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ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. 193 The Free Chlorine in Town Drinking Waters. G. A. LE ROY (Compt. rend. 1916 162 327-329).-Ten litres of the water under examination are placed in an enamelled metal vessel which is immersed in a brine-bath kept below Oo and the water is allowed t o freeze until only about' 200 C.C. are left taking care not t o stir the water o r aerate it. The last 200 C.C. of water are poured off and examined for free chlorine by means of magnesium iodide and starch. The method can be made' quantitative by accurately measuring the volumes of water and estimating the chlorine oolori- metrically and can be madel more delicate by starting with a larger volume of water and leaving still only 200 C.C. after freezing. W. G. Rapid Method of Estimating Ghloric Acid and Chlorates.R. L. TAYLOR ( J . SOC. Dyers 1916 32 66-68).-The liberation of iodine from potassium iodide by chloric acid o r chlorates is quanti- tative in the presence1 of moderate concentrations of hydrochloric acid and a method f o r their estimation either alone o r in presence of hypochlorites as for example in bleaching powder is based on this reaction. From one and a-half to two volumes of concen- trated hydrochloric acid are added to the solution t o be titrated together with a few crystals of potassium iodide and the liberatedii. 194 ABSTRACTS OF CHEMICAL PAPERS. iodine titirated with thiosulphate after diluting somewhat with water. The high concentration of hydrochloric acid does not affect the accuracy of the titration.Water Analysis. 11. L. W. ~VINKLER (Zeztsch. aizgew. Chem. 1916 29 44-46. Compare A. 1915 ii 173).-For the estimation of dissolved oxygen in water containing nitrites and organic matter the water should be treated previously with a small quantity of sulphuric acid and a slight excess of calcium hypochlorite solution; the oxygen estimation is then carried out as usual by the man- ganous chloride method. Allowance is made for the effect of the excess of chlorine by treating a similar quantity of the water with the same quantities of sulphuric acid and calcium hypochlorite solution then adding a crystal of potassium iodide and titrating the liberated iodine. Total alkalis may be estimated by evaporat- ing a definite quantity of water with the addition of barium carbon- ate extracting the dry residue with successive quantities of hot water and evaporating the filtered aqueous extracts t o dryness with the addition of a drop of hydrochloric acid.The residue consisting of potassium sodium and magnesium chlorides is extracted with isobutyl alcohol t o remove the magnesium chloride then dried a t 150° and weighed. The potassium is estimated by dissolving the mixed alkali chlorides in one hundred times their weight of lithium hydrogen tartrate solution (0.5 gram of lithium carbonate and 2 grams of tartaric acid dissolved in 100 C.C. of water the solution mixed with 50 C.C. of alcohol and then satnrated with potassium hydrogen tartrate) collecting the' precipitated potassium hydrogen tartrate after the lapse of two hours washing the precipitate with a small quantity of 30% alcohol saturated with potassium hydrogen tartrate and titrating it with standard alkali solution.Water supplies sometimes contain zinc owing t o the water having been passed through '' galvanised " iron pipes. Small quantities of zinc in water may be detected and their quantity estimated approxi- mately by the following test 100 C.C. of the sample are treated with 1 C.C. of 10% hydrochloric acid and 1 C.C. of hydrogen sulphide solution and 5 C.C. of 15% ammonium acetate solution are then added. A turbidity develops almost immediately if the water contains 10 mg. of zinc per litre whilst the turbidity is not seen until after the lapse of about one minute if only 2 mg. of zinc per litre' are present. An equal volume of the water similarly treated but without the ammonium acetate serves as a comparison solution; this remains clear if the water contains up t o 10 mg.of ferrous iron per litre but it becomes turbid if ferric salts are present. Ferric salts therefore render the test untrustworthy. The zinc may also be estimated by a method described previously H. KOELSCH (Chem. Zeit. 1916 40 174).-The fusion method with sodium peroxide is recommended. A quantity of 0.625 gram of the blende or 1.25 grams of roasted blende is fused with 15 grams of sodium peroxide G. F. M. by the author (A. 1913 ii 246). w. P. s. Estimation of Sulphur in Zinc Blende.ANALY'I'ICAL CHEMlSlXY ii. 195 in an iron crucible cooled the mass dissolved in about 150 C.C. of water the solution nearly neutralised with hydrochloric acid then diluted to 250 c.c.filtered and the sulphuric acid is estimated in 200 C.C. of the filtrate by precipitation as barium sulphate. The presence of a small quantity of silica in the ore does not appreciably affect the results and the latter agree with those found by fusion with a mixture of sodium carbonate and potassium chlorate. w. P. s. Estimation of Free Sulphur in Antimony Sulphides. A. HUTIN ( A ? L I Z . C'him. atzaZ. 1916 21 32-33).-For the exbraction of free sulphur from various antimony sulphides the use of acetone is recommended in place of carbon disulphide since the latter when warm is capable of converting antimony pentasulphide into the tetrasulphide. Owing to the slight solubility of sulphur in acetone a t least eight hours' extraction is necessary in order to obtain the A New Method for the AnalysirJ of Mixed and Spent Acids.L. WUYTS ( J . SOC. Chem. I d . 1916 35 149-151).-A modifica- tion of Schloesing's method suited for the estimation of nitric and nitrous acids in mixed and spent nitrating acid consists essentially in the conversion of the nitrogen into nitric acid by slowly dropping a known weight of the acids from a tap-funnel with a capillary stem bent twice a t right angles into a boiling solution of ferrous chloride and hydrochloric acid contained in a Kjeldahl flask of about 200 C.C. capacity. The evolved gas is led by a delivery tube t o the base of a graduated burette standing over water care being taken that the water does not suck back into the flask owing t o a slackening of the boiling.The weight of nitric acid is calculated either directly from the volume of nitric oxide obtained o r preferably by comparison with a standard tube of gas obtained by treating a known weight of pure sodium or potassium nitrate in a similar manner. The accuracy of the estimations is of the order of 0*1% and Seven or eight samples can be analysed per hour. Detection of Nitrates in Presence of Organic Matter. ALFRED TINGLE (J. SOC. Chem. Ind. 1916 35 77-78).-The sali- cylic acid test for nitrates previously described (A. 1915 ii 576) is modified as follows to admit of their detection in presence of organic matter 2-5 C.C. of the reagent consisting of a solution of 3 grams of salicylic acid in 100 C.C. of concentrated sulpliuric acid is gently warmed with the substance and the charred mass extracted with 10 C.C.of water. The aqueous extract is shaken with an equal volume of ether and the ethereal solution which contains nitrosalicylic acid if nitrates were present is shaken with aqueous ammonia which assumes an orange colour o r with a 1% aqueous solution of ferric chloride whereby a red coloration is slowly developed in the aqueous layer. Examples are given of the employ- ment of the test t o detect 0.1% of potassium nitrate in a saturated solution 'of sucrose and cellulose nitrate in a photographic film. whole of the free sulphur. w. P. s. G. F. M. G. F. M.ii. 196 ABSTRACTS OF CHEMICAL PAPEltS. Influence of Fluorspar on the Solubility of Basic Slag in Citric Acid. G. S. ROBERTSON ( J .SOC. C‘hem. I?d 1916 35 216-217).-The use of fluorspar in the manufacture of steel by the open-hearth process results in the production of a phosphatic slag of low citric acid solubility performing the test in the usual way with one extraction only. By repeated extraction with 2% citric acid a much larger amount of phosphate is rendered soluble and as the amounts of silica removed by the successive extractions bear no definite ratio to the phosphate the latter does not appear to be in conibiiiation with silica in the slag as is usually supposed. The results indicate that the citric acid test gives no idea of the solubility of the phosphate in fluorspar slags and is worthless as a guide t o its agricultural valuel as a fertiliser. Solubility of Mineral Phosphates in Citric Acid.G. S. ROBERTSON ( J . SOC. Chem. Ind. 1916 35 217-220).-Provided that sufticient time be given to’ the extraction minezal phosphates are as completely soluble in 2% citric acid solution as is basic slag and as a source of phosphoric acid f o r the plant they are doubtles just as valuable. I n the majority of the rock phosphates examined five extractions removed 90-100% of the phosphoric acid present. Small amounts of free lime or calcium carbonate appreciably decrease the solubility as judged by the citric acid test but from the agricultural point of view there is absolutely no reason why the citric solubility should be used t o judge of the phosphatic value rather than thatl in a dilute mineral acid. Fineness of grinding also considerably affects the total citric solubility of mineral phosphates and in all cases but one calcination caused a decrease in solubility.G. F. M. G. F. M. Estimation of Carbon Dioxide in Air by Haldane’s Apparatus. ROBERT C. FREDERICK ( J . SOC. Chem. Ind. 1916 35 96-99).- The use and construction of Haldane’s apparatus comprising several modifications is described and figured in detail. The principal novel- ties include a special arrangement of taps t o regulate the flow of air into the potash absorption bulb a graduated scale on the stem of the potash bulb t o enable larger quantities than 100 parts per 10,000 to be estimated and a stand with pulley wheels and counter- noise to facilitate the manimlation of the niercurv reservoir. For I I J a complete description the original paper must be consulted.G. F. M. Carbonic Acid in Mineral Waters. R A M ~ N LLORD Y GAMBOA (A?zaI. Fis. Quim. 1916 14 36-38).-A description of the results of investigations of the percentage of carbon dioxide in various mineral waters by different methods. A. J. W. Estimation of Alkalinity of Water. F. W. BRUCKWILLER (Chem. News 1916 113 104-105).-Them water is first titrated with N / 50-sulphuric acid using phenolphthalein as indicator ; methyl-orange is then added and the titration continued. Ery-ANALYTICAL CHEMISTRY. ii. 197 throsin solution and chloroform may be used in place of methyl- orange in the second titration. If the alkalinity of the water is due to hydrogen carbonates alone no coloration is obtained when phenolphthalein is added to the water and the alkalinity towards methyl-orange is expressed as '' bicarbonate " alkalinity.When the phenolphthalein titration is less than the methyl-orange titration carbonates and hydrogen carbonates are present and the alkalinity is due solely to normal carbonates if the two titrations give equal results. The prmence of hydroxides causes the phenolphthalein titration to be greater than the methyl-orange titration. The quan- tities of carbonate hydrogen carbonate and hydroxide respectively (all expressed in terms of CaCO per million parts of water) may be calculated from the results of the titrations. w. P. s. Estimation of Free Alkali Hydroxide in Soap. F. H. NEWINGTON (J. SOC. Chem. Ind. 1916 35 95-96).-To obviate the sources of error and the difficulties which are attendant on the usual method of estimating alkali hydroxide in soap namely titra- tion of an absolute alcoholic solution with standard acid the follow- ing method is suggested 10 grams of the sample are dissolved in 50 C.C.of freshly boiled hot distilled water and 50 C.C. of a hot saturated solution of sodium sulphate are added. The mixture is transferred to a separating funnel which is lightly corked and placed in a hobwater oven until the soap separates out on the surface of a clear aqueous layer. The latter which contains all the hydr'oxide originally present in the soap is run off and titrated with N/lO-sulphuric acid using a 5% silver nitrate solution as a spot indicator on a porcelain plate. The end-point is attained when a brown precipitate of silver oxide is no longer formed; silicates carbonates etc.which may be present in the aqueous solution cause no confusion. G. I?. M. Potassium Metabisulphate. A. A. BESSON (Chem. Zed. 1916 40 165-167).-1f the salt has a normal composition the quantity of sulphur dioxide present may be estimated either alkali- metrically or iodometrically but the latter method is to be p r e farred since the results obtained are not affected by the presence of other hydrogen salts. The weighed quantity of the sample should be treated directly with an exc0ss of N/lO-iodine solution and the mixture then titrated with thiosulphab solution. The sulphur dioxide content of the commercial salt varies between 54.45% and 55'97% (K,S,O requires 57.66%); sulphate is almost always present. Pure potassium metabisulphite does not smell of sulphur dioxide but if exposed to air and moisture gradual decom- position takes place and an odour of sulphur dioxide is noticed.w. P. s. An Investigation of the Chromate Method for Separating the Alkaline Earths. HUBERT BRADFORD VICKERY (Trans. Nova S c o t i m Inst. Sci. 1914-1915 14 30-4O).-Experiments have been made in order to ascertain the sensitiveness of the chromate method VOL CX. ii. 9ii. 198 ABSTRACTS OF CHEMICAL PAPERS. of separating the alkaline earths and the best conditions for carrying out this process. Comparative tests showing the minimuin quantities of barium strontium and calcium which yield precipitates on the addition of the same quantity of ammonium carbonat'e of potassium chromate and of ammonium sulpliate were made.Further tests were made in order to determine the minimum quantities of each of the alkaline-earth metals which could be detected in presence of rela- tively large quantities of the other two when the separation is carried out in a normal manner. In presence of 200 mg. of calcium and strontium the limiting quantity of barium which can be detected is 4 mg. With 200 mg. of barium and calcium the limit- ing quantity of strontium is 15 mg. and with barium. and strontium present in large mcess the limiting quantity of calcium was found to be about 1 mg. H. M. D. Application of the Paper-pulp Filter to the Estimation of Calcium and Magnesium. S. L. JODIDI and E. H. KELLOGG ( J . Franklin Inst. 1916 181 217-232).-The use of paper-pulp filters for the separation of calcium oxalate and magnesium ammonium phosphate precipitates from the mother liquors has been found t o yield vesy satisfactory results.The estimation of both calcium and magnesium requires much less time than when the separation is effected by the use of filter papers. Method for the Analysis of Magnesium Chloride. L. BOUKDET (J. Pharm. Chim. 1916 [vii] 13 102-104).-1f magnesium chloride is twice evaporated with nitric acid (D 1.4) and the residue then ignited a t a bright red heat all the hydrochloric acid is expelled and the residue will consist of magnesium oxide; the quantity of nitric acid used should be about three times the weight of the magnesium chloride. In cases where impurities are present in the magnesium chloride the magnesium chlorine sulphuric acid ammonia etc.must be determined separately. The total amount of impurity is found approximately by the difference between the weight of the ignited residue obtained as described and the sum of the weights of the magnesium oxide ammonia (if present) insoluble substances and the excess of chlorine (that is the chlorine F. CHANCEL (Bull. SOC. chim. 1916 [iv] 19 59-63).-1n order t o obtain a satisfactory deposit of zinc it is necessary t o have a uniform current density on the cathode and t o ensure that the acidity of the solution &odd be constant. The estimations were made with the small platinum cathodes in the apparatus previously described (compare A 1913 ii 236) the cathode being first coated with mercury or copper preferably mercury.The solution for dectrolysis was prepared as follows About 0.3 gram of the zinc was dissolved in 1.5 grams of sulphuric acid and 2 grams of nitric acid the nitric acid then being evaporated. The residue was taken up with water neutralised H. M. D. not combined with the magnesium). w. P. s. Estimation of Zinc by Electrolysis.ANALYTICAL CHEMISTRY. ii. 199 with aqueous ammonia and then 0.25 C.C. of X-sulphuric acid was added followed by 0.2 gram of sodium formate f o r every deci- gram of zinc present. A current of 4-5 amperes was used and the electrolysis took three hours. Provided that a sufficiently thick deposit of mercury is obtained the deposition of the zinc is com- plete the results being on the average 0.2% too high. For the analysis of brass the solution in nitric acid and precipi- tation of the copper are carried out in the usual manner the filtrate from this being first evaporated with sulphuric acid then saturated with ammonia t'o precipitate the iron the excess of ammonia boiled off and then 0.25 C.C.of N-sulphuric acid and the requisite amount of sodium formate added. W. G . Electro-analysis of Copper without Platinum Electrodes. J. GUZMAN and T. BATUECAS (Anat?. Fis. Quim. 1916 14 38-47). Continuing their investigations of the electro-deposition of copper without platinum electrodes the authors have employed an anode of graphite and a cathode of copper f o r the estimation of copper dissolved in hydrochloric nitric and sulphuric acids and also in presence of arsenic antimony and tin. A. J. W. Action of Mercuric Salts on Aluminium Foil.Application of the Reaction to the Detection of Mercury in Chemical Analysis and Toxicology. ST. B~INOVICI and EM. GROZEA (Bull. Sci. Acad. h'oumaiize 1915-1916 4 227-230).-A solution containing mercuric chloride when allowed t o dry on aluminium foil gives rise t,o a dendritic structure resembling that produced by calcium nitrate on damp walls. This reaction is not prevented by the presence of various other substances and may be conveniently employed as a test for mercury especially in toxicological investiga- tions. S. B. S. Action of Oxidising Agents on Cerous Salts. G. A. BARBIERI (Atti R. Accad. Lincei 1916 [v] 25 i 37-43. Compare A. 1907 ii 467; 1910 ii 779).-The oxidation of cerous salts by perman- ganate or by persulphates has been investigated (compare Muth- mann and Weiss A.1904 ii 406). A solution containing not more than 1% of cerous sulphate and not' leas than 25% of mlphuric acid is readily oxidised by potassium permanganate in the hot ceric sulphate being formed 5Ce,(SO,) + 2KMnO4 + 8H,SO = lOCe(SO,) + K,SO + ZMnSO + 8H,O ; if 30% of sulphuric acid is present the oxidation proceeds rapidly even in the cold. This inethod is however unsuitable for the volumetric estimation of cerium since the yellow colour of the ceric sulphate renders the end-point indefinite. If to a solution of a cerous salt are added excess of iodic acid and then sufficient nitric acid to' dissolve the cerous iodate precipi- tated complete and rapid oxidation to ceric iodate is effected by permanganate in the h o t 5Ce(IO,) + KMn04 + 5HI0 + 3HNO,= 5Ce(IO,-) + KNO + Mn(N03) + 4H,O. This reaction cannot be employed for the volumetric estimation of cerium since after corn-ii.200 ABSTRACTS OF CHEMICAL PAPERS. plete oxidation of the latter reduction of the permanganate is continued although more slowly by the manganous salt formed. It does however s a v e for the quantitative separation of cerium from the other elements of its group f o r instance lanthanum which form iodates soluble in dilute nitric acid and form compounds of only one type. Permanganate is reduced even in the cold by a solution of cerous phosphate in excess of phosphoric acid a bulky white gelatinous precipitate being formed which contains all the cerium as basic ceric phosphate the ratio Ce P,O being about 4 3.Since the super- natant liquid remains colourless this reaction may be employed for the estimation of cerium the procedure being as follows. The cerous solution is diluted where necemary so as to contain not more than 0.1 gram of cerium per 100 C.C. To 100 C.C. of the liquid are added 20 C.C. of phosphoric acid solution (D 1-35) and then drop by drop decinormal permanganate solution until the precipitate acquires . a faint rme-red colour. The liquid is next heated ,on a water-bath and the addition of permanganate continued until the supernatant liquid assumes a pale pink colour persistent in the hot. This method gives good results even when the cerium is accom- panied by other rareearth ele'ments ; the quantity of phosphoric acid added should be sufficient to keep these elements in solution even in the hot.I f thorium is present addition of phosphoric acid produces a precipitate of basic thorium phosphate which is but slightly soluble in acids but the presence of this precipitate does not disturb the oxidation of the cereus phosphate. Further the titra- tion is not affected by small proportions of manganous salts whereas no volumetric method hitherto known is applicable when the cerium is accompanied by manganese. The investigations of von Knorre (A. 1898 ii 311) Witt and Theel (A. 1900 ii 403) and Meyer and Marckwald (A. 1901 ii 21) show that persulphates oxidise cerous salts in the hot but not in the cold. The author finds that if a little silver nitrate is added to a solution containing an alkali persulphate and cerous nitrate or sulphate oxidation of the cerous salt by the persulphate commences immediately and proceeds until all the cerium is con- v&d into ceric salt which forms a yellow solution or a precipitate according as the liquid is acid or neutral.The catalytic action of the silver depends on its conversion by the persulphata from the univalent t o the bivalent form. This reaction serves for the puri- fication of a crude cerium salt since in neutral solution any other ra+r*earth metals remain dissolved whilst almost the who10 of the cerium is precipitated as basic salt. Crum's and Marshall's Tests for Manganese. LEONARD DOBBIN ( J . SOC. Chem. Ind. 191 6 35,80-81 *).-The author points out that the credit for the application of the oxidation of manganese salts to permanganic acid by means of lead pe'roxide and nitric acid as a qualitative test for manganese which has been variously ascribed * and Chem.News 1916,113 133-136. T. H. P.ANALYTICAL CHEMISTRY. ii. 201 t o Crum Volhard and Hoppe-Seyler properly belongs to the former of those investigators. The modification of this test using a per- aulphate in prwence of sulphuric or nitric acids and a drop of silver nitrate solution as the oxidising agent whereby 0.001 mg. of manganme in 0.5 C.C. of water could be detected was suggested by Marshall (A. 1901 ii 350) and not by Walters to whom many writers have given the credit. Estimation of Toluene and the Application of the Method to Benzene and Xylene. HUGH W. JAMES (J. SOC. Chem. Ind. 1916 35 236-240).-Details are given of a method for the estima- tion of toluene in naphthas and crude benzols depending on a determination of the volume of the fraction obtained between two definite hmperatures by the distillation under specified conditions of the mixed hydrocarbons which have been previously separated into two parts by a double fractionation of the original naphtha the on0 part boiling below 110*6O and the second between 110.6O and 140O.Each of the latter fractions is distilled from a 150-180 C.C. flask with a 5-inch neck and side delivery-tube a t the rate of 2 drops per second and the fractions are collec-5ed a t 85O 90° 95* looo and 1 0 8 O for the first part and 115O 120° 125O 130° and 137O for the second part. Tables are given showing the percentage volumm of mixtures of benzene toluene and xylene in known pro- portions which distil between these temperatures and from the observed percentage the amount of toluene in the fraction under- going distillation is directly read off.Benzene may be taken as the difference between the total volume of the fraction up to 110'6O and its toluene content and xylenes the corresponding difference in the' second fraction 110~6-140°. "he results have an accuracy of the order of 1%. For the estimation of toluene in tar a prelimin- ary t a r distillation must first be undertaken details of which are given. G. F. M. Solubility of Naphthalene in Ammonia ; Cause of Naphtha lene Stoppages in Pipes. SIEGFRIED HILPERT (Zeitsch. angew. Chem. 1916 29 57-59).-The following table shows the solubility of naphthalene in ammonia solution and in ammonia the results being expressed as gram per 1000 grams of solution 'lo NH,.0. 5. 10. 25. 100. G. F. M. At 0" ... 0.019 0.030 0.042 0.064 33.0 At 25' ... 0.030 0.044 0.074 0.162 120.0 When the ammonia contains 2% of pyridine the solubility of naphthalene a t Oo increases to 0.082 and a t 25O to 0.245. Phenol does not affect the solubility. If carbon dioxide is passed into 25% ammonia containing naphthalene in solution the greater part of the latter is precipitated. During the distillation of ammonia contain- ing naphthalene the condenser tubes etc. should be kept a t a temperature not lower than 30° otherwise the naphthalene will condense in the tubes. For the estimation of naphthalene in ammonia the picrate method is recommended.The ammonia is cooled in a freezing mixture neutralised gradually with sulphuricii. 202 ABSTRACTS OF CHEMICAL PAPERS. acid and distilled about 30 C.C. of distillate being collected. The naphthalene is extracted from the distillate and condenser with ether and an excess of N/20-picric acid solution is added t o the ethereal solution. After two minutes the ether is evaporated under reduced pres>ure the residue cooled in icewater the precipitate collected on a filtRr washed with 5 C.C. of ice-water and titrated with N / 10-sodium hydroxide solution using litmus as indicator. w. P. s. Lewis and Benedict Method for the Estimation of Blood Sugar. VICTOR C. MYERS and CAMERON V. BAILEY ( J . Biol. Chenz. 1916 24 147-161).-See this vol.i 300. The Presence in Industrial Sugars of Reducing Substances Other than Invert-sugar. L. MAQUENNE (Corn$. wzd. 1916 162 277-282).-Artificial mixtures of pure sucrose and pure invert-sugar can be readily analysed and the amounts of each sugar present accurately determined by the method already described (compare t-his vol. ii .56 156) working either a t 65O o r looo or with boiling solutions. Working with commercial sugars however the reducing effect obtained with boiling solutions is much greater than when the estimation is made at 65O. The author considers t h a t this difference is due t o the presence of reducing substances other than invert-sugar in the commercial sugars the difference being an approximate measure of the amount of these substances present.W. G. Recovery of Copper Sulphate from the Filtrates Obtained in the Gravimetric Estimation of Sugars with Fehling's Solution. KRUMHAAR (Chem. Zeit. 1916 40 174).-The alkaline copper solu- tion is hested t o boiling a quantity of dextrose solution is added sufficient t o precipitate all the copper as cuprous oxide and the latter is collected and washed. The cuprous oxide is then heated with hydrochloric acid and oxidised by the addition of hydrogen peroxide; when the oxidation is complete the solution no longer becomes turbid on dilution with water. The solution is now evapor- ated the hydrochloric acid expelled by a second evaporation with sulphuric acid the copper sulphate is dissolved in a small quantity of boiling water the solution filtered and porured into three times its volume of 96% alcohol.The sulphate is thus precipitated in the form of finel crystals which are collected on a filter washed with alcohol and dried. w. P. s. Use of Enzymes and Special Yeasts in Carbohydrate Analysis. WILLIAM A. DAVIS (J. SOC. Chem. Ind. 1915 35 201-21 1) .-Processes based on t'he differential behaviour of enzymes in the hydrolysis of carbohydrates are described for the estimation of individual sugars and starches in plants o r other carbohydrate mixtures. Thus the selective hydrolysis exerted by invertase (from autolysed top yeast) and rnelibiase (from autolysed bottom yeast) is utilissd for the estimation of raffinose the former preparation converting i t into melibiose and hvulose and theANALYTICAL CHEMISTRY.ii. 203 latter into galactose dextrose and lam,dose whence by determining the difference polarimetrically a measure of the raffinose present is obtained. The use of invertase preparations for the estimation of sucrose is recommended in preference to hydrolysis by citsic o r hydrochloric acid since the presence of sodium acetate derived from the lead acetate used in clarification exerts an inhibitive action on the acid hydrolysis. Maltose cannot be estimated accu- rately by acid hydrolysis in presence of sucrose o r lzvulose. By using a maltase-free yeast such as Saccharomyces marxianus or S. exi,quus however every trace of dextrose laevulose o r sucrose can be fermented away by a three t o four weeks’ incubation a t 25O and the maltose then estimated by the residual reducing power. The estimation of starch in plant material by acid hydrolysis is like- wise vitiated by the pentosans hemicelluloses etc.present which may give reducing sugars which count as dextrose. Hydrolysis by taka-diastase a t 38-40° results in the quantitative conversion of the starch into a mixture of maltose and dextrose#. Full details f o r the carrying out of the above-cited methods are given in the paper. G. F. M. Detection of Glycuronic Acid in Urine. H. ROGER ( J . I’knrm. Chim. 1916 [vii] 13 119-120).-Five C.C. of the urine are treated with 0.2 C.C. of ammonia and 2 C.C. of lead acetate solution a quantity of 1% ammonia is added and the mixture subjected to centrifugal action. The sediment is separated washed with 1% ammonia then mixed with 5 C.C.of water and treated with 0.5 C.C. of a 1% alcoholic naphtliaresorcinol solution. The mixture is now acidified with 5 C.C. of concentrated hydrochloric acid heated for fifteen minutes in a boiling water-bath cooled and shaken with 10 C.C. of ether. If the urine1 contains glycuronic acid the ethereal layer shows a violet coloration; in the absence of glycuronic acid the ether is coloured faint red. w. P. s. Use of Soluble Ferments in the Estimation of Urea. MODESTO MAESTRE IBAREZ (A~znl. Pis. Quinz. 1916 14 %3-35).- An account of results obtained in the estimation of urea by Marshall’s urease method. A. J. W. Estimation of Urea by the Urease Method. DOXALD. VAN SLYKE and GLENN E. CULLEN (J. Biol. Chem. 1916 24 117-122. Compare Fiske this vol. ii 119).-The use of a slower rate of aeration in driving the ammonia over into the standard acid as recommended by Fiske is considered unnecessary if the authors’ original directions are strictly adhered to.The substitu- tion of a saturated solution of potassium carbonate f o r the solid subst,ance is desirable and the authors emphasise the necessity for applying corrections for traces of ammonia. in the reagents employed. H. W. B. Quantitative Estimation of Urea. C. P. MOM (Chem. TTieelcbZad 1916 13 72-75).-A method for the estimation of ureaii. 204 ABSTRACTS OF CHEMICAL PAPERS. in urine. The urea is converted into ammonium carbonate by the action of a culture of Urobacillzss Pnsteurii and the carbonate estimated volumetrically. A. J. W. Use of Nickel Hydroxide in Tannin Estimation.PURAN SINGH and T. P. GHOSE ( J . SOC. Chem. Ind. 1916 35 159-160).- Instead of the nickel hydroxide paste as originally proposed (A. 1911 ii 946) the substance is preferably used in the form of dry powder washed free from sulphates with hot water and finally with water containing a trace of tannic acid. The method is; considered as trustworthy as the hide powder method. G. F. M. Limits of Sensibility of the Golour Reactions of Proteins and Peptonising Enzymes. M. A. RAKUZIN (MLLE.) EK. M. BRAUDO and (MLLE.) G. F. PEKARSEAJA ( J . Buss. Phys. Chenz. Soc. 1915 47 2051-2066).-A number of proteins of different types and also various proteolytio enzymes have been examined to ascertain which of the following colour reactions each gives and with what sensitiveness the biuret Millon’s Liebermann’s Adamkie- wicz’s the xanthoprotein Molisch’s Pettenkofe’r’s and Ostromiss- lenski’s (A.1915 ii 602). The compounds examined were egg- albumin peptone from egg-albumin a- and B-gelatins chondrin elastin casein nucleic acid nuclein agar-agar gluten pepsin trypsin diastase and pancreatin. Only egg-albumin its peptone and its adsorption products (com- pare Rakuzin A. 1915 i l015) give all the above reactions. Casein from cows’ milk (nucleo-albumin) and nutrose (sodium caseinate) give all except Liebermann’s reaction. a-Gelatin gives only the biuret Molisch’s and Ostromisdenski’s reactions and chondrin gives these and also the xanthoprotein reaction. Agar- agar gives only Molisch’s and Pettenkof er’s reactions. Molisch’s reaction is given by all the above proteins and enzymes. Elastin gives only the biuret and I\/Iolisch’s reactions. It is noteworthy that the sclero-proteins chondrin gelatin and elastin do not give Millon’s reaction although according to Abderhalden elastin yields 0.34% of tyrosine. The biuret reaction is given by all the proteins except nucleic acid and agar-agar and Liebermann’s and Adam- kiewicz’s mactions are given only by egg-albumin and its peptone. Pepsin which approximates to the proteins in elementary com- position gives only Molisch’s reaction. Trypsin on the other hand gives the biuret xanthoprotein and Molisch’s reactions ; diastase and pancreatin give the biuret and Molisch‘s reactions. None of the four enzymes gives Pettenkofer’s reaction and neither pepsin nor krypsin gives Ostromisslenski’s reaction. The most sensitive of the protein reactions is that of Millon which detects 1 part of protein per 13,560 of solution. Any one reagent is &fferently sensitive t,owards different proteins in depend- ence on the varying proportions of the amino-acids present. Of the reactions for tryptophan that of Adamkiewicz is more sensitive than that of Liebermann. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9161005193

