method using thymolsulphonphthalein as indicator serves as a ready means of detecting the presence of mineral acids.The presence of 0.24% of sulphuric acid in vinegar alters the pH value at 18" from 2.67 to 1.96. Estimation of p-Hydroxybutyric Acid. Estimation of Acetone Substances in the Urine. Estimation of Acetone Substances in the Blood. ROGER S. HUBBARD ( J . Biol. Chem. 1921 49 351-357 357-374 375-384).-A modification of Shaffer's method (A. 1914 ii 77; 1916 ii 352) for the estimation of P-hydroxybutyric acid is described in which the time required for the oxidation is reduced to half an hour. The method is applied to urine after removal of interfering substances by precipitation with basic lead acetate copper sulphate and sodium hydroxide.The estimation of acetone plus acetoacetic acid in urine is made more accurate by adding to the technique of Shaffer a distillation from acid potassium permanganate solution. The same method is applied to blood after treatment of the latter with colloidal iron basic lead acetate and sodium hydroxide. It is found that in normal urine the total acetone averages about 2 mg. per 100 c.c. the greater part representing (3-hydroxybutyric acid; in blood the total acetone varies normally between 0.1 and 1.0 mg. per 100 C.C. Effect of the Presence of Filter-paper on Permanganate- Oxalate Titrations. STEPHEN G. SIMPSON ( J . Ind. Eng. Chem. 192 1,13 1152-1 154).-Filter-paper reduces permanganate rapidly especially when the paper is highly disintegrated.In the titration of calcium oxalate precipitates with permanganate solution the develops in the mixture. w. I?. s. W. G. C. R. H.ANALYTICAL CHEMISTRY. ii. 235 precipitate should be washed off the flter-paper with hot water and the paper added only when the titration is nearly complete. w. P. s. The Estimation of H-Acid. HENRY R. LEE (J. I n d . Eng. Chem. 1921 13 1049-1051).-The choice of a diazonium salt for use as a standard solution for the estimation of the hydroxyl group should depend on the stability of the salt in the solution in which it is prepared and in which it is to be used the completeness of the coupling with the intermediate product in question and the rate of coupling. Comparative experiments in which H-acidwas titratedwith benzenediazonium chloride and with p-toluenediazonium chloride re- spectively show that the rate of decomposition of diazobenzene is approximately eight times as rapid in acid solution and one and a half times as rapid in alkaline solution as that of p-diazotoluene.Moreover the rate of coupling of p-diazotoluene is slightly more rapid than that of diazobenzene whilst the secondary coupling which is marked in the case of commercial samples of H-acid titrated with diazobenzene is very slight when coupled with diazo- toluene and consequently in the latter case the end-point is more definite. The use of p-diazotoluene in the estimation of H-acid y-acid J-acid 8-acid and other naphthol- and aminonaphthol- sulphonic acids is recommended. A stock solution of p-toluidine hydrochloride is prepared by dissolving 10.7082 grams of pure p-toluidine in 40 C.C.of pure concentrated hydrochloric acid and diluting with water to 1 litre. One hundred C.C. of this solution are placed in a 250 C.C. graduated flask cooled in ice and salt until frozen and diazotised with 102 C.C. of N/lO-sodium nitrite solution. After thirty to forty minutes this is made up to 250 C.C. with water and shaken well. This solution should be kept at 0” and protected from light. In carrying out the estimation 5 grams of dry H-acid or 10 grams of press-cake are dissolved in 400 C.C. of water and sufficient sodium hydrogen carbonate to produce a clear solution and made up to 500 C.C. with water. Twenty-five C.C. of this solution are placed in a 600 C.C. beaker 200 C.C.of ice-water added and 2 grams of sodium hydrogen carbonate. This solution is cooled in ice and the diazonium solution is added from a burette jacketed with ice- water with good agitation. When the titration is almost finished about 2 grams of sodium carbonate are added to increase the rate of coupling and 10-15 grams of salt are added near the end-point. The titration is continued to the point when a spot on filter-paper gives a faint purple ring when spotted with H-acid solution. The titration is complete if this purple colour develops again when tested after the solution has been left for five minutes. Chlorohydrocarbons and Carbon Chlorides. 11. The Knowledge of the Saturation Character of the Di- Tri- and Tetra-chloroethylenes. B. M. MARGOSCHES and RICHARD BARU ( J .pr. Chem. 1921 [ii] 103 216-226).-The iodine numbers of act- and @-dichloroethylene trichloroethylene and tetrachloro- ethylene are practically zero as determined by the Hubl Wijs or other “iodine solution” in which the active agent is iodine F. M. R.ii. 236 ABSTRACTS OF CHEMICAL PAPERS. rnonochioride and therefore these solvents can be used safely as solvents for fats in the determination of their iodine number. This is in accordance with previous work on the influence of chlorine on the degree of unsaturation of a double bond. w. 0. I<. Detection of Coconut Oil in Butter. C. F. MUTTELET (Compt. rend. 1922 174 220-223).-The met,hod is based on the fact that pure butter contains cholesterol but not phytosterol whilst the vegetable fat contains phytosterol and the melting points of the acetates of these two sterols differ.The sterols in the but'ter are precipitated by the addition of 20 C.C. of a 1% alcoholic solution of digitonin to the fatty acids from 50 grams of the butter. The precipitate is collected and washed free from fatty acids by chloro- form and ether and then boiled with 2 4 C.C. of acetic anhydride. The acetate is twice crystallised from alcohol and its melting point determined. The acetate from pure butter has m. p. 113.6-114.2". With 10% of coconut oil present in the butter the resulting acetate has m. p. 114.5" and the m. p. increases as the percentage of coconut oil in the butter increases. W. G. A Simple and Exact Method for t h Direct Estimation of Acetaldehyde in the Presence of Acetone.WILHELM STEPP and ROBERT FRICKE (2. physiol. Chern. 1921 116 293-301).- To estimate the acetaldehyde the solution is treated with an excess of alkaline-ammoniacal silver of known strength the reduced silver is filtered off and the unreduced silver is titrated in the acidified filtrate with N /lO-ammonium thiocyanate using am- monium iron alum as indicator. An accuracy of 0.1 mg. can be obtained. In order to estimate the acetone the acetaldehyde is removed by boiling with silver oxide or with Pehling's solution the residual liquid is distilled and the acetone estimated in the distillate by the Messinger-Huppert method. If acetaldehyde has to be estimated a t the same time a known suspension of silver oxide is used and the residual silver oxide is dissolved in ammonia Spectrochemical Reaction of Methylfurfuraldehyde and Hydroxymethylfurfuraldehyde Phloroglucides.TETS UTARO TADOKORO ( J . Coll. Agric. Hokkaido Imp. Univ. 1921 10 52-56; cf. Oshima and Tadokoro A. 1918 ii 255).-The difference in the colour reactions of methylfurfuraldehyde and hydroxymethyl- furfuraldehyde as phloroglucides was observed by means of the ultra-violet spectroscope. The colour reaction when the two aldehydes are allowed to react with phloroglucin and hydrochloric acid changes with the time and is complete in five minutes. At a half to two minutes after the beginning of the reaction the two phloroglucides give almost the same absorption band in the visible spectrum (AX 4200-5000 and hh 4100-5000) but the methyl- furhraldehyde phloroglucide shows an absorption b a d in the ultra-violet at Ah 2400-3800.Five minutes after the beginning of the reaction methylfurfuraldehyde phloroglucide givm an and estimated volumetrically. s. s. 2.ANALYTICAL CHEMISTRY. ii. 237 absorption a t AA 4300-4800 whilst hydroxyfurf uraldehyde phlom- glucide shows an absorption band a t hh 5000-5500. A Supposed Method for the Quantitative Separation of ’ ‘ Saccharin “ from pSulphaminobenzoic Acid. WALTHER HERZOG and J. KREIDL (Oesterr. Chem. Ztg. 1921 24 165-166).- A method for the estimation of p-sulphaminobenzoic acid in com- mercial “ saccharin ” has been described by 0. Beyer (“ Kontrolle und Herstellung von Saccharin,’’ p. 97) which consists in dissolving the material in a slight excess of ammonia adding a 50% excess of acetic acid and keeping for twelve hours.The para-acid is said to be completely precipitated under these conditions whilst the more strongly acidic ‘‘ saccharin ” remains in solution as undecomposed ammonium salt. Experimental investigation of the method with known mixtures of the two pure substances showed however that the results were inaccurate to the extent of 2-3%. For example in mixtures containing 5 and 25% respectively of para-acid only 3.33 and 23.11y0 were found. G. I?. M. Apparatus for Use in Titrating Intermediates with Unstable Diazo-solutions. C. P. ATKINSON ( J . SOC. Dyers und Col. 1922 38 15-16).-The apparatus is intended for the estimation of intermediates for azo-dyestuff manufacture by titration with standard diazonium solutions.An iron tripod about thirty inches high supports a circular tin trough containing a supply of ice-water and inside the trough is a circular glass vessel with an outlet through the centre of the trough to contain the supply of diazonium solution. The burette,jacketed with the outer tube of a condenser through which the ice-water flows is supported by a triangle attached to the three legs of the tripod. In one of the three legs of this support a funnel holder is fitted to receive the waste water as it flows from the jacket and conduct it to the sink. Mercury or Water Ureometer €or the Estimation of Urea in Urine or in Blood. R E N ~ CLOGNE ( J . Pharm. Chim. 1922 vii 25 99-100).-The method of graduation in the usual form of ureometer is modified so that the graduated tube immediately below the inlet tap is very narrow and is marked in twentieths of a C.C.as far as the 2 C.C. graduation and then in fifths as far as the 25 C.C. graduation. This has the advantage of enabling the same apparatus to be utilised for estimating the small amount of urea usually present in blood as if the same quantity is taken as of urine for an estimation namely 2 c.c. the reading of the volume of liberated gas will fall within the range of the 0.05 C.C. graduations and an amount as small as 2.5 grams per litre can be accurately estimated. G. F. M. Silicotungstic Acid Applied to the Estimation of Caffeine. A. AZADIAN (BUZZ. Xoc. d i m . BeZg. 1922 31 15-18).-Silico- tungstic acid gives with caffeine in the presence of 5% hydro- chloric acid a precipitate having the composition G.W. R. F. M. R. 12WOs,Si0,,2H,O,3C,H,,O,N 6HZO.ii. 238 ABSTRACTS OF CHEMICAL PAPERS. On ignition it leaves a residue having the composition 12WO3,Si0 and the factor for converting the weight of this residue into weight of caffeine is 0.2646. For the estimation a known volume of an extract containing caffeine is evaporated to a syrup which is extracted with hot water the extract being made up to 50 C.C. Sufficient hydrochloric acid is added to bring the acid concen- tration up to 5% and then a solution of silicotungstic acid is added. The mixture is boiled and then left for twenty-four hours; the precipitate is collected dried ignited and weighed. New Method for the Detection of Thymine. OSKAR BAUDISCI~ and TREAT B. JOHNSON (Ber.1922 55 [B] 18-el).- The method depends on the conversion of thymine into carbamide acetylcarbinol and pyruvic acid the latter being identified as indigotin. Preliminary experiments show that the action is not influenced by the presence of uracil cytosine or sugar. A solution of sodium hydrogen carbonate in water is treated successively with aqueous solutions of thymine and ferrous sulphate ; the mixture is well-shaken with air which causes the gradual conversion of the white ferrous hydrogen carbonate into ferric hydroxide. The latter is removed and the filtrate concentrated on the water-bath when the original odourless solution which does not reduce Fehling’s solution acquires a characteristic odour and strong reducing properties probably owing to a Cannizzarro reaction resulting in the formation of acetylcarbinol and pyruvic acid.The presence of the former is conveniently established by distillation of the liquid and treatment of the distillate with o-aminobenz- aldehyde; the solution is boiled until the odour of the latter dis- appears cooled acidified with hydrochloric acid and made alkaline again with sodium hydrogen carbonate. The presence of 3-hydr- oxy-2-methylquinoline is shown by the blue fluorescence of the solution ; the reaction is unusually sensitive. The residue from the distillation contains p p v i c acid the presence of which is detected by the formation of indigotin after addition of 0-nitro- benzaldehyde and sodium hydroxide. The dye is extracted with chloroform. The presence of 2 - 4 mg.of thymine is established readily by the formation of the blue chloroform solution. W. G. H. W. Application of Folin and Denis’s Phosphotungstic Reaction to the Estimation of Uric Acid in Urine. THIBRY ( J . Pharm. Chim. 1022 [vii] 25 87-92).-All the methods for the estimation of uric acid in urine hitherto propos$ have the disadvantage of requiring a t least 100 C.C. of urine for each estimation. The author considers that the direct application of Folin’s phosphotungstic reagent to urine without any preliminary treatment gives results sufficiently accurate for all ordinary purposes a t least in such cases where the volume of urine at disposal is small. The reagents required are Folin’s reagent a solution containing 120 grams of anhydrous sodium carbonate per litre and a standard solution of uric acid containing 0.2 part per 1000 prepared by means of mono- and di-sodium phosphate.Into a 100 C.C. graduated tube 1 C.C.ANA LYTICAL CHEfilISTRY. ii. 239 of urine and 2 C.C. of the phosphotungstic reagent are introduced and into a further series of tubes 1 2 3 4 etc. C.C. of ~ ~ a ~ d a r d uric acid solution are placed each with 2 C.C. of the reagent. The contents of all the tubes are made up to 40 C.C. with the sodium carbonate solution aid after keeping fifteen minutes when the blue colour has reached it's maximum intensity the volume is made up to 100 C.C. with distilied water and the uric acid is estimated colorimetrically by comparison with the standard colours in a Duboscq colorimeter. The results furnished by this method are very close to those given by the present a~t~lior's volumetric silver method after treatment of the unne with potassium zinc ferrocyanide (A.1921 ii 527). The Estimation of Purine Bases in Urine. H. STEUDEL and SUNG-SHENQ CHOU (2. physiol. Chem. 1921,116 223-225).- It is suggested that the filtrate from the second copper sulphate precipitation obtained in Kriiger's method for the estimation of the purine bases in urine should after its decomposition with hydrogen sulphide be boiled with magnesium oxide in order to eliminate all traces of ammonia the nitrogen of which might otherwise be ascribed Electrometric Titration of Azo-dyestuffs. D 0. JONES and XI. I<. LEE ( J . Ind. Eng. Chem. 1922 14 4648).-The difficulties encountered in the analysis of azo-dyestuff s with titanous chloride by previous methods are enumerated and an analytical procedure is described whereby the electrometric method of following oxiclimetric reactions (cf.A. 1919 ii 471 480) is used in conjunction with titlanous chloride for the analysis of azo-dyestuffs and nitro - compounds. A sample of the finely powdered dye (0.,5-1*0 gram) sufficient to require 30-45 C.C. of N/4-titanous chloride for reduction is placed in a reaction flask with 25 C.C. of distilled water and heated on a steam-bath for ten minutes to dissolve or soften the particles. Twenty-five C.C. of 40% sulphuric acid are added the flask is stoppered and a current of carbon dioxide is passed through for five minutes; 35-50 C.C. of titanous chloride being a t least 5 C.C.of N/4-titanous chloride in excess of that required for reduction are added the mixture is boiled for five minutes and cooled to 30". In the back titration the pot'entiometer is adjusted and the voltages read for each addition of X/W-ferric alum solution. The latter is added in 5 C.C. portions at first gradually decreasing to 0.1 C.C. or less. When passing over the end-point the poles are reversed in the usual manner and the voltages read as the additions of ferric alum become larger. Volts are plotted as ordinates and C.C. of ferric alum solution as abscissz and the end-point is determined from the curve. For routine analysis almost all azo-dyestuffs can be analysed with sufficient accuracy without reading the voltmeter or plotting a curve. The potentiometer is adjusted a t the beginning of the back titration until on closing the circuit the galvanometer shows no deflection.A permanent large swing of the galvanometer is obtained a t the end-point. G. P. M. to the purine bases. s. s. z. F. M. R.ii. 240 ABSTRACTS OF CHEMICAL PAPERS. Estimation of the Percentage of Fibrin in Blood and Plasma. H. C. GRAM ( J . Biol. Chem. 1921 49 279-295).-Citrated plasma is recalcified and heated at 35' for one and a half hours; the clot is then washed and dried treated with alcohol and ether to remove lipoids and weighed. The whole estimation,. including the platelet count and the cell volume is performed on 4.5 C.C. of blood. E. s. Chemical Blood Analysis. 111. The Importance of the Ultra-filtration Method for the Analysis of Blood.M. RICHTER- QCTITTNER (Biochem. Z. 1921 124; lO6-113).-Examplee arc given of the use of the Zsigmondy-Raen ultra-filtration apparatus for the estimation in blood of residual nitrogen uric acid chloride sodium free potassium and calcium. The residual nitrogen the uric acid the chloride and sodium are completely dialysable but only a portion of the potassium calcium or dextrose is free and dialysable . H. K. Colorimetric Estimation of the Concentration of Hydrogen Ions in Very Small Quantities of Blood by Dialysis. J . LINDHARD (Compt. rend. Trav. Lab. Cadsberg 1921 14 No. 13 pp. 13).-A modification of the method of Dale and Evans (A. 1921 i l42) in which the required quantity of blood is reduced to three drops so that tlhe process can be applied repeatedly by f i n e r pricks. Hirudin is used and phenolsulphonephthalein as indicator. The dialysnte is not titrated but compared with a colour scale of phosphate-indicator mixtures. The error for the dialysis of phosphate mixtures compared wi$h a separate scale is about P 0.02 but compared with the original mixture the PI tigrees in the second place of decimals. Bicarbonate solutions gave by the electrornetric method a PI 0.2 tlo 0.3 higher than by tho colorimetric but this discrepancy the a,uthor attributes to loss of carbon dioxide in dialysis and inapplicability of the electrometric control (cf. however Evans; A. 1921 i 904). Preparation of Colhidal Gold Solution for Testing Spinal Fluid. A. 0. GETTLER and J. W. JACKSON (Arch. Neurol. Psychiatry 1921 6 70-71).-To one litre of water (distilled in copper vessels from potassium permanganate) are added in turn 10 C.C. of ly0 auric chloride solution 7 C.C. of 20/ potassium carbon- ate solution and 0.5 C.C. of ly0 oxalic acid solution. The liquid is heated until it boils then removed from the flame and vigorously shaken 0.2 to 0.3 C.C. of concentrated formaldehyde solution being simultaneously added and the shaking 'continued for one minute ; after three or four minutes the colour usually commences to develop. If it does not do so an additional 0.1 to 0.2 C.C. of formaldehyde solution is added with agitatJjon during and after the addition. A deep red colour should rapidly develop. G. B. CHEMICAL ABSTRACTS.