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i. 194 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. A Colorimetric Method of Adjusting Bacteriological Culture Media to any Optimum Hydrogen Ion Goncentration. S. H. HURWITZ K. F. MEYER and Z. OSTENBERG (Proc. SOC. Expt. BioZ. ilfed. New York 1915 13 24-26).-The method involves the use of phenolsulphonephthalein as indicator and standard phosphate mixtures for comparison. If necessary the hydrion concentration of the medium must be subjected to a preliminary rough adjustment so as to bring it between the limits H- =6.4 and H+ =8.4. H. M. D. Primary Changes of the Hexoses in Alcoholic Fermentation. H. EULER and E. HILLE (Bied. Zentr. 1915 44 575-576; Zeitsch. Garungsphysiol. 1915 3).-It was found that the decrease during fermentation as indicated by the optical method failed to agree with the amount of carbon dioxide produced and the conclusion was drawn that a compound intermediate between glucose and carbon dioxide was formed.Attempts to obtain an intermediate compound -by suppressing the second reaction by anti- septics and by hiat' failed to give the desired results. In presence of antiseptics the intermediate product is used up as quickly as i t is formed whilst the reaction is stopped altogether by slightly heating. N. H. J. M. Production of Lactic Acid in Fermentation. OTTO BURGER (Bied. Zentr. 1916 45 72; Centr. Bakt. ii 43 245. Compare Moutang Zeitsch. ges. Brauwes. 1913 No. 24).-Dilute solutions of maltose lmulose and dextrose were fermented with pure yeast and the acid estimated with N / 2 0 barium hydroxide.The barium salt like barium lactate dissolved in alcohol. N. H. J. M. Vegetable Oxidation Ferments. 0. BEGEMANN (Biol. Zentr. 1915 44 547-548; Zeitsch. allg. Physiol. 1914 16 352-358). -Oxidation ferments were found in all the plants which were examined. Direct oxydases were found in the living cells but not catalase and peroxydase. The influence of temperature and of light. was investigated. The methods employed are described. N. H. J. M. Plant Ferments. IV. The Invertase of Potato Leaves. P. DOBY (Biochem. Zeitsch. 1915 71 495-500).-The presence of invertase in potato leaves was confirmed. The degradation of sugar by the ferment is a unimolecular reaction and the velocity constant is proportional to its concentration. The juice expressed by low pressure is more powerful as regards invertase action than that expressed by high pressures.The reason for this phenonienoii has not yet been ascertained. S. B. S.VEGETABLE PHYSIOLOGY BED AGRICULTURE. i. 195 The Complex Carbohydrates and Forms of Sulphur in Marine Algze of the Pacific Coast. D. R. HOAGLAND and L. L. LIEB ( J . Biol. Chem. 1915 23 287-297).-The carbohydrates of Macro cyst i s pgri f era and I r idnea Zccminarioides were investigated. From the acid-precipitate complex known as ‘‘ algin ” a pent- osazone closely resembling I-xylosazone was prepared ; in the alcohol-insoluble carbohydrate fraction of d-lncrocystis a methyl peiltose having the properties of fucose is present; a similar frac- tion from Iridiieci yielded only galactose.Marine a l p as exempli- fied by i5TZvu fnsciuta have a high sulphur content and estimations are presented of the sulphur held in various forms. W. D. H. Plant Chemistry. P. Q. KEEGAN (Chewz. hTezus 1915 112 295-296).-Qualitative organic analyses of hair moss (Poly- trichum commune) early purple orchis (0. mascula) and marsh marigold (CcrZth palzistris) estimations of ash and cf calcium magnesium phosphoric acid sulphates and chlorides in the ashes. N. H. J. &;I. Microchemistry of Plants. I. A Readily Crystallisable Tannin in Dionea muscipula. HANS MOLISCH (Ber. Deut. bot. Ges. 1915 33 447-451).-The stems and roots of Dioiiaea nzuscipula contain a crystalline tannin which can readily be obtained by treating sections with glycerol with concentrated solu- tions of sugar or with diluted mineral acids.N. H. J. M. The Measurement of Toxicity. W. J. V. OSTERHOUT ( J . Bzol. Chem. 1915 23 67-70).-Toxicity is recommended to be measured by ascertaining the electrical conductivity of living tissues. Instead of determining the time necessary t o cause death which the curves show is approached asymptotically the criterion selected should be some convenient point on the curve for example when half-way between the normal state and death is reached. It is also desirable to select a standard temperature for the observa- tions. The action of a large number of toxic substances follows the course of a unimolecular reaction. W. D. €I. Principles of Crop Production. EDWARD JOHN RUSSELL (TI 1915 107 1838-1858).-A lecture delivered before the Chemical Society on November 18th 1915.J. C. W. The Identity of the Proteins Extracted from Wheat-flour by the Usual Solvents. C. H. BAILEY and Ail. J. BLISH ( J . Biol. Chenz. 1915 23 345-357).-Extracts of flour with 1% solution of sodium chloride contained a large proportion (more than half) of gliadin in the total protein present. Ten per cent. solution of this salt or 5% solution of potassium sulphate contained about 15% of protein in the form of gliadin; 50% alcohol extracts more gliadin than 3076 o r 70% alcohol and the extraction is not complete unless the temperature is raised t o 8 3 O for three hours; in these extracts 93:L of the nitrogen is present as gliadin. The amount ofi. 196 ABSTRACTS OF CHEMICAL PAPERS. non-gliadin proteins extracted by 50% alcohol was constant regard- less of their amount in the flour.The separation of gliadin from non-gliadin proteins by heat coagulation was not quantitative considerable amounts of gliadin not being coagulated by boiling. W. D. H. Influence of Potassium Ferrocganide on the Growth of Plants. E HASELHOFF (Bied. Ze?ztr. 1915 44 474-4’75; Landw. Jnlzrb. 1914 47 338).-The results of pot experiments with beans in which potassium ferrocyanide (0.5 and 1 gram) was added t o the soil (25 kilos.) showed that in a loam soil the production of both seed and straw diminished whilst in a sandy soil only the yield of straw was reduced. I n water-culture experiments also with beans the results were less definite. It was however shown that the toxic action of potassium ferrocyanide begins when the solution contains 0*1-0*5 gram per litre and that the latter amount is strongly toxic.N. H. J. 33 Action of Sulphur on Plant Production. TH. PFEIFFER and W. SIMMERMACHER (Bied. Zentr. 1916 45 18-20 ; Fiihling’s Lcludw. Zcit. 1915 64 243).-Application of sulphur t o oats grown in plots on a soil containing plenty of organic matter failed t o increase the yield and the amount of nitrogen taken up. Similar results were obtained with sugar-beet grown on the same soil with- out further applications of sulphur. 0. M. SHEDD (Kentzicky Exper. Station BUZZ. 188 Dec. 1914).-The results of soil culture experiments showed that addition of sulphur and calcium sulphate resulted in a decided increase in the yields of tobacco soja beans and turnips whilst clover did not seem to be benefited.I n the case of beans the best results were obtained with sulphur. Several sulphates gave good results with mustard and in some cases with radishes. I n sand cultures with lucerne the best results were obtained with magnesium iron sodium potassium and ammonium sulphates and good results were obtained with sulphur. When sulphur is employed the soil must contain calcium carbonate in order to neutraliae the acidity produced by oxidation. Adsorption Power of Soil. 11. PAUL ROHLAND (Bied. Zeiztr. 1915 44 575; Internat. Mitt. Bodenk. 1915 5 102).-The red soil is a silicat’e which in contact with water forms numerous colloids as is shown by its power of adsorbing complex dyes such a6 aniline-red aniline-blue methyl-violet etc. As in the case of clay soils the adsorptive power of the red soils is greater with blue and violet dyes than with red and green dyes and least with brown and yellow dyes. The colorimetric method carr accordingly be employed far estimating the colloids of red soils. N. H. J. M. Relation of Sulphur t o Soil Fertility. N. H. J. M. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9161000194

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i 19'7 Organic Chemistry Process for Accelerating and Assisting the Fixation of Acetylene in Chemical Reactions Requiring the Presence of a Gatalyst. G. BOITEAU (Fr. Pat. 475553; from J. SOC. Chem. Ind. 1916 35 72).-The fixation of acetylene takes place mor0 quickly and completely and with less tendency to form tarry matters when the catalyst is formed in presence of the reacting sub- stance. Thus in the preparation of ethylidene diacetate from acetic acid and acetylene instead of adding mercuric sulphate as such it is formed by dissolving the oxide in the acetic acid and then adding the requisite quantity of sulphuric acid. C. R. MARSHALL and ELIZABETH GILCHRIST (Proc. Roy. Soc. Edin. 1915 35 227-23l).-When methylene iodide is mixed with an equimolecular quantity of alcoholic silver nitrate solution a crystalline precipitate of the composition AgNO,,CH,I separates almost immediately (compare Scholl and Steinkopf A.1907 i 116; Donnan and Potts T. 1910 97 1895). For the formation of this substance the silver nitrate solution should not be weaker than decinormal and gives the best results when saturated. The crystalline product which is best preserved under an alcoholic solution of silver nitrate decomposes slowly in the air giving a residual mixture of silver iodide and silver nitrate. When heated it decomposes a t 79-80° with evolution of iodine and nitrous fumes. Water causes decomposition with formation of nitric acid formaldehyde formic acid and silver iodide together with some of the unaltered constituent substances the change being facilitated by the addition of an alkali hydroxide.Potassium cyanide solution effects the liberation of the methylene iodide with simultaneous formation of potassium argentocyanide. From the fact that in alcoholic solution the conductivity of the above additive compound does not differ materially from that of the corresponding solution of silver nitrate it appears probable that in alcoholic solution the substance is almost entirely resolved into its constituents. G. F. M. Interaction of Methylene Iodide and Silver Nitrate. D. F. T. Esters of tert.-Trichlorobutyl Alcohol and their Pharmacology. R. WOLFFENSTEIN A. LOEWY and M. BACHSTEZ (Ber. 1915 48 2035-2043).-The idea of administering a phenol in the form of an ester which shwly hydrolyses in the alkaline fluid of the intes- tine has occasionally been extended to' alcohols.It has been assumed that just as the corrosive action of a phenol can be masked and the pharmacodynamical value be slowly and continu- ously brought out by using an ester so the esters of alcohols would have an additional pharmacological advantage over their com- ponents. As a matter of fact however such compounds as the- VOL. CX. i. ki 198 ABJl'RACrd OF CKEbfICAL PAPERS. nitrate and acetate of glycerol are known to act quite differently from either component and as most alcohols are so indifferent in themselves they can scarcely be expected t o lend any typical activity to their esters. The authors have therefore studied a number of esters of gem.-tricliloro-tert.-butyl alcohol OH*CMe,*CCl which is a powerful narcotic.It is found that most of the esters are unchanged in the organism however and that they frequently have a totally different action from the alcohol usually causing convulsions. 9 em .-Tric hloro- t e r t . -butyl alcohol is remarkable in many chemical respects. It seems very indifferent towards dehydrating agents sulphuric acid decomposing it like a hydroxy-acid namely with the evolution of carbon monoxide. Like chloral i t restores the colour t o Schiff's reagent and forms a hydrate. No sodium compound is known and an attempt t o prepare one using the granulated metal resulted in an explosion. The esters were usually made by the interaction of the acid chloride and the alcohol in the presence or absence of a tertiary base but some could be obtained by merely warming the acid and the alcohol together.gem .-Trichloro-tert .-butyl acetate CCl,*C Me,- 0 Ac was described by Willgerodt and Durr under the name acetoxy- butyric trichloride " (A. 1889 690). It is less narcotic but more toxic than the alcohol. The propionate is a pale yellow oil b. p. 88-90°/14 mm. and is still less narcotic; the isoualerate b. p. 108-110°/20 mm. is a non-narcotic convulsant ; the bromoiso- valerate CHMe,-CHBr*C0,*CMe,*CC13 b. p. 152O/17 mm. is a convulsant ; the1 chloroacetate m. p. 48O and the trichloroacetate long needles m. p. 40° are less active than the acetate. The die th y Za rnirz oacetat e NEb* CH,*CO,*CM.e,*CCl prepared from the chloroacetate by the action of diethylamine is an oil b. p. 142-145O/ 20 mm.which forms a crystalline hydrochloride and a IplatirLicfiloride platelets m. p. 2 1 2 O ; the dimethylaminoacetate also forms a hydrochloride rhombic plates m. p. 220O; both esters are powerful narcotics. The piperidylacetate C,H,,N*CR2*C0,* C,H6C1 is a very bitter oil and is a convulsant and not a narcotic. The allophanate NH,*CO*NH°C'0,*C,H6C13 m. p. 114O is also a con- vulsant although most allophanates are narcotics. The hydrogen rrzalouate CO,H*CH,*CO,*C,H,Cl six-sided platelets m. p. 116O and the mdonate m. p. 102-103° are remarkable in that they are not toxic or narcotic but lower the threshold of excitation. The ap-dibromo-P-pl~e,zylln.op.io,7ate CHPhBr°CHBr*C0,*C,H6C13 m. p. 99-looc is almost indifferent. J. C. W. Etherates of Magnesium Haloids.N. DOMANICKI ( J . RZLSS. Yhys. Chem. SOC. 1915 47 1790-1792).-Etherates of magnesium bromide and iodide were prepared by Menschutkin (A. 1904 i 215). Magnesium chloride forms a monoetherate MgCl,,Et,O which is obtained in white acicular crystals turning black and decomposing when heated by the action of magnesium on eitherORGANIC CHEMISTRY. i. 199 an ethereal solution of aj3-dichloroetliane or a mixture of dry ether with sulphur chloride Mg + S,C1 + Et,O = NgCl,,Et,O + S,. Mag- uesium chlorobromide ?noi/oethcrnte AiigC1Br,Et2.0 is obtained by the action of magnesium on an ethereal solution of a-chloro-y- bromopropane. A similar compound of magnesium chloro-iodide could not however be obtained probably because magnesium chloride forms only a mono-etherate and magnesium iodide only a di-etherate.T. H. P. Kephalin 11. Brain Kepbaiin. P. A. LEvmEund C. J. WEST (J. Biol. Chem. 1916 24 41-53. Compare Levene and West A. 1914 i 12).-The discrepancy between the formula of kephalin as calculated from the identified constituents (compare Parnas A. 1910 i 4; 1913 i 1253; Baumann A. 1913 i 1041; Renall A. 1913 i 1254) and the results of analysis appear to indicate either the presence of impurity or the existence of a constituent which has hitherto escaped detection. By submitting kephalin to treatment with various solvents it was not found possible tot alter the composition of the phosphatide the analytical results agreeing with a formula C4,H7,0,,NP whereas the hydrolytic products suggest C,,H@,NP. Conversion into and recovery from the lead salt also failed to effect any change in the composition of the original material.It is therefore probable that so-called kephalin contains some other substance in addition to the recognised components kephalinic acid stearic acid aminoethyl alcohol glycerol and phosphoric acid. The constituent which is unaccounted f o r may not form an essential portion of the molecule but may be a very persistent impurity. By reduction of a solution in a mixture of ether and acetic acid with hydrogen and colloidal palladium kephalin is reducible t o hydrokephalin an almost' colourless amorphous powder. D. F. T. Glyceryl Ester of Tetrachlorotetraiodoterapic Acid. Josh J. CERDEIRAS (Anal. Fis. Quim. 1915 13 439-441).-A substance isolated from cod-liver oil proved on analysis to be the glyceryl ester of tetrachlorotetraiodoterapic acid C3H,(C,7H,302Cl,14),.A. J. W. Syntheses by means of Mixed Organomstallic Derivatives of Zinc. Method of Preparation of a-Ketonic Acids. E. E. BLAISE (Bull. Soc. Chirn. 1915 [iv] 19 10-18. Compare Bouveault and Locquin A. 1904 i 551 847 848; 1905 i lo).- a-Ketonic acids can be prepared by the following series of reactions. Ethyl oxalyl chloride is condensed with a-hydroxyisobutyric acid and the crude acid product converted into its acid chloride by means of thionyl chloride. This acid chloride is then condensed with the requisite zinc alkyl iodide and the mixed cycloacetal obtained is decomposed by alcoholic hydrochloric acid the ethyl a-hydroxyisobutyrate and the ethyl ester of the a-ketonic acid being separated by fractional distillation.The ester is best hydro- A 2i 200 ABSTRACTS OF CHEMICAL PAPERS. lysed by boiling with aqueous oxalic acid. The following example is given. Ethyl oxalyl chloride when condensed with a-hydroxyisobutyric acid yields eth yloxalyloxyisobut yric acid OEt*CO*CO,*CMe,*CO,H in. p. 83O which gives a chloride b. p. 120*5°/12 mm. and an anilide. m. x). 95O. The acid chloride when condensed with I OEt c0.c; pl-oyo zinc propyl iodide yields the cyclometai 0-CMe b. p. 123-124°/11 mm. which when boiled with 5% alcoho1:c hydrochloric acid gives ethyl butyrylformate C,H,-CO*CO,Et b. p. 71-74O/ 12 mni. (compare Locquin loc. cit.) together with ethyl a-hydroxyisobutyrate and some diethylacetul of ethyl butysyl- formate b. p.96O/41 mm. which can also be prepared by the action of ethyl orthoformate on ethyl butyrylformate and on hydrolysis with aqueous oxalic acid gives butyrylformic acid in the same way as ethyl butyrylformate. Ethyl butyrylformate when isolated has b. p. 70*5O/ 11 mm. and gives a phenylhydrazone m. p. 8O-8l0. Butyrylformic acid obtained by hydrolysis of its ester has b. p. 79O/12 mm. (compare Moritz T. 1881 39 17) and gives a phenylhydrazone m. p. 101-102° (Locquin loc. cit. gives 9B0) a p-nitropheizylkydrazone brown needles m. p. 2 0 5 O and a semi- carbasone m. p. 2 2 0 O . When boiled in alcoholic solution for half an hour with benzaldehyde and P-naplithylamine butyrylformic acid yields a-phenyl-P-ethylnaphthacinchonic acid N W. G. Preparation of Formaldehyde from Methane. VEREIN ~ u i e CHEMISCHE INDUSTRIE IN MAINZ (D.R.-P.286731; from J . SOC. C'hem. Ind. 1916 35 73).-Methane is oxidised t o formaldehyde when it is passed mixed with a large excess of air or oxygen over a metal o r metallic couple a t 150-220°. Thus 3 parts of methane and 100 parts of moist air when passed over copper o r silver or both a t 150-200° is partly converted into formaldehyde and by means of a circulatory system the aldehyde is washed out with water and the unchanged methane mixed with morel oxygen returne'd to the catalyst. E. E. BLAISE (Bull. S'oc. chim. 1915 [iv] 17 425-428).-The chloro-ketones are best charactarised by preparing their semicarbazones under suitable conditions. Owing t o the unstable nature of these compounds their melting points are not always sharp unless taken on a mercury-bath.The semicarbazones are best prepared by adding t o the chloro-ketone semicarbazide hydrochloride1 (1-1.5 mols.) in aqueous solution filtering washing the precipitate with water and benzene or chloroform and without drying crystallising the semi- G. F. M. The Characterisation of Chloroketones.ORGANIC CHEMISTRY. i. 201 carbazone from warm benzene. The semicarbazones of the a-chloro-ketones with aqueous potassium carbonate readily yield the semicarbazones of the corresponding keto-alcohols and with an alcoholic solution of sodium acetate give the acetates of the latter semicarbazones. Under the above conditions the dichloro-ketones of the type CHCl,*CO*R give normal semicarbazones butl with an excess of semicarbazide hydrochloride they yield disemicarbazones of the1 type CH(CH,ON,)*C(CH,ON,)R whereas the dichloro- ketones of t.he type R*CC12*CO*R’ always give the disemicarbazones R*C(CH30N3)*C(CH30N3)R’.These disemicarbazones are in- soluble in all organic solvents except formic and acetic acids. Methyl chloroethyl ketone gives a semicarbazone C,H,Cl*CMe:CH,ON micaceous plates m. p. 143-145O which is converted by aqueous potassium carbonate into the semicarbazone OH. C,H,o CMe CH,ON m. p. 202O (compare Kling A. 1905 i 172) and with alcoholic sodium acetate ,gives the semicarbazone - m. D. 161O. CH,*CO,* C,H,*CMe:CH,0N3 Dichloroniethyl ethyl ketone with 1 mol. of semicarbazide hydrochloride gives the1 semicarbazo n e CHCI,* CEt:CH,ON 1x1. p. 142O and with 3 mols.of semicarbazide in aqueous alcoholic solution gives ethylglyoxaldisemicarbuzone CH( CH30N3) *CEt :CH,ON plates m. p. above 230O. Methyl aa-dichloroethyl ketone gives with free semicarbazide or its hydrochloride only dicxcetytdisemicarbazolze [CMe(CH,0N3)*] a sandy crystalline precipitate m. p. above 230O. Chloromethyl a-chloroethyl ketone gives a semicnrbuaone CH,Cl*C(CH30N,)*CHClMe m. p. 114O. Ammonia DerivFttives of ths SugRrs. P. A. LEVENE ( J . Bid. Chem. 1916 24 59-62).-1t has been recently suggested that the so-called glucosimines are in reality not imino-compounds a t all and that from a structural point of view a more correct term would be aminoglucosides (Irvine Thomson and Garrett T. 1913 103 238). An examination of glucosimine galactosimine xylosimine and lyxosimine was made by comparing the nitrogen values obtained by the Kjeldahl process and by the van Slyke method with nitrous acid (A.1912 ii 1008). The results indicate the presence of a primary amino-group in the molecule and thus confirm the view of Irvine Thomson and Garrett. Of the four compounds named lyxosimine was found to be most stable and glucosimine least stable. D. F. T. The Biochemical Synthesis of Alkpl Glucosides. IJI. Mono- glucosides of Polyhydric Alcohols. EN. BOURQUELOT ( A m . Chim. 1915 [ix] 4 310-379).-A more detailed account of work already published (compare A. 1903 i 544; 1913 i 323 428 663 747 781 989 1080 1305; 1914 i 499 662 1080; 1915 i 76 382 674 703 829 940 1076). W. G. W. Gi. 202 ABSTRACTS OF CHEMICAL PAPERS. Modification of Starch by Gaseous Hydrogen Chloride.FRANCIS C. FRARY and ARTHUR C. DENNIS ( J . Znd. Eng. Chem. 1915 7 214-216).-Results of experiments in which dry starch was treaied with gaseous hydrogen chloride a t temperatures vary- ing from 20° t o looo showed that for a given acidity there is a definite temperature range within which heating for thirty minutes will convert the starch into the soluble variety; a t higher temperatures tl;e starch is rapidly converted into dextrin. Similarly for a given temperature the range of acidity within which a soluble starch is produced in definite larger quantities of acid producing dextrin whilst smaller quantities fail to pro- duce the soluble starch. The react,ion does not however proceed in two stages; dextrin begins t o be formed in small quantity as soon as the formation of soluble starch commences.A good white dextrin could be prepared by treating starch with gaseous hydro- chloric acid & looo (the residual acid in the product would have to be neutralised) but the method is not well adapted t o the Saccharification of Starch by Hydrofluoric Acid. EDUARD KUNZ (Chpm. Z e n f r . 1915 ii 783 ; from Zeitsch. Spiritusind. 1915 38 295-296. Compare Deussen A. 1905 ii 31l).-Tlie hydro- lysing action of hydrofluoric acid on starch is only one-seventeenth a9 great as that of hydrochloric acid. When the starch is boiled with the more dilzte solutions of the acid the attainment of a high degree of saccharification requires a disproportionately long time. The action of the pure acid is considerably weaker than that of the conimercial acid this being attributed t o the presence i r i the latter of sulphuric and hydrofluosilicic acids comparatively small admixtures of such acids causing marked increases in the saccharifying power.At higher pressures (and temperatures) the time of saccharification is curtailed but the decomposition of the sugar is likewise facilitated. Increase in the proportion of the acid leads t o rapidly increasing decomposition and reversion of the dextrose . T. H. P. production of soluble starch. w. P. s. Ethylaminochromi-compounds. Ha. %$mrhiL (Re?.. 1915 48 2055-2057) .-Among the co-ordinated cobalt and chromium compounds there are not many which contain primary aliphatic amines. Such are Tschugaev's compounds (A 1906 i 814) and the products obta&ed by Lang with Carson and Joliffe (1903-1904) by the action of methylamine and ethyl- ainine on chromium chloride.The author has now prepared some chromium salts of the chloro- purpureo-series. Thus by the interaction of anhydrous ethyl- ainine and chromium chloride at below Oo he has obtained chloro- 2x7'7 fne fh.?/7cr mi11 OC?I ro ?n ich 7oridc [CrCl(NH,Et),]Cl a red com- pound which gives characteristic precipitates with a number of reagents. J. C. W.ORGANIC CHEMISTRY. 1. 208 Aminoglucoheptonic Acid. P. A. LEVENE (J. Biol. Chem. 1916 24 55-57).-For the purpose of an investigation having as its aim the determination of the configuration of the amino-deriv- ative8 of the sugars for example glucosamine aminoglucoheptonic acid was required.This substance of which an amorphous copper salt has already been”’described (Neuberg A. 1903 i 74; Neuberg and Wolff A. 1903 i 319) was prepared by the interaction of glucosamine hydrochloride hydrocyanic acid and ammonia in aqueous solution and was obtained in needles m. p. 169O (corr.). D. F. T. Dibufyramide and Dipropyltriezole with its Salts. W MILLER (Monatsh.; 1915 36 929-939).-The author has extended to butyric anhydride the process by which acetic anhydride has recently been made to yield diacetamide (Brunner A. 1915 i 1007) but finds that for the production of a good yield of dibutyr- amide certain modifications are necessary. When potassium cyanate is gradually added to butyric anhydride a t 120° interaction ceases to occur before the theoretical quantity has been introduced; as soon as this stage is reached it is necessary to cool and to remove the crystallised dibutyramide when the butyric anhydride mother liquor can again be heated and treated with more cyanate.In this way most of the anhydride can be finally converted into the secondary amide. Bibutyramide NH(C,H,O) prepared in this way forms a crystalline solid m. p. 108O and separates from benzene (probably with benzene of crystallisation) in needles m. p. near 80°. By heating with semicarbazide hydrochloride and calcium butyrate a t 130° it is converted into hydrazoformamide and dipropyltriazole together with a small quantity of a crystalline nitrogenous com- pound m. p. 155O. The dipropyltriazole purified by fractional distillation and recrystallisation was obtained as hygroscopic leaflets m.p. 67.5O; the silver and mercuric derivatives were obtained as crystalline solids ; hydrochloride apparently octahedral crystals m. p. 1 3 3 O . D. B’. T. Preparation of Carbamide. BADISCHE ANILIN &. SODA FABRIK. (Eng. Pat. 1914 24042; from J . SOC. Chem. Id. 1916 35 71-72).-The formation of carbamide from ammonium carbamate is accelerabd by the addition of neutral acidic basic o r saline catalysts such as water (set free from ammonium carbonate) char- coal sugar gum thiocarbamide carbamide itself oxides and salts of alkali or alkaline earth metals and various acids either free or as ammonium salts. Thus ammonium carbamate (from solid carbon dioxide and liquid ammonia) mixed with l0-20% of normal ammonium carbonate and heated a t 135-140° in closed vessels yields carbamide more quickly than when heated alone and with better yield than from ammonium carbonate alone.G. F. M.i. 204 ABSTRACTS OF CHEMICAL PAPERS. A New Series of Platinum Compounds Analogous to Cossa’s Salts. L. TSCHUGAEV and W. LEREDINSKI (Compt. r.end. 1916 162 43-45) .-By the action of acetonitrile on potassium platino- chloride Hofmann and Bugge (A. 1907 i 489) obtained platinous chloride bisacetonitrile PtC1,,2CH,.CN. Prom the mother liquors of this reaction the authors have isolated another substance. To the aqueous filtrate the chloride of Reiset’s base I was added and the precipitate treated with warm water containing a few drops of hydrochloric acid. A yellow solution was obtained from which Magnus’s salt separated and from the filtrate on cooling the compouiad (Pt4NH3)[PtC13(CH,*CN)] was deposited in quadratic plates.This when warmed with an excess of hydrochloric acid was decomposed giving Magnus’s green salt’ (Pt4NH3)PtC1 chloroplatinous acid and acetonitrile which was in turn hydro- lysed. I n aqueous solution with a solution of potassium platino- chloride in the presence of a little hydrochloric acid the com- pound gave a potassium salt K[PtCl,(CH,*CN)] from which the original compound was regenerated by the addition of the chloride of Reiset’s base I. When warmed with hydrochloric acid the potassium salt was decomposed forming potassium platinochloride and with acetonitrile in neutral solution i t yielded platinous chloride bisacetonitrile.From these experiments it follows that acetonitrile behaves in a manner analogous to ammonia and organic amineq towards platino- chlo’ridea. W. G. Hydrolytic Products of Bimolecular isovaleryl Cyanide and a New Preparation of zsoButyltartronic Acid. JOSEF PLATTNER (Monatsh. 1915 36 899-910).-Three methods of preparation have hitherto been applied t o the bimolecular acyl cyanides namely the polymerisation o f the simple acyl cyanides especially under the influence of solid alkali hydroxide or of sodium the action of the acid anhydrides on potassium cyanide and the action of acyl chlorides on hydrogen cyanide in ethereal solution in the presence of pyridine. By one or other of these methods the bimolecular cyanides derived from the acetyl propionyl and the two butyryl radicles have been obtained and the author has now extended the knowledge in this field by the preparation and examination of derivatives of birnolecular isovaleryl cyanide.Bimolecular isovaleryl cyanide was obtained by the’ interaction of isovaleric anhydride and potassium cyanide in the cold but the product was an oil and could not be freed from admixed anhydride and acid. On treatment of the cyanide with hot hydrochloric acid there was liberation of carbon dioxide and hydrolysis was therefore effected by treating in the cold with the calculated quantity of water mixed with sulphuric acid (1 7 by weight); in this way there was obtiined together with the corresponding uni- molecular amide the bimolecular isovalerylformamide CHMe,*CH,-C(CO*NH,),*O*CO*CH,*CHMe lustrous leaflets m.p. 167* which was further hydrolysed by boil-ORGANIC CHEMISTRY i. 205 ing dilute hydrochloric acid to isobutyltartronic acid CHMe,*CH:,*C(CO,H),*OH deliquescent microscopic tablets m. p. 107O with decomp. (compare Guthzeit A. 1882 239); the lead silver barium and phenyl- iiydrazine salts were obtained as crystalline solids the last having m. p. 136O (decomp.). is0 Valerylf ormamide (a-he to- y-met hylvaleramide) CHMe,* CH,*CO-CO*NH obtained in the preparation of the bimolecular compound and pro- duced in better yield by using for the hydrolysis d the dicyanide a cold mixture of sulphuric acid and water in the proportions 70:5 forms large tablets m. p. 60°. This substance on hydrolysis with warm dilute hydrochloric acid gave a-keto-y-methyl-n-vnleric acid an uncrystallisable syrup which was analysed as the silver salt a yellowish-white granular crystalline powder and as the phenyl- hydrazone yellow silky needles. D.F. T. Syntheses of Hydrocarbons in the Aryl and cycZoHexane Seriee. PAUL SABATIER and MARCEL MURAT ( A m . Chirn. 1915 [ix] 4 253-309).-A r6sum8 of work already published (compare A. 1903 i 393 453 454 733; 1905 i 254 267 333 401 587; 1907 i 587 747; 1910 i 668 669; 1912 i 353 414 547 617 757; 1913 i 255 330 362 468 700 716 845; 1914 i 168 323 400 404 547 548 1068; ii 276 729). W. G. Aromatic Nitro-derivatives. V. Reactivity of the Nitro- group in Aromatic Compounds. MICHELE GIUA (Gazzetta 1915 45 ii 348-362. Compare A. 1915 i 659).-The compound by the action of sodium hydroxide on s-trinitrobenzene in acetone soIution forms reddish-brown crystals exploding when heated and yields the original trinitrobenzene when treated with acid.The following further systems have been analysed thermally. With m - dinitrobenzene-diphenylaminel 2 4 - dinit’rotoluene- diphenylamine and 2 4 6-trinitrotoluene-diphenylamine com- pounds are formed which dissociate in the fused state but in no case is any indication obtained of the formation of a compound with a definite melting point. The system m-dinitrobenzene- acenaphthene forms a compound m. p. 72*3O containing 50 mols. % of each component and two eutectics. 2 4-Dinitrotoluene- acenaphthene yields a similar compound m. p. 61O (compare Buguet A. 1910 i 105). 2 4 6-Trinitrotoluene-acenaphthene yields a compound m.p. 109*7O which may be obtained in shining yellow needles by crystallising a fused mixture of the components in molecular proportions from alcohol (compare Buguet Zoc. cit.). To the saline products of nitro-derivatives which were described by Hantzsch and do not give the original nitro-derivatives when treated with an acid constitutional formulze such as those of Angeli (A. 1898 ii 216) or Meisenheimer (A. 1902 i 795) can scarcely be attributed. I n these cases the nitrogen of the nitro- C(No2’:UH> C:NO*ONa prepared H OH>C<C( KO9) c H k*i. 206 ABS'P'KAC'I'S OF CHEMICAL PAPERS. group also exerts a function and becomes less strongly linked to the carbon atom of the aromatic nucleus a less stable complex resulting; it is indeed found that all these substances explode more or less readily when heated.With scjdium ethoxide m- dinitrobenzene forms only the compound C,H,(NO,),,NaOEt ; 2 4-dinitrotoluene gives the compounds C,H,Me(NO,),,NaOH and C6H,Me(N0,),,2NaOEt,EtOH and 2 4 6-trinitrotoluene the com- pound C,H,Me(NO,),,NaOEt. T. H. P. An Anisotropic Aqueous Solution. H ~ K A N SANDQVIST [Bey. 1915 48 2054-2055).-For every concentration there is a definite point a t which solutions of IO-bromophenanthrene-3(or 6)-sulphonic acid (A. 1913 i 846) become clear or turbid as the case may be. Thus a 0*5N-solution shows a sharp transition a t 22*83O a 0.319N- solution a t 9'47O. The agreement between the points at which the solutions become clear or turbid shows that the turbid phase is not a supersaturated solution.The microscope reveals it to be rather a liquid crystal." J. (3. W. The Resolution of Asymmetric Quinquevalent Nitrogen Compounds. JOSEPH REILLY (Proc. Carnb. Phil. Soc. 1915 18 l77).-Weak acids like tartaric or camphoric so.netimes effect the resolution of quinquevalent nitrogen derivatives when stronger acids such as P-camphorsulphonic or a-bromocamphor-rr-sulphonic fail and vice versii. The active phenylbenzylmethylallyl- ammonium iodide originally obtained by Pope and Peachey (T. 1899 75 1127) was obtained by fractional crystallisatim of p hen yl b enzylmeth ylall yl d- or Z-j3-c amp horsulphonat e and subse- quent decomposition of the resulting product with potassium iodide. The resolution is much more difficult if a-bromocamphor-a- sulphonate is used.It has been suggested that this selective action may be due to racemisation or to hydrolytic dissociation of the salts but the author considers that similar solubilities of the dBdA and ZBdA compounds is a more likely explanation. By the action of anhydrous silver d- and Lu-bromocamphor-rr- sulphonates and d- and I-phenylbenzylmethylallylammonium iodides under different conditions the compounds dBdA dBZA ZBZA and ZBdA were obtained. These compounds are of the same order of stability as the corresponding P-camphorsulphonates and show only a very slight tendency t o racemise a t the ordinary tem- perature in water. The first-mentioned compound can be recrystal- lised from dry ethyl acetate without change of activity but on recrystallisation from alcohol a slight fall and on crystallisation from chloroform a greater fall in rotation was observed.T. s. PA. Preparation of Diaminodiphenylcai~bamidetetrasulphonic Acid. FARBWERKE VORM. MEISTER LUCIUS AT BRUNING (D.R.-P. 286752; from J . SOC Chem. Ind. 1916 35 36).-A diamino- diphenylcarbamidetetrasulphonic acid in which the sulphonic groups are in the met,a-position to the carbamide residue is obtainedORGANIC CHEMISTRY. i. 207 by the action of carbonyl chloride on p-phenylenediaminedi- sulphonic acid in presence of a substance capable of combining with an acid. I n the azo-dyes derived from this acid the sulphonic groups will occupy the orkho-position t o the azo-group in which position they exert a favourable influence on the affinity of the dye for cotton and its fastness to light.G. F. M. Action of Derivatives of Phenols on Ethyl Diazoacetate. 11. G. CALCAGNI (Gazzetta 1915 45 ii 362-368).-By the method previously employed (A. 1915 ii 14) the author has investi- gated a t the ordinary temperature the hydrogen-ion concentration of saturated aqueous solutions of 0- m- and p-nitrophenols a- and &naphthols tribromo- and trichloro-phenols rosolic acid phenolphthalein alizarin and helianthin and of an N / 10-solution of pchlorophenol and an N/20-solution of picric acid; the water used had the conductivity 1.5 x 10-6. I n some cases constant con- ductivity could not be attained and in others the values found are extremely small owing t o the very slight solubilities. For those of the compounds with which satisfactory results were obtained the results are as follows pLchloropheno1 K = 0*0001072 C = 0'0,2784 ; picric acid I< = 0.2061 C,= 0.005353 ; o-nitro- phenol IT = 0.0005485 C = 0-0,1425 ; p-nitrophenol I< = 0*001230 C,=0*0,3195 ; helianthin K=0*001226 C,=O.O,3184.The val-aes of C given are not very accurate owing to the lack of strict proportionality between K and C,. The specific conductivities at 25O are picric acid 0.003631 ; p-chlorophenol 0*0,2341; o-nitro- phenol 0.0,4960 ; p-nitrophenol 0'0,1373 ; helianthin 0'0,1923 ; a-naphthol 0'0,327 ; &naphthol 0'0,2336 ; trichlorophenol 0'0,5215 ; tribromophenol 0*053252 ; alizarin 0.0,1992. I n the case of derivatives of phenol the acidity depends on the nature and number of the groups introduced into the molecule.T. H. P. P8- Dinaphthol and 2-Hydroxy-a-naphthyl 6-Naphthyl Ether. 0. HINSBERG (Ber. 1915 48 2092-2095. Compare A. 1915 i 810).-A reduction product m. p. 1 9 7 O was recently obtained from dehydro-P-naphtholsulphone which was supposed to be a PP-dinaphthol. It is now found that i t gives only mono-acyl deriv- atives and from its mode of formation and properties it is regarded as 2-h~drox~-a-?zaphthyl P-nupJi thy1 e t h e r OH*C,,H,*O*C,,H,. The acetate has m. p. 115O and retains solvent acetic acid some what firmly whence i t was originally regarded as a diacetate. The m-nitrob e ? ~ z enesulpho rzate C,,H,,O*O*SO.;,*C,H,*NOz forms colourless clusters of needles m. p. 139O and the p-nitrobenzoate crystallises in pale yellow rosettes m. p. 154O.An attempt was made t o synthesise the compound by condensing 1-bromo-&naphthol with &naphthol in the presence of a solution of sodium in dilute methyl alcohol but the product of the reaction was PP-dinaphthol m. p. 216O. This dinaphthol was also prepared by heating 1-bromo-&naphthol with copper powder at 230O. k+ 2 J. C. W.i. 208 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Aromatic Tellurium Compounds. KARL LEDERER (Ber. 1915 48 2049-2054. Compare A. 1915 i 1056). -Further examples of the preparation of tellurides and ditellurides by t.he action of tellurium dihaloids on magnesium aryl haloids. The p-anisyl and pphenetyl tellurides obtained in this way differ from those obtained by Rohrbaech (A. 1901 i 273) by reducing the products of the action of tellurium tetrachloride on the two ethers (Rust A.1898 i 137) with zinc. It is believed that the earlier compounds are not para-substituted tellurides but methylene compounds thus 2C,H,-OMe + TeCl + TeCI,(CH,-OPh) (Rust) ; -+ Te(CH,*OPh) (Rohrbaech). Magnesium ptolyl bromide reacted with tellurium dibromide or di-iodide to give a little di-ptolyl some resinous di-ptolyl ditelluride and chiefly di-ptolyl telluride which was purified by conversion into the dibromide and reducing this by sodium sulphite. It had m. p. 69-70° and bl. p. 211-212°/18 mm. (com- pare Zeiser A. 1895 i 512). Magnelsium o-tolyl bromide was also treated with tellurium dichloride or dibromide and di-o-tolyl telluride was obtained with m. p. 37-38O b. p. 202-203°/15 mm. (ibid.). Anisole and phenetole were heated with tellurium tetrachloride until solid products were obtained and these were reduced to tellurides by means of sodium hyposulphite.The telluride from anisole formed dark red needles m. p. 50°; the phenetole com- pound orange-red leaflets m. p. 64O. The anisole derivative was warmed with methyl iodide and the product was converted into a picrate which seems to be aitisylcFimethyltelluronium picrate TeM~*C,H,O,C,H,O(NO,) yellow crystals m. p. 126-127O. The elimination of one anisyl residue on methylation is evidence in favour of the assumption that the tellurium is attached tol the alkyl group in these tellurides. J. C. W. Isomerieation of cjycZoPentylcarbino1 on Conversion into Halogen Derivatives. 8. S. NAMETKIN and (MLLE.) 0. N. MOROZOVA ( J .RUM. Phys. Chem. SOC. 1915 47 1607-1610).-1t has been previously shown (A. 1912 i 172) that the action of fuming hydriodic acid on cyclopentylcarbinol and reduction of the result- ing iodo-derivative by means of zinc dust in aqueous alcohol yields a product containing cyclohexane. Further experiments on this question have now been carried out in the following manner. cycZoPentylcarbino1 was converted in various ways into the corre- sponding haloid derivatives which after distillation under diminished pressure were converted by the Grignard reaction into the organo-magnesium compound the latter being then transf orined by the action of oxygen etc. into the alcohol. The properties of this alcohol and of its urethane were compared with those of the original alcohol and the formation of adipic acid by oxidation of the final alcohol with nitric acid was also investigated.The results show that in aqueous solution hydrochloric hydro- bromic or hydrio'dic acid causes partial isomerisation of the five-ORGANIC CHEMISTRY. i. 209 membered ring-system of cyclopentylcarbinol into a six-membered one a t 100-105°. The extent of the isomerisation is in all cases of the order of SO% and appears t o depend but little on the nature OE the halogen hydracid. Less marked but undoubted isomerisa- tion takes place when the cyclopentylcarbinol is treated with iodine and red phosphorus. Since such a stable alicyclic system as that of cyclopentane is so easily isomerised under the influence of halogen hydracids the question arises whether the same may not occur under similar conditions with the analogous cyclohexane.T. H. P. PI oduction of o-Sulphamidobenzovl-p-phenetidiue. CHEMISCHIC FABRIK VORM. SANDOZ (Eng. Pat. 1915 9511; from J . SOC. Cheni. Znd. 1916 35 72).-o-Sulphamidobenzoyl-pphenetidine is ob- ta,ined as a crystalline powder by heating pphenetidine with o-benzoylsulphiniide or with methyl or ethyl o-sulphamidobenzoate for some hours a t 120° out of contact with air and after boiling with water treating with sodium carbonate to slight alkalinity. It is non-poisonous has antipyretic and hypnotic properties and although comparatively easily saponified by dilute alkalis is resistant to dilute acids. G. F. M. The Action of Sunlight on the Cinnamic Acids. A. W. K. DE JONG (Proc. iT.Akad. TVetensch. Amsterdam 1916 18 751-756). -The author finds that the methods described by Erlenmeyer and Barkow (A. 1906 i 429) for the preparation of a- and P-storax- cinnamic acids are1 not entirely satisfactory and indeed the method for the conversion of the a-acid into the P-isomeride by heating above the m. p. of the former is stated not t o achieve the desired result. According t o the author’s experience the P-acid is most conveniently obtained by pouring an alcoholic solution of the a-isomeride saturated a t the ordinary temperature into a large quantity of water. It may also be obtained by allowing warm solutions of cinnamic acid t o crystallise the lower the temperature of crystallisation the more favourable being the conditions for the formation of the P-acid.Experiments on the spontaneous change of the 8-acid into the a-isomeride indicate that both a t the ordinary temperature and also at higher temperatures the former acid is metastable. On the assumption that in the solid condition these acids exist in a birnolecular condition the author suggests the structures for the a- and P-acids respectively. This view receives confirma- tion from the fact that the solid potassium calcium and barium salts of either the a- or the P-acid when exposed to light yield only P-truxillic acid which result indicates that only the P-isomeride is capable of forming salts. D. F. T.i. 210 AHSTRACTS OF CHENICAL PAPERS. The Nitration of Phenylpropiolic Acid. S. REICH (Compt. rend. 1916 162 129-130).-Phenylpropiolic acid can be nitrated without the side-chain being oxidised if the acid is added in small portions t o nitric acid (D 1.50) a t -ZOO.The product of the nitration is p-iiitrophenylpropiolic acid. If the nitration is effected a t Oo a small amount of o-nitrophenylpropiolic acid is also obtained. I n neither case could any m-nitrophenylpropiolic acid be detected. The group *CiC*CO,H thus orientates the *NO group into the para- and secondarily into the ortho-position. I n this respect phenylpropiolic acid resembles cinnaniic and phenyl- propionic acids in its behaviour. W. G. Abietic Acid. YJWER POOTH (Clicm. Xentr. 19 15 ii 790 ; from Parbenseit. 1915 20 1056-1059).-A critical discussion of publications dealing with the constitution of abietic acid. T. H. P. Phenyl Propyl Ketone.E. G~LUIANO (Gaxzettu 1915 47 390-396).-Phenyl propyl ketone (compare Senderens A. 1910 i 179) forms colourless crystals m. p. 1l0 b. p. 231°/727 mm. 1):' 0.992 and yields a highly fluorescent solution with concen- t r a t ed sul p hu r ic acid . Its 0- t ol y Zh y d ra s o n e CPhPr:N*NH*C6HaMe is an oil and its p-tolylhydruzone forms colourless or faintly yellow needles m. p. 7 2 O . CPhPr N NH*C,H,Me forms colourless or faintly yellow needles m. p. 1 0 5 O . The as.-rn-ay7yZhydm z o n e CPhPr N*NH*C6H3Me2 f onns colourless or pale yellow needles and like the two preceding compounds is moderately stable in alcoholic solution but unstable in the solid state determination of the melting point in this case being impossible . The oxime undergoes the following series of transformations CP1iPr:NOH -+ CPhPrXC1 + CPrC1:NPh -+ OH*CPr:NPh The s-3/-curnylhydrazone7 -+ C,H,-CO*NITPh 4 NH,Pli+C3H7*C0,H so that it has the configuration i '3 1 1 c *C',FJ i.i!*OH The energetic action of nitric acid on the ketone yields benzoic and propionic acids but when the action is moderated (compare Fileti and Ponzio A.1895 i 499) the products appear t o contain phenyl ethyl diket one and a dinitroso-derivative decomposing violently at looo with evolution of nitrous vapours. T. H. P. Stereochemistry of the Quinone-oxinies. F. KEIIRRIANN (Bu. 1915 48 202r-Z035).-An account of some orienting work on the quinone-oximes completed in 1902 in extension of earlier work (A. 1900 i 180). VII. Monoximes of t h e 3-Hnlogeno-2 ; 5-tolupuinones. [With F.MUSSMANN and CARLO FACC HINETTI.1-The preparation and reactions of 3-iOdO 2 5-toluquinone monoxime have already beenORGANIC CHEMISTRY. i. 211 described (A.) 1889 993) and an account of the chloro- and bromo- compounds is now given. 3-Chloro-2 5-toluquinone prepared by oxidising dichloro-o-cresol with chromic and acetic acids was converted into 3-chloro-2 5- tolupuinone-5-oxime O:C,H,Cl:N.OH which crystallised in glisten- ing pale yellow leaflets and yielded an acetyl derivative C,H80,NC1 which crystallised in two forms namely pale yellow st'able needles rn. p. 7 2 O and stout amber-coloured prisms m. p. 6 2 O . The oxime was reduced by means of stannous chloride t o 3-chZoro-5-amino-o-cresoZ colourless needles m. p. 1 3 7 O which quickly darkened in the air and also oxidised by means of cold dilute nitric acid to 3-chloro-5-nit~~o-o-cresoZ pale yellow prisms m.p. 122O. 3-Bromo-2 5-toZuqz~inone was obtained from dibromo-o-cresol in long orange-yellow needles m. p. 93*5O and Converted into 3-bronro-2 5-to~z~quii&o?z e-5-oxime C,H80,NBr which crystalked in lemon-yellow leaflets and yielded two acetyl derivatives the stable one having m. p. 7 4 O the labile one ni. p. 7 1 O . The oxime was reduced t o 3-brorno-5-crnzino-o-cresoZ needles m. p. 142O (hydro- chloride colourless needles ; acetyl derivative needles m. p. 165O) and oxidised by cold dilute nitric acid t o 3-bromo-5-nitro-o-creso1 m. p. 120.5O and by h o t dilute nitric acid to 3:5-dinitro-o-cresol yellow needles m. p. 85-5O. VIII. Dioxime of 4-chloro-2 5-tolupinone and the ilfouoximrs of 4 6- and 3 6-Dichloro-2 5-tolitq.ztinones.[With GIUSEPPE' SILVA and CORNELIUS I<ELETI.]-Bo~~ modifications of 4-chloro-2 5- toluquinonemonoxime (A. 1899 i 128) yielded the dioxirne C,H70,N2Cl when boiled with an excess of hydroxylamine hydro- chloride in concentrated alcoholic solution with the occasional addi- tion of sodium carbonate. The dioxime was obtained as a micro- crystalline powder decomp. about 240° which formed a sodium salt in stout golden-yellow prisms and yielded only one dicrcetyl derivative C,,H,,O,N,Cl in stout prisms decomp. about 185O. It was reduced to 4-chlorotolylene-2 4-diamine which was character- ised by the hydrochloride CH,*C6H,C1(NH,),,2HC1 and the diacetyl compound silky snow-white needles.The dioxime was also oxidised by means of an alkaline solution of potassium ferri- cyanide to 4-chloro-2 5-d~nitrosotol2~ene a lemon-yellow powder decomp. 163-165O and this was oxidised by warm concentrated nitric acid to 4-chloro-2 5-dinitrotoluev e which crystaNised in stout amber-yellow prisms m. p. 1 0 7 O . 4-Chloro-2 5-toluquinone was treated with fuming hydrochloric acid when it yielded a mixture of di- and tri-chloroquinols. This was oxidised and 4 6-dichloro-2 5-tolup~iiirouf was isohteri from the product in golden-yellow leaflets m. p. 85-86O) which yielded 4 6-dichloro-2 5-tolupz~inone-2-oxime O:C,H,Cl,:N-OH pale yellow needles. The oxime formed a benzoyl derivative m. p. 1 5 4 O was oxidised by dilute nitric acid to 2 4-dichZoro-6-nitro-m-crPsol long pale yellow glistening needles m.p. 128O and converted by nieans of stannous chloride into 4 6-dichlorotoluquinol. 3-Chloro-2 5-toluquinone was converted as above into 3 6-i. 212 ABSTRACTS OF CHEMICAL PAPERS. dichloro-2 5-toluquinone7 leaflets m. p. 76O with alcohol of crystal- lisation in long golden prisms m. p. 67O and this yielded the corresponding quinol C,H60,C1 needlels m. p. 85O which formed a &acetate m. p. 110.5O. The quinone gave rise t o 3:6-dichloro- 2 5-tolupuinone-5-oxime pale yellow needles m. p. 135O (decomp.) and t'his formed an acetyl ,derivative C,H,O,NCl compact rhombic pleochrol'c crysbals [a b c = 0.86265 1 1.15921 m. p. 8 5 O . The oxime was also reduced to 3 6-dichloro-5-arnino-o-cresol7 stout needles m.p. 128O (diacetyl derivative m. p. 129O) and oxidised to 3 6-dichloro-5-nitro-o-cresol7 pale yellow crystals m. p. 135O (acetate m. p. 98O). J. C. W. Acenaphthenequinonearylhydrasones. A. CRUTO (Gaxxetta 1915 45 ii 329-335).-Acenaphthenequinonephenylmethyl- hydrazone (compare Auwers A. 1911 i 171) may be obtained directly from methyl sulphate and acenaphthenequinonephenyl- hydrazone Auwers's view that the latter is a true' phenylhydrazone of the formula c]@6<e0 and not a hydroxyazo-compound :N,HPh being thus confirmed. Various CON NPh of the structure C,,,H,<E.OH other arylhydrazones of acenaphthenequinone have been prepared their N-methyl derivatives that is the arylmethylhydrazones being in some cases obtained by the action of met'hyl sulphate. A cenaph t hene puinone-o-tolylhydrazone C,,H60:C:N*NH*C6H,Me forms shining red needles m.p. 175O and dissolves in concentrated sulphuric acid giving an intense blue coloration. The m-tolyl- hydrazone forms small shining yellow prisms m. .p. 134O and gives a deep red solution in concentrated sulphuric acid. The p-tolylhtydrazone forms long orange-red crystals m. p. 163O and is only slightly hydrolysed on prolonged boiling with concentrated hydrochloric acid. The as.-m-xylylhydrazone C,,H,0:C:N*NH*C,H3Me2 forms long ruby-red prisms m. p. 183O and gives a reddish-brown solution in concentrated sulp huric acid. The as .-m-xyTyZme t hylh ydrazoiz e C,,H,0:C:N*NMe*C,H3Me2 forms small red prisms m. p. 157O. The1 +-cumylhydrnzone C,,H,0:C:N*NH*C6H2Me3 forms long bright red needles m.p. 292O and dissolves in concentrated sulph- uric acid with a red coloration. The o-anisylhydrazone CI9Hl4O2N2 forms dull deep red prisms m. p. 218O and in concentrated sulphuric acid yields an intense blue solution. The p-anisylhydrazone forms intense garnet-red needles m. p. 157O and in concent,rated sulphuric acid gives a brownish-yellow solut?ion showing intense blue fluorescence. The p-pli eizeth?/Zhydrazone C,,H,,O,N forms minute bright red needles m. p. 151° and dissolves in concentrated sulphuric acid giving a yellow solution which shows blue fluorescence. The pbromophenylhydraeone CI8H,,ON2Br forms minute yellow neadlw m. p. 193O and gives an intense ruby-red coloration withORGANIC CHEMISTRY. i. 213 concentrated sulphuric acid. The p-bromopltenylmethtylhydrazone CI,H130N2Br forms shining orange-yellow needles m.p. 143O. T. H. P. Synthesis of Terpineols and Terpins. 0. WALLACH [with HANS BERTHOLD LOUIS AUGSPURGER HANS WOERLITZER and FRIEDRICH POHLE] (Chem. Zentr. 1915 ii 824-829; from Nachr. K. Ges. lvzss. Gottingen 1915 1-27).-[Witlh HANS BERT'IIOLD.]-T~~ saturated liydroxy-ketone \/ \Ac obtained as an inter- RI e OII/\- / mediate product in the oxidation of /3-terpineol t o 1 4-methylcyclo- hexenyl methyl ketone is also formed when the latter is hydrated by shaking with 4% sulphuric acid solution for six to eight weeks; it forms a semicarbazone m. p. 197-198O. The dibromide CgH140Br2 m. p. 61° does not lose its bromine when treated with aqueous potassium hydroxide; when boiled with acetic acid i t undergoes marked resinification and yields a little p-tolyl methyl ketone.When reduced by means of nasceryt hydrogen 1 4-methyl- cyclohexenyl methyl ketone yields the low& homologue of terpineol Me/-\CHMe*OH (compare A 1902 i 803) which gives 1 8-dihydroxy-l-methyl-4-ethylcycZohexane C,H,,O m. p. 94-95O when treated with dilute sulphuric acid. Reduction of 1 4-methyl- cyclohexenyl methyl ketone with palladium-hydrogen gives 8-h ydroxy-l-methyl-4-e th ylcyclohexa?ze Me /-\CHMe*OH b. p. 203-205O D17 0.9110 m 1.46405. Treatment of the 1 4-methyl- cyclohexenyl methyl ketone obtained from 8-terpineol with mag- nesium methyl iodide leads t o the formation of a-terpineol which can thus be synthesised from the /3-modification. Homo-a-terpheol Me/-\CMeEt*OH b.p. 235-237O D20 0.9390 n 1.4850 is similarly prepared by the action of magnesium ethyl iodide. When heated with sodium methoxide the oily dibromide C11H19Br2*OH yields a homologous pinol which passes readily into' the higher homologous cymene l-methyl-4-isobutylbenzene C,H,Me*CHMeEt. Treatment of homo-a-terpineol with permanganate gives a trihydric alcohol C,,H,,(OH) b. p. 140-150°/5 mm. difficult to1 purify. The homologous 1 8-terp-n \('-\cM%-oH m. p. 65-67O is obtained by shaking homo-a-terpineol with dilute sulphuric acid. The homologous menthanol Me/-\CMeEt*OH b. p. 106-108°/5 mm. or 223-225O/760 mm. D19 0.9115 nD 1.4683 formed by reducing homo-a-terpineol with palladium- hydrogen gives a phenylurethane m. p. 115-120° and seems to \ -/ \-/ \-/ Rl0 OH/ \-/ \-/ be a mixture.The homo-a-terpineol Ety \CMe,*OH m. p \-/i. 214 ABSTRACTS OF CHEMICAL PAPERS. 92-94O b. p. 226-227O Dl* 0.943 72 1.4811 obtained from ethyl- nopinol (A. 1908 i 429) is isomeric with that described above. The corresponding terpin 1 8-dil~ydroxy-l-etl~yZ-4-iso~opyZcyclo- hexane ',' \-CMe,*OH m. p. 75-76O (with water of crystallisation) is obtained by treatment with 5% sulphuric acid solution. [With HANS BERTHOLD.]-T~~ simple unsaturated alcohols described above were converted into aromatic hydrocarbons by treatment with bromine (I mol.) in acetic acid and boiling until evolution of hydrogen bromide ceases. I n this way a-terpineol dibromide yields cymene b. p. 174-175O D20 0.8575 n 1.4909; 7-hydroxy-l-metliyl-4-ethyl-A~-cycZoliexene gives 1-methyl-4-ethyl- benzene ; homo-a-terpineol o r the homologous pinol (vide supra) yields l-methyl-4-isobutylbenzene and the homo-a-terpineol from ethylnopinol gives 1-ethyl-4-isopropylbenzene. [With LOUI s AUGSPURGER.]-~-I~~~ t h y ~ - ~ - p r o ~ ~ ~ c y c ~ o ~ e x e n 3fe/-\PrY prepared by heating 1-methyl-4-propylcyclohexan- 4-01 with dilute sulphuric acid was not obtained of constant boil- ing point.The fraction b. p. 173-176O yields a nitrosochloride m. p. 134-135° a nitrosate in. p. 119O and a nitrolpiperidide m. p. 150-152O. Scission of hydrogen chloride from the nitroso- chloride gives the liquid oxime of $-met I~yZ-l-~opyZcyclohexen-6- one (annexed formula) b. p. 220-223O (darkening) 95-98O/ 12 mm. D20 0.9225 n 1.4732; the semicarbazone 0 C,,H,gON3 has m.p. 153-154O. Reduction of this ketone yields l-methyl-4-propylcyclohex~~3-one N f ' p ~ . (normal menthone) CloHI8O. b. p. 215-217O '-' D19 0.8960 nD 1.4511 which is a colourless liquid having no odour of mentlione; its semicarbazone C,,H,,ON m. p. 149-15Z0 arid oxime m. p. 87-88O were prepared. Oxidation of the ketone by means of chromic acid gives a ketonic acid with the same number of carbon atoms; the semicarbazone of the acid C!,H,,O,N has m. p. 156-158O. The hemicyclic hydrocarbon 1-me t h yl-4-propenylcyclo hexnn e Me ' ' CHE t b. p. 173-1 74O D20 0.8110 n 1.4571 which is isomeric with 4-methyl-1-propyl- cyclohexene (vide supra) is obtained by the method previously given (A. 1908 i 405) from the condensation product of ethyl a-bromo-n-butyrate and l-methylcycZohexan-4-one and yields a nitrosochloride m.p. 138-140° and a nitrolp*periclide m. p. 148-149O. From the nitrosochloride is obtained the oxime m. p. 105-106° of the unsaturated Jietone Me/-'COEt b. p. 230-231O. Reduction of the ketone by Skita's method gives the saturated extracyclic ketone Me'-' COEt b. p. 210-211° Dl* 0*9090 nD 1.4541 which forms a semicarbazone m.,p. 182-183° and an oxime C,,H,8:NOH m. p. 95-96O; the specific gravity of the saturated extracyclic ketone is higher than that of I'k - ()Z/'\-/ \-/ /- \- / \-/ '\- /ORGANIC CHEMISTRY. i. 215 the cyclic ketone. The -me normal menthone is obtained by the reduction according to Skita’s method of i-l-methyZ-4~ZyZcyclo- hexan-3-one which is prepared from i-l-methylcycZohexan-3-one has an odour resembling that of isonitriles and yields an oxime m.p. 99-looo (not sharp) and a semicarbasone m. p. 125-128O (not sharp). [With HANS WOERLITZER.]