ISSN:0368-1769    

DOI:10.1039/CA9222205221

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 241 General and Physical Chemistry. Relation between Atomic Volumes [of Elements in Com- bination] and Optical Refractivities. GERVAISE LE BAS (Nature 1921 108 272-274).-A periodic relationship is known to exist between the atomic volumes of elements in combina- tion the differences between the atomic volumes of successive members of the same series being of the order of that of hydrogen. Similar serial and group relations are observed with the atomic refractivities the serial differences again being of the order of the atomic refractivity of hydrogen. When the atomic volumes of carbon nitrogen oxygen fluorine silicon phosphorus sulphur chlorine arsenic selenium bromine and iodine are plotted against their atomic refractivities the points obtained lie approximately on a straight line.Molecular Refraction of some Molten Salts and their Degree of Dissociation. G. MEYER and HECK (2. Elektrochem. 1922 28 21-23).-The molecular refraction of molten sodium hydroxide and nitrate and potassium hydroxide and nitrate has been measured a t a series of temperatures between 320" and 440". The method adopted was to allow a ray of light (sodium) to fall into a prism of the molten substance and be reflected from a metallic mirror inside the prism. The densities of the molten salts were determined for all the temperatures used. The mean molecular refraction over the whole temperature range is found to be sodium nitrate 11-54 potassium nitrate 14-09 sodium hydroxide 5-37 and potassium hydroxide 7-71. These values which are accurate to one unit in the second decimal place the refractive index being accurate to one unit in the third decimal place are in good agree- ment with the values calculated from the atomic refractions.Using the values 2.80 and 2.59 respectively for the atomic refrac- tions of the sodium atom and the sodium ion it is calculated that molten.sodium nitrate is dissociated to 6107%. The influence of temperature on the molecular refraction of all the substances examined is very small. F. W. ASTOX and R. H. FOWLER (Phil. Mag. 1922 [vi] 43 514-528).-A mathematical discussion of some points raised by the performance and further design of the mass spectrograph. J. FRANCK (Festschrift Kaiser Wilh. Ges. Ford. Wiss. Zehnjkhtrigen Jubilaum 1921 77- Sl).-A summary of the manner in which the broadening of spectral lines has been explained or is capable of explanation both by classical methods and in terms of the quantum theory.Radiation damping has been fairly adequately explained on the quantum A. A. E. J. F. S . Some Problems of the Mass Spectrograph. J. R. P. The Broadening of Spectral Lines. VOL. CXXII. ii. 9ii. 242 A%Tl!RACrS OE’ CHEMICAL PAPERS. theory by Stern and Volmer ; the Doppler effect may be explained by the influence of radiation pressure whilst collipion damping is considered to be due to the electron transitions produced by a collision together with a sudden warping of the electron orbits. CHEMICAL ABSTRACTS. Intensity and Broadening of Spectrum Lines. CHR. BUCHT- BAUER and G. JOOS (Physikal. Z. 1922 23 73-8O).-The form of a spectrum line broadened by another gas depends on the latter not on the absorbing gas.The constant representing the broaden- ing is with hydrogen and nitrogen proportional to the density. I n the first pair of the principal series of czesium the number repre- senting the dispersing electrons on the classical theory is equal to the number of cmium atoms. For the mercury line 2537 the number of resonators is one forty-fifth of the number of atoms. The maximum of 2537 is less displaced towards the red by hydrogen than by carbon dioxide and nitrogen. Excitation Stages in Open Arc-light Spectra. I. Sodium Potassium Calcium Strontium Barium and Magnesium. 11. Silver Bismuth Cadmium Zinc Air and Copper. B. E. MOORE (Astrophys. J. 1921 54 191-216 246-272).-An investigation of the variation of the spectrum with current using a potential of 2000 volts and currents of 0.02 to 1 ampere dis- tinguishes between five stages of excitation; the features of each are described and a number of intensity-current curves are given.The relation of the results to previous work including the Bohr theory is briefly discussed. J. R. P. A. A. E. Influence of the Pressure of Foreign Gases on the &Lines in Saturated Sodium Vapour. R. MINKOWSKI (Physikal. Z. 1922 23 69-73).-Measurements of the magnetic rotation of the 1)-lines of sodium vapour in presence of nitrogen under various pressures showed that the constant representing on the classical theory the number of dispersion electrons in unit volume is affected by pressure. The difference in the values of this constant deter- mined by absorption measurements and extrapolated from the magnetic rotations is largely perhaps entirely to be ascribed to the influence of pressure.The broadening of the lines under the influence of pressure is largely confined t o the side near the red. The method may be used in the determination of small partial pressures of monatomic vapours in mixtures. J. R. P. The Production of Enhanced Line Spectra. R. A. SAWYER and A. L. BECKER (Science 1921 54 305-306).-When calcium wires are exploded by the Anderson method (Astrophys. J . 1920 51 37) i t is found that as the size of the wires employed is decreased the energy of the stimulus remaining the same the intensity of the enhanced lines is increased indicating a more complete ionisation of the calcium atoms.A fine asbestos fibre about 3 em. in length was therefore saturated with an aqueousGENERAL AND PHYSICAL CHEMISTRY. ii. 243 solution of a calcium salt and the charge of the high-tension con- densers thrown across it. The fibre remained uninjured and the calcium spectrum thus produced showed a striking enhancement of the spark lines of calcium over the arc lines indicating that a large proportion of the emitting atoms were ionised. A table giving the relative intensities under various conditions of prominent spark- and arc-lines of calcium shows that the new source of light provisionally called the “ super-spark,” yields a degree of ionisation comparable with or perhaps in excess of that existing in the high chromosphere of the sun and in the early (or hot) type B stars.Very minute amounts of material suffice for the production of intense spectra by this method and practically only metallic lines are produced; the spectra of hydrogen oxygen or of the acid radicle of the salt used do not appear and only the strongest air lines could be observed. A. A. E. The Evolution of the Spectrum of Magnesium under the Influence of Increasing Electric Fields. Applications to Astrophysics. A. DE GRAMONT and G. A. HEMSALECH (Compt. rend. 1922 174 356-361).-1n a discussion of previous work (A. 1921 ii 611) it is shown that the spectral effects of intense electric fields are particularly marked in the initial stage of it luminous phenomenon (arc or spark) when the temperature and the electrical conductivity of the vapours are not very high.As the temperature increases the emission which depends on rapid falls in potential diminishes or disappears. In consequence the authors consider it dangerous to conclude that a star has a high temperature because the spark rays predominate in its spectrum. W. G. The Lines K of the Light Elements. V. DOLEJSEK (Compt. rend. 1922 174 441-443).-The author has again measured the K lines of the elements from zinc to chlorine. He has found for these elements the lines a3 and a4 which Hjalmar had measured for the elements sulphur to sodium. They are inseparable above scandium. The line a7 according to Siegbahn’s notation was also found for the elements calcium to chlorine. In addition a new satellite of ccl of shorter wave-length has been found.It appears to be an emission band and is denoted by a:. The line cc3 found by Duane and Stensfrom for tungsten could not be observed. W. G. The Complexity of the K Series of the Light Elements and its Theoretical Interpretation. A. DAUVILLIER (Cornpt. rend. 1922 174 443-445).-Ten components of the K series for copper have previously been reported. Their wave-lengths are now recorded. Working under the same conditions (cf. A. 1921 ii 669) the K series of molybdenum has been studied without observing any rays other than those found by Duane. The line a3 found by Duane for tungsten does not exist either for copper or molybdenum. An attempt is made to show the relationship 9-2ii. 244 ABSTRACTS OF CHEMICAL PAPERS. between the author’s measurements of the rays u a3 and a(4 of copper and those of Hjalmar for the elements calcium t o sodium.W. G. Wave-lengths Longer than 5500 A. in the Arc Spectra of yttriwn Lanthanum and Cerium and the Preparation of Pure Rare Earth Elements. C. C. KIESS B. S. HOPKINS and H. C. KREMERS (U.S. Bureau of Standards Xci. Papers 1921 No. 421 318-351).-Photographic determinations were made in the yellow red and infra-red regions of the arc spectra as follows yttrium 170 lines to 7881.868 A lanthanum 410 lines to 9078.99 A. cerium 1700 lines to 9024.68 A. A description is given of t h methods used in the purification of the substances employed corn- pounds of cerium samarium lanthanum neodymium and gado- linium being obtained from a sample of “ Welsbach ” sodium rare- earth sulphate and those of yttrium dysprosium and erbium from qadolinite and xenotime. The cerium was removed from the ’ Welsbach ” residues by precipitation with potassium bromate as basic ceric bromate; the other elements were then separated by way of the fractional crystallisation of the double magnesium nitrate.The yttrium-group material was freed from the elements of the cerium group and then fractionally crystallised as bromate. D. COWER (C‘ompt. rend. 1922 174 378-379).-The author has again measured the spectra of a large number of elements (tantalum to rubidium) and in general the new results confirm the conclusions of previous work and in addition lend support to Bohr’s theory of the structure of the atom (cf. this vol. ii 277). Certain of the author’s results are more or less opposed to the results and conclusions of Dauvillier (cf.A. 1921 ii 421,475 699) and these divergences are summarised. The Infra-red Absorption Spectra of Alkali Hydroxides. G. E. GRANTHAM (Physical Rev. 1921 18 340; cf. Howe and Gibson ibid. 1917 10 767).-When the absorption of solutions of sodium potassium and lithium hydroxides (of various concen- trations) and of ammonium and caesium hydroxides (one solution each) was determined with reference to that of water all the curves showed a broad intense absorption band with a maximum at about 2*29p except in the case of the ammonium hydroxide solution for which the maximum was found to be at 2.20~. The absorption was found to be proportional t o the concentration but not to vary systematically with the atomic weight of the metal used.It is suggested that the band is due to dissociated hydroxide ions although in the case of other hydroxide solutions such a band has not previously been observed. Maximum absorption of water was observed at 1.48 and 1.98,u. The effect of dissolving an alkali hydroxide is to decrease the absorption of the water in the band a t 1 . 4 8 ~ by an amount proportional to the concentration of the solution and to the atomic weight of the metal of the base. CHEMICAL ABSTRACTS. The L Series of the X-Ray Spectrum. W. G. A. A. E.GENERAL AND PHYSICAL CHEMISTRY. ii. 245 The Ultra-violet Absorption Spectra and the Optical Rotation of the Proteins of Blood Sera. S. JUDD LEWIS (Proc. Roy. Soc. 1922 [B] 93 178-194; cf. A 1917 ii 62).- Eleven sera six from the horse and five from man were used for the separation and purification by modifications of well-known methods of the albumin euglobulin and $-globulin.The optical rotation and the ultra-violet absorption spectra of the individual proteins were examined in detail. $-Globulin euglobulin and albumin from horse sera had specific rotations of -5Y -43" and - 57-4" respectively the corresponding values for human being -46" and -48" for the globulins and varying values for the albumin. The absorption curves are similar in form and ceharacter to that of serum well-developed bands being best found a t concentrations of O.OS~o for albumin and 0.040,/ for the globulins. The absorption curve of $-globulin is the same for the horse and man and differs from euglobulin in the extinction coefficients but riot in general form.For horse and human albumin the curves are the same except for a constant ratio in their magnitudes due possibly to physical or chemical associntion of an aggregate of little or no absorptive power. The Fluorescence of Mercury Vapour. J. 8. VAN DER TANGEN and 1%. w. WOOD (Astrophys. J . 1921 54 149-160).- Since the fluorescent spectrum of mercury vapour cannot be excited in quiescent vapour but only in vapour which is being distilled from the metal a t a temperature not less than 150" the active molecules are presumably not neutral monatomic molecules but others possibly diatomic present only during distillation. The spectrum consists of lines a t 2636 3539 and 2346 8. and four structureless bands with maxima a t 2346 2540 3300 and 4850 A.The complete spectrum is excited by light from a zinc spark but single lines excite only a part. The relation of the spectrum to Hydrates of Boron Trioxide as a Constituent of Systems Capable of Strong Phosphorescence and containing Organic COIIIgQlalldS. ERICH TIEDE and PETER \vULFI? (BPI.. 1!)22 55 1 B] 588-597).-The phosphorescencc of partly dehydrated boric :wid (A. 1921 ii 75) originates from t!rnces of organic compounds is reuiovablc not by recrystallisation ignition in a stream of oxygen boiling with nitric acid or fusion with potassium nitrate Ijut by boiling with fuming nitric acid for twenty-four hours subsequently recrystdlisiiig three times from water specially purified and finally igniting the upper portion of the filtered mass (which had not been in contact with filter-paper) in a platinum crucible.Phospliorescence could not be induced in such a product by any means other than by introduction of organic impurities. For this purpose even those present in ordinary distilled water suffice. A number of fluorescent boric acid compounds were prc- pared by the respective additions to purified boric acid of flumes- cein its sodium salt (uranin) phenolphthalein benzoic acid quinone H. K. the exciting light is examined in some detail. A. A. E.ii. 246 ABSTRACTS OF CHEMICAL PAPERS. aniline dimethylaniline diphenylamine phenol quinol naphthol terephthalic acid pyridine and quinoline-in short aromatic or heterocyclic compounds but not aliphatic compounds unless these (for example ethylene glycol or ' sugar) undergo some decom- position-followed by fusion of the mixtures to transparent glasses or by heating for two hours in the vacuum of a water-pump until a partly sintered mass is produced.Inorganic compounds even those of uranium or the platinocyanides with the exception of boron nitride (Tiede and Biischer A. 1921 ii 74) do not produce phosphorescent materials nor can the boric acid be replaced by silicic or phosphoric acids Hydration to orthoboric acid consequent on exposure of the products to air largely destroys the phosphorescence as does also too intense dehydration. Phosphor- escence is excited by daylight but usually best by the ultra-violet light of the quartz lamp and does not usually persist for more than two minutes.The intensity however is frequently much greater than that from the phosphorescent alkaline earths and sufficient momentarily to illuminate comparatively large spaces. Blue tones predominate but reddish-yellow and green effects have been observed Rontgen cathode and radium rays have no effect. The new produots show only slight tendency towards thermoluminescence down to the temperature of liquid air. In common with analogous cases they are produced when the medium (boric acid) suffers contraction. They offer no support for the view that luminescence of organic compounds is dependent on their slow decomposition (Perrin A. 1918 ii 418; 1919 ii 177). Pure anthracene in spite of its fluorescence causes no fluorescence in boric acid but compounds like ethyl dihydrocollidinedicarboxylate which are excited by radium rays give a product in which fluor- escence is produced by ultra-violet illumination but is indifferent to radium.It is presumed that the phosphorescence emanates from definite organic derivatives of boric acid (cf. Dimroth and Faust A. 1922 i 155; Pictet A 1903 i 601). Thus orange crystals result from evaporation of a solution of boric acid con- taining uranin (1 3000) but these on fusion become light green and simultaneously acquire capacity for phosphorescence. J. K. Action of Red and Infra-red Rays on the Phosphorescent Sulphides. MAURICE CURIE (Compt. rend. 1922 174 550- 553) .-AS an explanation of the extinguishing action of the less refrangible part of the spectrum on certain phosphorescent sub- stances it is suggested that the action of the extinguishing rays will consist in rendering the medium a conductor by the detach- ment of electrons from the atoms of sulphur in the case of the sulphides.In support of this theory experiments are described in which an increase of conductivity was found for finely-powdered sulphur and certain sulphides when they were exposed to the action of red rays. This hypothesis also gives an explanation of the fact that the extinguishing action is not limited to the red and infra-red portions of the spectrum. W. G.QENERAL AND PHYSICAL CHEMISTRY. ii. 247 Preparation of Phosphorescent Magnesium Sulphide. ERICH TIEDE and PRIEDRICH RICHTER (2. EEektrochem. 1922 28 20-21) .-Strongly phosphorescent preparations of magnesium sulphide containing small quantities of bismuth antimony or manganese may be prepared. These substances exhibit a violet golden-yellow or dark red phosphorescence and an afterglow which in every way corresponds with that of the well-known preparations of the alkaline earth sulphide.Details of the method of preparation of phosphorescent magnesium sulphide are not given in the paper. J. F. S. Experimental Proof of some Theories of Natural Rotatory Power of Optically Active Solutions. PAUL WETTERFORS (2. Physik 1922 8 229-242).-With the object of testing the hypotheses of optical rotation put forward by Lorentz and Livens (" Theorie elektr. opt. Erscheinungen," 1906 ; A. 1913 ii 543 ; 1914 ii 830) the author has measured the specific rotation [a] the refractive index n and the rotatory dispersion of solutions of camphor in ethyl alcohol propyl alcohol acetone benzene and toluene and of a-bromocamphor in the three last-named solvents. The measurements were made with solutions of various concen- trations from 10.02 to 49.98 grams per 100 C.C.of solution at temperatures from 11.1" to 18.0". Four series of measurements were made in each case with light of wave-lengths 589pp7 546pp 436pp and 710pp the first being obtained from a sodium lamp and the three latter from a quartz mercury lamp by the use of suitable light filters. The specific rotation of a-broinocamphor in acetone solution in various concentrations c is given by the equations [cc]~=710=86.87+0.0625~ ; [ a ] ~ ~ ~ ~ ~ = ~ ; [E]A=546= 172.01+0.1389c ; [a]h=ass=350.25+0.3561. It is shown in general the rotation increases with increase of temperature since the concentration of a solution decreases with increasing temperature the specific rotation is also greater.An exception is found in the case of acetone solutions of a-bromocamphor ; here the rotation decreases with increasing temperature but the specific rotation is independent of temperature. The rotatory dispersion defined as the ratio [a],\ [a]!1589 where [a],\ is the specific rotation for the wave- length A and the same quantity for h=589 changes in general with the concentration. Bromocamphor shows an increase camphor a decrease for the wave-lengths A=546pp and 436pp (h>589pp) but for X=710pp (X(589) an increase when the con- centrations are greater. Solutions of camphor in acetone are exceptional for here the rotatory dispersion is constant.According to Livens's theory the expression [a]=rv2/2 . (m2- l)[a(n2- l)+ 11 must hold; this has been rewritten in the form [ a ] = ~ y ~ ( n ~ - l ) ~ - k ~ ~ ( n ~ - l ) where yo=rv2/2. On plotting the values of [a]/(n2-1) against (n2-l) a straight line should be obtained. Treating the present experimental values in this way actually leads to straight lines for solutions of camphor in benzene and toluene and for bromocamphor in benzene; in all other cases a straight line passes only approximately through the points. The values of a and goii. 248 ABSTRACTS OF CHEMICAL PAPERS. have been evaluated by the method of least squares and it is shown that the value of a is always negative its shown by Peacock (T.1914 105 2782; 1915 107 1547). The numerical values of a are largest for bromocamphor in toluene and benzene and smallest for camphor in ethyl alcohol. The a value for camphor in toluene is the same for A=546pp and A=436pp. It is shown therefore that the Lorentz-Livens hypothesis can only claim to give qualitative representation of the present material. According to Oseen’s hypothesis the expression k=[a] (n2+2)2 must be constant. The experimental data show that this is not the case for in the case of solutions of camphor in benzene toluene and the alcohols the Ic value increases with increasing concentration but decreases with acetone solutions. Further except in the case of solutions of camphor in propyl alcohol the value of k is a linear function of the concentration. Photochemical Studies.XIV. Fundamental Photochemi- cal Laws. J. PLOTNIKOW (2. wiss. Photochem. 1922 21 134- €40) .-A theoretical paper in which Einstein’s photochemical cq uivalent law and the Grotthus-van’t Hoff photochemical absorp- tion law are critically examined. It is shown that Einstein’s law leads to the following improbabilities. On calculating the energy absorbed by one gram molecule from light of various wave-lengths i t is found that the extreme ultra-violet lOOpp gives up 300,000 cal. and Rontgen rays 3 x lo9 cal. which indicates that with decreasing wave-length light becomes much more active until with Rontgen rays all molecules will be simply destroyed. Further all atoms in all reactions in all solvents must react with the same velocity a t all temperatures and must take up the same quantity of energy.It is showp that the Grotthus-van’t Hoff law is diametrically opposed to thc Einstein law. Nine classes of photolytic reactions are quoted in which the Einstein law in no way represents the facts and two further classes are noted in which deviations from the law of -8% to 22y0 are observed. The photolysis of hydrogen iodide and hydrogen bromide alone give an approximate agreement but here there is a divergence varying between -3.374 and +4%. Weigert’s recent paper (2. Physik 1921 5 421) which shows the applicability of the Einstein law and characterises the Grotthus-van’t Hoff law as untenable is criticised. It is shown that the reactions studied and the method of operation is much too complicated to makt1 i t possible to draw conclusions of the type drawn by Weigert from the results.I n the present author’s opinion the Einstein law in its present form cannot be maintained. Photosynthesis and the Electronic Theory. 11. HENRY H. DIXON and NIGEI G. BALL (Sci. Proc. Roy. Dubl. SOC. 1922 16 4 3 5 4 4 1 ; cf. Dixoii and Poole A. 1920 ii 343).-1n con- t,inuation of previous work the photo-electric properties of chloro- phyll were investigated. The electronic theory of sensitisation is supported by experiments in which sensitised photographic plates were affected by light at a temperature of --185’ chemical J. F. S. ?J. F. S.QENERAL AND PHYSICAL OHEMISTRY. ii. 249 action being thereby precluded. Using collodion hlms it mas shown that sensitisationiby chlorophyll is also effective even a t the temperature of liquid air.Since only light of visible wave- lengths is absorbed by chlorophyll and since earlier experiments have shown that electrons are not expelled from chlorophyll it follows that the light absorbed is wholly used in the displacement of electrons within the molecule thereby making some atomic group or groups reactive. In photosynthesis these groups may react with carbon dioxide and water according to the scheme chlorophyll-a+CO,=chlorophyll-b+CI-I,O and chlorophyll-b+ H,O=chlorophyll-a+ 0,. It is assumed that these reactions only take place during illumination and depend on its intensity. The velocity of the first reaction would only increase with intensity of illumination so long as carbon dioxide is in excess whilst the velocity of the second reaction would only be indirectly influenced by this factor.G . W. R. Absorption of Rontgen Rays. K. A. WINGHRDH (2. Physilc 1922 8 363-376).-A method for the determination of the absorp- tion coefficients of substances in solution for the homogeneous Rontgen rays of the K line of molybdenum is described. The atomic absorption coefficients are calculated and it is shown that the logarithms of these when plotted against the logarithms of the ordinal numbers of the elements give two straight lines. Oxygen showed a marked deviat'ion. J. R. P. Spark Lines in the RSntgen Spectrum. GREGOR WENTZEL (Ann. Physilc 1921 [iv] 66 437461).-1t is assumed that the inner shells of the atom may under certain conditions undergo repeated ionisation.By the spontaneous transition of an atom from such a state to a stat,e of equal level Rontgen lines will be emitted which correspond with spark lines in the optical spectrum. It is shown that the emission can have only one he-structure of known Rontgen lines which is extended usually towards the region of short wave-lengths. All the lines which previously caused difficulty in the systematic arrangement of Rontgen spectra can be regarded as spark lines; in particular the hard Ku satellites from Kor to a6 can be derived from two combination relations and the complex structure of the K-absorption edges observed by Fricke is also elucidated. The magnitudes of the frequency differences and their linear change with ordinal number are satisfactorily explained.J. R. P. X-Rays and Thermodynamic Equilibrium. L. DE BROGLIE ( J . Phys. Radium 1922 [vi] 3 3345).-The conditions of thermodynamic equilibrium between atoms electrons and radiation in an enclosure maintained a t a temperature T are considered. The statistical equilibrium between the atoms is described by the law of Maxwell and Boltzmann which may be applied to systems in which the total energy may assume only a certain number of discontinuous values. The equilibrium density of 9"ii. 250 ABSTRACTS OF CHEMICAL PAPERS. radiation in the region of frequencies considered may be reprc- sented by Wien’s law. The free electrons are considered as forming an ideal gas with density proportional to F. The atomic coefficient of absorption of a substance is then shown to be given by p=CA32:,nPE2 where C is a constant A the wave-length np the number of electrons in the level p (in the sense of Bohr’s theory) and Ep=hvp the energy emitted when the atom passes from the ionised to the normal stat’e.This result is compared with experi- ment. J. R. P. Stopping Power and Atomic Number. J. L. GLASSON (Phil. Mag. 1922 [vi] 43 477-481).-Hy a discussion of known results it is shown that the stopping power of an atom is propor- tional to N% where A7 is t!he atomic number rather than to AS where A is the atomic weight as previously supposed. This agrees with the higher stopping power of hydrogen as compared with helium. J. R. P. M. L. NEUBURGER (Nature 1921 108 180).-Meitner’s (this vol. ii 15) nucleus model of the radio-elements permits of the division of the radioactive isotopes into four classes (1) those which possess only the same nuclear charge and the same arrangement of their outer electrons for example radium and mesothorium-I (2) those which have in addition the same atomic weight and the same total number of nuclear “ building stones,” for example ionium and uranium- Y (3) those having the same number of each nuclear building stone but a different arrangement of these in the atomic nucleus for example radium-D and actinium-B (4) those possessing the same arrangement of building stones and thus the same probability of disintegration for example radium-G and actinium-l).Such elements cannot at present be designated isotopes since there is no available means of distinguishing between them.ELIZABETH RONA (Ber. 1922 55 [B] 294-301).-Ionium has been estimated in various radium residues according to the “ indicator ” method with the aid of uranium-X and. the content has been compared with that of pitchblende. The final residues obtained during the extraction of radium in Austria still contain approximately 16% of the ionium present originally in the pitchblende. Thorough extraction of the latter with nitric acid on a laboratory scale gives insoluble residues which are almost completely free from ionium. The importance of the estimation of ionium for that of proto- actinium in uranium minerals and for the inter-relationships of the actinium series is discussed. H. W. A Lecture de- livered before the Chemical Society on February 9th 1922.SIR ERNEST RUTHERFORD (T. 1922 121 400415). H. GREIN- ACHER (Physilcal. Z. 1922 23 65-69).-When a flame coloured Isotopy of the Radio-elements. A. A. E. The Ionium Content of Radium Residues. Artificial Disintegration of the Elements. Luminescence of Flame Ions in the Air Spark.GENERAL AND PHYSICAL CHEMISTRY. ii. 251 with a salt vapour is brought into a strong electric field the ions may be caught on two platinum wires outside the flame on which they may afterwards be detected spectroscopically by heating. When a spark is passed between a wire in the flame and a brass sphere a few centimetres from the flame or two wires similarly placed the spectrum of the spark shows the lines of hydrogen and the metal ions. Lithium sodium potassium rubidium cesium thallium and strontium were examined.The metals move principally to the negative electrode but partly to the positive. In the case of strontium all the lines leave the flame but in the other cases only a limited number. In spite of the strong field in the spark only the lines with a small exciting potential (small hv) appear. The ions are partly produced in the flame and partly in the spark. An apparent change in wave-length occurs. J. R. P. Ionic Equilibria on Metallic Surfaces. H. VON EULEE [with ARVID HEDELIUS and ZIMMEBLUND] (2. Electrochem. 1922 28 2-Ci).-An account is given of the sorption of gold silver and mercury ions on the surfaces of the metals. The method consisted in determining analytically the change in the concen- tration of solutions of silver nitrate and silver sulphate after they had been in contact with metallic silver and gold respectively.Similar experiments are described for solutions of mercuric chloridc in contact with mercury. It is shown that 1 sq. metre of silver surface absorbs 0.35 mg. ion from silver nitrate and 0.6 mg. ion from potassium chloride solution whilst the same area of gold absorbs 0.063 mg. ion from silver nitrate. A sq. metre of mercury surface absorbs 0.004 mg. ion from mercuric chloride solution. The results are discussed in connexion with the charge of an electric double layer. J. F. S. Evidence for the Existence of Homogeneous Groups of Large Ions. P. J. NOLAN (Physical Rev. 1921,18 185-198).- Using as did Blackwood (ibid. 1920 16 85) the Zeleny method for the measurement of the mobilities of ions instead of that previously employed by McClelland and Nolan (Proc.Roy. Irish Acad. 1919 35 [ A ] 1 and previous papers) evidence has been adduced to confirm the author’s original statement that when large ions are produced in air in various ways the ions can bc divided into a number of groups each group having a definite mobility. It is considered that Blackwood’s negative results were due to ions changing from group to group when the time spent in thc measuring chamber is relatively long. The Scattering of Electrons by Nickel. C. DAVISSON and C. H. KUNSMAN (Science 1921 54 522-524).-When a nickel target is bombarded by a stream of electrons there is observed besides the emission of slowly moving secondary electrons char- acteristic of all metals an appreciable emission of electrons of higher speed.After experimental and mathematical examination of A. A. E. 9*-2ii. 252 ABSTRACTS OF CHEMICAL PAPERS. the phenomenon it is suggested that the sharp deHexions experi- enced by these scattered electrons must result from their pene- tration into the atomic structure and their deflexion by the st,rong field which they encounter. Dielectric Constants of some Esters at Low Temperatures. L. C. JACKSON (Phil. Hag. 1922 [vi] 43 481-489).-A method is described for the determination of the dielectric constants of solid and liquid substances by the use of triode valve circuits. The result's with a frequency of 4.7 x 105 per second were a t the absolute temperatures indicated as follows methyl formate 2.56 a t 78.65"; ethyl formate 2.40 a t 81.3"; n-propyl forma(te 2-39 a t 79.5"; n-butyl formate 2.43 a t 78.7"; methyl acetate 2-58 at 77.3"; ethyl acetate 2-48 a t 79.15"; n-propyl acetatc 2-42 a t 80.9"; n-butyl acetate 2.41 a t 77.6".The values are smaller than those found a t the ordinary temperature (5 to 9). The acid radicle apparently contributes but little to the value of the dielectric constant. The dielectric constant of n-butyl acetate increases linearly with decrease of temperature to the melting point a t which there is a sudden fall followed by a very gradual rise as the temperature is still further lowered. Conductivity of Concentrated Solutions of Sodium and Potassium in Liquid Ammonia. CHARLES A. KRAUS and WALTER W. LUCASSE ( J . Amer. Chem. Xoc.1921 43 2529- 2539) .