-u- and P-Tanacetonedicarboxylic acids may be converted into tanacetophorone in the following manner (compare A. 1912 i 262). Esterification of the ketonic acid by means of alcoholic hydrogen chloride yields an ester hydro- chloride which is transformed into tanacetophorone by sodium alkyloxide. 2-Methyl-4-isopopyZ-Ai :3cyclopentadiene obtained by the action of magnesium methyl iodide on tanaceto- phorrone is a liquid b. p. 166-167O D21 0.845 nD 1.4913 which readily undergoes change in the air. isoPropylcyclopenterisopropy1- cyclopentanone C16€1260 m. p. 77-78O prepared by the action of sodium ethoxide on isopropylcyclopentanone yields an oxime m.p. 125-149O and a semicarbazone m. p. 192-5O. Reduction of the unsaturated ketone with palladium-hydrogen in methyl alcohol yiellds isopro~~Zcyclope 12 tylisopropylcyclopentanone (annexed formula) as a colourless odourless oil m. p. j-1-i-1:~ 157-165O/11 mm. which solidifies in a freezing \/ \/ mixture and forms an oxime m. p. 136O (decomp. PrP Pro a t 120O). Reduction of the saturated or un- saturated ketone with sodium ethoxide gives iso~o~Zcyclopentylisolrro;mJlcyclopen~ol C,,H,,-OH b. p. 160- 164O/11 mm. which solidifies in the cold and forms a phe?zyZ- urethane C23H3602N m. p. 106-107O. Reduction of the sodium salt of ethyl tanacetophoronecarboxylate (compare A. 1912 i 262) and treatment of the sodium compound of ethyl isopropylcyclo- pentanonecarboxylate thus obtained with diazobenzene chloride (I mol.) in the cold gives a clear yellow solution from which sodium acetate precipitates a pale yellow product gradually becom- ing darker.As would be expected from Dieckmann’s work (A. 1901 i 539) this represents l-isopropylcyclopentan-3-o~~ephenyl- hydrazone CHPrP< which forms yellow crystals with metallic lustre m. p. 233O; from acetic acid it separates in deep red crystals of somewhat lower melting point the red colour being probably due to the formation of a condensation product. Treatment of 1-isopropylcyclopentan-3-one with zinc and ethyl bromoacetate in benzene gives the condensation product C,,H2,0 (vide supra) and the ester of the oily hydroxy-acid C,,H,,O,. The action of acetic anhydride on this hydroxy-acid followed by distillation in a current of water vapomur gives l-isop+opyZcyclo- pentylidene-3-acetic acid CHPrB< m.p. 107- 1 0 8 O (compare Wallach (‘ Terpene und Campher,” 11. ed. 160). [With FRIEDRICH Po~~~.]-Treatment of fencholenamine with C( N €1 P I I 1 ? ) CH,-- CH CH,*vH2 CH,*C:C ZI -CC),H’i 216 ABfiTBdcT8 OF CHEMICAL PAPEM. 12 mm. probably C7H3@- Reduction of the latterORGANIC CHEMISTRY. i. 217 cyclo-derivatives has therefore taken place. may have either of the two structures Me/’ \:O The ketone obtained ,-.- Me or 1 \:o. I-.-/ \-/ Me Me Me T. H. P. [Mixtures of Phenol and Camphor in the Light of the Phase Rule]. R. KREMANN F. WISCHO and R. PAUL (Nonatsh. 1915 36 911-921).-With a view to the explanation of the antiseptic properties of liquid mjxtures of phenol and camphor the authors have determined the freezing-point diagram.Mixtures containing from 25% to 60% of phenol could not be cryetallised but the curves actually realised suggest that a compound is formed and this is supposed to be present in liquid mixtures (Chlumsky’s solution). I n agreement with previous observations the freezing-point data for the system camphor-resorcinol show the existence of a com- pound. On the other hand the freezing-point data for mixtures of camphor and P-naphthol although incomplete seem t o show that no compound is formed by this pair of substances. H. M. D. Konovalov’s (‘ Hydroxyfenchone.” 8. S. NAMETKIN and (MLLE.) V. A. CHOCHRJAKOVA (1. Russ. Y h y s . Chem. SOC. 1915 47 1611-1615).-1t is a general rule that when saturated bicyclic hydrocarbons are nitrated by Konovalov’s method the tertiary hydrogen atom united to the carbon atom common to’ the two rings is not replaced by the nitro-group.I n this connexion interest attaches t o Konovalov’s observation (A. 1904 i 257) that nitration of fenchone yields besides a secondary nitro-ketone also a tertiary nitro-compound and that reduction of the latter yields mainly a compound of the composition C10Hl6O2. I f ? as Konovalov assumed this compound is formed from the’ tertiary nitro-derivative by replacement of the nitro-group by hydroxyl these two compounds would have the C(0II) annexed formulz. The authors have prepared the I Q H z I t crr2 I 126.5-12Tojll mm. DY 1.0028 1.4641 [a] -46.59O (in alcohol). \ / This compound remains unchanged when heated with acetic anhydride or phthalic anhydride and contains therefore no hydroxyl group.It yields however a disemicarhazone CIOH16(N2H-CO*NH2)2 de- composing a t 220° and a dioxime Cl,H16(NOH) m. p. 123-124O and is in reality a diketone such structure being in excellent agree- ment with the molecular refraction. The simplest method of formation of such a compound would consist in a rupture during C( NO,) C (“Cble CRIe so-called hydroxyfenchone b. p. CH21 (” C RIo wei. 218 ABSTRACTS OF CHEMICAL PAPERS. an intermediate stage of the reduction and under the influence of the strongly acid medium of the bicyclic fenchone system a t the carbon atom connected with the nitro-group. According to this view the compound would have one of the two formulze both of which reprwent optically active compounds. T.H. P Some [Japanese] Essential Oils. So UCHIDA (RdZ. Forest. Expt. Stat. Meguro Tokyo 1915. Reprint 6 pp.).-Hinoki oil is obtained from the leaves and wood of the hinoki tree (Chamae- cypam's obtusa) a valuable timber tree growing extensively in Japan. The wood yields 2.4% of the oil which has a brown colour and empyreumatic odour. When rectified the oil has D15.5 0.8821 and [a] -50*61° (in a 10% chloroform solution). The oil contains about 60% of a-pinene and a considerable quantity of cadinene. The fraction of the oil b. p. (below) 170°/760 mm. and amounting to 60% of the total is a good substitute for hrpentine oil. Sansho oil has a strong aromatic odour and is prepared from the berries of a shrub (Xanthoxylum piperiturn) growing wild in Japan; it has D15-5 0.8504 [u]Eo +46*5O nE0 1.46 ester number 19.28 ester number after acetylation of the non-aldehyde constituent 23.23 and co'ntains free acid (as palmitic acid) 2.0% aldehyde 15% esters (as acetic ester of C,,H,,*OH) 5*7% free alcohol (C,,H,,-OH) l*l% and terpene (chiefly dipentene) 77.0%.This oil is useful for the preparation of perfumes confectionery liqueurs etc. Sugi oil is obtained from the green leaves of the sugi tree (Cryptomerza japo~zica) a conifer indigenous t o Japan; the! yield of oil is 0.70%. The oil has D15.5 0.9217 [a]: + 19.29O nio 1.4985 acid number 1.0 ester number 6.56 and ester number after acetylation 14.35. The relative proportion of the constituents of the oil is as follows free acid (as acetic acid) 0.1%; free alcohol (C,,H,,*OH; b.p. 212-21407 n 1*4832) 3.14%; ester (as octoic ester of C,,H,,*OH) 3.28% ; terpene (chiefly a-pinene) 34% ; sesquiterpenes 30% ; a sesquiterpene alcohol (C,,H,,*OH ; b. p. 284-286° D15.5 0.9623 [a] +16*76O) 12%; diterpene (a-cryptomerene m. p. 61° b. 11. 345O [a];' -34.22') 18%. w. P. s. Action of Nitric Acid on Colophony and t h e Related Auto- oxidation of the Latter. LUDWIG PAUL (C7tC717. Zenty.. 1915 ii 790; from Seife.nsieder Zeit. 1915 42 640-641 659. Compare A. 1915 i 828 829 1066).-The action of nitric acid on colophony proceeds even a t the ordinary temperature. y-Pinic acid (A-8 acid) yields a so-called nit\ro-product m. p. 125-130° whilst when diluted with water the product gives a-pinic acid (KLw) in p.100-105°. The action of nitric acid on finely divided colophony furnishes a substance m. p. 120-125O the nitro-compound separating as a yellow pasty mass which gives the KLw-sub- stance m. p. 135-136O on treatment with water. ExplosiveORGANIC CHEMISTRY. i. 219 properties are not observed with the substances obtained by the action of nitric acid. The nitlro-compound obtained from y-pinic acid is readily soluble in water containing sodium carbonate and from the solution sodium chloride throws down a frothy precipitate very difficultly miscible with water. Addition of hydrochloric acid to the filtrate yields a yellow precipitate which is soluble in water and like 6-pinic acid (fl-KLw) has m. p. 120-125O; the residue from the extraction becomes transparent a t 122O.Since both R8 and colophony are almost free from p-pinic acid the formation of the latter is attributed to the action of the nitric acid. If the use of sodium chloride is omitted from the preparation of a-pinic acid and the nitro-product is precipitated the latter shows a consider- ably lower melting point ; washing with water yields not 6-pinic acid but a product resembling a-pinic acid. On the assumption that fl-pinic acid is separated from the1 nitro-product if the initial product contains a considerable proportion of sodium chloride whereas a-pinic acid is obtained when the oxidation ceases owing to lack of hydrogen chloride or chlorine the conclusion is drawn that the primary transformation product is a-pinic acid which is only converted into the 6-compound by oxidation.The basis of the auto-oxidation of colophony is not the latter itself but a-pinic acid which undergoes conversion into P-pink acid. The a-com- pound is formed by treating colophony with alkali o r nitric acid or by storing it in a closed vessel; nitration takes place only t o a very subordinate extent. Sphingosine. I V . Some Derivatives of Sphingosine and Dihydrosphingosine. P. A. LEVENE and C. J. WEST (3. Biol. Ghem. 1916 24 63-68).-The identification of sphingosine by the analysis of the sulphate is considered t o be scarcely satisfactory on account of the inconstancy of the composition of this salt. On this account the authors have prepared the picrate and picrolonate of sphingosine and dihydrosphingosine but although these are of constant composition their solubility in organic solvents is too great to make them very useful for the purpose of analysis.Sphingosine picrolonate forms yellow crystals m. p. 87-89' after softening a t 8 1 O . Dibromosphirngosine sulphate is a light grey crystalline powder. Dihydrosphingosine picrolonate forms long yellow needles m. p. 120-121O after softening a t l l O o . Dihydrosphimgosine picrate forms yellow crystals m. p. 88-89O. It has already been shown (Levene and West A. 1914 i 308 1123 1141) that the probable structure of sphingosine is C,,H,?*CH :CH*CH (OH)*CH (OH) -CH "H the relative position of the amino- and hydroxy? groups being un- certain but the isolation of n-pentadecoic acid as an oxidation product of dihydrosphingosins establishes the presence of a normal chain of fifteen carbon atoms.This knowledge is extended by the following observations. On treating a eolution of dihydrosphingosine sulphate in acetic T. H. P.i. 220 ABSTRACTS OF CHEMICAL PAPERS. acid with the theoretical quantity of sodium nitrite dihydro- sphinyosol (tm’hydrozyheptadecalze) C,,H,(OH) is obtaineld as a colourless crystalline solid m. p. 54-55O. When dihydrosphingosine sulphate in acetic acid solution is heated with hydriodic acid solution for five to seven hours reduc- tion is effected to hydroxyheptadecylamine OH*C17H34*NH2 scales m. p. 8 5 ’ 5 O ; sulphate rosettes of slender needles m. p. 206-208O (compare Levene and Jacobs A 1912 i 284 575). D. F. T. Sphingomyelio. 111. P.A. LEVENE ( J . BioZ. Chem. 1916 24 69-89. Compare A. 1913 i 917; 1914 i 1147).-An extension of the earlier investigation to sphingomyelin obtained from kidney liver and the yolk of hen’s egg. Brain sphingomyelin prepared by a modification of the earlier method was obtained of constant composition and optical rotation. Hydrolysis by successive treatment with barium hydroxide and hydrochloric acid yielded lignoceric acid and another acid of lower molecular weight possibly containing a hydroxyl group ; no cere- bronic acid was obtained the occurrence of this acid amongst the products in the earlier investigation being probably due t o the presence of cerebrin as an impurity in the sphingomyelin. The hydrolytic products included as before the bases choline sphingosine and the substance C,,H,,ON the last on reduction with hydrogen and colloidal palladium yielding sphingine (hydroxyheptadecylamine) (compare Levene and West preceding abstract) OH*C,,H,*NH plates m.p. 83-507 resembling chole- sterol in appearance ; sulphate glistening scales; dincetyl derivative needles m. p. 109.5O (corr.). It is believed that the occurrence of this substance in the mixture obtained by reducing the hydrolytic products is due t o ‘a secondary formation of an anhydrosphingosine from sphingosine because hydrolysis of sphingomyelin with 3% sulphuric acid in a sealed tube gave sphingosine without the new compound whereas a sample of pure cerebrin on successive treat- ment with barium hydroxide and sulphuric acid followed by reduc- tion gave pure sphingine. The primary hydrolytic product6 of sphingomyelin therefore are phosphoric acid two fatty acids choline and sphingosine and the constitution may be expressed OH~PO(O~C,H,,N~OH)~O~C,7H,,(OH)~NH~CO~C,,R,,,~ the final acid radicle being uncertain.This assumption receives confirma- tion from the formation of l i g n o c f r ~ l s p l ~ i n g i n e OH*C,,H,,*NH* CO*C,,H, needles on reducing the hydrolytic products of sphingomyelin obtained from beef kidney. Sphingomyelin was also prepared from liver and yolk of hen’s egg. It is probable that the products from all these sources are identical. Whether sphingomyelin is a diphosphatide o r a mixture of two phoephatides of the described type it is not possible t o say; if it is a mixture the proportion of the two monophosphatides present may vary according to the source of the material.I>. F. T.ORGANIC CHEMISTRY. i. 221 Periodic Variation of t h e Properties of Organic Compounds. P. PETRENKO-KRITSCHENKO ( J . Buss. Phys. Chem. SOC. 1915 47 1796-1797).-Periodic variation of the melting point and of the reactivity is shown by the oximes of homologous compounds of the hydropyrone series (compare Biron A. 1915 ii 762). The Alkaloids of t h e Calabar Bean. IV. Partial Synthesis of Eeerine and Geneserine. K4x POLONOVSKI and CH. NITZBERG (Bull. SOC. chim. 1916 [iv] 19 27-37. Compare A. 1915 i 891 892 987).-The authors have examined the action of methyl- carbimide on eseroline and geneseroline under varying conditions. For the preparation of eseroline from eserine they now find that it is more satisfactory to use mineral acids instead of alkalis for the hydrolysis.The same applies to the preparation of geneseroline. Methylcarbimide (1 mol.) reacts with eseroline (1 mol.) in benzene solution when heated in a sealed tube a t looo f o r four hours t o give isoeserine (OH*C,,H,6N):N*CO*NHMe m. p. 195-196O [aID - 236O in alcoholic solution. This substance is isomeric with eserine but differs from it in several respects. Its aqueous solution is neutral but it dissolves readily both in dilute acids and in dilute aqueous sodium hydroxide the latter solution rapidly turning red on exposure t o air. It gives a picrate m. p. 170° but no methiodide could be obtained. It is much more slowly decomposed by aqueous barium hydroxide than is eserine.When methylcarbimide in benzene solution is added to a solu- tion of eseroline in anhydrous ether in the cold a precipitate of eseroline methylcarbimide m. p. 110-115° is obtained which when heated a t l l O o f o r one hour or dissolved in benzene and the solution warmed is converted into isoeserine. When moistened with water i t slowly dissolves giving a yellow alkaline solution which gradually turns red and on warming drops of a red oil separate. I f in the second method of condensation of methylcarbimide and eseroline a small amount of sodium is introduced then the product is eserine. Attempts were made t o add two methylcarbiminic groups t o eseroline one to the *OH group and the other to a *N atom but no crystalline product could be obtained although there was an indication that the reaction took place to a certain extent when the two substances were heated in requisite proportions in benzene solution in a sealed tube.Geneserine was readily synthesised by the action of methyl- carbimide on geneseroline in the presence of sodium by the method described above but an isogeneserine could not be obtained from geneseroline using the first method given. Preparation of Condensation Products of Papaverine and its Derivatives with Aldehydes or Subetances Capable of Pro- ducing Aldehydes. S O C I ~ T ~ POUR L'INDUSTRIE CHIMIQUE k BALE (Fr. Pat. 475654; from J . SOC. Chem. Ind. 1916 35 72).- Dihydropapaverine tetrahydropapaverine their substitution pro- T. H. P. W. G.i. 222 ABSTRACTS OF CHEMICAL PAPERS. ducts and the phenolic bases formed from them by the hydrolysis of one o r more methoxy-groups condense with aldehydes to form tetracyclic bases similar in constitution to some of the natural alkaloids.It is often preferable t o use the' acetal instead of the aldehyde and saponify by a weak mineral acid. Details f o r the preparation of methylene- and ethylidene-tetrahydropapaverine and of amin oet hylidesz etetra h ydropapaverine hydrochlom'de are given. G . F. M. The Friedel-Crafts' Ketone Synthesis in the Pgridine SerieP. RICHARD WOLFFENSTEIN and FRANK HARTWICH (Ber. 1915 48 2043-2049).-The authors have found t h a t pyridine and quino- line and their derivatives cannot be condensed with acetyl or benzoyl chloride in the presence of aluminium chloride and that no reaction takes place on the other hand between pure pyridine- carboxylic acid chlorides and aromatic hydrocarbons or ethers.If however a trace of thionyl chloride is also used with the con- densing agent ketones are readily .obtained. Sufficient thionyl chloride will remain with the) acyl chlorides if in the preparation of these the excess i s removed merely by evacuation a t the room temperature. The necessary acids were obtained by oxidising the alkyl- pyridines and it is stated t h a t pyridine-2 6- and 2 5-dicarboxylic acids can be readily purified by crystallisation from water without the usual intervention of the silver salts. Another difference is brought to light between the 3- and 4-acids and pyridine-2-carb- oxylic acid (picolinic acid). The chloride of the latter condenses with pyridine to give a deep cornflower-blue dye which however soon decomposes.The following ketones are described 2-Pyridyl phenyl ketone from picolinoyl chloride and benzene b. p. 182O/14 mm. (compare Tschitschibabin A. 1902 i 175) ; platinichloride m. p. 193O (decomp.). 2-Pyridyl arzisyl ketorz e Cl3Hl1O2N long silky needles in. p. 9 3 O ; p!ntitrichloridu m. p. 210° (decomp.); picrate m. p. 176O; phenylhyd'razone pale brown m. p. 1 0 3 O . 3-Pyridyl phenyl ketone b. p. 180°/12 mm. m. p. 39O; platinichloride m. p. 2 4 5 O (decomp.) (compare Bernthsen and Mettegang A. 1887 737). 3-Pyrzdyl anisyl Icetone soft needles in. p. 99O ; platinichloride m. p. 267O (decomp.); pcrate m. p. 1 8 5 O ; phenylhydrazone pale yellow nodules m. p. 157O.3-1)yridyl naphthyl ketone a brown resin; platinichloride m. p. 213O (decomp.); picrate m. p. 142'. 2 5-Dihenzoyl~ricli~,r spikeleis m. p. 123O ; platinichloridp unstable; diphenylhydraxonp C31H25N5 m. p. 129'. 2 6-Diben zoyl- pyridiiae a very weak base m. p. 1 0 8 O ; diphenylhydrazone m. p. 1 8 3 O . J. C. W. Isomeric Phenylmethyliso >xazolecarboxylic Acids. MARIO BETTI and REMO PACINI (Gazaetta 1915 45 ii 377-384).-The action of hyroxylamine o n ethyl benzoylacetoacetate (compare Claisen A. 1894 i 32) yields a phenylmethylisooxazolecarboxylicORGANIC CHEMISTRY. i. 223 acid m. p. 189O (compare A. 1915 i 713) isomeric with the acid m. p. 157O. It is now found that the amide of 5-phenyl-3-methyl- isooxazole-4carboxylic acid obtained by oxida,tion of 4-benzylidene- 3-inethylisooxazolone in presence of benzaldehyde yields mainly tlie acid m.p. 157O o r that with m. p. 189O according as i t is boiled with dilute or concentrated sodium hydroxide solution. Further just as is the case with the ester of 3 5-diphenylisooxazole- 4-carboxylic acid (compare Betti and Berlingozzi A. 1915 i 997) the ester obtained by the interaction of hydroxylamine and ethyl benzoylacetoacetate yields solely the acid m. p. 189O when hydro- lysed by either concentrated o r dilute sodium hydroxide solution. I n some instances the corresponding salts of the two acids exhibit marked differences. The nature of tlie isomerism of these acids is not yet established. T. H. P. Nitro-derivatives of Alkyl Benzidines. G. VAN ROMBURGH (Proc. IK. Akad.TVetensch. Amsterdam 1916 18 757-760).- The compounds obtained earlier by the nitration of dimethyl- aniline and described as isodinitrodimethylaniline and dinitro- phenylmethylnitroainine (Mertens A. 1886 l022) were shown by van Romburgh (A. 1887 245) t o be derivatives of tetranitro- benzidine. Details are now given by which the yield of tetranitrotetra- methylbenzidine obtained from dimethylaniline by nitration can be very considerably improved. The method of formation from dimethylaniline suggests that the nitro-groups occupy the 3 5 3/ 5’-positions and this view is now confirmed in the follow- ing way. 4 4l-Diphenyl diethyl ether when treated with fuming nitric acid was converted into tlie tetranitrodiphenyl diethyl ether colourless needles m. p. 256-257O.When heated with an alcoholic solution of dimethylamine a t 120° this substance gave tetranitrodihydroxydiphenyl a result- t h a t helped to fix the posi- tions of the nitro-groups because on boiling with nitric acid this conipound was converted into picric acid. With methylamine tetranitrodiphenyl diethyl ether gave 3 5 31 5’-tetranitrodi- methylbenzidine decomp. a t 2 8 2 O and the prooE of the structure of this substance by synthesis also applies t o the above tetranitro- tetramethylbenzidine and its derivatives. By allowing other monoalkylamines t o react with the tetranitro- diphenyl diethyl ether the corresponding ethyl prowl isopropyl isobutyl and allyl compounds were obtained m. p. (decomp.) 248O 2OZo 250° 194O 208O respectively which were convertible into the corresponding nitroamine3 m.p. 230° 213O 209O 205O looo respectively . Tetranitrotetramethylbenzidine and tetranitrodimethylbenzidine are both slowly reducible by tin and hydrochloric acid giving t r tm-amino t e t ru m e t h y l b eizziditi e t etrn-am in odim ethyl b ens- idine ; tetrahydrochlorides needles with 2H,O and 1H,O respec- t i d y ; stannichlorides crystalline scales. and D. F. T.i. 224 ABSTRACTS OF CHEMICAL PAPERS. Diazotisation and Diazo-reactions of 2- Aminopgridine. A. E. TSCHITSCHIBABIN and M. D. RJAZANCEV ( J . Rziss. Phys. Chem. SOC. 1915 46 1571-1589. Compare A. 1915 i 590 591 992). -By treating 2-aminopyridine with nitrous acid in hydrochloric acid solution the authors were unable t o obtain a higher yield than 50% of 2-chloropyridine much 2-pyridone being always formed (compare Marckwald A.1893 i 727; 1894 i 381). Use of con- centrated hydrofluofic acid in place of the hydrochloric acid results in the formation of 2-fluoropyridine in about 25% yield. I n the case of hydrobromic acid the concentrated acid cannot be employed since i t reacts with nitrous acid liberating bromine ; with more dilute solutions 2-bromopyridine is obtained in small yield the principal product being the pyridone. It is evident that 2-aminopyridine reacts considerably more slowly than aromatic amines with nitrous acid. The extraordinarily great stability of pyridyl-2-nitroarnine leads the authors t o suppose that with 2- and 4-substituted pyridines only the salts of the diazonium bases are unstable whilst the diazo-compounds C,H4N*N:N*ONa and also the nitroso-amines C,H,N*NH*NO should be a t least as stable as the corresponding compounds of the aromatic series.The appli- cation of Bamberger and Rust's reaction (A. 1901 i 171) t o 2-aminopyridine yields the isodiazoxide which may also be obtained by the action of amyl nitrite on the sodium derivative of 2-aminopyridine; it is extremely stable and in the pure state remains unchanged indefinitely only decomposing a t a high temperature. Decomposition of a concentrated aqueous solution of the diazoxide (1 mol.) in the cold with not more than 1 mol. of acetic acid yields the crystalline diazo-hydrate which however readily decomposes with formation of pyridone ; the sliglitest excess of acid results in the rapid decomposition of the diazoxide which probably undergoes isomeric change into the unstable diazonium salt.Faint acidification of a solution of the diazoxide containing potassium iodide yields 2-iodopyridine. Like the alttidiazoxides of the benzene series the diazoxide of pyridine exhibib little tendency to the formation of azo-dyes by coupling with phenols and amines; small yields of such dyes are however obtainable with naphthols and certain amines in alcoholic solution. The assumption concerning the stability of diazoxidea or nitrosoamines of the 2-pyridine series is also confirmed by other experiments. Thus in absence of other acids nitrous acid gives with 2-amino- pyridine aqueous solutions which generate nitrogen either slowly or not a t all and are capable of yielding products of the diazo- reaction.2-FZuoropyridzne C,H,NF is a volatile liquid with an odour resembling that of 2-chloropyridine b. p. 125*75O/ 752.9 mm. I); 1.1489 DY 1.1281 n 1.46'78. It forms either no salt or a highly unstable one with picric acid. The extreme weakness of the basic properties is shown also by the fact that the pZntini- chloride (C,H,NF)2,H,PtCl + H,O m. p. 145-153O (decomp.) loses water and hydrogen chloride a t looo giving (C,H,NF)2PtC1,. 2-Pyridone exhibits dimorphism crystallisation from hot chloro-ORGANIC CHEMISTRY i. 226 form or benzene giving large prismatic crystals which gradually assume a milky opaque appearance. Its sodium salt shows marked stability towards air and light. Sodium Pyridi/ze-Z-diazoxzde C,H4N*N:N*ONa is obtained as a pale yellow powder.2-lodopyridine C,H,NI is a liquid b. p. 93O/13 mm. D 2.0039 D? 1.9735 n;’ 1.6366; its picrate C1,H7O7N4I m. p. 119-120° and pZatinichZoride (C,H,NI),,H,PtCl red needles m. p. 210° (decomp.) were prepared. Nitrates of Aminoazo-compounds. L. CASALE (Gnxxetta 1915 45 ii 397-405).-ln conjunction with Casale-Sacchi (A. 1915 i 723) the author has described two series of nitrates of various aminoazo-compounds stable salts containing 1 mol. of nitric acid and urrstable ones 2 mols. of nitric acid per 1 mol. of the bass. It is now shown that under the action of heat or in one case even a t the ordinary temperature all these salts are decomposed with liberation of the diazonium salt which serves to prepare the colouring matkr and formation of a nitro-derivative of the amine.An analogous decomposition was observed with the nitrates of hydroxyazo-compounds by Charrier and Ferreri (A. 1914 i 599 748) and termed by them “diazo-scission.” The explanation of this reaction advanced by them authors and extended by Charrier (A. 1915 i 66) to’ the nitrates of aminoazo- compounds does not seem to be in accordance with the fa&. Indeed almost all nitrates of aminoazo-compounds containing 2 mols. of acid to 1 mol. of the base dissociate spontaneously a t the ordinary temperature losing gradually 1 mol. of nitric acid. With 4-o-tolueneazo-1-naphthylamine nitrate this decomposition takes place especially rapidly and with generation of heat; in other cases the change is readily brought about by gentle heating.That such decomposition occurs under the influence of heat is regarded as a proof of the invalidity of Charrier and Ferreri’s hypothesis since heat can only displace from left to right the equilibrium of the system nitrate of the azo-compound LZ azo-compound + nitric acid. The author considers the decompositions of the two types of nitrates t o be represented thus (1) NAr:N-Ar*NH2,2HNO = NAr:N*Ar*NH + 2HN03= NO,*Ar*NH + N03*NAriN + H,O and (2) 2NAr:N*Ar*NH,,2HN03 = 2NAr:N*Ar*NH2 + 2HN0 = NO,-Ar=NH + NO,*NAriN + NAr:N*Ar-NH2. The thermal decom- position of the nitrates of the azo-compounds thus consists in the action of concentrated nitric acid on the azo-compounds; this action was studied by Schmidt (A. 1905 i 951) who however wrongly supposed that three o r more mols.of nitric acid act on 1 mol. of the azo-compound. The investigations have been extended to the nitrates of dimethylaminoazobenzene and ptolueneazo-/3- naphthylamine. Dirnethylaminoazobenzene forms the two .nitrates (1) C,,H1,N3,2HN0 which f orms a deep blood-red crystalline precipi- ‘bate and (2) C,,H,,N,,HNO which forms large violet rhombic plates and loses its colour a t about l l O o its melting point being T. H. P.i. 226 AUYT LtACTY OF CREMI CAL PAPEM. that of the free base. Salt (I) undergoes almost quantitative and salt (2) somewhat less complete decomposition into phenyldiazonium salt and 4-nitro-l-dimethylaminobenzeiie when heated. ~-Tolueneazo-P-aaphthylanline gives two nitrates (1) C,H,~~~~~N:T\:OC,~H,*NH,,~MNO which foirms deep garnet-red prisms with metallic lustre and is stable in cold dry air; and (2) C17H,,N,,HN03 which forms shin- ing green crystals.When hea.ted these salts yield ptolyldiazonium nibrate and I-nitro-2-naplithylamine small or quantitative yields being obkained according to the way the heating is carried out. Similar results have been obtained with the nitrates of benzene- azo-a-naphthylamine 4-0- and 4-m-tolueneazo-l-na~plithylamine p-tolueneazo-a-naphthylamine 4-o-methoxy- and 4-o-ethoxy-benzene- azo-1-naphthylamines and 4-naphthaleneazo-1-naphthylarnine. T. If. P. The Formation of Pyridine and isoQuinoliue Bases from Casein. AME PICTET and TSAN Quo CIIOU (Compt. ?*md. 1916 162 127-129).-The authors have hydrolysed 50 grams of casein by heating i t on a water-bath with 150 grams of hydrochloric acid (U 1.19) f o r six hours whilst adding 25 grams of methylal drop by drop during the operation the hydrolysis of the casein being thus effected in the! presence of a permanent source of formaldehyde.The liquid was then evaporated to dryness the residue mixed with three times its weight of calcium oxide and distilled. The distillate was a yellow oil entirely soluble in dilute hydrochloric acid and containing primary Mcondary and tertiary bases. The tertiary bases were freed from the others by treatment with sodium nitrite and fractionally distilled. From the different fractions the follow- ing bases were isolated and characterised Pyridine 2 6-dimethyl- pyridine ; a base C,H,N isomeric with this which decolorid potassium permanganats in tlhe cold and gave a +crate m.p. 238O an aurichloride m. p. 225O a merctrrichloride m. p. 235O and a platinichloride m. p. 285O ; isoquinoline ; 4-methylisoquino- line ; a base C,,HllN probably an ethyl- o r a dimethyl-isoquinoline giving a picrate m. p. 240° and aurichToride m. p. 195O and a platinichloride m. p. above 300O; a base C,,H,,N giving a picrate m. p. 185’. They could not discover the slightest trace of quinoline. W. G. Pure Pepsin. W. E. RINGER (Proc. K. Akcrd. Wetensch. Amsterdam 1916 18 738-751. Compare Pekelharing and Ringer A. 1911 i 1051).