-The specific conductivity of solutions of sodium and potassium in liquid ammonia a t its boiling point (-33.5") has been measured for concentrations from O96N to saturated solutions. It is shown that as the concentration increases the specific conduc- tivity increases enormously reaching the values 0.5047 x lo4 and 0.4569 x lo4 for saturated solutions of sodium and potassium respectively. The specific conductivity of solutions of sodium and potassium a t the same equivalent concentration is very nearly the same. The equivalent conductivity of saturated solutions of sodium and potassium in liquid ammonia is of the same order of magnitude as that of such metals as strontium and iron. The solubility of sodium and potassium in liquid ammonia at its boiling point has been found to be 5.367 and 4.866 mols.of ammonia per atom of sodium and potassium respectively. The general result of the work is the furnishing of further evidence in support of the hypothesis that the conduction process in metals consists in a motion of negative carriers of sub-atomic dimensions which carriers are identical for all metals. Potentials at the Junctions of Univalent Chloride Solutions. DUNCAN A. MACINNES and Yu LIANG YEn ( J . Amer. Chem. soc. 1921 43 2563-2573).-Using a slightly modified form of Lamb and La<rson's flowing junction apparatus (A. 1920 ii 347) the contact potentials of the type MClIM'Cl in which MI and M' are either hydrogen or an alkali metal (lithium sodium potassium caium or ammonium) have been determined. The measurements were made a t 25" and were for solutioiis of equal concentrations. A.A. E. J. R. P. J. F. S.ORNRRATI AND PRYSTCAT CHEMISTRY. ii. 263 Tables of results of all possible combinations are given for t)he concentrations @1,V and O - O l N and the values compared wit f i those calculated by Lewis and Sargent's formula (A. 1909 ii 369). Tn all cases reproducible values were obtained within a few hundredths of a millivolt). The Lewis and Sargent form of Planek's original equation E,=IiT/F log A / R ~ ' expresses the results for most of the cases studied and gives a qualitative agreement in all cases. The experimentally determined potentials can however be obtained from the differences between numbers which arti characteristic for each ion a t each concentration.This is equivalent to the expression given above except that for the lithium and potassium ions values of A which are slightly different from thost. obtained from conductivity measurements would have to be used. J. F. 8. A Quick Acting Hydrogen Electrode. P. J. MOLONEY ( J . Physical Chem. 1921 25 758-761).-A new form of hydrogen electrode is described. The electrode consists of a short length of platinum wire sealed into the end of a glass tube and projecting 4 mm. from the end; the tube should have an internal diameter of about 4 mm. A loop of 1 mm. diameter glass rod is sealed to the end of the tube so that the platinum wire occupies the centre of the loop. A glass tube of slightly greater diameter than the electrode tube blown into the form of a bell a t one end and having a bulb a little higher up which is pierced near the top by a small hole fits over the electrode tube and is kept in position by a piece of rubber tube.The platinum wire is platinised in the usual way. The object of the electrode is to ensure a rapid equilibrium between the hydrogen in the platinum and the hydrogen ion in the solu- tion. To use the electrode it is drawn up the tube until the wire and glass loop are in the middle of the bulb in the jacket tube and the whole is immersed in the liquid to be measured until the tube connecting the bell and bulb is filled then the electrode is pushed down until the wire and loop are in the bell hydrogen is admitted under the bell and the whole adjusted so that the wire is sur- rounded by hydrogen whilst the lower end of the loop just dips into the main bulk of the liquid.In this way only a small volumc of liquid namely that held in the loop has to be saturated with hydrogen and be in equilibrium with the wire. Equilibrium values are rapidly reached with this electrode. Behaviour of a Non-attackable Electrode in the Process Loading to the Equilibrium 3 m O 2 f 2N8+HN03+H20. ALFONS KLEMENC (2. EZektrochenz. 1922 28 55 5 6 ) ; H. PICK (ibid. 56-57).-Polemical; cf. A. 1920 ii 409; 1921 ii 297. J. F. S. J. F. S. Overvoltage on Electrodes and its Connexion with the Hydration of Ions. N. ISGARISCHEV and SOPHIE BERKMANN (2. Elektrochem. 1922 28 40-47) .-The decomposition voltage of N - and N/10-solutions of sulphuric acid and the sulphates of rubidium aluminium potassium ammonium sodium lithium,ii.254 ABSTRACTS OF CHEMICAL PAPERS. magnesium zinc copper manganese and nickel has been determined and the values have been compared with the degree of dissociation the surface tension the molecular hydration and the ionic hydration. It is shown that there is only one break in the anode current- voltage curve and this is attributed to the discharge of the SO," ion. The results show that the surface tension is in no way related to the discharge potential of the anion ( E ) ; the degree of dissociation also stands in no direct relationship to the value of E ; in some cases it is found that an increase in the value of the degree of dissociation is accompanied by an increase of E. It is concluded therefore that the discharge voltage is dependent on the velocity of the anode process that is a lower potential will be required for decomposition the greater the velocity of the anode process.To investigate the cause of the difference in the velocity of the anode process in different cases the authors have compared the value of E with the hydration of the molecules and the ions. It is shown that there is no connexion between the value of E and the number of molecules of water combined with the molecules of the electro- lyte. The more hydrated the kations the smaller is the decom- position voltage found to be and since the more hydrated the kation the less hydrated is the anion it follows that the lower is the potential required to discharge it. The anode process is expressed by the scheme (a) S0,"+23=S04; ( b ) SO,=SO 0; ( c ) %2S04(H20) 2Na(H20),,+S0,"(H20) ; (d) S0,'((H2Cfj~~ SO +mH,O.The cause therefore of the retardation of the anode process is the insufficiently rapid formation of SO," ions from the hydrate. It is shown that there is a definite periodicity hetween the value of E and the atomic weight of the kation. J. I?. S. Influence of Colloids on Overvoltage. N. ISGA~~ISCHEV and SOPHIE BERKMANN (2. Eleklrochem. 1922 28 47-50).-Thc discharge potential of the hydrogen ion on copper silver and platinum cathodes has been measured in 2N-sulphuric acid con- taining various concentrations of gelatin (0-6%). It is shown that the nature of the cathode has no influence on the discharge potential. The value of this quantity a t 18" rises to a maximum with increase in the gelatin concentration and then commences to fall.There is a corresponding increase in the anode discharge voltage with increase in the gelatin concentration. The change is explained as due to the formation of a complex between the hydrogen ion and the gelatin which is slowly decomposed a t the electrode (see preceding abstract). The maximum potential repre- sents the point where all the ions have combined with gelatin and a calculation based on an approximate value of the molecular weight of gelatin shows that a complex consisting of one hydrogen ion and 1173 molecules of gelatin is formed. Free Energy of Dilution and the Activities of the Ions of Potassium Bromide in Aqueous Solutions. J. N. PEARCE and HARRY B. HART ( J . Amer.Chem. Soc. 1921,43,2483-2492).- Measurements of the E.M.P. of cells of the type AglAgBr,K.Br(c)l J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 255 KHg have been made for various concentrations (c=2.0-0.001N) at 25" 30" and 35". The decrease of free energy and the decrease in heat content attending the reaction in these cells have been calculated. The free energy decrease accompanying the transfer of 1 mol. of potassium bromide from various concentrations (c) to O-lOK have also been calculated. The E.M.P. of concentration cells with ion transference of the type Agl AgBr,KBr(c,)/ KBr ( c z ) >AgBr] Ag and of concentration cells without ion transference of the types Ag 1 AgBr,KBr(c,) I KHg,-Hg,KI KBr(c2) ,AgBrl Ag and KHg,l KBr (c J,AgBr I Ag-Ag I Ag Br ,KBr ( c 2 ) I Hg,K have been deter - mined and from these values the transport number of the potass- ium ion has been calculated.The results show that dilution has very little influence on the transport number of potassium and there is only a very gradual increase with increasing dilution whilst the effect of temperature is practically negligible between 25" and 35". The decrease of free energy and heat content accompanying the transference of 1 mol. of potassium bromide from a concentra- tion c1 to a concentration c2 have been calculated. The activity coefficients of the bromide ion have been calculated and a com- parison made of the activity coefficients of the chloride and bromide ions. For all concentrations up to 0 4 N the activity coefficients of these two ions are practically equal Electro-chemical Behaviour of Metallic Conducting Com- pounds.G. TAMMANN (2. Elelitrochem. 1922 28 36-40).- A discussion on the electromotive behaviour of compounds which exhibit a metallic conductivity. It is shown that of the five cobalt silicides only those are attacked by acids which contain more than one atom of cobalt to one atom of silicon. In the case of thc lead palladium intermetallic compounds it is found that they have the palladium potential but if there is an excess of lead over that required for the formation of a compound in the lead palladium alloy the mixture shows the lead potential. A number of other cases are cited and discussed. Activity Coefficients and Colligative Properties of Electro- lytes. HERBERT S. HARNED ( J .Amer. Chem. Soc. 1922 44 252-267).-A theoretical paper in which on the basis of the em- pirical equation log Pa'= dc-p'c"'' (A. 1920 ii 664) which connects the activity co?fficient of an electrolyte with the molecular con- centration a t a given temperature and Duhem's equation equa- tions are derived for calculating the vapour pressures of solutions at this temperature. The validity of the above equation has been rigorously tested and it is found to hold for all electrolytes over the whole range where data were examined with the exception of sulphuric and hydrochloric acids. I n these cases it holds up to a concentration 3M. The activity coefficients of solutions of hydrochloric acid sodium chloride and potassium chloride have b.een investigated and the values of the parameters of the above equation for these electrolytes and others have been collected and tabulated from which tbe vapour pressures and osmotic pressures of their solutions may be calculated.It is suggested that the J. F. S. J. F. S.ii. 256 ABSTRACTS OE' CHEMICAL PAPER$. equation and method employed here although empirical and an approximation will prove useful in testing the consistency and accuracy of activity data and also will be of service in organising the colligative data of concentrated solutions. Ghosh's Theory of Electrolytic Solutions. CHARLES A. KRAUS ( J . Amer. Chem. Soc. 1921 43 2514-2528).-A theoretical paper in which the hypothesis of electrolytic solutions put forward by Ghosh (T. 1918,113 449 627 777 790) is discussed. Ghosh's equation expressing the conductivity of solutions of electrolytes as a function of the concentration is compared with the experi- mental values in aqueous and non-aqueous solutions.On plotting the values of log A against those of the cube root of the concentra- tion the experimental points lie on a curve which is concave toward the axis of concentration. If Ghosh's equation were applicable the points should lie on a straight line. The deviation of the points from a linear relation is consistent throughout and cannot be accounted for by errors in the original observations It is held that in its present form Ghosh's hypothesis does not satis- factorily account for the properties of solutions of electrolytes. The postulates and assumptions on which the hypothesis is based are discussed and several inconsistencies indicated.The use of Maxwell's law for the distribution of velocities and Clausius's virial J. P. S. theorem to systems of charged particles is open to serious objections J. F. S. Distribution of Thermal Energy in the Qwadrivalent Chlorides of Carbon Silicon Titanium and Tin. WENDELL M. LATIMER ( J . Amer. Chem. Soc. 1922 44 90-97).-The specific heats of carbon silicon titanium and tin tetrachlorides have been measured from the temperature of liquid air to 298" Abs. and in addition the specific heat of carbon tetrachloride was measured at still lower temperatures down to 39.1" Abs. in order to deter- mine the whole specific heat curve for these compounds. The following values of CpM/5 are recorded Carbon tetrachloride solid I 39-1" 0.60; 40.7" 0.65; 63*8" 2-05; 79.6"' 2.81 ; 91.0" 3-40; 99-5" 3-60; 199*5" 5.84; 208.0" 5-90; solid 11 229.4" 6.20 ; 235.6" 6-25 ; 238*0" 6.77 ; liquid 253-8" 6-40 ; 265-1" 6.30 ; and 290" 6.34.Silicon tetrachloride solid 77.4" 3.60 ; 86*6" 3.83; 94*8" 4-14; 131-3" 4.80; 168*6" 5-68; 181*0" 5.95; liquid 208*8" 6.74 ; 294-3" 6-94. Titanium tetrachloride solid 86*7" 4-26; 92-8" 4-40 ; 194*6" 6.19 ; 231-8" 6.31 ; 247*7" 6.21 ; liquid 251*6" 7-26 ; 294*3" 7.32. Tin tetrachloride solid 89*0" 4-59 ; 95-9" 4.71 ; 161-2" 5-89 ; 200.7" 6-33 ; 227.3" 6-62 ; liquid 266*1° 756 ; 294.0" 7-86 All temperatures are in absolute degrees. The heat of transition of solid I to solid I1 in the case of carbon tetrachloride at 224.6" Abs. is 7.10-7.19 cal./gram. The heat of fusion has been determined as follows carbon tetrachloride 4 - 1 4 .2 2 cal. /gram at 249" ; silicon tetrachloride 10.85 cal. /gram a t 203.3" ; titanium tetrachloride 11-77 cal. /gram at 248.0" and tin tetrachloride 8-38-8-42 cal. /gram qt 239.9". The entropy S298 of each of the compounds a t 298" Abs. anti the entropy changeGRNEZA TJ A NI-1 PTIYSTCATI CTIEMISTRP. ii. 25'7 in the formation A82983 of each compound from its elements have been calculated. The following values are recorded carbon tetrachloride X298 49.06 AX298 -50.84 ; silicon tetrachloridch 8298 56-43 AX29s -48.27 ; titanium tetrachloride BZg8 59.51 -47-09 ; tin tetrachloride X298 61.84 -49.66. J. F. S. Relation between Statistical Mechanics and Thermo- dynamics. RICHARD C. TOLMAN ( J .Amer. Chem. Xoc. 1922 44 75-90) .-A theoretical paper in which the relationship between statistical mechanics and thermodynamics is investigated by a method which is based like that of Boltzmann and Planck on a consideration of the arrangement of the elements or molecules of a system. Instead however of arbitrarily defining entropy by the equation X=k log W as do Planck and Boltzmann an attempt is made to discover a statistical mechanical quantity which has the same derivatives with respect to energy volume and number of molecules as does the thermodynamic quantity entropy. I n this way an expression for entropy is developed which differs from that of Planck by an additive term; it is further shown that tho addition of such a term is necessary in order that the derivative of the entropy of the system with respect to number of molecules shall have its correct value.The equation thus developed has the form S=(NE-N+)/(I' in which N is the number of molecules E has a significance defined below and T is the temperature. 111 cmnexion with the derivation of the above expression it is shown that the quantity E occurring in the Maxwell-Boltzmann dis- tribution law dN=Ce-+T dq . . . dp7& must be taken not as the energy of a molecule having co-ordinates and momenta falling in the region dq . . . dp but rather as the rate of increase in the total energy of the system per molecule added in the region dq . . . dpn when the system is in its configuration of maximum probability. These two quantities are the same for dilute gases but for concentrated systems may be quite different. Hence the new methods introduced may be of considerable importance in dealing with the properties of imperfect gas or rather concentrated systems. It is pointed out that the equations developed whicb connect the statistical mechanical quantities with thermodynamic quantities do not agree with the equations of Marcelin and Adams (A.1915 ii 328; 1921 ii 628). J. F. S. Integration of the Entropy Equation. GEORGE A. LINHART ( J . Amer. Chem. SOC. 1922 44 140-142).-Two equations are deduced which express the change of specific heat of an element or compound with the entropy. The equations are based on the assumptions that the change depends on the probability of the '' randomness " of the individual particles the certainty that particles will have a fixed position a t the point of zero kinetic energy and the zero probability that this condition persists a t high temperatures.The equations deduced are tested by means of recently published work on the specific heat of copper when a good agreement between the Relation between Entropy and Probability.ii. 258 ABSTRACTS OF CHEMICAL PAPERS. observed and calculated values of the specific heat over the range 14.61-390.0" Abs. is found. Latent Heats of Fusion. I. Benzophenone Phenol and Sulphur. (JIM.) K. STRATTON and J. R. PARTINGTON (Phil. Mag. 1922 [vi] 43 436446).-The following values of the latent heats of fusion in gram-calories per gram were measured at the melting points by electrical heating benzophenone 21-70; phenol 29.06 ; sulphur (monoclinic) 8.85.In a theoretical dis- cussion it is suggested that intramolecular vibrations as well as rotations are indicated in the case of some liquid molecules. J. F. S. J . R. P. The Freezing Points of Pure Organic Liquids as Thermo- metric Constants at Temperatures below 0". JEAN TIMMER- MANS (MLLE) H. VAN DER HORST and H. KAMERLINGH ONNES (Cmpt. rend. 1922 174 366-367).-The following organic liquids have been carefully purified and their boiling points densities and freezing points accurately determined so that these constants may be used as references by working with specimens kept in sealed tubes. All boiling points are given a t 760 mm. pressure and f . p. is the freezing point obtained under conditions where the thermo- dynamic equilibrium between the liquid and crystalline phases can be maintained for a long time to within 0.01".Carbon tetrachloride b. p. 76-75"; di 1,63255; f. p. -22.9"; chlorobenzene b. p. 132.00"; di 1.12795 ; f. p. -45.2"; chloro- form b. p. 61.2"; dj 1.52635; f. p. -63.5"; ethyl acetate b. p. 77.15"; d! 0.92450; f . p. -83.6"; toluene b. p. 110.70"; d' 0.88445; f . p. -95.1"; carbon disulphide b. p. 46.25"; di 1.29270; f . p. -111.6"; ethyl ether (stable form) b. p. 34-60"; dj0.73625; f . p. - 116.3" ; (unstable form) f. p. - 123.3" ; methylcyclohexane b. p. 100.3"; d 0.78640; f . p. -126.4"; isopentane b. p. 27.95"; dj0.63950; f . p. -159.6". W. G. Hydration of Ions. S. ASCHKENASI (2. EZektrochem. 1922 28 58-59) .-A theoretical paper in which Faj ans's treatment of the hydration of ions (Naturwiss.1921 729) is discussed and a possible connexion with the known irregularities in the vapour pressure curves of aqueous solutions of electrolytes suggested. J. F. S. A Receiver for Fractionation in a Current of Gas or under Reduced Pressure. T. S. WHEELER and E. W. BLAIR ( J . SOC. Chem. Ind. 1922 41 59-60~).-The device consists essentially of an upper and a lower receiver connected together through a two-way tap which makes the connexion alternatively with the top or bottom of the upper receiver. In the former case the vacuum is maintained in or the gas is passed through the upper and lower receivers whilst the distillate collects in the upper re- ceiver. When it is desired to collect a new fraction the two-way tap is turned into the second position and the fraction which has collected in the upper receiver passes into the lower one which is then detached another put in its place and evacuated (if neces-GENERAL AND PHYSICAL CHEMISTRY.ii. 259 sary) and the distillation continued with the two-way tap in the first position as before. If it is desired to keep the distillate out of contact with air the lower receiver is provided with inlet and outlet taps which are turned off before detaching it from the apparatus and t.he liquid thus remains enclosed in the inert atmo- sphere in which it was distilled. Comparison of the Linking of Carbon Atoms in Graphite and in Aromatic Hydrocarbons. J. P. WIBAUT (Rec. truv. chim. 1922,41,96-102).-A theoretical paper based on the work of Fajans (A.1920 ii 354) and criticising the theory put forward by von Steiger (A. 1920 ii 355) that the linking of the carbon atonis in aromatic hydrocarbons is from the point of view of energy equiva- lent to the linking in graphite. H. J. E. I. and 11. HANS BEUTLER (2. anorg. Chem. 1921 120 24-30 31-47).- I. Assumptions that periodic oscillations of melting points and boil- ing points in homologous series are due to heteropolar linking of the carbon atoms in the chain (cf. Cuy A. 1921 ii 429) are shown to be untenable on account of the non-dissociation of the carbon compounds. The heats of combustion also vary in an oscillatory manner in homologous series and this may be explained by con- sidering the lattice-energy of the crystal structure. Compounds with an even number of carbon atoms probably have a more highly symmetrical lattice than those with an odd number and as a result they have higher melting points and lower heats of combustion. Even in liquids a kind of potential lattice structure probably exists and influences the periodically varying physical properties.As the critical temperature is approached the influence of the lattice is weakened by the strong thermal forces and the differences between odd and even members of the series disappear. The electron structure of stable ions such as the C1' or SO," ion is discussed and it is shown that ion formation is due to the splitting of a compound into parts each of which has an electron structure similar to that of a noble gas with an outer shell of eight electrons. (This is identical with the Lewis-Langmuir theory to which how- ever no reference is made.) The structure of a non-dissociating substance of the type of Pt(NH,),Cl is probably such that the co-ordinated groups are attached tetrahedrally to the central atom; in the electron system the central atom is surrounded by eight electrons forming the corners of a cube four edges of which are common each to one edge of the electron cubes of one of the co-ordinated groups.The possibility of two isomerides is a t once apparent in this arrangement. 11. In the preceding section it was shown t,hat isomerism is possible in the compound of the formula Pt(NH,),Cl,; this is due to the fact that free rotation about the central Pt atom is inhibited probably by directing forces from the inner layers of electrons in the Pt atom.I n carbon compounds CR,R,R,R? free rotation is possible since only two electrons are contained within the shell of eight electrons and restraining forces are absent. The electron G. 3'. M. Atomic Linkings in the Carbon Compounds.ii. 260 ABSTRACTS OF CHEMICAL PAPERS. structures of methane its halogen substitution products ethylene acetylene and aromatic hydrocarbons are discussed. The methane molecule is represented by a central carbon nucleus surrounded by four electrons and four hydrogen nuclei arranged tetrahedrally at the eight corners of a cnhe with the other four electrons between the carbon and hydrogen nuclei. I n CH,Cl there are fourteen electrons two of which . -0 . . . are common to the eight surrounding the 0 0 0 carbon atom and the eight surrounding H ( 1 ( ’1 the chlorine atom.Diagrammatically the 0 0 0 electron structure can be represented thus o . . where the electrons of the outer shell are 11 represented by small circles. In ethylene it is supposed that the eight electrons which are not situated directly between the hydrogen and carbon nuclei revolve in an elliptical path of which the major axis is parallel to the C-C axis. The observed paramagnetism attributed to the double bond confirms this view. The electron structural formula for benzene shows three electrons between each pair of adjacent carbon atoms. In naphthalene three electrons are shown between each pair of adjacent carbon atoms except between the carbons common to both rings where there are only two.Reduc- tion to 1 4-dihydronaphthaleneY however converts one ring into a true benzene ring and a true ethylenic bond appears between t,he carbon atoms 2 and 3 in the other ring. A Method €or Measuring Vapour Densities €or the Deter- mination of Atomic Weights. A. MAGNUS and E. Scmm) (2. a72org. Chem. 1921 120 232-240).-An apparatus is described for the measurement of vapour densities the distinguishing feature of which is the total enclosure of the manometer and measuring vessel in a double-walled chamber which can be kept constant at the temperature of boiling water. The apparatus was used for determining the relation between the pressure p and pv/mT where v is the volume m the weight of the vapour and T the absolute temperature for benzene and chloroform.Contrary to the results of Ramsay and Steele the relation was found to be truly linear. The molecular weights calculated from the results are 78.096 for benzene and 119.380 for chloroform whilst the atomic weight of chlorine calculated from these is 35.455 showing that the apparatus gives results of a high degree of accuracy. Regularities in the Molecular Volumes of Inorganic Com- pounds. FR. A. HENQLEIN (2. anorg. Chem. 1921 120 77- S4).-1t was recently shown by Biltz (A. 1921 ii 437) that there is a linear relationship between the molecular volumes of the halogens and of their compounds. This is now shown to be a particular case of a more general law that the molecular volumes of certain groups of inorganic compounds of like crystalline form bear a linear relation to constant magnitudes characteristic of their kations or anions.For the halogens these magnitudes x may be expressed by the constants F‘ 0.8525 C1’ 1.000 Br’ 1.066 I’ 1.179 and I T . . r) . () . E. H. R. E. H. R.GENERAL AXD PHYSICAL CHEMISTRY. ii. 261 the magnitudes y for tlie alkali metals Li' 1.000 Na' 1.428 I<' ; 2.108 Rb' 2.478. The molecular volumes of the haloids of the allcali metals can be calculated from the general equation mol. vol. = 14.67~ . y+0.73~+56.6Sy-51.60. CEsium is abnormal in this series its constant being smaller than that of rubidium although in other series for example in the sulphates selenates manganates and chlorates it is normal. The cubic haloids of copper silver and thallium form a good series in which the following constants appear Cu' 1.00 Ag' 0.920 T1' 1.40.Hexa- gonal silver iodide does not fit in with the other cubic substances. The same law is shown t o hold lor numerous other isomorphous series containing metals of the second and fourth groups. The following density determinations were made lithium fluoride d20'4 2.597 ; sodium fluoride d?"" 2.726 ; potassium fluoride d'* ' 2.369. E. H. R. The Variation of the Mechanical Properties of Metals and Alloys at Low Temperatures. LBON GUILLET and JEAN COURNOT (Compt. rend. 1922 174 384-386).-The hardness and resilience of a number of metals and alloys have been measured a t Z O O -Zoo -80" and -190". The results show that there is in general an increase in the hardness with cooling there being a fairly big jump from the value at -80" to that a t -190".Fragility a t low temperatures is a characteristic of ferrite the rapidity of the fall in resilience as a function of the temperature being greater as the ferrite content is higher. * Nickel and copper on the other hand do not icad to fragility and aluminium if present to any great extent tends to produce a slight increase in the resilience. Pure austenitc snfficienily iich in nickel does not show fragility a t low temperatures. Special perlitic steels containing nickel have a high fragility in liquid air but the addition of nickel retards the lowering of the fragility with decrease in temperature. Measurements of hardness and resilience after a specimen has been kept for sixteen hours a t -190" and then for twenty-four hours a t +SO" give evidence of a return to normal properties a t the ordinary temperature.W. G. Surface Tension of Corresponding States. RICHARD LORENZ and W. HERZ (2. cnorg. Chem. 1922 120 320-328).-The ex- ijression ya/ye=( 1 - T,/Tk)/( 1 - Te/Tk) . ( Ve/Vk)2n is deduced. Tj/T'k and T,/Tk have been shown by Lorenz (A. 1916 ii 311) to be practically constant. According to the best average values T,/Tk=0*64 Te/Tt=0*44 (Ye/ V,)=0.855 and therefore ys/ys= 0.578. This was tested on results obtained by Jaeger (A. 1917 ii 33) and figures are given for 89 organic compounds. The average value for ?/3/Ye was found to be 0.52 75% of compounds agreeing very closely. Twenty-one inorganic compounds of known boiling points gave an average for ys/ye=0-58. Assuming ys/ye= 0.578 the authors have calculated the boiling points of several salts.The higher the critical temperature the further does ys/ye deviate from the mean. t W. T.ii. 262 ABSTRACTS OF CHEMICAL PAPERS. Surface Tension of Aqueous Solutions of Night-blue. R. DE IZAGUIRRE (Anal. 2%. Quim. 1922 20 40-55; cf. Traube A. 1912 ii 740 74Z).-The surface tension of aqueous solutions of night- blue of varying concentrations and with the addition of different electrolytes was investigated by means of the stalagmo- meter. The increase of surface tension with concentration is fairly rapid at first but then slows down. I n the experiments with addition of electrolytes i t T V ~ found that an abrupt fall in surface tension to that for pure water took place a t the point where coagul- ation of the solution occurred.The coagulating power of various ions can thus be studied by means of the stalagmometer. Other physical properties including the aspect under the ultramicroscope do not show this abrupt change a t the point of coagulation. Solu- tions purified by dialysis give results analogous to those obtained with unpurified material but the stability of the solutions obtained is less since smaller concentrations of salts are necessary for coagulation. G. W. R. Theory of Adsorption Processes. A. EUCKEN (Z. Elebro- chem. 1922 28 6-16).-A4 theoretical paper in which the process of physical absorption is considered. By physical adsorption is understood that adsorption for example of argon by charcoal where it is unlikely that the adsorbed molecules are held by the attrac- tJions of chemical forces.It is shown that the adsorption forces are similar to the forces which are responsible for condensation phenomena. They are practically independent of the temperaturc and are operative over a relatively small distance which is of the same order as the molecular radius. J. F. S. Adsorption of Ammonia by Silica Gel. L. Y. DAVIDHEISER and W. A. PATRICK (J. Amer. Chem. Xoc. 1922 44 1-8).-A continuation of previous work (A 1920 ii 417). The adsorption of ammonia by silica gels containing respectively 4.98% and 0.33y0 of water has been determined for a series of pressures a t O" 30" 40° and 100". A smaller amount of ammonia is adsorbed by the less hydrated gel than by thc more hydrated compound although the less hydrated gel is still capable of adsorbing large amounts of ammonia.It is shown that the adsorption of ammonia may bc satisfactorily explained on the basis of capillary condensation provided corrections are made for the amount of gas which dissolves in the water. Adsorption by Precipitates. V. Adsorption during the Precipitation of Colloids by Mixtures of Electrolytes. HARRY B. WEISER ( J . Physical Chem. 1921 25 665-683; cf. A. 1919 ii 269 ; 1920 ii 228 ; 1921 ii 625).