-The theoretical portion of the paper is mainly directed against tho1 views of Michaelis and his co-workers (Michaelis and Davidsohn A. 1910 i 795; Michaelis and Mendelssohn A. 1914 i 1007). Pure pepsin free from chlorine and phosphorus was obtained by Pekelharing’s method from the gastric juice of a dog. Whether dissolved in pure water o r in an aqueous solution of sucrose1 i t does not exhibit an isoelectric point as stated by Michaelis and Davidsohn (loc. cit.) but is always electronegative tending t oORGANIC CBEMISTRY.i. 227 move towards the anode if in an electric field. I n the presence of albumoses however the behaviour of the pepsin may be so modified as to give indications of an isoeiectric point and this is probably the explanation of the mistake of other investigators. Certain of the author's results confirm the view that pepsin may be a combination of a real enzyme and protein; thus under elec- trical stress in acid solution the enzyme constituent appears t o move ttowards the anode whilst most of the protein mattes migrates towards the cathode ; also in hydrochloric acid solution .pepsin combines chiefly with hydrogen ions refuting the hypothesis that the whole of the niaterial consists of enzyme which is known t o be invariably charged negatively through combination with anions. Experimental examination also disposes of the suggestion (Zoc.cit.) that the action of pepsin depends entirely o n the concentration of the hydrogen ion. Tests made with different acids lead t o the conclusion that the optimum for the digestion of the fibrin is situated a t the point of maximum swelling; this maximum does not lie a t the same hydrogen-ion concentration for different acids but depends on the nature of the anion.With an acid such as sulphuric acid containing a very hydrophilous anion the effect of the latter is so marked that i t prevails even in comparatively dilute solution so that the maximum swelling is small and concurrently the digestion is relatively inappreciable the optimum occurring a t a low concentration of hydrogen ion. Tile relation between diges- tion and swelling of fibrin is even more distinctly shown in the influence of various salts. If a list of sodium salts is drawn up in the' order of their inhibitory effect on swelling it is found that the power of impeding tlie action of pepsin falls in thO sarn0 order. To avoid as far as possible any effect of the salts on the concen- tration of the hydrogen ion lactic acid was selected for the experi- ments the dissociation of this acid being only slightly influenced by the addition of the salts chosen.D. F. T. The Total Nitrogen and a-Aminc-nitrogen of Pepsins of Different Strengths. T. B. ALDRICH ( J . Biol. C'lzem. 1915 23 339-343) .-Various pepsins examined showed wide variations in activity. I n the different samples total nitrogen showed very little variation but what did vary was the a-amino-nitrogen the decrease in percentage of which runs parallel with an increase1 in tlie activity; pepsin therefore seems t o approach the proteins in corn- plexity. W. D. H. The Effects of Electrolytee Non-electrolytes 61kal ids etc. on the Urease of Soja-bean. N A O S U I ~ O ~ o u ~ i i a (Urochent. J. 1915 9 544-574).-The inhibitory effects of acids depend mainly on hydrogen-ion concentration and also on the effect on surface' tension; these have a great effect on surface tension and facilitate the adsorption of hydrogen ions on the surface of the urease particles.The inhibitory effect of sodium hydroxidet is ascribed t'o hydroxyl-ion concentration but ammonia has some further action. 131-methyl ethyl propyl and .W/ 40-amyl alcohols accelerate ureasei 228 ABSTRACTS OF CHEMlCAL PAPERS activityj but 3*3M of the former group and M/12-amyl alcohol retard it. Isocapillary alcohol solutions have equal effects. Osmotic pressure (Traube’s capacity factor) will not explain these effects but the intervention of attraction pressure represented here by surface tension (Traube’s inttensity factor) will. The alcohols do not causo dispersion o r aggregation of urease particles.Aldehyde inhibits urease notably. The actions of neutral salts are merely those of their metallic bases. Alkaloid salts accelerate urease action in the first stage of hydrolysis but the alkaloid bases themselves inhibit markedly. The effects of atropine and pilocarpine are additive not antagonistic. NAOSUKE ONODERA (Biochenz. J. 1915 9 575-590).-The soja-bean urea~e loses its activity on dialysis; this is restored by adding a small amount of frmh urease which indicates that the latter contains coenzyme. The coenzyme was not separated nor its nature known; but it probably consists of two1 components on0 of which is dialys- able the other not; the formelr undergoes some irrevessible change during dialysis. It also consists of fixed and free parts; heating and dialysis destroy the free part first and then the fixed part; the last portion of the fixed coenzyme is found in the) precipitate produced by dialysis and it sesists the1 influence of heat and dialysis tenaciously.The inhibitory effects of heat acid and alkali are exertfed on the coenzyme not on the urease proper. During germination urease accumulates in the germ of the bean but’ free coenzyme is absent’. Ox-serum has an accelerating influence but this is small compared with that of the coenzyme. Influence of the Bromine-ion on Uricolysis. ANTOBIO JA PPELLI (Cltem. Zentr. 1915 ii 965 ; fxom Arch. Farnzacol. sperim. 1915 19 529-534).-The prewnce of sodium bromide in isotonic solution inhibits the oxidation of uric acid by pressed liver juice.This action on the uricase of the liver is a special case of the anti- fermentative prope’rties of the bromine ion. Preparation of Arseno-phosphorus Derivatives A. MOUNIWHAT (Eng. Pat. 1915 9234; from J . Soc. C’hem. Id. 1916 35 72).- Arseno-phosphorus compounds are obtained by the’ action of phos- phwyl chloride on m-amino-p-hydroxyphenylarsinic acid in pres- enc0 of aqueous sodium hydroxide and subsequent reduction with sodium hyposulphite. These compounds the composition of which varies with the proportions of the o’riginal reagents form yellow powders soluble in dilute sodium carbonate solution and in hydro- chlorio acid and their alkaline solutions reduce Fehling’s solution and Nmler’s and Tollen’s reagents. They are only slightly toxic but have marked spirillicidal and trypanosomicidal properties.W. D. H. The Urease of the Soja-bean and its Coenzyme. W. D. H. T. H. P. G. F. M. A Method of Preparing Mercurised Aromatic Alcohols. V. GRIGNARD and A. ABELMANN (Bull. SOC. chim. 1916 [iv] 19 18-25).-Whilst it has been possible to obtain mercury derivativesPHYSIOLOGICAL CHEMISTRY. i. 229 of hydrocarbons phenols amines acids sulphonic acids ketones etc. by the action of mercuric oxide chloride or acetate (compare Dimroth A. 1899 i 154 428; 1902 i 656) up to the present no such derivatives of aromatic alcohols have been obtained but these have now been prepared indirectly from the mercurised ketones by the action of organo-magnesium compounds. The two ketones used were acetophenone and benzophenone their mercury compounds being condensed with magnesium ethyl bromide. o-Chloromercuriacetophenone has been prepared by the method of Dimroth and Ilzliofer (compare A. 1902 i 849) a small amount of o-o-dichloromercurincetophenone being found to be present in the product. o-Cliloromercuribenzophenons wae prepared as described by Dimroth and Metzger (compare A. 1902 i 849) and the authors at the same time isolated a small amount of dichloro- mercuri b enzophenone CO (C,H,=HgCl),. w-Chloromercuriaceto- plienonel when condensed with the calculated quan€ity of mag- nesium ethyl bromide gavel a solid product and an ethereal solution. The solid product when purified by crystallisation from chloroform was shown t o be a-chZoromercuri-&pheizyZbutan-fl-ol OH CPhEt-CH,*HgCl m. p. 129-131O (decomp.). It reacted vigorously with magnesium ethyl bromide gave a precipitate of mercuric sulphide with am- monium sulphide and with concentrated sulphuric acid gave a green coloration which disappeared on the addition of water. The ethereal solution yielded a small amount of a compound m.. p. 138-139O (decomp.) which exhibited all these properties and was shown to be o-chloromercuriphenylchloromercurimethyl- ethyl casbinol (a-chloromercuri-P-o-chloromercuriphenylbutan-fl-ol) HgCl*C,H,*CEt (OH)*CH,*HgCl. o - Chloromercuribenzophenone when condensed with magnesium ethyl bromide gave a-phenyl-a- chZoromercuriphenyZpv-opn-a-oZ OH*CPhEt*C,H,-Hgcl m. p. 1 0 6 O (decomp.) which exhibits the above properties except that it is not attacked by ammonium sulphide in the cold. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9161000197

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

11. 205 General and Physical Chemistry. The Spectra of Some Intermetallic Compounds. G. TAMMANN (Zeitsch. anorg. Chem. 1915 92 76-8O).-The arc spectra of some alloys in air have been compared with those of their com- ponent metals. It is found that the spectrum of the alloy Cu,Sb is the sum of the spectra of copper and antimony. The compound Cu,Zn also gives a spectrum which is the sum of those of copper and zinc. It is therefore to be assumed that these compounds are fully dissociated in thO state of vapour. On the other hand the spectra of the compounds Mg,Sb Bi,Mg3 and Mg,Sn show slight difterences in the relative intensities of different lines and the reversal of the magnesium line 285.2 is favoured by bismuth and tin although not by antimony. The spectroscopic method is not very suitable for the detection of intermetallic compounds (compare Berry A.1912 ii 161; Wartenberg A. 1915 ii 226). C . H. D. The High Frequency Spectra. (K Series) of the Element@ Chromium to Germanium. MANNE SIEGBAm and WILHELM STENSTROM (Physikal. Zeitsch. 191 6 17 48-51).-Measurements have been made of the wavelengths of the four lines in the high- frequency spectra. of chromium manganese iron cobalt nickel copper zinc and germanium. The results obtained confirm the relation pointed out by Moseley that the square root of the fre- quency of corresponding spectral lines is a linear function of the atomic number. H. M. D. Absolute System of Coloure. J~ILHELM OSTwALD (.zeztsch. physikal. Cheni. 1916 91 129-142).-A theoretical paper in which a method.of defining th0 colour of any substance is discussed. It is held that a colour depends on the absolute dimensions of three variables-t.one brightness and purity. A method of esti- mating these three factors is outlined. Foundation of a Scientific Theory of Pigments. I. The Fundamental Properties of Pigments and the Size of the Particles. WILHELM OSTWALD (KoZ102d Zeitsch. 1915 16 1-4).- Attention is directed t o the fact that' the processes involved in the manufacture and application of paints are almost wholly empirical and that no attempt seems to have been made to. lay the founda- tions of an exact scientific treatment of the problems which this branch of industry presents. The paper deals mainly with the influence of the size of thO pigment granules on the chief properties which are defined as colour.covering power and effectiveness (Ausgiebigkeit). The colour is determined by the selective absorption and the covering power which depends on the scattering of the incident light is J. F. S. VOL. CX. ii. 10ii. 206 ABSTRACTS O F CHEMICAL PAPERS. determined essentially by the refractive index of the pigment. As a measure of the covering power the author suggests the maximuni number of cm.2 of surface which can be covered by 1 gram of pig- ment so that the underlying surface is invisible. The effectiveness measured by thel number of grams of white pigment with which 1 gram of the coloured pigment must be mixed before the colour of the latter begins t o disappear is determiiied by the magnitude of the coefficient of light absorption.The influence of the size of the particles on the colour of many substances has already been examined in some detail and the cbserved changes in colour have been explained satisfactorily on a physical basis. I n regard to covering power it seems that this increases t o a maximum with diminution in the size of the particles and decreases again when the size of the' particles approaches the wave-length of visible light rays. Pigments which consist of smaller particles than this have no scattering power towards light and the covering power approximatw t o zero. The effectiveness of a pigment is well known to increase with the fineness of subdivision and in general no niaximuin is t o be expected as the size of the particles is continuously diminished.The effectiveness appears t o be greatest when the degree of fineness is that corresponding with molicular dispersity. H. M. D. The Relation of Position Isomerism to Optical Activity. X. The Menthyl Alkyl Esters of Phthalic Acid and its Nitro- derivatives. JULIUS BEREND COIIEN DAW ID WOODROFFE and LEONARD ANDERSON (T. 1916 109 222-235).-Esterified by the Fischer-Speier method 3-nitroplithalic acid gives mainly the /3-ester in which the alkyl group is remote from the nitro-group whereas the anhydride gives mainly the a-ester. This was com- pared with the case of camphoric acid and its anhydride but here it was found t h a t the same product the ortho-alkyl ester was obtained by both methods the allo-alkyl ester having t o be pre- pared by half hydrolysis of the normal ester.Monobromosucciiiic acid yielded by treatment with alcohol and hydrogen chloride a product differing from the mono-alkyl ester obtained from the znhydride and alcohol as was shown by converting both into alkyl- meathyl esters. An attempt t o discriminate between the latter however by comparison of their rotations with those of correspond- ing nitrophthalic esters leads to inconsistencies. The1 effect on the rotation of menthyl methyl phthalate of the introduction of a nitro-group firstly in the position adjacent t o the carboxymenthyl group and secondly in that' adjacent t o the carboxymethyl group has been studied. The rotation is raised in both cases but t o the greater extent when the nitro-group is in the position remote from the menthyl group.As the weight of the alkyl group increases the rotation diminishes so that menthyl hydrogen phthalate has a higher rotation than menthyl methyl phthalate but a minimum rotation is reached a t menthyl isoamyl phtlialate after which with increase of weight of the alkyl radicle the rotation begins to rise.GENERAL AND PHYSICAL CHEMISTRY. ii. 207 A similar diminution of rotation is noticeable f o r the a-mentliyl P-alkyl 3-nitrophthalates whereas in this respect the P-menthyl a-alkyl 3-nitrophthalates show no particular regularity. T. S. PA. The Effect of Light on Solid Silver Chloride and Bromide. RICHARD LORENZ and K. HIEGE (Zeitsch. amrg. Chem. 1915 92 27-34).-Colloidal metallic ' fogs' are usually prepared by fusing salts in contact with the corresponding metals.The silver haloids also form fogs when the solid salts are exposed to light. Optically clear crystals of silver chloride and bromide purified by the method previously described (A. 1915 ii 2GO) become more o r less opaque and dark in colour when exposed t o a beam of light butl remain a t first optically clear the beam being invisible. Later the surface a t which the beam enters becomes brown and particles visible in the ultramicroscope become visible. The particles grow rapidly and will continue t o grow if the crystal is removed from the light and heated a t 350O. Heating in the absence of light does not pro- duce particles. The growth of the particles is acconipanied by a diminution of the coloration in their immediate neiglibourhood. The effect i s evidently due to the separation of metallic silver in a colloidal form growing in size as the illumination is continued.These facts strongly support the view that the latent photo- graphic image consists of colloidal silver in ultxamicroscopic form. C. H. D. Action of Light on Mixtures of Potassium Ferrocyanide and p-Nitrosodimethylanilioe. W. GALLEN~ZAMP (Chem. Zeit. 1916 40 235).-Mixtures of potassium ferrocyanide and p-nitroso- dimethylaniline solutions originally yellow develop a green colour on exposure t o light. Thee change is very rapid even in diffused light and appears t o be an indirect photochemical catalysis since after only a very short exposure the cliange slowly continues in the dark whilst solutions prepared and kept in darkness remain yellow. Tlie green colour is reconverted to yellow by heating the solution to the boiling point but appears again on further exposure t o light.Decomposition of t"h0 nitroso-compound by potassium nitrite o r boiling potassium hydroxide results in the permanent destruction of the green colour. The author is of opinion thatl it is due t o the production of colloidal Prussian-blue from the ferrocyanide under the influence oE a catalyst generated from the nitroso-compound. G. F. M. Interaction of Hydrogen and Chlorina under t h e Influence of a-Particles. Hucxr STOTT TAYLOR ( J . Amer. C?LC??Z. Xoc. 1916 38 280-285).-A recalculation of results and a reconsidera- tion of conclusions 'previously published (A. 1915 ii 80). J. F. S. The Absorption and Diffusion of High Speed Cathode Rays (@-Rays) in Gases and Vapours.EINAR FRIJIAN ( A m . Ph?ysik 1916 [iv) 49 373-418).-Measurements have been made of the 10-211. 208 ABSTRBCTS OF CHEMICAL PAPERS absorption of the high-speed /3-particles emitted by uranium-X in various gases and vapours. I n particular attention was directed to the elimination of errors resulting from the special design of the apparatus and froin the diffusion of the rays. The actual pro- cedure involved measurements in which the pressure of the absorb- ing gas was varied and others in which the distance between the source of the rays and the measuring apparatus was subjected to variation. The data obtained show that the absorption in oxygen carbon dioxide and acetone is proportional t o tlie mass of the molecules but this relation does not hold for substances containing halogen.The absorption in isobutyl chloride chloroform carbon tetra- chloride ethyl broaide and methyl iodide is greater than would correspond with the above relation and the deviation incream with increasing atomic weight of the1 halogen. The behaviour of these substances towards high-speed @-rays is theref ore quite similar t o t h a t which has been already observed in experiments with cathode rays of smaller velocity. The diffusion measurements show that the diffusion is mainly determined by the mass of the molecules but deviations are also shown in respect) of diffusion by the halogen-containing substances which increase with the atomic weight of the halogen. H. M. D. The Action of Radium Rays on Mixtures of Hydrogen Areenide and Oxygen.H. RECKLEBEN and G. LocImnimN (Zeitsch. anory. Chem. 1915 92 145-167).-A mixture of hydrogen arsenide and oxygen is enclosed in a glass vessel with a thin aluminium window over water or salt solution. The temperature and pressure of the gas are read from time t o time the room being darkened. The vessel is a narrow glass cylinder with manometer the gas capacity bseing 185 C.C. For some of the experiments the cylinder is divided into short sections by narrow constrictions each of which bears a mark t o the level of which the liquid niay be broughtl by raising or lowering the reservoir. I n the spontaneous reaction of hydrogen arsenide with oxygen even when the latter is in large excess the arsenic is liberated in the free state only the hydrogen being oxidised but when exposed to fl- and y-rays this reaction is accelerated and also proceeds further arsenious acid being formed according t o the equation 2H3As+30,= 2H,AsO,.a-R-ays being excluded the oxidation cannot be due to the intermediate formation of ozone. C. H. D. Recent Work on X-Rays and Crystals and its Bearing on Chemistry. WILLIAM HENRY BRAGG (T. 1916 109 252-269). -A lecture delivered before the Chemical Society Radioactivity of Swedish Spring Waters and its Connexion with Geological Formations. NAIMA SAHLBOM (Arkiv Kem. Min. Geol. 1916 6 No. 3 1-51).-Zn continuation of a previous in-GENERAL AND PHYSICAL CHEMISTRY. ii. 209 vestigation (A. 1908 ii 749) the author has examined the radio- activity of about 400 different spring waters consisting of deep- bore springs and opeii drinking-water springs from different goo- logical formations.The difference in the radioactivity between springs froin sedimentary formations and those from the primary rocks is very niarked the former having a radioactivity correspond- ing on the average with 4 &lache units and the latter with 23 Mache units. Of the springs coming from sedimentary rocks those froin chalk have' the lowest radioactivity namely 1.9 Mache units; then coiiie the shale springs with 2.7 Mache units and the sand- stone springs with 7.1 units. The unexpected activity of the latter is confined to the water coming from the Cambrian sandst'ones and appears t o be caused by the small radium content of the overlying alum shales. Most of the open springs come from loose glacial deposits formed chiefly from primary rocks (moraines etc.) and their activity forms a transition stage to that of the water from the primary rocks.I n connexion with the springs from the primary rocks i t is shown that there is a well-marked relation between the radioactivity of the water and the geological character of the rocks; for example the wat'ers with the highest radioactivities up to 172 Mache units come from deep borings in the acid rocks-granites and syenites. The chemical composition of the rocks through which the water flows has an effect in that rocks with normal lime and silica content have the greatest radioactivity whereas a too high content of either lime o r silica diminishes the radioactivity. Variations in the radio- activity of waters coming from the same geological formation must be due t o variations in the1 chemical composition of the rocks.The Swedish spring waters are much more radioactive than other waters indicating a relatively high radium content of the rocks and mountains. T. S. P. The Influence of Some Hydroxy-compounds on the Electrical Conductivity of Boric Acid. J. BOESEKEN L. W. KANSEN and S. H. BERTRAM (Rec. trau. chim. 1916 35 309-319. Compare this vol. ii 73) .-With three aromatic hydroxy-ketones examined namely benzoyl- p-toluoyl- and panisoyl-carbinols the results obtained show that the action of these substances on boric acid is not important. The actions of pyruvic and lactic acids were compared and i t was found that' whilst pyruvic acid in normal solution increased the conductivity of boric acid enormously this high value rapidly diminished with dilution and at' a concentration AT/ 64 became' slightly negative.Lactic acid in Nsolution did not exert quite such a great effect on the conductivity but the values obtained did not diminish so rapidly with dilution as in the case of pyruvic acid. The authors explain this on the hypothesis that the hydrate of pyruvic acid has five hydroxyl groups whilst that of lactic acid only has four. The influence of r-amygdalic acid on tho conductivity of boric acid was also examined and was found to be only slightly less than t h a t of pyruvic acid in X-solution but it did not diminish nearly as rapidly with dilution. W. G.ii. 210 ABSTRACTS OF CHEMICAL PAPERS.Conductivity. 111. Further Studies on the Behaviour of the Alkali Metal Formates in Anhydrous F'orrnic Acid. H. I. SCHLESINGER and CLYDE COLEMAN ( J . Anze].. Chenz. SOC. 1916 38 271-280).-A continuation of the work of Schlesinger and Martin (A. 1912 ii 26; 1914 ii 703). The conductivities viscosities and densities of a large number of solutions of different concentrations in formic acid of the formates of lithium sodium rubidium and cesium have been determined a t 1 8 O and 25O. The following conductivity values have been obtained lithium formate E 2 5 = 0530 K18 = 0.515 A = 64.6 x,8= 56.8 ; rubidium formate X25= 1.082 K,,= 0.989 A = 69.9 61.3 ; czesium formate X2,=1*181 h2,=65*0. The K values are the ionisation constants and the A values the equivalent conductivities.The following formulze represent the densities of solutions of the salts in formic acid sodium formate Dl*= 1.2233 + 0.0335~; lithium formate D23= 1.2142 + 0-021c; DlS= 1.2224 + 0.0222~; rubidium formate D25= 1.2142 + 0.085~; Dl8+ 1.2233 + 0.080~. It is shown that the solutions of these salts i n formic acid obey the dilution law when the degree of ionisation is calculat'ed from the conductivity data with correction for viscosity. The valuer of the ionisation constant increases with the' atomic weight of the metal' as also does the con- ductivity a t infinite dilution caesium being however exceptional. The ionisation constant a t 1 8 O is less than that a t 25O which indi- cates that ionisation in these cases proceeds with absorption of heat.Using these1 values the heat of dissociation is calculated t o 700 2180 and 2200 cals. for lithium sodium and rubidium formates respectively. J. F. S. Electrical Conductivity of Acids in Absolute and Aqueous Alcohol. 11. HEINRICH GOLDSCHMIDT [with MAX E. FEIGL CARL GORBITZ HAAKON HOUGEN KRISTIAN PAHLE JENS SCHJERVE and OLAF UDSY] (Zeitsch. physikczl. Chem. 1916 91 46-74. Compare A. 1915 ii 136).-Tlie electrical conductivity of trichlorobutyric acid trichloroacetic acid dichloroacetic acid salicylic acid trinitro- benzoic acid and picric acid as well as t h a t of the sodium salts of these acids and in many cases the piperidine salts has bean deter- mined a t 2 5 O in solutions of absolute alcohol and in alcohol con- taining measured amounts of water. It is shown that all acids which are slightly dissociated in alcoholic solution are affected in the same way by the addition of water.The change is controlled by the equilibrium constant of the system hydrogen ion-alcohol-water and by the factor (1 + 0*9n+ 0.3~~2) in which n is the normality of the water. The following values were found f o r the conductivity a t infinibe dilution f o r 2 5 O salicylic acid 86 ; dichloroacetic acid 94 ; trich1orobutyric acid 87 ; trinitrobenzoic acid 86.5 ; trichloro- acetic acid 88; and picric acid 93. The affinity constants f o r the same acids are 2.2 x 10-9 5.2 x 10-8 1.04 x 10-7 7.0 x 10-7 1.5 x 10-6 and 1.75 x 10-4 respectively. Conductivities of Certain Organic Acids in Absolute Ethyl Alcohol. H. H. LLOYD JOHN B. WIESEL and HARRY C.JONES (J. Amer. Chem. Soc. 1916 38 121-131).-The conductivities of J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 211 a large number of organic acids have been determined in absolute alcohol and the molecular conductivities calculated for the tem- peratures 1 5 O 2 5 O and 3 5 O . It is shown that the values are extremely small being in nearly all cases about several hundred times smaller than in aqueous solution. Dilution increases the molecular conductivity and in many cases the increase is almost proportional t o the volume. The1 connexion between the conduc- tivity and constitution of the acids is discussed. Malic acid has a conductivity a t 1 5 O and N / 3 2 which is about thirty times as large as the conductivity of fumaric acid; itaconic acid at 15O and N / 3 2 has a value about five times as large as citraconic acid.A t 2 5 O and N / 3 2 the following molecular conductivities are obtained f o r the substituted malonic acids malonic acid 0.055 ; ethylmalonic acid 0.083 ; diethylmalonic acid 0.080 ; propylmalonic acid 0.105 ; dipropylmalonic acid 0-090 ; butylmalonic acid 0.036 ; allylmalonic acid 0.039 ; and benzylmalonic acid 0.062. Phenylpropiolic acid has a molecular conductivity which is about ten times that of cinna- mic acid. The conductivities of the para-substituted benzoic acids are generally less than those of the ortho-substituted acids. The strongest acids in alcoholic solution as judged by their conduc- tivity are sulphosalicylic acid and picric acid. The former acid has about the same strength as hydrochloric acid in alcoholic solution.This similarity of strength of the two acids is also found in aqueous sol u. t i on. J. F. S. The Conduction of Electricity in Anisotropic Liquids THEODOR SVEDBERG (Anr,. Physik 1916 [iv] 49 437-455).- Using pazoxyphenetole and p-azoxyanisole as solvents the author has investigated the influence of temperature on the electrical con- ductivity of the isotropic and anisotropic solutions which these solvents afford. The results obtained show that the temperature- coefficient f o r anisotropic solutions is about twice as great as the coefficimt for the same solutions in the isotropic condition. A t the transition point the conductivity shows a sharp change. With falling temperature this change amounts t o 14% for solutions of hydrogen chloride and t o 20-23oA f o r solutions of various organic acids.The magnitude of the change is approximately the same f o r both the anisotsopic solvent's examined. H. M. D. Anodic Relations of Passive Iron witb Notes on Polarisation Potentials as Influenced by External Gas Pressures. H. G. BYERS and SETH C. LANGDON (1. Amer. Chem. Soc. 1916 38 362-374).-A number of E.M.F. measurements have been carried out with passive iron under various pressures of hydrogen and oxygeln respectively. Other experiments have been made on the polarisation potentials of platinum anodes and copper iron and platinum cathodes in 0*2N-sulphuric acid under various pressures of hydrogen and oxygen. The single potentials were measured using a calomel electrode of special construction which is described in the paper.On application of gaseous pressures anodes of passive iron. o r any other metallic anode from which oxygen wasii. 212 ABSTRACTS OF CHEMICAL PAPERS. being evolved became more electropositive and cathodes more electronegative. The change was a function of the mechanical pressure. and not of the degree of saturation of the electrolyte with dissolved gas. Measurements of the variations of polarising current and of anodic potential during the process of passivication gave curves which indicate that passivication was here a two-process operation. It is pointed out that there is no one general explana- tion of passivity but rather that in each case the loss of activity is dependent on the conditions. J . F. S. Convenient Dip Electrode.G. J. VAN ZOEREX ( J . Avzer. Cliem. SOC. 1916 38 652-653).