-The precipitation of colloidal ferric hydroxide and colloidal arsenious sulphide by the simul- taneous addition of pairs of electrolytes and the adsorption of ions during the precipitation of the colloids by mixtures of electro- lytes have been investigated. The precipitation experiments were carried out with pairs of the electrolytes potassium chloride J.I?. 8.GENERAL AND PHYSICAL CHEMISTRY. ii. 263 barium chloride strontium chloride potassium oxalate potassium sulphate and potassium bromate. The adsorption of the oxalate ion in the presence of the chloride and sulphate ion respectively and the barium ion in the presence of tlhe potassium ion was investi- gated. It is shown that the precipitating action of mixtures of pairs of electrolytes is approximately additive if the precipitating power of each is of the same order of magnitude but may be far from additive if the electrolytes have widely varying precipitating power. In the latter case the action of the electrolytes is antagon- istic in the sense that relatively more of each is necessary than if the other were absent.In the simultaneous adsorption by solids from mixtures of two electrolytes having no common ion the most strongly adsorbed kation and anion are taken up most and the other pair least readily; from mixtures having one common ion the oppositely charged ions are each adsorbed less than if the other were absent but the most readily adsorbed ion is displaced the least. Factors which influence the precipitating action of mixtures of electrolytes are the effect of the presence of each precipitating ion on the adsorption of the other and the stabilising action of the ions with the same charge as the colloid. The second factor is of minor importance with mixtures of electrolytes that have similar precipitation values and have stabilising ions in common.The precipitating action of mixtures of electrolytes with similar precipitating power is additive since the adsorption of the pre- cipitating ions is similar and consequently the adsorption of each is affected but slightly by the presence of the ot'her within the limits of the precipitation concentration With mixtures of electro- lytes of widely varying precipitating power the precipitating action rnay be approximately additive when the influence of both factors mentioned above is small but may be far from additive when the influence of both factors is large. These extreme cases are realised experimentally. J. F. S. Use of the Water Interferometer as a Pressure Gauge. L. VAN DOREN H. K. PARKER and P. LOTZ ( J . Amer. Chem. SOC. 1921 43 2497-2501).-The Zeiss water interferometer can be modified so as to serve as a pressure gauge.The modification consists in replacing the two water cells by two brass cells fitted wifh stout plate glass windows a t the ends. One cell is filled with water a t atmospheric pressure and the other with water under pressure. On calibrating the instrument it was found that pressures up to sixty atmospheres could be measured. The range of the instrument may be increased by inserting a thin glass plate in the path of the beam passing through the non-pressure chamber of such a thickness that it will compensate for a pressure of sixty atmospheres in the other chamber. Thus by means of a series of glass plates of different thickness the range of the instrument can be extended to almost any pressure.In the calibration of the instrument for pressures up to 270 atmospheres a t 20" and 30" it is found that a t the higher temperataure the effect of increased pressure on the refractive index diminishes. J. F. S.ii. 264 ABSTRACTS OF CHEMICAL PAPERS. Osmotic Pressures of Concentrated Solutions of Sucrose as Determined by the Water Interferometer. PAUL LOTZ and J. C. W. FRAZER ( J . Amer. C'hem. Soc. 1921,43 2501-2507). -The authors describe a modification of the method used by Frazer and Myrick for measuring the osmotic pressure (A. 1916 ii 603). The principal feature of the new apparatus is the use of the water interferometer (preceding abstract) for determin- ing the magnitude of the pressures developed. The apparatus is a decided improvement on that of Frazer and Myrick being more rapid in action and more trustworthy. Pressures up to 273 atmospheres have been measured but the instrument has been calibrated up to 330 atmospheres.Pressure measurements are recorded for sucrose solutions of concentrations up to saturated solutions a t 30" and 55.7". Attention is directed to the results of Woods as calculated for vapour-pressure measurements and it is shown that his results (Trans. Paraday Xoc. 1915 11 29) show- ing a decrease in osmotic pressure with rise in temperature in concentrated solutions are relatively correct although his actual values for the osmotic pressure appear to be high when compared with these direct measurements. System Ammonia-Water as a Basis for a Theory of the Solution of Gases in Liquids. BENJAMIN S.NEUHAUSEN and W. A. PATRICK ( J . Physical Chem. 1921 25 693-720).-A static method has been developed for measuring the partial pressure of a component of a liquid mixture which has a very small partial pressure compared with that of the second component. This method has been used to determine the partial pressures of water and ammonia solutions a t 0" Z O O and 40" a t partial pressures of ammonia varying from 1000 mm. to 4000 mm. The measurements in the case of ammonia are made to 2-4 mm. and in the case of water to 0.08 mm. The solubility of ammonia in water was deter- mined at 0" Z O O and 40" a t pressures from 750 mm. to 3600 mm. and the densities of the saturated solutions were also measured. A theory of the nature of solutions of gases in liquids first advanced by Graham has been amplified and solutions of various gases in liquids classified on the basis of some of the physical and chemical properties of the gas.The formula V=K(Pu/P,)"" has been found to represent the solubility of ammonia hydrogen chloride sulphur dioxide and carbon dioxide in water a t various tempera- tures and pressures. In this formula V is the volume occupied by the liquefied gas dissolved per gram of water Po is the vapour pressure and (+ the surface tension of the liquefied gas a t the tern- perature whilst P is the equilibrium gas pressure. The constant K for ammonia has value 0.49 and l / n the value 0.69. The solubility data of hydrogen chloride sulphur dioxide and carbon dioxide have been plotted according to this formula.Change of State of Aggregation and Polymorphism. KARL SCHAUM (2. anorg. Chem. 1921 120 241-260).-The assumption of Ostwald that there is SL relatively broad region of metastability below the normal melting point in which spontaneous crystallisation J. F. S. J. P. 8.GENERAL AND PHYSICAL UHEMISTRY. ii. 265 is impossible appears unnecessary. On the other hand it is highly improbable that in a small quantity of liquid in a limited time the necessary number of molecules in the correct space-lattice orientation to form a nucleus in equilibrium with the liquid at a given temperature will ever come together. It is reasonable to assume with Ostwald the existence of “ anisotropic ” molecules but these cannot alone have a “ resonance ’’ effect on other “ iso- tropic ” molecules and so cause crystallisation.The ageing of a liquid by keeping it some time above its melting point whereby the tendency to supercooling is increased is doubtless due to the change of anisotropic molecules into the isotropic form. Aniso- tropic molecules probably become associated with one another to form space-lattice fragments and when a crowd of these come together they may cause a field of force strong enough to bring about the formation of a crystal nucleus. As the temperature falls this process is facilitated through the slowing down of trans- latory and rotatory motion but on the other hand the probability of the crowding together of anisotropic molecules and space-lattice fragments is lessened. [With ELLI RIFFERT.]-T~~ crystallisation process is investi- gated statistically by counting the number of nuclei formed when a thin film of liquid is allowed to crystallise between microscope slide and cover-glass under different conditions.A large number of organic substances were used for the purpose. There is a strong tendency for the nuclei to form in the outer zone of the cover- glass particularly a t the edge and sometimes they will form again and again a t a particular spot. The tendency to nuclei formation a t boundary surfaces especially a triple boundary such as air- glass-liquid is probably a surface tension phenomenon. The number of nuclei formed increases as the temperature is lowered finally reaching a maximum. I n these experiments the melted substance was brought suddenly down to the temperature at which the nuclei were to be formed.Pressure may cause the develop- ment of nuclei. The substances examined (about 200) fall into five different types according to the manner in which they crystal- lise ; the states of aggregation assumed by crystallisation from nnclei are described as radiating bunching star-like tabular and mosaic. E. H. R. The K Doublet with New Determinations of the Lattice Constants of some Crystals. WALTHER GERLACH (Physikul. Z . 1922 23 114-120).-When a somewhat coarse powder is used in the Debye-Scherrer method the K lines appear double. A method for the measurement of the fine structure of R’ontgen lines is described. The lattice constants in 10-8 em. of the follow- ing crystals were determined silicon (identical within the limit: of error with “ amorphous,” graphitoidal and crystalline silicon) 5.415 (&0*3y,) with copper radiation 5,410 ( &0.3y0) with nickel radiation ; regular zinc blende 5.390 ( *0.3~0) with copper radiation ; calcium fluoride 5.455 (rt0.1 yo) with copper radiation ; 5.478 (-_t0*2O/,) with nickel radiation.The doublet distance Kna-a,ii. 266 ABSTRACTS OF CHEMICAL PAPERS. was determined with an accuracy of about 3% as 3-842 X.U. (1 " X-Unit "=10-11 cm.) for copper and 3.772 X.U. for nickel. Bragg's model for fluorite was confirmed. J. R. P. Freezing of Hydrosols. A. LOTTERMOSER (KoEZoid Z. 1922 30 133).-A complaint that Gutbier (this vol. ii 142) has used the author's statements in connexion with the influence of freezing on sols in a manner opposite to that which the author ha.s intended.This has arisen because the author's statements have not been understood in the sense demanded by the context. J. P. S. Influence of the Concentration of Colloids on their Pre- cipitation by Electrolytes. HARRY B. WEISER and HENRY 0. NICHOLAS (J. Physical Chem. 1921 25 742-757).-The precipit- ation of colloidal chromic oxide Prussian blue ferric oxide and arsenious sulphide of various concentrations by electrolytes with precipitating ions of different valency has been investigated. With colloidal chromic oxide Prussian blue and ferric oxide the pre- cipitating values of all electrolytes decrease as the concentration of the colloid decreases irrespective of the valency of the pre- cipitating ion; but the decrease is least marked with electrolytes having univalent precipitating ions.With colloidal arsenious sulphide the precipitating value of electrolytes with univalent precipitating ions increases as the concentration of the colloid is decreased. The manner in which the precipitation value of an electrolyte varies with the concentration of colloid is determined to a large extent by the relative adsorbability of the precipitating ion and the stabilising ion. If the adsorption of the stabilising ion of an electrolyte is negligible and the adsorption of the pre- cipitating ion is very large the precipitation value vanes almost directly with the concentration of the colloid. This condition may be realised experimentally with electrolytes which have tervalent and quadrivalent ions which precipitate in extremely low concentration.If the adsorption of the stabilising ion of an electrolyte is appreciable the precipitating value is increased. This effect is more pronounced the greater the dilution of the colloid since the decreased opportunity both for the collision and the coalescence of particles combines to render t,he colloid propor- tionately more stable so that relatively more of the precipitating ion must be added for complete coagulation. The influence of adsorption of the stabilising ion is more marked with electrolytes having univalent precipitating ions which precipitate only in very high concentration. Under these conditions the precipitation value decreases much less sharply than under the conditions obtain- ing when the stabilising ion is only slightly adsorbed and may even increase as the concentration of the colloid is decreased.The laws put forward by Burton and Bishop (A. 1921 ii 176) in con- nexion with the variation in the coagulative power of ions with the concentration of the disperse phase are shown to be quite limited in their applicability. The hypothesis of Kruyt and van der Spek (A. 1919 ii 498) on the nature of the process of coaglzl-GENERAL AND PHYSICAL CHEMISTRY. ii 267 ation is inadequate since it fails to take into account the influence of the stabilising ions of electrolytes. Relation of Anomalous Osmosis to the Swelling of Colloidal Material. F. E. BARTELL and L. B. SIMS ( J . Amer. Chem. XOC. 1922 44 289-299).-The authors discuss some seven hypotheses put forward .previously to account for the swelling of colloids and find none of them is applicable to all cases of swelling.The relationship of the swelling of gels to the osmotic effects is con- sidered and as a working hypothesis it is assumed that a gel may be considered as composed essentially of a framework of membranes and that the hypothesis which accounts for the flow of a liquid through membranes also accounts to a certain extent for the f l o ~ of n solution into a cellular gel. The view is held that swelling is the result of imbibition together with the operation of effects which produce anomalous osmosis. It would therefore follow tlhat in swelling the tendency for normal osmosis is always operative solution in the membrane may take place in some instances forces of attraction and repulsion are operative capillarity plays a part negative or positive adsorption of solute may have an effect electrical effects due to electrical orientation of the system may enter in and swelling unaccompanied by electrical effects may occur as with solutions of non-electrolytes with some gels. For the purpose of comparing anomalous osmotic effects with swelling effects a series of osmotic pressures using parchment membranes and a series of swelling experiments using Laminaria have been carried out with solutions of potassium citrate (0*05111) sodium hydroxide (O*OOOlAT) hydrochloric acid (0*0001N) and aluminium chloride (0.05M).The results show that those solutions which exhibit IL negative osmotic tendency with parchment produce a swelling effect with Laminaria and those which have a positive osmotic tendency produce a shrinking of the Laminaria.A further series of experiments with solutions of various electrolytes of several concentrations confirms the foregoing results. In all cases the osmosis-concentration curves have the exactly opposite form to those of the concentration-swelling curves. J. F. S. Lecture Experiment. Protective Colloids. J. NEWTON FRIEND (ATalzcre 1922 109 341).-It appears to be a general law that protective colloids or organic emulsoids tend to retard the velocities of such reactions whether chemical or physical as involve a change of state in one or more of the components. Examples of such retardation the rate of which conforms in many cases to the requirements of the adsorption law are to be found in the solution of metals in acids corrosion in neutral media solution and precipitation of salts and replacement of one metal by another.An illustration is afforded by the precipitation of mercuric iodide from solutions of mercuric chloride and potassium iodide the unstable yellow form first precipitated ordinarily turning rapidly into the more stable red variety. In the presence however of 1 yo of gelatin after a momentary formation of colloidal mercuric iodide a fine canary-yellow precipitate is produced and remains J. F. S.ii. 268 ABSTRACTS OF CHEMICAL PAPERS. practically unchanged for half an hour or niorc. The slow change to the red variety is markedly accelerated by sunlight. A. A. E. Pure Aniline and Water Emulsions. SHANTI SWARUPA BHATNAGAR ( J .Physical Chem. 1921 25 735-741).-The rate of coagulation of aniline-water emulsions by potassium chloride sodium chloride and sulphate barium strontium chromium and aluminium sulphates has been investigated a t 46". The results show that in general the precipitating power of electrolytes is the same as in the case of many sols tervalent ions being more effective than bivalent ions and these more so than univalent ions. The order of the precipitating efficiency of the kations is given as Al>Cr>Ba>Sr>K>Na. The effect of dilution on tho emulsions is t o increase the time required for precipitation; thus an emulsion which is normally precipitated in ten minutes by barium chloride requires eighteen minutes seven seconds when diluted by an equal volume of water saturated with aniline and when again diluted by the same volume of saturated water forty minutes.J. F. S. R. T. A. MEES (Chem.' WeekbZaad 1922 19 82-85).