-A dip electrode which is very rigid in construction and suit'able f o r determination of the conductivity values and volumetric lead numbers of maple syrups is described. It consists of two platinum plates 2 cm.2 of 30 gauge. These are fastened by platinum wires to two hard-glass tubes which pass through an eb9nite stopper and contain mercury for making the connexions. The platinum plates are 1 cm. apart and are held in this position by four glass rivets one a t each corner. The ebonite stopper which also; carries a thermometer fits on t o a Jena-glass cylinder 3.7 cm. in diameter and 6.5 cm. high and is clamped in position by two sebscrews. The electrode as thus designed is not affected by stirring the very viscous syrups in it as is the case' with all other forms.J. I?. S. The Hydrogen Electrode t h e Calomel Electrode and Contact Potential. W. F. CLARKE C. N. MYERS and S. F. ACREE ( J . Physical Chew. 1916 20 243-265).-1n previous papers Loomis and Acree (A,? 1912 ii 124 and 125) and Desha and Acree (A. 1912 ii 125) studied the hydrogen electrode and its applica- tion t o the determination of hydrogen-ion concentration in organic reactions etc. whilst Myers and Acree (A. 1914 ii 164) worked on the improvement of the constancy of the hydrogen electrode and on the standardisation of the calomel cell. I n view of its applica- bility to the study of many questions such as the hydrolysis of salts organic and inorganic the work has been continued it being desirable eventually t o be able t o reproduce the' potential of the hydrogen electrode accurately to 0.000001 volt. Attention was first paid to improvemsents in method and appara- tus including a better form of thermostat a new type of calomel battery which can be easily and quickly recharged and a storage reservoir in whie'h hydrogen electrodes can be kept active and constant to 0*0001 volt,.The O*lN-KCl-HgCl-Hg system is constant and reproducible to 0.01 millivolt. The1 system Hg-HgC1-0~1N-KC1-0*1N-H@1-Pt-H2 is a particul'arly accurate and constant element whilst the system 0-1N-HC1-HgC1-Hg is rather unsatisfactory over long periods of time. Full directions and precautions are given which must be carefully observed in order t o obtain an accuracy and reproduci- bility of 0.01 millivolt.These relate ti; purification of materials regulation of temperature storage of electrodes when not in use,GENERAL AND PHYSICAL CHEMISTRY. ii. 213 and a device for short-circuiting the individual electrodes of a battery t o maintain a close agreement. E. H. R. A Calomel Standard Cell. G. F. LIPSCOMB and G. A. HULETT ( J . Amer. Chem. SOC. 1916 38 20-27).-The necessary conditions f o r the production of a trustworthy standard cell are considered. Based on these considerations it is shown t h a t a standard cell can be made with calomel instead of mercurous sulphate as depolar- iser. CdHglO% 1 CdC12,2+H,0(sat.) 1 Hg2C1 I Hg and is contained in the usual H-shaped vessels. The mercurous chloride is obtained by the electrolysis of a N-solution of hydro- chloric acid between a mercury anode and a tantalum cathode in a divided cell; the product is grey due to the presence of finely divided mercury.Tested over many months this cell is shown t o be 111010 constant than either the Clark or Weston oell. It has an E.M.F. 0.67080 volt a t 2 5 O and a temperature-coefficient dl'/dE'= -0.000067 volt. The heat change of the reaction Hg + CdCl = Hg,C12 + Cd which occurs in the cell is calculated from the above data by means of the Gibbs-Helmholtz equation and found t o be 30060 cal. This value agrees well with the value 30036 cal. fodnd from thermochemical data. Measurements have also been made with cells containing non-saturated solutions of cadmium chloride. With a solution containing 52 grams of cad- mium chloride in 100 grams of solution an E.M.P.0.68120 volt was found a t 2 5 O with a temperature-coefficient 0.000285. Other values are given in the paper which show that the temperature- coefficient does not change much with the conoentration of the solution. J. F. S. This cell is built up Inclusions in Silver Voltameter Deposits. G. 'CV. VINAL and WM. M. BOVARD ( J Amer. Chem. SOC. 1916 38 496-515).-The mechanically held inclusions in the deposits of silver in silver volta- meters have been made the subject of a searching investigation. Silver deposits have been heated a t temperatures slightly above 600° both in the Bunsen flame and in an electric furnace. The losses in weight indicate the presence of foreign material in the deposits to the extent of 0.0040% on the average for pure elect'ro- lytes and higher values for impure electrolytes.It is found that such heating of the deposits produces an alloy of silver and platinum which when the silver is dissolved leaves a thin film of platinum-black that may lead t o serious errors the next time the cup is used if proper precautions are not taken. As the result of the work it is shown that the most accurate value f o r the electro- chemical equivalent of silver is 1.11800 mg. per coulolmb and therefore the value of the Faraday becomes 96494 absolute coulombs but for general purposes 96500 as a round number is to be recommended. Inclusions in silver deposits made on smooth platinum surfaces are the same t o within the experimental error as when the deposits are made on matte surfacm.Inclusions between the crystals and cup have been measured by an application lo*ii. 214 ABSTRACTS OF CHEMICAL PAPERS. of the conductivity method and found to be a negligible part of the total inclusions which with pure solutions were about 4 parts per 100,000. I n cases where the deposit in large cups exceeds that in small cups that is where the volume effect is appreciable i t is not found that strong heating of the deposits diminishes the differ- ence. Two experiments on the anode liquid ‘support the conclusion of the American Bureau of Standards that a heavy anode ion is iion-existent. J. F. S. Factors Affecting t h e Electromotive Force of Binary Solid Alloys. DONALD P. SXITH and NEWELL T. GORDON ( J . Physical Chem. 1916 20 228-242).-1n studying the1 physical proper- ties of alloys thel greatest’ difficulty encountered is the preparation of samples of uniform composition and structure. Particular care was taken in the preparation of samples of brass to eliminate traces of oxide and t o obtain uniformity of structure by preparing surfaces from horizontal layers of the solidified mass by long annealing of the specimens in a vacuum a t 700-750°.The factors most in need of investigation affecting the E.M.F. of a binary alloy against an electrolyte are the effect of heat and surface treatment and the composition of the electrolyte. I n order t o test the theory developed by Nernst and Reinders a method is needed for ascertaining the composition of the equil- ibrium electrolyte. I n one set of experiments described the E.M.F.with reference t o the electrode Hg/ Hg,S04,2ilrH,S0 of a brass containing 49.9% of copper was measured using electrolytes 1.10-5 to 1.10-6 normal in copper and normal in zinc and sodium sulphates. So long as the surface was untreated between the experiments the E.M.F. was reproducible t o within a few millivolts a steady ‘‘ drift’’ with change in composition of the electrolyte being observed in every case. For instance with the electrolyte 1.10-5 normal in copper the E.M.F. fell from 0.480 t o 0.470 volt in one hundred and fifty minutes. The necessity f o r employing the equilibrium electrolyte is emphasised. Surf ace treatment of the specimen between experiments with rouge or emery was found t o produce marked and inexplicable variations in B.M.F. The influence of sawing grinding and polish- ing on the potential must be first investigated.Law of Thermal Expansion of Liquids Below the Normal Boiling Point ALFRED ALBERTOSI (J. Chim. phys. 1915 13 390-398) .-By combining DuprB’s empirical formula for the change of -the vapour pressure of a liquid with temperature log p= m / T + .n log T + z in which m 72 and 2; are constan& with Clausius’s thermodynamic formula the reflation p ( n / T - m/ T2) = L / T ( v r - v ) is obtained in which I is the latent heat of vaporisa- tion vr and v the specific volumes of saturated vapour and liquid respectively. By substituting for L the value given in an earlier paper (this vol. ii 218) and assuming that the saturated vapour satisfies the simple gas laws the above equation gives E.H. R.GENERAL AND PHYSICAL CHEMISTRY. ii. 215 d5/3= RT(n,- 1) Ja- Rm Ja which may be written in the form d5/3=A -BT where A and B are constants. Comparison of the experimental data for the expansion of a number of liquids shows that the results are in remarkably good agreement with those calculated with the aid of this formula. It may be noticed that the constant A represents the density of the liquid a t absolute zero and that the formula may be applied in the calculation of such limiting densities. Simultaneous Action of Very High Pressures and Ternpera- tures on Chemical Phenomena. Cosm ogonical Applications Chemical Origin of Solar Radiation ; Discussion of Arrhenius’s Theory. E. BRINER ( J . Chinz. phys. 1915 13 465-487).-A consideration of the influence of very high pressures on high tem- perature systems which a t moderate pressures would consist almost entirely of elementary atoms shows that the temperature elffect would in a large measure be counterbalanced by the pressure effect and that simple and compound molecules should be capable of existence under these conditions.The formulae expressing the relation between the pressure tem- perature and degree of dissociation are applied to the dissociation of hydrogen ammonia and nitric oxide and the influence of pressure a t high temperatures is derived in each case. Arrhenius’s theory according to which the energy of solar radia- tion is attributable t o the decomposition of endothermic compounds is adversely criticised. The possibility t h a t this energy has its origin in the combination of elementary atoms to form molecules is also examined but i t would seem that the1 energy which would thus become available is far too small to account f o r the sun’s radiant energy.To account f o r this it would seem necessary to assume t h a t the entities involved in the process of molecular synthesis are of sub-atomic character. H. M. D. H. M. D. Equation of State for Gases and Liquids. F. H. MACDOUGALL ( J . Amer. Chem. Soc. 1916 38 528-555).-A mathematical paper in which the Dieterici equation p= RT/ (v - b ) . e-a/vRI’ is discussed in detail and the extent t o which this equation repro- duces the experimental facts is shown in several ways. A number of methods are developed for calculating the values of a.and 6 below at and above the critical temperature. A formula is deduced for calculating the pressure1 of saturated vapour from the densities of liquid and vapour. This equation has the form ps = (d + d,)RT . e -a(di+d2)l”HT in which d and d are the densities of the liquid and satarate’d vapour respectively. A formula is deduced €or calculating the latent heat of vaporisation from the densities of the liquid and saturated vapour. This formula has the form L=2RT log v2/v1=a/vl.-a./u,. The previously observed values of isopentane carbon dioxide and hydrogen are studied in colnnexion with these formulz. I n the case of isopentane a de- creases and b increaH from Oo up t o the critical temperature. The same is true of carbon dioxide. Above the critical temperature in lo*-2t i .216 ABSTRACTS OF CHEMlCAL PAPERS. the case of carbon dioxide a continues to decrease whilst b remains fairly constant up t o ZOOo. I n the case of hydrogen a decreases from the critical temperature up t o the ordinary temperature whilst h does the same froin -183O a t least. The inversion temperature is calculated in the case of hydrogen and also the temperature a t which i t is in accord with Boyle’s law for moderate pressures. The latter temperature was found to be -171’4O. On combining the law o€ Cailletet and Mathias with a result obtained in many cases by Young it is shown that the1 density of a substance a t the absolute zero is four times the critical density. The author’s conclu- sions in regard to the variations of Z with temperature are in accord with some of the views of Richards in connexion with the compressibility of atoms.J. F. S. Cansideration of the Critical Opalescence. ETTORE CARDOSO ( J . Chim. phys. 1915 13 414-425. Compare A. 1913 ii 109 110 Ill).-The opalescence exhibited by carbon dioxide and other substances in the neighbourhood of the critical temperature has been found in agreement with previous observations t o vary in character with the filling of the tube containing the substance. This variation shows itself in the temperature at which the opales- cence is a maximum and also in the length of the interval in which the opalescence is visible. The phenomenon has not been observed in the author’s e’xperiments with oxygen ‘nitrogen carbon inon- oxide and methane and it is suggested that this may be due t o the shortness of the opalescent interval in the case of gases of low critical temperature.An examination of the hypothesis that the opalescence is due to the formation of an emulsion leads to the conclusion that this offers no satisfactory explanation of the facts. On the other hand i t is claimed that the apparent absence of the phenomenon in gases of low critical temperature is in accord with Smoluchowski’s view that the heterogeneity which gives rise to the opalescence is connected with the velocity distribution of the molecules. An analysis of Naxwell’s formula indicates that the velocities of the molecules will tend towards a uniform value as the temperature falls and local differences in density will consequently become less marked.H. M. D. Variations of the Spec;fic Heata of Gases with the Pressure. THADBE PECZALSKI (Ann. Physique 1916 [ix] 5 113-120. Com- pare A. 1914 ii 527).-A mathematical discussion of the subject. W. G. Determination of the Velocity of Sound and of the Ratio of the Specific Heats of Gases by Kundt’s Dust Figure Method GUSTAV SCHWEIKERT (41zn. Physik 1916 [iv] 49 433-436. Com- pare this vol. ii 79).-An addendum to the previous paper giving a summary of recent determinations of the specific heat ratio and of the specific heatl a t constant pressure. H. M. I).GENERAL AND PHYSICAL CHEMISTELY. ii. 217 The Ratio of the Specific Heats K= cp/cu of Nitrogen. 3'. A. SCHULZE and H. RATHJEN (Aim Physik 1916 [iv] 49 457-469). -The specific heat ratio has been determined for carefully purified nitrogen by Kundt's method giving c p / c = 1.4144 +_ 0.0002 a t room temperature and a pressure of 1 atmosphere.This value leads to 4.193 x 107 erg for the mechanical equivalent of the calorie. Recent measurements of the specific heat ratio for air oxygen and hydro- gen afford for the mechanical equivalent 4.309 4.188 and 4.202 x 107 erg respectively. The agreement between these several valces is much closer than that indieabed by older measurements. H. M. D. The Latent Heat of Fueion of Ice. A. LEDUC ( A n u . Pliyszyue 1916 [ix] 5 5-17).-A report presented to the third International Congress of Cold (Washington-Chicago September 1915) in which the work o n this subject is summarised and the value 79.6 cal. deduced f o r the latent heat of fusion of ice a t 1 5 O .W. G. Cryoscopic Measurements at Low Temperature@. H. S. REID and D. MCINTOSH ( J . Amer. Chern. SOC. 1916 38 615-625). -The molecular weights of a number of oxygen-containing organic liquids of low melting point have been determined in solution in hydrogen bromide by the cryoscopic method. The liquids examined were ethyl alcohol methyl alcohol ethyl acetate ethyl ether acetone acetic acid paracetaldehyde and acetaldehyde. Experi- ments were also made with bromine. The cryoscopic constant for hydrogen bromide was found t o be 103'1 from experiments 011 t'oluene chloroform and carbon tetrachloride. The results show t h a t all the compounds which form cornpounds with hydrogen bromide! are both associated and dissociated the amount of associa- tion varying very much with the substance.The amount of associa- tion agrees fairly well with the figures obt'ained f o r the molecular conductivity the substances showing the greatest amount of asso- ciation having the greatest conductivity. A comparison of the properties of ethyl ether and ethyl alcohol in hydrogen bromide is made with similar solutions i n chlorine. Oxonium compounds are formed in both cases and a study of the slopes of the freezing curves shows that in solution these compounds are1 largely broken down into their constituents. Solutions in chlorine are non-con- cluctors that is they exhibit no electrolytic dissociation. The determinations of molecular weights in liquid chlorine made recently by Waentig (A. 1910 ii 581) show normal results for ethyl ether over a considerabfe concentration whilst methyl alcohol and ethyl alcohol are greatly polymerised.There are therefore systems in which the compounds are broken down partly into their constituents which are further complicated by association and in some cases by electrolytic dissociation. Hence it is a t present im- possible to assign to these three factors their proper proportion and t o give formulze t o oxonium compounds. The increase in complexity in solution shown by the increasing values of the molecular weights points to the correctness of the view previously expressed t h a t theii. 218 ABSTRACTS OF CHEMICAL PAPERS. ions are much more complex than would be expected from the oxonium theory. J. F. S. Mathematical Relationship between the Boiling Point and Absorption Coefficient of Gams.A. IMIIOF (Zeitsch. ylzysikal Chem. 1916 91 124-128).-A theoretical paper in which the connexion between the boiling point and thel absorption-coefficient of gases is studied. It is shown that for the majority of the gases which obey Henry's law the boiling point is approximately propor- tional t o the logarithm of the1 absorption-coefficient a t Oo and 760 mm. f o r water if -looo is taken as the zero of temperature. On the other hand if the temperatures are measured in absolute degrees the boiling points of various gases bear the same relation- ship t o one ancther as do the logarithms od their absorption- coefficients T = h log al ; T = A log a2 or T / T = log al /log a2. The value of the constant has been determined and found to be 27.4 so that T = 27.4 log .a or a = eT127.4. J. F. S. Formula for the Calculation of the Heat of Vaporisation of Non-associated Liquid s. ALFRED ALBERTOSI ( J . Ch2'712. phys. 1915 13 379-389).-0n the assumption t h a t the attraction between two spherical molecules varies directly as the produd of the masses and inversely as the sixth power of the distance between them the author has derived the formula L=a(d5/3 - 6 ' 5 1 3 ) - Pd'(1- d / / d ) + p(d - u) for the latent heat of vaporisation L. In this ct and /3 are constants v and d the specific volumes of liquid and saturated vapour respectively atl pressure p and d and dl are the corresponding densities. A t low temperatures d' is very small and the formula reduces t o L - p(d - v) / (d5/3d/5/3) = a .It is shown by reference t o the data f o r a number of organic liquids that the heats of vaporisation calculated by means of this formula over a considerable temperature rangel are in good agree- ment with those derived thermodynamically from Young's data for the vapour pressures. The deviatiopq are of the order of 0.2-0*5%. H. M. D. Vapour Pressure of Solutions. Lowering of the Vapour Pressure of Water Produced by Dissolved Potassium Chloride. B. F. LOVELACE J. C. W. FRAZER and E. MILLER ( J . Amer. Chem. SOC. 1916 38 515-528).-The authors have previously (A. 1915 ii 11) deecribmed an apparatus f o r the det,ermination of the vapour pressure of solutions. This apparatus has now been impro'ved by a more sensitive' temperature regulation which makes it possible to keep the temperature constant t o within O'0lo f o r twelve hcurs by the introduction of a mechanical device f o r stirring the solutions under investigation during the1 experiment and by the addition of a more sensitive McLeod gauge for measuring the residual air pressure after the absorption of the water-vapour. The actual observations of the vapour pressure were only made after the McLeod gauge had shown a residual air pressure of less than 0.0001 mm.Under thew conditions the vapour pressure of a givenCfENERAL AND PHYSICAL CHEMISTRY. ii. 219 solution remains constant for days t o 0.001 mm. A number of solutions of potassium chloride of concentration 0.2-2-0N have been investigated with regard to their vapour pressure by the above-mentioned apparatus.It has been shown by analysis of the solutions from the apparatus after the measurements have been made that the change of concentration of the solutions during the process of removing the dissolved air and measuring the vapour- pressure lowerings is small enough t o be neglected. The most notable feature of the experimental results is that the molecular lowering is the same f o r all solutions investigated. Thue a 0'2N- solution gives a lowering of 0.110 mm. whilst a 2n'-solution gives a lowering of 1.1102 mm. Similar results have1 been obtained by Tower and Gerniann (A. 1915 ii 11) from the vapour tension of alcoholic solutdons of potassium bromide and lithium chloride. The authors are unable t o decide whether this phenomenon as sug- gested by Tower and Germann is due t o the combination of solvent and dissolved substance o r not.J. F. S. The Relation between Surface Tension and 0 ther Quantities. MASAO KATAYAMA (Sci. R e p Tohoku Imp. Univ. 1916 4 373-391).-The surface tension a t the surface of a liquid in contact with its saxurated vapour is influenced by the vapour as well as by the liquid. An attempt is made to eliminate the effect. of the vapour by subtracting the number of molecules in unit volume of the vapour from the number in unit volume of the liquid. The molecular volume of the fictitious liquid resulting thereby is given by the1 equation V'=M/DI-D in which Di and D are the orthobaric densities of liquid and vapour respectively and iM is the molecular weight of the substance.The molecular surface energy measured by YE" is then found t o be a linear function of the temperature until the critical temperature is nearly reached. This is shown by reference t o the data f o r benzene chlorobenzene carbon tetrachloride ethyl ether ethyl acetate and methyl formatc From van der Waals's equation connecting the surface tension and temperatnre and the Eotvos equation the author deduces the relation Di - D,= 3*03(1- 0)0*351Dk between the orthobaric densities 1)l and D a t the reduced temperature 0 and the critical density Dk. A further relation is that connecting the total surface energy cc and the free surface energy y which has t'he form and this is found t o be in good agreement with experiment. ~/y=(1+0*2346)/(1-0) H. M. D. Changes in Volume OM Solution in W a t e r of the Halogen Salts of t.he Alkali Metals.11. GREGORY PAUL BAXTER and CURTIS CLAYTON WALLACE ( J . Amer. Chem. SOC. 1916 38 70-105. Compare A. 1911 ii 557).-The densities of aqueous solutions of the chlorides bromides and iodides of the metals lithium sodium potassium rubidium and czsium have been deter- mined for a large number of concentrations from saturation down-ii. 220 ARSTRAC rs OF CHEMICAL PAPERS. wards a t temperatures of looo 70'19O 50.04O 25O and Oo. From the density values the change1 in volume is calculated and also the change in volume per gram of dissolved salt and per gram-molecule of salt. Voluminous tables of results are given which include the whole of the experimental data and the calculated quantities. The changes in volu$me observed can be explained by Richard's hypo- thesis of compressible atoms and that of hydration.This explana- tion assumes t h a t the following two changes which take place during solution and dissociation are the chief causes of the observed effects (i) When the molecules dissociate they are to a large extent freed from compression due t o chemical affinity and in consequence there is a large expansion amounting to 15-56% of the volume1 of the uncombined elements; (ii) when the ions and probably the molecules are combined with water both the hydrated substance and the water undergo compression. The latter effect varies regularly with the compressibilities of the substances involved as well as with their affinities f o r each other.Thel change in volume in the formation of the solution from the free halogens and {he alkali metals amd water is found t o be nearly additive at all concentrations ; a t low concentrations because the changes involved are chiefly due to the formation of ions from the elements which are independent of the salts involved; a t high concentrations because the molecules being less hydrated and less compressible produce smaller contractions and because the molecular volumes of the salts are very ne'arly additive. The effect of rising tempera- ture is found in general t o diminish contraction o r increase expan- sion owing t o lessened hydration of all the substances concerned. Marked exceptions exist a t the ordinary temperature in lithium chloride and bromide and also in the case of potassium bromide at high temperatures.It is pointed out that no simple method exists for separating the effects due to ionised and non-ionised material because of the varying magnitude of the change for each ion or molecule with changing concentration. J. F. S. Densities and Cubical Coefflcients of Expansion of the Halogen Salts of Sodium Potassium Rubidium and Cesium. GREGORY PAUL BAXTER and CURTIS CLAYTON WALLACE ( J . Amer. Chem. SOC. 1916 38 259-266. Compare preceding abstract). The values of the densities of the above-mentioned salts were required a t various temperatures in thel calculations connected with the work described in the previous paper. The densities and coeffi- cients of cubical expansion were deduced from results obtained by weighing known quantities of the material in toluene and by measuring the volume of toluene displaced by known weights of the materials a t various temperatures.The following densities were found sodium chloride 70.19O. 2.153; 50.04O 2-156; 25O 2.161 ; O.OOo 2.168 ; sodium bromide 50.0407 3.194 ; 25'0° 3-203 ; Oo 3.213 ; sodium iodide 50'04O 3.653 ; 2 5 O 3.665 ; Oo 3.677 ; potassium chloride 70*19O 1.978; 50*04O 1.981; 25* F957; Oo 1.992; potass- ium bromide 50.04O 2.740 ; 25O 2.749 ; Oo 2.756 ; potassium iodide 50*04O 3.114; 25O 3'123; Oo 3-133; rubidium chloride 50*04",GENERAL AND PHYSICAL CHEMISTRY. ii. 221 2.792 ; 25O 2.798 ; Oo 2.806 ; rubidium bromide 50*04O 3.340 ; 25O 3.349; Oo 3.358; rubidium iodide 50'04O 3.542; 25O 3.550; Oo 3.560; czsium chloride 70*19O 3.952 ; 50*04O 3.961 ; 25O 3.974; Oo 3.988; czsium bromide 50*04O 4.418; 25O 4.433; Oo 4.449; caesiuni iodide 50'04O 4.493; 25O 4.509; Oo 4.525.A list of values found by other observers is included in the paper. J. F. S. Densities and Cubical CoefBcien ts of Expanraion of Certain Substances As20S PLCI PbBr PrCl,. GREGORY PAUL RAXTER and CHAI~LES FRANCIS HAWKINS (J. Bmer. Chem. SOC. 1916 38 266-27l).-The densities of the above-named substances have been determined by weighing in a toluene-filled pyknometer a t 50° 25O and Oo. The following values were obtained arsenious oxide (octahedral) 50° 3.851 ; 25O 3.865 ; Oo 3.874 ; lead chloride 50° 5.872; 25O 5.885 ; Oo 5.899; lead bromide 50° 6.644; 25O 6.669 ; Oo 6.676; praseodymium chloride 25O 4.020. The coefficients of cubical expansion of the first three substances have been calcu- lated.A list of previous determinations of these quantities by other observers is included in the paper. J. F. S. Van der Waals's Equation. 147. V. METCALF (J. Physical Chem. 1316 20 177-187. Compare this vol. ii 85).-By rearrangement of its terms van der Waalds equation becomes an expression of equilibrium between opposing prexmres P + P = P,. Here P2( =n Iu2) is the cohesive pressure due t o the attraction between the molecules and P,(=RT/u- b ) is the elastic pressure tending t o increase the volume of the mass P being the external pressure. Certain conclusions were reached in the previous paper connecting important points on the volume+temperat8ure curves with the rate of change with volumel (or density) of these opposing pressures and in the present paper these conclusions are confirmed by a rigid mathematical analysis of the equation.E. H. R. Sources of Error in Viecosity Measurement. EUGENE C. RIKGHAM H. I. SCHLESINGER and ARTHUR B. COLEMAN ( J . Amer. Chew,. Soc. 1916 38 27-41).-Whilst working with the Bing- ham viscosimeter (A. 1914 ii 342) the authors found t h a t the viscosities when calculated by the generally accepted formula were not constant but varied with the pressure applied. They were thus led t o investigate the various points in the construction method of use and interpretation of various factors of viscosi- meters. It is shown t h a t the average pressure t o be used in the calcuIation of a viscosity measurement is not strictIy one-half the sum of the initial and final pressures as ordinarily assumed and t h s use of this value may lead t o considerable error.The method of arriving a t the true averace pressure has been deduced and tested experimentallv. I n the flow of a liquid through a capillary tube it is immaterial f o r purposes of viscosity me'asurement whether the capillary is horizontal or vertical. When a liquid flows from a capillary with a trumpet-shaped opening there is aii. 222 ABSTRACTS OF CHEMICAL PAPERS. definite loss of kinetic energy but whether the correction for this is the same as that in the case of a capillary with a uniform bore has not bee2 proved. As a result of the work it is suggested that the capillaries of viscosimeters should have ends which are as nearly square as possible so that the kinetic energy correction may Ee readily calculable also that the bulbs should be as short as possible.The latter is achieved by making each bulb approxi- mately of the shape of two cones placed base to base. J. F. S. Change of the Internal Friction of Metals with Temperature. P. LUDW;K (Zeitsch. physikal. Chem. 1916 91 232-247).-With the object of investigating the change of internal friction with temperature the hardness of the metals tin bismuth cadmium lead zinc antimony aluminium and copper has been determined a t temperatures from 20° t o the melting point in most cases and in those cases where the metal melts above 600° the measurements have been carried out up to that temperature. The method employed was the cone pressure method the pressure applied vary- ing from 5 to 1000 kilograms foer fifteen and three hundred seconds.From curves of the experimental results it is shown that' the decrease of the hardness and internal friction with increase of temperature is fairly steady. Irregularities due t o changes in the modification of the metal do not seem t o be important. A com- parison of the hardness figures a t similar and a t homologous t.em- peratures shows that the change in hardness is not the same for various metals since the curves repeatedly cross one another; con- sequently the hardness is to be regarde'd as dependent on the temperature a t which it is determined. A t the meltJng point the hardness still possesses a considerable value; thus for tin and bismuth i t has 10% of its original valuel; cadmium 2%; lead 7%; zinc l+%. A sudden fall in the' hardness only occurs as the metal melts.The internal friction of a solid metal therefore passes as the metal melts suddenly into the viscosity of the molten metal. J. F. S. Surface Tension I. Drop Weight Method for the Determi- nation of Surface Tensicn. WILLIAM D. HARKINS and E. C. HUMPHERY ( J . A mer. Chem. Soc. 1916 38 228-236).-The drop method offers the most exact means of determination of surface tension but owing t o faulty theoretical treatment of experimental data widely divergent results are obtained. The ideal conditions are represented by the1 equation W = 27rra where IV is the weight of the drop r the radius of the tip of the dropping tube and a the surface tension.This equation is only true i f the pendant drop isentirely supported by the1 surface tension and if the whole of the drop falls. Neither condition obtains in practice. The subject was treated theoretically by Lohnstein (A. 1909 ii 25) who evolved the formula l;t7=2maf(r/a) in which a is the square root of the capillary constant. The function f ( r / o ) therefore represents a correcting factor which was calculated by Lohnst'ein for various values of rla. These the authors find are not sufficiently accurateii. 223 GENERAL AND PHYSICAL CHEMISTRY. if values of the surface tension more accurate than 4% are required. They have therefore determined experimentally the values of f ( r / a ) using a two-liquid interface a t temperatures of loo ZOO 2 5 O and 30°. The receiving liquids were benzene ethyl carbonate dimethyl- aniline xylene toluene hexane whilst the dropping liquid was water benzene or solutions of sodium chloride o r strontium bro'mide.Some experiments were carried out by allowing the drop to fall into air. The experimental values are compared with the theoretical values of Lohnstein; the former give a very much smoother curve than the latter. J. F. S. Surface Tension. 11. Apparatus for the Determination of the Surface Tension at the Interface between Two Liquids. WILLIAM D. HARKINS and E. C. HUMPHERY ( J . Amer. Chem. SOC. 191 6 38 236-242. Compare preceding abtsract).-A description of apparatus for determining surface tension by both the drop method and the capillary rise method is given in the paper.The apparatus in the former case consists of a pipette of about 10 C.C. capacity graduated in 1/10 C.C. above and below the bulb. Below the lower graduations a capillary tube of 0.3 mm. diameter is attached; this is bent upward and a t the height of the bulb bent dow*rwartl agii:i. The end of the capillary tube passes through a stopper in a small vessel designed t o hold the second liquid. The dropping end of the tube was 9.4 mm. diameter since i t was found that with this dimension the value of the correcting factor f ( ~ / a ) is most accurafely known. A second tube attached t o a suction apparatus also passes through the stopper of the containing vessel. The method of effecting a determination consists in filling the pipette t o slightly above the zero graduation and then just bring- ing the level t o the zero mark.The end is then placed in the second liquid and the temperature of the whole allowed to become constlant. The exhausting pump or tube is then so arranged that a drop of liquid will form and fall in three t o t h e e and a-half minutes. When this has happened the volume of the drop is read off from the pipette and the weight calculated. A piece of appara- tus is described f o r measuring the surface tension at the interface of two liquids by the capillary rise method. F o r the actual details the original paper must be consulted. A very novel feature is the method of producing capillary tubes of uniform bore. The tubes are of Jcna glass and of about 1.4 mm. diameter uniformity being obtained by turning the bore in an accurate and sensitive lathe.J. F. S. Surface Tension. 111. Surface Tsnsion at the Interface be- tween Two Liquids and the Effect of Acide SFtItfr and Bases on the Interfacial Tension. WILLIAM D. HARKINS and E. C. HUMPHERE' (J. Amer. Chem. Soc. 1916 38 242-246. Compare preceding abstracts).-The surface tension a t the interface between water and benzene has been determined a t loo ZOO 2 5 O 30° and 40° by the capillary rise method. The value of the surface tension a t any temperature is given by the formula a = 35*54(1- 0.056t). Theii. 224 ABSTRACTS UF CHEMICAL PAPERS. surface tension a t the! interface between water and ethyl carbonate dimethylaniline xylene toluene and hexanel has been determined a t 2 5 O by the same method. The values found are' about 6% higher than those previously obtained by von Lerch (A.1913 ii 13) and Antonoff (A. 1907 ii 606). The effect of acids bases and salts on the surface ttension a t the benzene-water interface has been studied. It is shown that inorganic acids (HC1 H,SO,) bases (NH,*OH) and salts' (NaCl) lower the surface tension only very slightly but organic acids (formic acetic and butyric) produce a marked lowering the value being greater the higher the molecular weight of the acid. The following figures for approximately N/2-solutions of the acid show the effect pure water 34.18; N/2-formic acid 32.49; AT/2-acetic acid 29.24 ; and NI2-butyric acid 22.45. These resuIts are particularly interesting in connexion with muscular action. J. F. S. Simple Apparatus for the Accurate and Easy Determination of Surface Tension with a Metal Thermoregulator for the Q k k Adjustment of Temperature. WILLIAM I).HARKINS and F. E. BROWN ( J . Srner. Chem. SOC. 1916 38 246-252).-An apparatus is described f o r the determination of surface tension by the drop-weight met3od. It consists essentially of two weigh- ing bottles fitted with glass or monel-metal stoppers. One of these bottles contains the liquid under investigation and the other receives the drops. The two bottles are connected by a capillary U-tube with a long and a short' limb; the end of the short limb furnishes the dropping surface. The dropping tip is so ground t h a t interchangeable tips of monel-metal can be attached thus enabling a rapid change of the diameter to be made.Into each stopper a capillary tube enters just passing through the stopper the one to produce a slightly reduced pressure in the dropping bottle and the other to admit air t o the reservoir. A mercury burette is described f o r the production of the suction. Both weighing bottles and their connexions are placed in a nickel-plated brass box with glass sides which enables the whole apparatus to he sunk in a thermostat. Complete working details for making the apparatus are given in the paper. J. F. S. r Properties of Mixed Liquids. I. Sulphuric Acid-Water Mixtures. J LIVINGSTON R. MORGAN and CLARKE EDWIN DAVIS (?7. Amer. Ghem. Soc. 1916 38 555-568).-A large number of surface-tension measurements have been made by the drop-weight method with solutions of sulphuric acid of concentrations from that of pure water t o pure sulphuric acid atl temperatures Oo 30° and 50°.Formuk have been deduced by means of which the surface tension and specific cohesion can be calculated a t any con- centration and temperature between Oo and 50°. I n the case of the more concentrated solutions difficulties were encountered in the formation of the drop owing t o the p o x way in which i t covered the tip. This was got over by rapidly forcing out the drop and then withdrawing i t several times until the tip was properlyGENERAL AND PHYSICAL CHEMlSTRY. ii. 225 covered and then allowing i t to form in the norinal manner. It is shown that both the addition of sulphuric acid to water and of water t o sulphuric acid cause an increase in the surface tension so that different concentrations of sulphuric acid may have the same surface tension a t the same temperature.The addition of sulphuric anhydride t o sulphuric acid also increases the surface1 tension. If the property-coniFosition curve has any chemical meaning it may be assumed froin the surface tension results that a hydrate H,S0,,H20 exists a t 85% sulphuric acid. The application of the theory of Denison (A. 1913 ii 30) that the deviation of a property from the mixture lay plotted against the compositioii sliows at the poinb of maximum deviation the presence of a coinpound of identical composition with that of the solution leading t o the maxi- mum deviation indicates the following hydrates in water solutions of sulphuric acid according t o the property whicli is taken as the criterion H,SO,,H,O (density compressibility viscosity refrac- tion) H2S0,,2H,0 (refraction) €I,S04,3H,0 (surface tension) SH,SO,,H,O (conductivity viscosity) H,S0,,12H20 (conductivity density) 4H,SO,,H,O or 5H,SO,,H,O (viscosity).J. F. S. Adsorption. V. GERHARU C. SCHMIDT and BERSIIARL) HINTELEH (Zeitsch. physikal. Chem. 1916 91 103-123. Compare A. 1912 ii 236; 1913 ii 677).-The adsorption of vapours of benzene hexane carbon disulphide chloroform acetone ethyl alcohol methyl alcohol and water by bone charcoal has been determined up to the saturation point a t 14.2O. It is shown that for those liquids which are normal the saturation value is approximately proportional t o the molecular volume of the liquid. For associated liquids no proportionality exists in some cases the product of the saturation value and the molecular volume being larger than in the case of normal liquids and in some cases smaller.The exponen- t i d formulae c1 = k~~~ and c1 = T ( c / S ) ~ express the experimental results up to saturation fairly accurately. I n these expressions c1 is the concentration of the vapour c2 the quantity adsorbed 7r the vapour tension S the saturation value and k and a con- stants. Schmidt’s formula (Zoc. c i t . ) ( a - - Z ) / V . S=lired(S-S)/s. cc where (a- X ) / V is the concentration S the saturation value x the adsorbed quantity and I< and A constants expresses the experi- mental results for benzene but fails entir-ely in all other cases. Consequently this formula is not t o be used further as the adsorp- tion isothermal.J. F. S. Geochemical M d a l Adsorption. OSKAI~ NAGEL (Kolloid. Zeitsch 1915 16 19-20).-Reference is made t o the natural occurrence of platinum gold silver and vanadium in deposits which seem to show t h a t the niet’als have been adsorbed by the matrix. I n this connexion the author calls attention t o the large adsorption of clays in respect of potassium compounds. H. M. D. Simultaneous Adsorption by Two Adsorbing Media. HILARY LACHS (Zeitsch. physikal. Chem. 1916 91 155-170).-A numberii. 226 ABSTRACTS OF CHEMICAL PAPERS. of adsorption experiments have been carried out a t room tsmpera- ture using simultaneously two of the following adsorbent8 char- coal wood alumina me'erschaum and quartz. Solutions of amtic acid butyric acid succinic acid sodium hydroxide pyridine and acetone were shaken with known quantities of each of the adsorbents separately and with a mixture of two of the adsorbents and the equilibrium conditions determined.The object of the investigation was to ascertain the equilibrium conditions in the presence of two adsorbents and to ascertain whether two oppositely charged adsorbents effected a change in the amount of adsorption of either or both of the individual adsorbents. It is shown that if the solutions are not too dilute irrespective of the nature of the adsorbents the quantity of material adsorbed by a mixture of adsorbents is the sum of the quantities adsorbed by the adsorbents separately. If the solutions are very dilute the amount adsorbed by a mixture is less than the sum of the amounts adsorbed by tfie adsorbents selparately.I n the case of solutions of acids and bases and to some extent in the case of acetone the1 equilibrium constant is the samce whether the adsorbents are mixed or are kept in separate compartments. I n the case of colour substances (met'hylene-blue crystal-violet new magenta and auramine) the equilibrium constant is different in the two cases. J. F. S. The Adsorption of Acids by Cellulose. ALAN LEIGHTOX ( J . Physical Chem. 1916 20 188-194. Compare this vol. ii 128).- The behaviour of sulphuric phosphoric o r hydrochloric acid of varying concentration towards cellulose in the form of surgeons' cotton purified by treatment with 1% sodium hydroxide was studied by shaking about 1 gram of cellulose with 100 C.C.of acid for three hours and then centrifuging for one hour. The acid retained by the cotton was estimat'ed gravimetrically and the centrifuged acid was titrated to determine1 if any change in concentration had taken place through selective adsorption. Curves were plotted illustrat- ing t$e increase in adsorption with increasing concentration of each acid. Selective adsorption is shown only a t high concentra- tion and is most marked in the case of hydrochloric acid; with sulphuric acid it begins at< a concentration of 400 grams per litre; it is not detected with phosphoric acid. The value of the adsorp- tion expressed in grams is greatest with sulphuric and least with hydrochloric acid. No evidence of the formation of a com- pound between acid and cellulose was discovered.The prasence of acid lowers appreciably the amount of water adsorbed by the cotton. E. H. R. The Adsorption of Dyes by Colloidal Clay etc. PAUL ROHLAND (KoZZoid. Zeitsch. 1915 16 16-18).-1n general the adsorption of dyes by colloidal silicates increases with increase in the colloidal nature of the dye. The constitution of the dye also seems to have an influence on the phenomenon. Dyes derived from tsiphenylmethane are in general readily adsorbed whilst those containing nitro- or azo-groups are adsorbed with greater diffioulty.GENERAL AND PHYSICAL CHEMISTRY. ii. 227 The differences exhibited by colloidal silicates towards dyes may be utilised in separating dyes from their mixtures. H. M. D. Abnormal Osmoais. H.FREUNDLICH (Kollozd. Zeztsch 191 6 18 11-1 6).-The author discusses certain apparently well-estab- lished cases of osmosis in which the solutions separated by the semi-permeable membrane are isosmotic or in which the direction of the flow of water is from the more concentrated to the less concentrated solution (negative osmosis). It is supposed that these anomalous effects are clue to electro-endosmose under the influenoe of local electric currents. Electso-endosmotic effects of this kind may occur when the membrane is permeable t\o the solvent as well as to electrolytes which may be present in solution and also when the membrane is permeable t o the solvent and to a particular ion. According to the explanation which is put forward there is a close similarity in the relation between electro-endosmose and abnormal osmosis on the one hand and between electrostenolysis and the Becquerel phenomenon on the other.I n other word8 the Becquerel phenomenon is attributable to electrostenolysis under the influence of local currents. H. M. D. Diffusion of Iodine in Potassium Iodide Solutions. GRAHAM EDGAR and STERLING H. DIGGS ( J . Amer. Chem. SOC. 1916 38 253-259).-The authors have determined the rate of diffusion of iodine into potassium iodide of various concentrations by the two- layer method. A layer of potassium iodide of concentration 0*5N 0.25N N 2 N 3N o r 4*5N was placed in a cylindrical vessel and below it a layer of N/ZO-iodine in potassium iodide of the same concentration as the upper layer was introduced by means of a funnel.The amount of iodine which diffused into the upper layer was determined by titration with sodium thiosulphate. Viscosity measurements were made of solutions of iodine of the same con- centrations and the fluidity calculated. It is shown that increase in the concentration of potassium iodide causes a marked increase in the rate of diffusion of the iodine; there is also an increase in the fluidity of the solutions. These results confirm the results of von Name (A. 1910 ii 280; 1911 ii 973) that the rate of reaction between iodine in potassium iodide solution and metals increases with increase in the concentration of the potassium iodide. Since these reactions depend on diffusion it follows that von Name's results demand an increase in the rate of diffusion of iodine with increase in the concentration olf potassium iodide.It is shown that the increased fluidity is insufficient to account for the increased rate of diffusion and all other possible reasons would lead t o a decreased rate of diffusion. J. F. S. Non-ideal Solutions. The Activity of a Sparingly Soluble Component. E. K. STRACHAN ( J . Anzer. Chem SOC. 1916 38 626-632).-A theoretical paper in which the partial pressure of a sparingly soluble component (iodine) has been calculated from its partition-coefficient in pairs of binary mixturee water andii. 228 ABSTRACTS OF CHEMICAL PAPERS. carbon tetrachloride carbon disulphide and bromoform. The partial prgssure of a sparinglv soluble component of a truly non- ideal solution is expressed by the relationship in which p is the partial pressure of the dissolved substance when its molecu1:tr fraction is AT po is the vapour pressure of the pure solute and iVs its molecular fraction in a saturated solution.C is a constant which is approximately inversely proportional to the square of the solubility of the dissolved substance. p = ( N /Ns)?Y* f C ( R - 3 7 ) * N J. F. S. A Theory of Multiple Ionidation. A Modificatim of t h e Electrolytic Dissociation Theory. FRANCIS FARHAM HEYROTH ( J . Amer. (7hem. SOC. 1916 38 57-65).-A theory of ionisation is proposed which brings into line a number of points which do not readily come under the Arrlienius dissociation theory. It is suggested that all electrolytes are amphoteric and ionise in two ways the mtio between the two forms of ionisation as expressed by their ionisation constants varying from 1 :1 t o very nearly 1 0 0 and depending on the nature of the solvent the concentra- tion of the solution and the average structure of the molecules dissociating. Thus for nitric acid it is assumed that the dissocia- tion occurs according t o the equations HNO H' +NO,' and HNO Z OH'+NO,'? the degrele of dissociation being given by u + P = ( i - l)/(n-1) in which a and fl are the degrees of dissocia- tion of the two schemes.On the basis of this theory the author explains the oxidising action of sulphuric and nitric acids. I n the case of the solution of copper by hot concentrated sulphuric acid it is suggested that the two equilibria exist H2S0 t S04/'+2H' and H2S0 S02:'+20H/ and that the SO," is discharged on the copper converting it into copper ions with the liberation of the gas.Explanations are also offered f o r the precipitation of silver and mercury oxides by sodium hydroxide for the heat of neutral- isation of weak acids and bases and for the existence of acid chlorides such as SO,Cl,. The bearing of the theory on the Ostwald dilution law is discussed. J. F. S. Crystallographic Relations of Allied Sub~ltances Traced by Means of the Law of Valency-volumes. IfT. BARLOW (&fin. Mag. 1916 17 314-323).-The equivalence-parameters of several pairs of sulphates (for example CuSO and MgSO,,H,O CaSO and CaS0,,2H,O etc.) are compared. By suitably selecting the axes i t is found that two of the parameters are nearly equal for the two members of the pair whilst the third parameter has the ratio of W W that is the ratio between the sums of the valencg-volunies of the two salts.From this i t is concluded that there is a stati- fication of the crystal-structure the atomic arrangement in layers in one plane direction being the same f o r both salts of the pair. L. J. S. Crystals as Molecular Compounds. PAUL PPEIFFER (Zeitsch. anorg. C'hem. 1915 92 376-380).-When Bragg's structure forQENERAT AND PHYSICAL CHEMISTRY. ii. 229 the crystal of sodium chloride is examined it is found that each sodium atom is symmetrically surrounded by six chlorine atoms and each chlorine atom by six sodium atoms. This accords with a co-ordination number of 6 for each of these kinds of atoms the union being partly by principal and partly by subsidiary valences.This is in accordance with the structure of such salts as [IAg,]NO I n the case of symmetrical compounds the diff wence between principal and sub- sidiary valences disappears. C. H. D. p g ] (NO,) [PAg,l(NO,) and rAsAg,l(No,)3. The Crystallisation of Phenyl Ether. C. DAUZORE (Con@. rejid. 1916 162 385-387).-The author has followed by micro- scopic examination the steady crystallisation of superfused phenyl ether a t ZOO when a small fraction of the solid material is intro- duced into the liquid. The surface of the crystalline fragment introduced which is generally very irregular soon becomes regular by ‘‘ cicatrisation ” (compare Ma:irain (( Les 6tats physiques de la matikre,” p. 92). This and the further growth of the crystal sets up two sorts of movements in the liquid.The first is a flow of the liquid towards the crystal which is manifest throughout the whole mass and produces eddies near the crystal. The second is of an undulating nature a t the surfaces of contact between the liquid and the solid. T t consists in a series of fine striata which pass continually along the growing faces and are termed waves of crystallisation. These bring about the1 ‘( cicatrisation ” of the irregular crystals and cause the formation of the faces and edges of the small crystals the edges being the lines of stoppage of the undulatory movement the stoppage being produced by an inverse undulation o r hv some other cause. W. G. The Growth of Crystals. PAUL GAUBERT (Compt. m i d . 1916 162 471-473. Compare Bull.SOC. franc. min. 1902 25 258; 1904 27 233).-A claim for priority over Dauzkre (compare pre- cedinp abstract) f o r the discoverv of the various movements of the liquiz towards ‘the’ crystal diiriig crystallisation of a fused salt. W. G. The Mode of Flow in Crystalline Solids. G. TAMMANN (Zpitsch. morg. Chem. 1915 92 37-46).-The view that the flow of crystalline solids is due t o a partial melting is criticised. Accord- ing to Poyntiiig the melting point of a solid is always lowered by pressure applied in such a way that$ the liquid formed is free to escape. This coaclusion is clue t o a wrong application of thermo- dynamical reasoning to1 a case in which the cycle is not’ reversible. It is improbable’ that a charact-eristic property such as the melting pressure should vary with a chance condition such as the permes- bility of the wall of the containing vessel.The similar conclusion of Ostwald derived from considerations of vapour pressure is due to1 a misunderstanding of the space model containing the equilibrium curves. Niggli (A. 1915 ii 242) reached the same conclusion by con-ii. 230 ABSTRACTS OF CHEMICAL PAPERS. sidering the bhermodynamical potential. This is also attributed t o the application of a principle t o a case in which i t is invalid. The actual influence of compression or tension en crystals iii equili- brium with their melt is so small as t o be negligible even when the stress applied approaches the elastic limit,. This is confirmed by observation. C. H. D. Colloidal Solid Solutions. D. MCINTOSII and K.EDSON ( J . Amer. Chem. Soc. 1916 38 613-615).-When a solution of a salt in water is plunged into a bath a t a very low temperature the mass freezes as a whole and the frozen mass is homogeneous. Such solid masses the authors t'erm colloidal solid solutions. The frozen material resembles ice but is more opaque1 and not so hard; when examined microscopically it is seen t o be homogeneous and if the solid is allowed t o melt undisturbed there is a clear solution formed. Hence in comparison with cryohydrate these solutions are reversible. On melting these solutions have the exact temperature a t which they would be in equilibrium with ice. These solutions conduct electricity and the conductivity of lo% ZO% and 30% solutions of potassium iodide has been determined a t temperatures from - SOo to -loG.The conductivity shows a maximum rate of increase a t -2l0 that is a t tlie cryohydric temperature. Similarly solu- tions of A T ,!V / 2- and A7/4-hydrochloric acid have been determined. The conductivity increases fairly regularly with increase of tem- perature. The conductivities of the acid solutions are much above those of salt solutions of the same concentsation. J. F. S. Effect of Freezing on Certain Inorganic Hydrogele. H. W. FOOTE and BLAIR SAXTON ( J . Amer. Chenz. Soc. 1916 38 588-609).--A method is described by which the free capillary and combined water in gels may be determined and consequently the composition of the hydrogel deduced. The method consists in cool- ing the hydrogel in a dilatometer filled with light petroleum to -20° or -30° and observing the motions of the thread.I n carry- ing out a determination the dilatometler readings a t first show a regular decrease as the temperature falls due t o contraction of tlie bulb and its contents. A t a temperature several degrees below zero sudden expansion occurs due to freezing. The water freezing in this first expansior consists of free water and that part of the capillary water which has reached its freezing point. After the volume has becorLe constant a further lowering of temperature causes more capillary water t o freeze and the volume usually expands somewhat further after which contraction sets in and if the temperature is sufficiently lowered the contraction becomes very nearly a linear function of the temperature as i t is before freezing occurs.The reverse of these c h s n p occurs on warming. A number of preliminary determinations were carried out with sand and water and lampblack and watler f o r the purpose of testing the method and observing the difference between the behaviour of free and capillary water. Experiments were then carried out with the hydrogels of silica alumina and ferric oxide. I n each case theGENERAL AND PHYSICAL CHEMISTRY ii. 231 total water content was known and from the expansion on freezing the free and capillary watler could be calculated. Hence t'he water actually in combination in the hydrogel could be deduced. I n the case of alumina a sample with a total water content of 38.18% was shown to contain all its water in the combined condition.The effect of ageing and repeated freezing on the gel is investigated. I n the case of silica two results are obtained which correspond with an amount of combined water agreeing with the formulae Si02,1*31H,0 and Si0,,1.35H20. I n the case of ferric oxide the amount of water remaining unfrozen corresponds with Fe20,,4*25H,O. J. F. S. Protective Colloids. Cetraria Islandica as Protective Colloid. I. Colloido-chemical Investigation of t h e Extract from Ice- land Moss. A. GUTBIER A. IRION and E. SAUER (KoZZoid. Zeitsch. 1916 18 1--11).-The preparation of aqueous extracts containing colloidal substances from Iceland moss is described. These colloids which are precipitated on the addition of alcohol t o the aqueous extract are characterised by great stability and in the dry condi- tion can be kept without change f o r an indefinite time.By means of viscosity measurements the authors have investigated the influ- ence of high temperatures hydrochloric acid sodium hydroxide and sodium chloride on the stability of tlie colloidal solutions with the result that the solutions are found to exhibit only slight changes under the influence of thesel agents. The colloidal particles are negatively charged and coagulation takes place a t the anode. H. M. D. Theoretical Study of Chemical Equilibrium. L. GAY ( J . Chim. phys. 1915 13 402-413).-A discussion of the displace- ment of equilibrium resulting from the addition of one of the reacting substances to tlie syst.em in equilibrium by making use of the conception of the expansibility tension.H. M. D. Non- Uni- and Bi-variant Equilibria. VI. F. A. H. SCHREINE- MAKERS (Proc. K . Akad. Wetensch. Amsterdam 1916 18 1175-1190. Compare this VOI. ii 180).-A theoretical paper in which the relation between the concentration- and pressure-tern- perature equilibrium diagrams is discussed. The two correspond in the sense thatt the one is a schematical representation of the other. R. M. D. The Mechanism of Reactions in Aqua regia. E. BRINER (Corn@. rend. 1916 162 387-389).-A study of the conditions governing the equilibrium of the reversible reaction NOCl + C1 + 2H20. The equilibrium pressure a t Oo is 2.84 atmos. and a t 20*5-21° i t is 5.1 atmos. Within the limits studied the system is univariant having three phases and two independent components.One liquid phase consists of nit?rosyl chloride and chlorine in equilibrium with the aqueous phase which contains in addition t o the original acids HNO + 3HC1ii. 232 ABSTRACTS OF C!HEMICAL PAPERS. some chlorine and nitrosyl chloride. The gaseous phase contains all tdie constituentls of tliel system. I f the acids used are too dilute thO phase conssting of the liquefied gases does not exist and the equilibrium pressures diminish as the dilution increases. If the two coi~centratecl acids are mixed in a Dewar vessel there is first a rapid rise of several degrees in the temperature which then descends steadily and remains constant a t about 2 O below the original temperature of the acids. The) preliminary rise in tem- perature is due t o the action of the hydrogen chloride on the water of solution of the nitric acid.Taking into account the heats of solution the heat of the reaction using 37% hydrochloric acid and 70% nitric acid is - 20 Cal. and if the dilution of the acids is double +,he value is -27 Cal. W. G. The Law of Mass Action a s a Special Case of a General Reaction Law. H. J. PRINS ( C h ~ n i . TVeelchZnc7 1916 13 344-350). -A theoretical paper dealing with the phases of chemical reaction and the condit'ions governing it. Partition Coefficiente of Hydrogen Peroxide between Water and Certain Organic Solvents. JANES H. WALTON and HAROLD A. LEWIS (J. Amer. Chem. Soc. 1916 38 633-638).-The parti- tion-coefficient' of hydrogen peroxide between water and each of the following liquids has been determined a t 25O ethyl acetate isobutyl alcohol amyl alcohol acetophenone ethyl ether and aniline.It is shown that those organic solvents which will dissolve water will a 'so dissolve hydrogen peroxide. Hydrogen peroxide does not undergo association in any of the above-named solvents. The values obtained by the authors in ethyl ether solution do not agree with those of Osipov and Popov. Hydrogen peroxide is soluble in phenol and in quinoline. The solution in quinoline is not one of simple peroxide molecules but probably consists of a com- pound of the solvent and hydrogen peroxide in equilibrium with hydrogen peroxidel. Qiiinoline is an unusually good solvent for hydrogen peroxide. A t Oo f o r certain concentrations of hydrogen peroxide the ratio R,O in water/H,O in quinoline may be as low as 0.276.Distribution of Caffeine Sodium Salicylate. RAPHAEL ED. LIESEGANG (Rolloid. Zeitsch. 