-The conception of Martin Vischer of a soap solution as a two-phase system is inadequate since i t does not exclude other gels for example gelatin solutions. Similarly the orientation theory of Langmuir and Harkins does not exclude other substances possessing polarity within the mole- cule. The unique power of soap solutions to stabilise emulsions can be explained by combining the tJwo theories since only soaps have the necessary polar character within the molecule without at the same time having molecules soluble as such in oil and water. A soap such as sodium palmitate has the reactive sodium ion which tends to confer solubility in water opposed within the molecule to the inert saturated carbon-hydrogen chain which t>ends to confer solubility in oily substances. When such n soap is intimately admixed with an oily substance and water it forms a bounding layer between the particles of each its molecules being orientated with the sodium ion towards the water the carbon- hydrogen chain towards the oil acting as a layer possessing polar solubilities ; in such a system surface tension disappears.Earthy impurities such as clays resemble soaps in stabilisirlg water-oil emulsions being lyophil towards both ; in presence of soap solution they are adsorbed by the latter in the bounding surfaces between the particles of oily matter and ~ a t e r .The detergent power of soaps is therefore primarily a chemical property due to the polarity of molecules insoluble as such in oil HARRY N. HOLMES and DON I€. CAMERON ( J . Amer. C'hem. SOC. 1922 4-4 (;Ct-'70).-The use of celhdose nitrate as an emulsifying agent has been studied. It is shown that this substance serves as an excel- lent emulsifying agent in dispersing water or glycerol throughout The Detergent Power of Soap Solutions. and water. s. I. 1,. Cellulose Nitrate as an Emulsifying Agent.GENERAL AND PHYElICAL OHEMISTRY. ii. 269 amyl acetate acetone or other solvents for the nitrate. Visible concentration films of cellulose nitrate were observed round large drops of water emulsified in amyl acetate-benzene mixtures. An increase in concentration of cellulose nitrate at the acetone- glycerol interface was observed and studied quantitatively.The properties of an ideal emulsifying film are discussed. Chromatic Emulsions. HARRY N. HOLMES and DON H. CAMERON ( J . Amer. Chem. Xoc. 1922 44 71-74).-Two immis- cible liquids can be emulsified with suitable emulsifying agents such as cellulose nitrate to produce a transparent emulsion when the refractive index of the two phases is the same and when the dispersive pon.cr (np-nc) of the two phases is the same. A chromatic (structural colour) emulsion is produced when the refractive index of both phases is the same and the dispersive power of one phase is much greater than that of the other phase. The greater the difference the more intense the resulting colour. J.F. S. J. F. S. Application of Statistics to Chemical Equilibria. K. F. HERZFELD (Physikal. Z. 1922 23 95-100 ; cf. A. 1921 ii 313).- Statistical principles have been applied to chemical equilibria in connexion with polymorphic substances and equilibria in gaseous systems a t low temperatures and at high temperatures. A reason is advanced for the good agreement found between experimental results and those calculated by the Mernst approximation formula and it is shown to be probable that the conventional chemical constant is always about 3. CHARLES A. KRAUS ( J . Amer. Chem. Soc. 1921 43 2507-2514).-A theoretical paper in which it is shown Chat the isohydric principle when applied to mixtures of electrolytes leads to a functional relationship of the form (Ci)2/Cu=F(SCi) in which C is the con- centration of the undissociated fraction Ci the ion concentration SCi the sum of the concentrations of all the negative and positive ions in the solution and F(8Ci) any explicit function of the total ion concentration of the solution.As the concentration of the second electrolyte diminishes the function Pi/C,=F(P,) in which Pi is the ion product reduces in the limit to the same form as the function resulting from the isohydric principle. The values of the specific conductivity of mixtures of sodium chloride and hydrochloric acid as calculated according to this principle are shown to furnish a better agreement with the measured values than are those on the isohydric principle. Partition of Chlorine between Water and a Gaseous Phase.W. S. TITOV (Nachr. Physik.-chem. Lab. Semsoinse's 1917 102-110 ; from Chem. Zentr. 1921 iii 1222).-The partition of chlorine at 20° between water and air. containing this gas is given by the formula (y- 1*748)3x2= (72.52)3 where x is the volume of chlorine per thousand volumes of air and y is the volume dissolved in the water under the corresponding partial pressure. For example J. F. S Equilibrium in Mixtures of Binary Electrolytes. J. F. S.ii. 270 ABSTRACTS OF CHEMICAL PAPERS. when x=10 parts per thousand y=74.27 under a partial pressure of 7.6 mm. Nature of Secondary Valency. 111. Partition Coefficients in the System Water-Ethyl Ether. HOMER W. SMITH (J. l'hysicnl Chem. 1921 25 605-615 616-627; cf. A. 1921 ii 316 324).-1n the first paper details are given of the determination of the partition coefficient of forty-nine organic acids and fifteen organic bases a t 23" in the system water-ethyl ether.The results obtained from a comparative treatment of these partition coefficients in terms of molecular volume are in good agreement with the results obtained previously (Eoc. cit.) in the systems water-xylene and water-chloroform. The results are discussed in connexion with the principles laid down in previous papers. The second paper is a supplementary note on the method of correction employed in the earlier papers. Corrected values for the partition of chloro- acetic acid in the system water-chloroform and for a number of organic acids and bases in the systems water-ether are given. G. W. R. J. F. S. Nature of Secondary Valency.IV. Partition Coefficients in the System Glycerol-Acetone. HOMER W. SMITH ( J . Physical C'hern. 1921 25 721-734 ; cf. preceding abstract).- The partition coefficients of fifty acids amines and amine acid phthalates have been determined in the system acetone- glycerol. The present results are in excellent agreement with those obtained in the systems previously investigated (Zoc. cit.). In the present series of experiments a fact which has not been observed previously is noted namely that under certain conditions concerning the nature of the solvents and the solutes a solute is not distributed but is concentrated entirely in one or other of the solvents. The series constants for the acids and amines have the same absolute value in this system as contrasted with the different values found in systems containing water as one solvent.Of the substances examined in the system glycerol- acetone benzilic acid benzoic acid a p-dibromopropionic acid 2 4dinitrobenzoic acid diieobutylarnine salicylic acid 2 4 6- trinitrobenzoic acid and n-valeric acid pass completely into the acetone layer. J. F. S. Equilibrium in the Reaction between Sulphur Dioxide and Water. F. RUSSELL BICHOWSKY ( J . Amer. Chem. SOC. 1922 44 116-132).-The reactions between liquid sulphur and aqueous sulphuric acid have been investigated over a wide range of conditions. At low concentrations of sulphuric acid two reactions occur simultaneously namely (1) S(,,)+BH,SO,(aq)- 2H,O(iiq) + 3S0 (gas) and ( 2 ) 4S(h,).+ 4H,O (11s) = 3H,S(gas) -t- H,SO,(aq).Both reactions are reversible. In the acids of a greater molecular fraction than 0.06 and a t temperatures up to the critical temperature of water the second reaction becomes negligible. Equilibrium pressures for the first reaction have been measured for acids of molecular fractions ranging from 0.041 toGENERAL AND PHYSICAL CHEMISTRY. ii. 271 0.363 and a t temperatures from 527" Abs. to 613" Abs. using an apparatus of a new type. The vapour pressures of sulphuric acid of various concentrations have been measured. Using these and other existing data the free energy for the reaction &A)+ 2H,SO,(dl) =2H2O(gas)+3SO,(gas) has been calculated to be 31500 cal. a t 25" and standard conditions. From the data the free energy of both aqueous sulphuric acid and sulphur dioxide may he calculated. A new type of apparatus for measuring equilibrium or vapour pressures of corrosive liquids up to high pressures and temperatures is described.This consists of a quartz tube contained in a mercury-filled steel bomb which communicates with a pressure gauge. The quartz tube is constructed so tha,t the material is contained in a chamber at the top; this communi- cates through a quartz capillary with a second chamber filled with mercury which is in contact with the mercury in the steel jacket. The upper part of the bomb only is heated. Equilibria in the Systems Carbon Disulphide-Methyl Alcohol and Carbon Disulphide-Ethyl Alcohol. E. C. MCKELVY and D. H. SIMPSON (J. Amer. Chem. Soc. 1922 44 105-1 15) .-The temperature of complete mutual miscibility of mixtures of carbon disulphide with ethyl and methyl alcohols respectively have been determined. The critical solution tem- perature of the system carbon disulphide-methyl alcohol is 35.7 O and the critical concentration is about 85% of carbon disulphide ; solid methyl alcohol separates from the layer rich in alcohol at -99.6". The critical solution temperature of the system carbon disulphide-ethyl alcohol is -24.4" and the critical concentration about 83yh by weight of carbon disulphide.All mixtures freeze at -111.7". It is shown that the critical solution temperature offers an extremely sensitive criterion of the purity or changes of purity of either component provided that the other component is either pure or of constant composition. Distillation of carbon disulphide from ceresin is shown to remove the impurities and yield a perfectly pure product.The Quaternary System Ammonium Chloride-Sodium Sulphate-Ammonium Sulphate-Sodium Chloride-Wat er . Induction Periods in Reactions between Thiosulphate and Arsenite or Arsenate. A Useful Clock Reaction. GEORGE SHANNON FORBES HOWARD WILMOT ESTILL and OSMAN JAMES WALKER ( J . Amer. Chem. SOC. 1922 44 97-102).-The precipita- tion of arsenious sulphide from an acidified solution (acetic acid) containing sodium thiosulphate and arsenite is preceded by an exceedingly sharp and reproducible induction period. The duration of the induction period is strictly in inverse proportion to the concentration of thiosulphate and is practically independent of the concentration of the arsenite or the acetic acid.Hy&ochloric acid prolongs the induction periods and is much better for experi- mental demonstration of induction periods of the relationship J. I?. S. J. F. S. ALBERT CHERBURY DAVID RNETT (T. 1922 121 379-393).ii. 272 ABSTRBCTS OF CHEMICAL PAPERS. between concentration and reaction velocity and of the temperature coefficient of the reaction velocity than the familiar sulphurous acid and iodate reaction. The prolongation of the periods by strong acids the limiting concentrations yielding precipitates when arsenates are used and the speed of precipitation were also investigated. J. F. S. The Combustion of Complex Gaseous Mixtures. WILLIAM PAYMAN and RICHARD VERNON WHEELER (T. 1922 121 363- 379). Oxidation of Nitric Oxide and its Catalysis.CHARLES LALOR BURDICK ( J . Amer. Chem. SOC. 1922 44 244-251).- The rate of oxidation of nitric oxide by oxygen in the presence of glass pumice pumice impregnated with tungstic acid nickel oxide cobalt oxide nickel cobalt and manganese dioxide platinised pumice platinised asbestos coke charcoal and coconut charcoal has been investigated at temperatures from 0" to 100". It is shown that the reaction 2NO+0,=2N02 is not catalysed by ordinary porous material either impregnated or unimpregnated but that in the presence of the highly absorptive forms of carbon or charcoal the rate of the reaction may be accelerated as much as five hundred times. The presence of water vapour in the gaseous mixtures greatly decreases the activity of the charcoal catalysts.Increase of temperature above the poinZl at which the aqueous vapour condenses counteracts this effect to some extent. The temperature coefficient of the velocity of reaction for both the catalysed and uncatalyQed change is generally negative. In the presence of water vapour the temperature coefficient of the catalysed reaction is apparently positive. This is probably due to the decreased absorption of water by the catalyst at elevated tern- peratures J. F. S. The Transformation of Ammonia into Carbamide. C. MATIGNON and M. FR~JACQUES (Comp?. rend. 1922 174 455- 457; cf. A. 1921 ii 33).-In continuation of previous work (Zoc. cit.) the yields of carbamide from ammonium carbamate at the equilibrium point at different temperatures are given. Applying the law of mass action to the system in equilibrium the authors calculate the heat of the reaction to be -6 cal.the experimental value being -7.7. The progress of the reaction with time at different temperatures from 130" to 145" has been studied. The curves indicate that the water formed has an effect on the velocity of the reaction. The effect of certain catalysts such as thorium oxide aluminium oxide kaolin etc. has been examined. The results indicate that whilst they may accelerate the reaction at low temperatures they are without benefit at about 150". The Processes NH,*@O*ONH,+H,O GS= (NH,),CO and CO,+H,O =+ SCO,. CARL FAURHOLT (2. anorg. Chenz. 1921 120 85-102) .-Experiments on the velocity of the conversion of ammonium carbamate into carbonate indicated that the reaction proceeded first with liberation of carbon dioxide and this con- W.G.GENERAL AND PHYSICAL CHEMISTRY. ii. 273 elusion was confirmed by an investigation of the velocity of the reaction CO,+H,O =+= H,CO,. A new method was devised for estimating the proportion of hydrated carbon dioxide that is of carbonic acid in a solution of the gas. When an aqueous solu- tion of carbon dioxide is added to a large excess of ammonia the anhydrous carbon dioxide immediately forms carbamate which is so stable in the concentrated ammonia that there is time to pre- cipitate the carbonate as barium carbonate filter wash and titrate it. By this method the dissociation constant of carbonic acid to Hf+HCO,- was found to be against to found by Thiel and Strohecker (A. 1914 ii 361).This method was applied to making approximate determinations of the velocity of hydration of carbon dioxide in solutions of sodium hydroxide sodium carbonate and mixtures of carbonate and hydrogen car- bonate. At 0" hydration is immediate in sodium hydroxide solu- tion but in a solution containing Na,CO, NaHCO in the ratio 6 4 only 77% of the carbon dioxide added is hydrated in the first eighty seconds. Hydration is thirteen times as rapid a t 18" as at 0". Velocity of hydration is inversely proportional to hydrogen-ion concentration. By strong acids carbonic acid is immediately dehydrated but by weak acids much more slowly. The same method of analysis was used for investigating the decomposition of ammonium carbamate in acid aqueous ammon- iacal and alkaline solution.Before analysis the solutions were made alkaline with 0.1N sodium hydroxide to stabilise the carbamate. I n aqueous solutions containing ammonia and ammonium chloride the proportion of carbamate present a t equilibrium increases with the concentration of either. The equilibrium constant for the reaction NH,*CO-O- +H,O e HCO,- +NH a t 0" had an average value of about 0.34. By even very weak acids carbamate is immediately decomposed. On adding alkali again however some carbamate is re-formed since two reactions proceed simultane- ously with nearly the same velocity carbamate being formed from ammonia and carbon dioxide and carbonate from carbonic acid which is formed at once by hydration of part of the carbon dioxide by the alkali added. I n a 0-05 mol.solution of carbamate in water a t 0" equilibrium is reached in about a day; in a 0-1N-ammonia solution three days are required in a O.4N-ammonia solution ten days; at 18" the reaction is twenty times as fast. I n sodium hydroxide solution the reaction is much slower requiring about three days in a 0.1N- solution and a month in a 1-ON-solution at 18". E. H. R. The Velocity of Formation of Barium Peroxide. NOBUJI SASAKI (Mem. CoZZ. Xci. Kyoto 1921 5 9-96).-For the investiga- tion of the velocity of formation of barium peroxide from barium oxide and oxygen at high temperatures 400-625" a special balance was devised so constructed that the specimen under examination could be weighed a t any time being suspended from one arm of the balance which was totally enclosed and operated from outside by means of magnets.A new type of gas washer was also devised. VOL. CXXII. ii. 10ii. 274 ABSTRACTS OF CHEMICAL PAPERS. It consists of a U-tube of glass one arm being narrow and the other expanded into an elongated bulb. The two arms are bridged by a narrow glass spiral in such a manner that the gases entering by the narrow arm bubble through the liquid in the spiral and escape a t the top of the wide arm which acts as a reservoir for the washing liquid. The velocity curves for the formation of barium peroxide were of an unusual form. The greater part of the paper is devoted to a mathematical analysis of these curves and it is shown that they may be explained on the assumption that the oxide consists of a great number of very small equal spherical particles which begin to react one after another the number of spheres becoming active in unit time being proportional to the quantity of peroxide already formed. The Influence of Protective Colloids on the Corrosion of Metals and on the Velocity of Chemical and Physical Change.JOHN ALBERT NEWTON FRIEND and REECE HENRY VALLANCE (T. 1922,121 4 6 M 7 4 ) . Influence of Temperature on Two Alternative Modes of De- composition of Formic Acid. C. N. HINSHELWOOD H. HARTLEY and B. TOPLEY (Proc. Roy. Soc. 1922 [A] 100 575-581).-The thermal decomposition of formic acid has been investigated a t 283" and from the results an hypothesis has been formulated in con- nexion with the mechanism of the reaction. Sabatier and Mailhe (A. 1911 i 515) have shown that formic acid may decompose according to the equations (a) H*C02H=C02+H2 ( b ) H*C02H= CO+H20 and ( c ) 2H*CO2H=H*CHO+CO2+H,0. Assuming that in the decomposition certain molecules are activated either by collision with other molecules or by the absorption of quanta of radiation the question arises whether every molecule which possesses the necessary critical energy reacts a t once or whether in addition to possessing this it must be in a certain phase.Under the con- ditions of the experiments described only reactions a and b come into consideration. If El and E2 are the critical energies for the two alternative reactions and N is the total number of molecules it follows from the kinetic theory that the number of molecules pos- sessing these respective energies are N 1 = N ~ - E J R T and N 2 = N ~ - B a / R T taking the system as of two degrees of freedom.Then N1/N2= c-(E~-EJIRT so that if one mode of reaction is associated with a slightly lower critical energy it would predominate very largely if the number of active molecules were the only factor. Actually it is found that although the two alternative modes of decom- position of formic acid proceed with the same velocity yet the critical increments are so different that one reaction should pre- dominate almost entirely unless a phase restriction is introduced and an interpretation of the phase factor is suggested for this case as follows. The critical increments for the two reactions are calculated to Eco= 16000 cal./mol. and Eco,=28000 cal./mol. The numbers of molecules activated for the two reactions are proportional to ~-280001RT and ~-16000/R~ respectively that is about d o molecules should yield carbon monoxide for one yielding the E.H. R.QENERAL AND PHYSICAL CHEMISTRY. ii. 275 dioxide but since the rates of both reactions are identical a phase restriction must govern the reaction yielding the monoxide. If the formic acid molecule is assumed to be adsorbed on the glass surface by the residual affinity of the carbonyl group then in the case of a sufficiently activated molecule a violent collision between the hydrogen- and hydroxyl-groups may occur and a molecule of hydrogen be split off. Although the requisite degree of activation may be attained but rarely nevertheless a high percentage of these collisions in activated molecules may result in this type of decomposition. On the other hand for water to bc eliminated and carbon monoxide left a high degree of activation is not necessary possibly since the removal of a hydroxyl group as a whole from an organic compound is a much less profound change than the fission of the hydrogen and oxygen but very few of the activated molecules may decompose because it is necessary to await the contingency that the forces holding the hydroxyl and hydrogen to the carbon should be weak enough to allow the simultaneous " uncoupling " of the molecule.The Replacement of Halogen in 4-Chloro-3-nitrobenzo- nitrile and in 4Bromo-3-nitrobenzonitrile. 11. T. J. F. MATTAAR (Rec. trav. chim. 1922 41 103-111; cf. this vol. i 251; also Conrad Hecht and Briickner A.1890 4 327 and 1046 ; A. l891,796).-1n order to measure the effect of the cyanogen group on the replacement of halogen the velocity of reaction of 1 - c hloro -2 4 - dinitro benzene 4- chloro -3 -nitro benzonitrile 1 - bromo - 2 4-dinitrobenzene and 4-bromo-3-nitrobenzonitrile with sodium methoxide with sodium ethoxide and with sodium phenoxide in both ethyl alcohol and methyl alcohol solution has been investi- gated. The following conclusions are drawn (1) the halogen atom is more active in the substituted dinitrobenzene than in the substituted nitrobenzonitrile (2) chlorine is more reactive than bromine in corresponding compounds (3) sodium ethoxide reacts more quickly than sodium methoxide (4) the reaction in ethyl alcohol takes place about twice as quickly as that in methyl alcohol.The Effect of Temperature and the Concentration of Hydro- gen Ions on the Rate of Destruction of Antiscorbutic Vitamin (Vitamin-C). V. K. LAMER H. L. CAMPBELL and H. C. SHER- MAN ( J . Amer. Chem. SOC. 1922 44 172-181; cf. ibid. 165). -Using the quantitative method previously described (Zoc. cit.) the authors claim to have shown that under the experimental conditions the velocity of destruction of vitamin-C by heat decreases with the time and in greater degree than would be expected if the reaction followed the unimolecular law or the square root rule of Schutz. The temperature coefficient is of low order namely Ql,(60-80")= 1.23 ; Q1,(80-1000)= 1-12. The effect of reducing the hydrogen-ion concentration from pH=4.3 to p,=5-2-4-9 is to increase the destruction during one hour at 100" from 50% to about 58%.When the material was made alkaline p,=10.9-8.3 the destruction was 61-65%. If re-acidification after heating in J. F. S. H. J. E. 10-2ii. 276 ABSTRACTS OF CHEMICAL PAPERS. alkaline solution was omitted there was still further destruction if the material was allowed to remain alkaline for five days a t 10". The material used as the source of vitamin4 was tomato juice. W. G. The Influencing of Catalysts and Specifically Active Cata- lysts. E. ABEL (Ber. 1922 55 [B] 322-323).-A final reply to Rosenmund and Zetzsche (cf. Abel A. 1921 ii 542; Rosen- mund and Zetzsche A. 1921 ii 320 392 393; this vol. ii 41). H. W. The Oxygen-Hydrogen Catalysis by the Platinum Metals and the Contact Potentials in Presence of Aqueous Electro- lytes.K. A. HOFMANN (Bey. 1922 55 [B] 573-588).-Since previous experiments (A. 1920 ii 240) were performed with platinised porous earthenware tubes whilst Willstatter and Wald- Schmidt (A. 1921 ii 185) employed platinum black these investi- gators are not justified in concluding that their results are incom- patible with the views of Hofmann and Zipfel (Zoc. cit.). In the present work no indication could be discovered of the peroxide- hydride to which Willstatter and Waldschmidt ascribe the favour- able effect of oxygen on the catalytic activity of hydrogen (D.R.-P. 301364 Willstatter and Waldschmidt Zoc. clt.). The volume of oxygen occluded by platinised earthenware is shown to be so small that any peroxide produced cannot bear any relation to the actual effect of oxygen on catalysis which is rather due to its influence on the catalyst surface.At the same time the small amounts of gas adsorbed by porous surfaces render them much more suitable than platinum for determinations of variations of contact potential during catalysis. Measurements of the potential difference between such an electrode and one of platinum in contact with hydrogen at atmospheric pressure show that whether the electrolyte be 17% sulphuric acid or 4% sodium hydrogen carbonate solution contacts impregnated with platinum palladium or iridium in contact with a mixture of hydrogen and oxygen are electrically modified in the opposite sense to that of their previous treatment (with one or other of the gases) and the more rapidly this occurs the more rapidly is water-formation catalysed.The activity diminishes on prolonged treatment with hydrogen or especially in the case of palladium with oxygen. It is improved by repeated variation of this treatment by repeated use with the stoicheio- metrical mixture of the gases and by varying galvanic polarisation. Light and moderate temperature changes are much less effective. Hydrogen exerts a greater effect on the catalysis potentials with increased hydrogen-ion concentration of the electrolyte whilst the reverse is true of oxygen. These results indicate that neither pure hydrogen nor hydrogen-oxygen mixtures produce any special oxidising or reducing compound on the catalyst surface of the kind suggested by Willstiitter which determines the potential.Direct instantaneous determinations of the effect on the same electrode potentials of the addition of hydrogen peroxide show that this always acts as a strong oxidising agent and renders itGENERAL AND PHYSICAL CHEMISTRY. ii. 277 highly improbable that any peroxide-hydride could exert a strong reducing influence apart from the extreme rapidity with which the known peroxides are decomposed by platinum metals. Although i t is not improbable that hydrogen peroxide is an intermediate product in the formation of water its existence is so transient as to elude all attempts t o detect it. N. BOER (Nature 1921 108 208-209 ; cf. ibid. 1921 107 104,17O).-Further examination of the orbits of the electrons postulated in the previous communication has shown that the conception of the atom there outlined cannot be reconciled with that which assumes the atom to be composed of a number of well-defined spherical shells of electrons moving in sharply separated regions.The electrons in the atom are still regarded as being arranged in groups in such a way that the orbit of every electron within a particular group is characterised by the same total number of quanta. In proceeding outwards from the nucleus the number of quanta characterising a certain group of orbits is larger by one unit than that of the preceding group. The electrons of certain sub-groups will also penetrate into the region of the orbits of electrons of inner groups giving rise to group-coupling which is reflected in the stability of the atom.These considerations are applied to the cases of the iron group and the rare earths. J. K. Atomic Structure. A. A. E. J. K. MARSH and A. W. STEWART (Nature 1921 109 340).-If the central magnetic pole in a tank is maintained a t a strength always exactly equal and opposite to the combined powers of a number of floating magnets and if the number of the latter corresponds with units of atomic weight in various elements the magnets arrange them- selves in two clearly defined and sharply separated groups termed for convenience the nucleus and ring respectively. It is a remark- able coincidence that the series of groupings obtained corresponds exactly with Aston’s suggestions regarding the atomic structure of a number of elements and isotopes. In the case of boron-11 and carbon both nuclei contain six magnets arranged in two pairs of concentric triangles a peculiarity which seems to have some con- nexion with certain chemical and physical similarities.Correlation of Atomic Structure and Spectra. HAROLD S. KING ( J . Amer. Chem. Xoc. 1922 44 323-328).-A theoretical paper in which it is shown that Bury’s modification (this vol. ii 43) of Langmuir’s hypothesis of the structure of elements is con- firmed in addition to the relationship between the atomic diameter and the number of electron shells also by the relationship between the atomic number and the number of lines in the arc and spark spectra respectively. J. F. S. J. S. TOWNSEND and V. A. BAILEY (Phil. Hug. 1922 [vi] 43 593-600).-1t is shown that when an electron moving with a velocity of the order of lo8 cm.per second collides with a molecule of argon it loses only about A Magnetic Model of Atomic Constitution. A. A. E. - Motion of Electrons in Atoms.ii. 278 ABSTRACTS OF CHEMICAL PAPERS. one ten- thousandth of its energy whereas previous experiments showed that in collision with oxygen nitrogen or hydrogen it loses more than 1% of its energy. The mean free path of an electron moving with these velocities in argon is about ten times that in the other gases at the same pressure. Relationship between the Internal Friction and the Chemi- cal Constitution of Gases. HARRY SCHMIDT (2. Elektrochern. 1922 28 50-55).-A theoretical paper in which the author has deduced equations by means of which the atomic radius of the elements and the mean cross-section of the simpler molecules may be calculated.Using the formula r = d 4 k / B / 7 ~ ~ in which r is the atomic radius k a constant M the molecular weight and v the coefficient of viscosity the following values of the radii have been obtained oxygen 1.000 ; nitrogen 1.035 ; hydrogen 0.752 ; chlorine 1.491 ; sulphur 1.477 ; bromine 1.841 ; helium 0-795 ; neon 0.946; argon 1-336; krypton 1.553; xenon 1.794. The mean cross-section of a number of simple compound molecules are also calculated and tabulated. J. R. P. J. F. S. Atomic Radius and Ionisation Potential. MEGH NAD SAHA (Nature 1921 107 682-683; cf. Basu Phil. Mag. 1920 [vi] 40 619).-The radius ax of an atom (the distance from the nucleus to the outermost electron of the Rutherford-Bohr model) may be calculated from the ionisation potential Vz of an element x from the equation ax=10-8x (0.532 x 13.56)/Vx cm.The atomic radii calculated in this way are smaller than those calculated either from crystal data or from the kinetic theory. The following values expressed as ax108 were obtained those derived from other methods being placed within brackets hydrogen 0.530 ; helium 0.28 (1.08); neon 0.33 (0-65 1.01); lithium 1.34 (1.50); sodium 1.41 (1.77) ; potassium 1.67 (2-07) ; rubidium 1.73 (2.25) ; cmium 1-86 (2.37) ; copper 0.94 (1.37) ; silver 0-95 (1.77) ; gold 0.83 ; magnesium 0.95 (1.42) ; calcium 1.18 (1.70) ; strontium 1.27 (1.95); .barium 1.39 (2.10); zinc 0.77 (1.32); cadmium 0.81 (1.60) ; mercury 0.69 ; thallium 0.99 (2.25) ; manganese 0.98 (1.47). A. A. E. New Method of Determining Molecular Diameters by the Electromagnetic Rotation of the Discharge in Gases. C. E. GUYE and R. RUDY (Compt. rend. 1922 174 382-384).-By applying the theory of ionisation by shock to the phenomenon of rotation of the electric discharge in gases the velocity of rotation is given by V=cH/12m~2mM. Thus with a constant magnetic field and for the same gas the product of the pressure and the velocity observed must be a constant. A new series of measure- ments has been made on a number of carefully purified gases. The molecular diameters obtained by this method show a close agreement in value with those deduced from viscosity measure- ments. Contrary to the general opinion the observed velocity of rotation is not inversely proportional to the density of the gas,INORGANIC C~IEMISTRY. ii. 279 but to the product of the square of the molecular diameter and the density. W. G. A. REYCHLER (BUZZ. SOC. chim. BeZg. 1922 31 67-72).-WarringtonYs formula for calculat- ing atomic weights (A. 1915 ii 160) gives too low a value for elements of the two short series. The author’s formula A=2fl+ 0.007N2 gives better values but is not applicable t o hydrogen and is not very satisfactory for elements of the first short series. Attention is directed to the relation of this formula to the equation v = y ( N - c ) ~ which expresses frequency of radiation of an element when used as an anticathode. R. M. CAVEN (Nature 1921,108 210- 211).-Polemical Langmuir’s (ibid. 1921 108 101) view that the sodium and chlorine atoms in sodium chloride are not united by a chemical bond is attacked and criticism offered regarding the postulation of covalency and electrovalency in certain cases. A. A. E. Atomic Weights and Frequencies. H. J. E. Qualities of Valency. A Theoretical Derivation of the Principle of Induced Alternate Polarities. ARTHUR LAPWORTH (T. 1922 121 416- 427). An Explanation of the Property of Induced Polarity of Atoms and an Interpretation of the Theory of Partial Valen- cies on an Electronic Basis. WILLIAM OGILVY KERMACK and ROBERT ROBINSON (T. 1922,121 427440). Friend’s Theory of Valency. J. D. MAIN SMITH (Chem. News 1922,124 84-86) .-Friend’s theory of valency as extended in a recent paper (T. 1921 119 1040) is subjected to a detailed criticism. I n particular the direct translation of Thornson’s physical conception of “ ionised ’’ and “ non-ionised ” valency into chemical terms is criticised on the ground that residual valency may partake of the properties of both. Friend’s criticisms of some aspects of Werner’s theory are discussed. J. J. VAN LAAR (2. anorg. Chem. 1921 120 203-208) .-A theoretical discussion of the theory of space-filling numbers in relation to van der Waals’s equation. E. H. R. Space-filling and the Equation of Condition. E. H. R.

ISSN:0368-1769    

DOI:10.1039/CA9222205241

出版商:RSC    

年代:1922

数据来源: RSC