1915 16 13-16).-1t has been found that the gelatinous residue which is obtained by evapcration ,)f a few drops of a solution of caffeine sodium salicylate on a glass plate shows a well developed banded structure. If a concentrated solution of the1 double salt is heated on a water-bath a similar dis- tsibution in layers of differerit refractive index is observed. The phenomenon which appears t o be dependent' on the existence of a temperature gradient in the solution has also been observed with solutions of gelatin and in lesser degree with solutions of sodium chloride magnesium chloride and sodium silicate. Dynamics of Scission of Carbon Dioxide from Organic Compound-.EMIL RAUR and R. ORTHNER (Zeitsch. p h y s i k d . Chewz. 1916 91 75-102).-The authors have studied the action of heat A. J. W. J. F. S. H. M. D.GENERAL AND PHYSICAL Cl~EMlS'l'l~J'. ii. 233 an substances which evolve carbon dioxide with the object of ascertaining whether these reactions are in accord with the law of mass action and are reversible. The three cases studied were (i) the decomposition of basic ferric oxalate into ferrous oxalate and carbon dioxide (ii) salicylic acid into phenol and carbon dioxide and (iii) sodium salicylate~ into sodium plieiioxide and carbon dioxide. It is shown in the case of basic ferric oxalate t h a t an equilibrium is set up a t temperatures between 160° and 200O; the equilibrium pressure was measured and the mass action constant deduced.I n the case of salicylic acid the mass-action constant was found to be 2.7 x 10-4 at. 203O; the dissociation pres- sure of sodium salicylate a t 220O and 230° was found to be 143 mm. and 183.5 mni. respectively. In no case could the equilibrium value be obtained from the other side even when carbon dioxide a t pressures considerably above the dissociation pressure was em- ployed. The three cases investigated theref ore represent reactions which proceed to an equilibrium that can only be obtained from one side t h a t is they are reversible reactions since they follow the law of mass action but the equilibrium can only be approached from one side. J. F. S. Effect of Dissolved Substances on the Velocity of Crystal- lisation of Water.JAMES H. WALTON and ALBERT BKANN ( J . -4rner. Chem. SOC. 1916 38 317-330. Compare A. 1915 ii 15). -In a previous communication the linear velocity of crystallisation of water supercooled t o - 9 O was measured. Using the same method the effect of dissolved substances on the velocity of crystallisation of water supercooled t o - 9 * l 0 has been determined f o r forty-five substances which include organic substances such as sucrose carb- amide dextrose mannose glycerol ethyl alcohol lievulose antipyrine and raffinose and a number of the commoner inorganic acids salts and bases. The dissolved substances all retard the velocity of crystallisation. Solutions of equimolecular concentration show different retarding effects. The retardation is not therefore a colligative property.F o r substances with more than eight atoms in the molecu1.e there is a rough relation between the number of atoms in the molecule and the inhibition of the velocity of crystal- lisation; the greater the number of atoms the slower the rate. F o r compounds with less than eight' atoms the power of retardation seems to be a specific property. That these effects cannot be explained by Marc's adsorption theory of the inhibition is evidenced by the fact that the sugars which are n o t greatly adsorbed are very active in retarding the rate of crystallisation. Certain inorganic salts also show no relation between the extent' t o which they are adsorbed and their retardation of the formation of ice crystals. Substances in the colloidal state such as gelatin ferric hydroxide and oertain dyes retard the velocity of crystallisation.The stability of the supercooled solutions toward spontaneous crystallisation varies with the dissolved substance. Solutions of AT/ 10-hydrochloric acid are exceptionally stable. Dilute solutions of certain dyes are also unusually stable. Solutions of brucine sulphate with a con-ii. 234 ABSTRACTS OF CHEMICAL PAPERS. centration less than 0.00125 gram.-mol. per litre do not affect tlie velocity of crystallisaticn. These sodutions however are much mom stable toward spontaneous crystallisation than pure water a t the same temperature. J. F. S. M. LE BLANC and G. WUPPERMANN (Zeitsch. physikal. Cheiiz. 1915 91 143-154).-The experiments of Winkelmann (dmta. Y h y s . C'henz. 1884 [ii] 22 1) on the connexion between velocity of vaporisation a i d velocity of diffusion have beeii repeated both in glass and in metal tubes.It is shown that the increase in the diff usion-coefficient with increasing diffusion height in the case of vapours is due t o the decreasing temperature lowering a t the surface of the evaporating liquid. When this temperature lowering is avoided i t is shown that f o r water ethyl alcohol benzene clilorobenzene and propyl acetate the quantity evaporated per unit of time other conditions being constant. is inversely proportional t o the length of the diffusion height and that the coefficient of diffusion remains constant. The velocity of vaporisation is therefore at the temperatures investi- Velwity of Vaporisation of Liquids. gated "(42-6f0) conditioned by the' velocity of diffusion.J. F. S. The Velocity of Hydration of the Anhydrides of some Batty Acids. 11. P. E. VERKADE (Bee. trav. chinz. 1916 35 299-308. Compare Boeseken and Verkade A. 1913 ii 256).-The velocities of hydration of two mixed acid anhydrides have been measured at 25O by the conductivity method and the unimolecular velocity- coefficie1it.s have been calculated. The values obtained for 0.4343k a t 2 5 O were for acetic propionic anhydride 0.0524 and for a-butyric isopropylacetic anhydride 0.0155. The influence of ionisation has been eliminated by dividing these hydration-coefficients by the mean of the ionisation-coefficients of the corresponding acids. The results obtained bear o u t the previous deductions (loc.c i t . ) . W. G. Action of Salts with Water of Hydration and without Water of Hydration on the Velocity of Saponification of Esters. J. E. L. HoraEs and HARRY C. JONES ( J . AVW. Chcm. Soc. 1916 38 105-121).-Jones and Guy (Ann. Physz'k 1914 [iv] 43 555) have shown that combined water is more transparent t o light than water in the free condition. The present paper deals with experiments which show that combined water is more active in effecting saponification than free1 water. The rate of saponifica- tion of methyl acetate and methyl format6 has been carried out in water solution and in solutions of pot,assium chloride potassium nibrate calcium chloride magnesium chloride strontium chloride lithium chloride sodium chloride calcium nitrate sodium nitrate sodium bromide potassium bromide barium chloride magnesium nitrate potassium iodide sodium iodide lithium sulphate and lithium nitrate a t temperatures of 1 5 O 25O and 35O.The solutions of the salts were AT N / 2 and N / 4 . The plan of work adopted was to investigate the difference in the velocity with which free waterGENERAL AND PHYSICAL CHEMISTRY. ii. 235 and combined water effect the saponification under the following conditions (i) Time and concentration constant with varying tem- perature. (ii) Ccncentration and temperature constant with vary- irig time and (iii) time and temperature constant with varying concenbration. 'I'he amount of saponification was determined by titrating measured quantities of tile solution by means of a solu- tion of ammonia using corallin as indicator. The salts magnesium chloride caicium chloride strontium chloride barium chloride inagnesiuin nitrate calcium nitrate and strontium nitrate produce the largest increase in the velocity of saponification and these salts are all hydrated. Then come the non-hydrated salts sodium chloride sodium nitrate potassium chloride and potassium bromide.Along with these howaver the hydrated salts sodium bromide calcium bromide lithium chloride lithium bromide lithium nitrate and magnesium bromide also appear. The salts lithium sulphate sodium iodide strontium bromide lithium bromide and potassium iodide give smaller velocities than pure water. On dilution the effect with salts having water of crystallisation decreases more rapidly than with salts which have no water of crystallisation which shows that the saponification cannot be due to the hydrolysis of the salts alone.The! large effect with salts with water of crystal- lisation is probably due in part t o their being hydrated combined water being more highly ionised than free water. The amount of saponiiication seems to be due t o the combined effect of both cation and anion. There is a definite dilution f o r each salt a t which the iliaximum saponiilcation occurs. Hydrated salts show a large tem- peratcre-coeiiicient notwithstanding the decomposition of hydrates with rise of teixperature probably due in part to' hydrolysis. J. F. S. The Velocity of Saponification of Fats and Oils by Potassium Hydroxide in Different Solvents. ERNEST ANDERSON and I€. L. B ~ ~ O W N ( J .Physical Chem. 1916 20 195-213).-The scope of the work was the determination of the order of the reac- tion the relative velocity of saponification of different' oils and fats the influence of the solvent and of temperature. The different solvents used mere methyl ethyl and amyl alcohols and t h e oils included cotton-seed castor olive and croton with butter fat. Check experiments were made with methyl acetate which is knowii t o be hydrolys,ed according t o a bimolecular law. I n every case the saponifichtion of the glyceride was found t o be a bimolecular reac- tion and all the fats and oils studied were saponified a t approxi- mately the same rate although this appeared t o increase slightly with the molecular weight of the fatty acid. The following con- stants were obtsined by saponifying 5 C.C.of the glyceride in 200 C.C. 0.2iT-amyl alcoholic potash Oil. Cotton-seed. Croton. Olive. Castor. Mol. wt. ......... 274 279 291 293 Vel. const. . . . . . . 0.001550 0.001578 0.001605 0.001 692 The velocity constant in amyl alcohol (D15.5 0'8140) is twice as great as in ethyl alcohol (D15.5 0.8171) and about ten times as greatii. 236 ABSTRACTS OF CHIEMICAL PAYERS. in this as in methyl alcohol (D15.5 0.8100). An increase in water content of the alcohol causes an increase in the velocity constant when pethyl alcohol is the solvent. I n ethyl alcohol the temperature-cotefficient 01 the reaction velocity between 15O and 25O is 2.36 for castor oil. TJie velocity is increased by increasing the concentration of the alcohol but the increase is not the same in alcohols of different strengths.The effect of increasing the concen- tration of the oil differs in different solvents and in amyl alcohol actually decre?ses the reaction velocity. Influence of Neutral Suhtances on the Rate of Ghange in Jellies. RAPHAEL XD. LIESEGANG (Kohid Zeitsch. 1'316 18 16-18).-Experiments are described which show that the rate of intaaction of LWO subst'ances one of which is present in a gelatin jelly and the other in a superimposed aqueous solution is not in general affected by the presence of neutral substances in the aqueous solution. I n other words the osmotic pressure of the aqueous solution is not a determining factor in reactions which take place under the special conditions referred to.A study of the progress of such diffusion reactions has shown that the initial stages are characterised by a relatively high velocity for which no explana- tion has as yet been found. E. H. R. H. M. D. Catalysis. I. NILRATAN DHAR ( P I oc. K. Akud. VV2tmsch. '4 msterdam 1916 18 1084-1096).-Experiments have been made with supersaturated Eolutions of various substances in order t o ascertain whether crystallisation is induced by the addition of isomorphous substances. No change was observed in supersaturated calcium chloride solutions on the addition of calcium fluoride or strontium chloride (SrC12,6H20). Copper sulphate solutions were unaffected by the addition of the crystalline sulphates of magnes- ium manganese iron cobalt zinc and cadmium. Cobalt sulphabe and magnesium sulphate solutions containing up t o 50% of salt in excess of that corresponding with the saturated solutions were also unaffected by the addition of crystals of the above isomorphous salts.Sodium selenate crystals produced no effect on supersatur- ated sodium sulphate solutions and the same result was obtained on the addition of sodium nitrate t o supersaturated solutions of silver nitrate. The supersaturation of benzoic acid solutions was unaffected by the addition of crystals o i salicylic acid and con- versely benzoic acid crystals were without influence on supersatur- ated solutions of salicylic acid. The results obtained are not in harmony with the frequently expressed opinion that induced crystallisation affords a means of identifying isomorphous substaiices.H. M. D. Catalysis. 11. NILRATAN DHAR (Proc. K. Aknd. Wetensch. Amsterdam 1916 18 1097-1133).-The influence of light on t.he velocity of a number of reactions has been examined by making parallel observations in the dark and in diffused light or sunlight. The rerctions examined include the action of bromine on aqueousGENERAL AND PHYSICAL CHEMlSTRY. ii. 237 solutions of various organic acids and their salts of bromine on ethyl and methyl alcohols of sodium persulphate on aqueous solu- tions of bromides of iodine on aqueous solutions of nitrites hydr- azine hydrochloride hydroxylamine hydrochloride hypophosphorous acid and its salts and acetone. Other reactions include the reduc- tion of mercuric chloride and auric chloride by olrganic acids and their salts and the reduction of potassium permanganate by various organic acids.I n all cases the reaction velocity was found to be greater under the influence of light. The reaction between iodine and oxalates I + M,C,O = 2MI + 2C02 where M represents ammonium o r potassium would see'm to afford a possible basis f o r actinometric measurements. The rate of the reaction is not influenced t'o an appreciable extent by either oxygen or carbon dioxide. H. M. D. Catalytic Oxidation of Hypophosphite Solutions by Palla- dium. A. SIEVERTS and E. PETERS (Zeitsch. physikal. Chem. 1916 91 199-231).-The conditions under which various forms of palladium effect the catalytic oxidation of hypophosphite solutions as well as the kinetics of the process have be'en investigated a t various temperatures.The progress of the oxidation was followed both by titration of the solutions with iodine and by measurement of the volume of hydrogen liberated. It is shown that aqueous solutions of sodium hypophosphite under the influence of palladium evolve hydrogen according t o the equation NaH2P02 + H20 = NaH,PO + H,. A further oxidation to phosphat,e also takes place according t o the equation NaH,Y03 + H20 = NaH2P0 + H The velo- city of the second reaction is small and it can generally be neglected in measurements of the velocity of the first reaction which is high particularly if an excess of hypophosphite is present. All kinds of palladium are not active in this reaction; palladium- black is active irrespective of its method of formation.Ignited palladium sponge is slightly active but wire and foil are inactive even though they are charged with hydrogen. If the metal is superficially oxidised it is reduced by the hypophosphite and a t once becomes active. The commencement of the catalysis is not dependent on the hydrogen content of the palladium. Palladium which has been electrolytically deposited on platinum o r copper gauze slowly loses its activity in a solution of hypophosphite. The experiments on the velocity of the oxidation were all carried out with palladium-black. The initial velocity of the reaction is given by the equation -c€c/dt=k'cO.18 in which c is the concen- tration and k' is a constant. I n one and the same experiment the velocity is disturbed because the catalyst loses some1 of its activity.The acid phosphite formed in the reaction has no marked influence on the velocity. The temperature-coefficient between 1 5 O and 3 2 O is that of a chemical reaction. The rate of stirring of the reaction mixture has little influence on the velocity. The quantity of hypo- phosphite oxidised in a given time is proport.iona1 t o t$e weight VOL. CX. ii. 11ii. 238 ABSTRACTS OF CHEMICAL PAPERS. of the catalyst present. The addition of hydrochloric acid sul- phuric acid o r sodium hydroxide retards the reaction whilst the addition of sodium hydrogen carbonate either slightly accelerates the seaction o r has no1 influence. The activity of colloidal pallad- ium is very much greater than that of palladium-black but the reaction in both cases proceeds according to the same laws. The expression giving the timevelocity equation is deduced from the assumption that the velocity of reaction is proportional tot the quantity of hypophosphite adsorbed by the palladium and that the adsorption takes place with a velocity which is very large when compared with the velocity of the chemical reaction. J.F. S. Kinetics of the Catalytic Oxidation of Phenylthiocarb- amide by Charcoal H. FREUNDLICH and ALF. BJERCKE (Zeztsch. physiknl. Chem. 1916 91 1-45).-The oxidation of phenylthio- carbamide in solution by blood charcoal has been studied a t Oo 25O and 35O both with regard to the nature of the oxidation products and the kinetics of the process. The conclusions reached have been considered in connexion with enzyme reactions.The kinetics of the oxidation of oxalic acid by blood charcoal have also been experiment'ally studied. It is shown that the decolmposition of phenylthiocarbamide by charcoal consists in an oxidation whereby sulphur is liberated and a basic organic substance formed. This basic substance whilst not definitely characterised is shown t o be probably the so-called Hector base the process being regarded as following the equation BNH,*CS*NHPh + 0 = N H < ~ ~ ~ $ ~ ~ p h + 2H,O + S. The velocity of the reaction is given by the equation dx/dt = k molv,[ J (@*)& + t)] which on integration gives k=vo/2mot[(x + [)2/ J(02),]. I n these equations x is the decrease in the concentration of phenylthiocarb- amide in the tlime t mo the original quantity of charcoal vug the original volume (QL the cofnstant oxygen pressure during the experiment ( is the decrease in concentration of the phenylthio- carbamide from the beginning of the experiment t o the time when the first quantity is removed f o r analysi-that is it is the quantity of phenylthiocarbamidet removed in the time required for the adsorption t o complete itself; k is a constant.Consequently the velocity of the reaction is proportiona1 to the square root of the oxygen concentration to the relationship mo/ yo and inversely pro- polrtional to the quantity of phenylthiocarbamide changed per unit weight of charcoal. The temperature-coefficient of the reaction is fairly large k350/k250=2.3 and is in keeping with the Arrhenius formula. The singular kinetic progress of the reaction can be reladily explained by the assumption that the reaction depends on diffusion phenomena the phenylthiocarbamide being strongly adsorbed by the charcoal whilst the oxygen diffuses into it through a layer of €lie decomposition products which surround the charcoalGENERAL AND PHYSICAL CHEMISTRY.ii. 239 particles. This assumption is not a t variance with the high tem- perature-coefficient because the equilibrium constant not only represents the diffusion constant but also other quantities which are influenced by temperature f o r example the solubility of oxygen in the diffusion layer. The adsorption of plienyltliiocarbamide is in accordance with the adsorption isothermals and decreases with increase of temperatare. The oxidation of oxalic acid by blood charcoal can also be regarded as a diffusion process and here again i t is the oxygen which diffuses into the charcoal.I n this case the products of the rextion water and carbon dioxide are without influence the diffusion layer in this case consisting of adsorbed oxalic acid which retards the reaction according to the equation -dc/dt=kr. l/cl/?L which on integration yields (1 + l / n ) k ' = k = ljt(col+l/n- c ~ + - I / ~ ) . . I n this equation co is the initial concentra- tion of the oxalic acid c the concentration a t time t and l / n the index of the adsorption isothermal of oxalic acid. The equation representing the velocity of the oxidation of phenylthiocarbamide agrees with the Schiitz rule for enzyme reactions. When i t is con- sidered that the oxygen remains coiistant during the operation and that in enzyme reactions vo is constant it follows that these quan- tities can be taken into the constant and the equations then become (x + 0 2 = z ./not or x + = drn3 To bring the present case into line with the Schiitz rule it is therefore only necessary to substitute enzyme concentration by charcoal concentration. J. F. S. Catalytic Reduction in the Presence of Platinum and Palladium. J. BOESEKEN [with (MLLE.) 0. B. VAN DER WEIDE and C. P. MOMJ (Rec. trav. chZm. 1916 35 260-287).-A quantitative study of the seduction of a number of unsaturated acids using as catalysts palladium and platinum prepared in different ways and used in varying amounts. Working with a very stable form of palladium prepared according to the method of Paal (compare A.1905 ii 397) and studying the reduction of crotonic acid it was found that there was a certain relationship between the velocity of absorption of the hydrogen and the number of shakes per minute until the latter reached 160 when the absorption became indepen- dent of the shaking. Similar results were obtained with isocrotonic and tetrolic acids. I n the case of substances containing more than one double bond no bre'ak was found in the absorption curves when the first molecule of hydrogen had been absorbed. I n the case of trichloroacrylic acid after the fixation of 1 molecule of hydrogen the absorption still continued regularly the chlorine atoms thus being removed with almost the same velocity as that with which the molecule of hydrogen was fixe'd by the unsaturated linking.I n the case of oleic acid the absorption of hydrogen is not complete probably owing to the formation of a soap which checks the action of the catalyst. Working with a less active and less stable form of catalyst a comparison was made of the reduction of muconic aconitic it'aconic citraconic mesaconic cyclopropane - 1 1 - dicarboxylic 11-2ii. 240 ABSTRACTS OF CHEMICAL PAPERS. ethylmenetricarboxylic and vinylglycollic acids. Of these all but the first- and last-named gave negative results. These acids were however very slowly hydrogenated using a palladium catalystl prepared by Skita’s method (compare A. 1913 i 53). The results obtained indicate that an accumulation of carboxyl groups around the double linking prevents the reduction o r if i t takes place the velocity is dependent more on the physical state of the catalyst and the solution than on the free energy of the reaction. The velocity of reduction of cinnamic acid in the presence of finely divided platinum shows a sudden diminution after the side- chain is saturated the benzene ring being apparently hydrogenated more slowly.The reduction then proceeds regularly until three more molcules of hydrogen have belen added when there is a further diminution in the velocity of the action. This is a physical effect since an increase in the amount of catalyst used lessens the differ- ence bet_welen the velocities of hydrogenation of the side-chain and the nucleus. The s t a b of the surface of the catalyst principally controls the reduction since a preliminary boiling of the catalyst with acetic acid considerably reduces the action whilst exposure to a mercury lamp f o r twenty minutes considerably increasee the velocity of absorption of the hydrogen.W. G. Baly’s Theory of Chemical Reaction and Reactivity. WILLIAM M. DEHN (J. Amer. Chem. SOC. 1916 38 1-15).-Po~lemical. A criticism of Baly’s theory of chemical reaction and reactivity (T. 1904 85 1029; A. 1915 ii 440). J. F. S. [Baly’s Theory of Chemical Reaction and Reactivity.] A E. C. C. BALY ( J . Anaer. Chem. SOC. 1916 A reply to Dehn’s criticism Reply to Dr. Dehn. 38 15-20 227-228).-Polemicsl. (see preceding abstract). J. F. S. Conception of Element and Atom in Chemistry and Radiology. FRITZ PANETH (Zeztsclz. physzkal. Chem. 1916 9 1 17 1-1 98) .-A theoretical paper in which the conception of the terms atom and element is discussed. It is shown that the discovery of radioactive disint’egration isotopy and the linear system of the elements of Moseley make it imperative that the definitions of atom and element should be revised.I n the literature of radio- activity isotopes are regarded as different elements ; this practice makes the conception of an element in chemistry quite meaningless because the law of the immutability of the elements must be given up and the number of the chemical elements will become exceedingly large. It appears therefore more practical to regard isotopes not as different elements but as varieties of one and the same element. This will be in accord with the Boyle definition of an element which will then only need extending by the phrase “That two substances which are non-separablel are to be regarded as the same element.” The definition theref ore proposed for an element isGENERAL AND PHYSICAL CHEMISTRY.ii. 241 as follows " An element is a substance which cannot be simplified by any chemical process." Substances which fulfil this condition must therefore be regarded as one and the same element if after being mixed they cannot be again separated. Atoms are those ultimate particles of matter which represent the limit of chemical division and are themselves unchanged by chemical processes. I n connexion with these definitions the following properties and facts are fundamental (1) The number of chemical elements is 92 and of these 5 have not yet been discovered.(2) Every element is charaderised by its chemical and electrochemical properties by its spectrum and X-ray spectrum and by its nuclear charge. (3) Atomic weight and radioactive properties are not constants of the elements. (4) There are morel varieties of atoms than of etlements. At tile moment 120 varieties have been identified; the number of varieties not yet discovered is unknown. An element can consist of aimiiar atoms (pure elements) o r of atoms differing in weight o r radioactivity or both (mixed elements). Isotopic elements can completely represent one another in mass actions so that in calculations in chemical and elect-rochemical experiments the conceiitrat'ion of a mixed element is to be regarded as the sum of the concentrations of the different varietiels of atoms.The radioactive disintegration of an atom always leads to the produc- tion of an atom of a different element but further disintegration can lead to an atom of the original element. Atomic Structure. V. Periodic System and the Properties of the Elements. WILLIAM D. HARKINS and R. E. HALL ( J . Amer. Chem. SOC. 1916 38 169-221).-A method of representing the periodic system graphically is described in the paper in which the relationships between the elements of the main and subgroups are clearly shown. The elements are arranged in the table in the exact order of their atomic numbers and there are no blank spaces for unknown elements which do not correspond with atomic numbers as found by Moseley's work on the X-ray spectra of the elements.The elements are also plotted according to their atomic weights so that the isotopic forms of an element may be shown graphically on the table and the group changes occasioned by a- and P-ray decom- positions of the radio-elements clearly depicted. Both the zero and eighth groups fit naturally into the system the latter appearing as the subgroup of the former. The table is best represented as a helix in space but may be shown as a spiral on a plane. The space form is represented by its vertical projection on a plane but drawn with line perspective so that it may be easily visualised. Beginning a t the zero group the maximum positive valency of a group is found by counting toward the front and toward the right Li=1 Be=2 etc. and the negative valency by counting toward the back F = - 1 0 = - 2 N = - 3 etc.The elements in the table divide themselves into cycles cycle 0 ; cycle 1 He-Cl 16 elements = 42 ; cycle 2 36 elements = 62 A-I ; cycle 3 64 elements= 82 Xe-U. The latter part of the third cycle is missing. Each cycle is divided into two periods; cycle 1 into first short period 2 x 22= 8 elements J. F. S.ii. 242 ABSTRACTS OF CEEMICAL PAPERS. He-F and second short period Ne-C1 2 x 22= 8 elements; cycle 2 icto first long period 2 x 32= 18 elements A-Br and second long period 2 x 32 = 18 elements Kr-I ; cycle 3 into first very long period 2 x 42= 32 elements Xe-EkaI and second very long period Nt-U. These relations are undoubt(ed1y a numerical expression of a func- tion connected in some way with the system according t o which the nuclei of the elements have been built up.Whenever the valency drops in passing along the continuous line connecting the elemenhs in order of their atomic numbers i t always drops by seven either from seven t o zero I+ Xe o r from eight t o one Pt +Au. I n the latter case a certain sluggishness is evidenced in the drop so that i t is not entirely complete and copper silver and gold the members which should have a maximum valency of one often exhibit a higher valency such as two for copper and three for gold. The groups are arranged in the table in five divisions 0 compris- ing groups 0 and 8; 1 comprising 1 and 7 ; 2 comprising 2 and 6 ; 3 comprising 3 and 5 ; and 4 comprising 4 and 4. The two groups of one division are said to be complementary.The sum of the group numbers of two complementary groups is always 8 as is also the sum of the maximum valencies. The algebraic sum of their characteristic valencies on the other hand is always zero. Thus the characteristic valency of group 1 is + 1 that for group 7 is -1. The characteristic valency of the eighth group needs t o be defined in this sense and must be takeln as -0 which accords with Abegg’s valency system. Another very important relationship given graphically in this table and not elsewhere is t h a t between the main and sub-groups in any one division. Whenever the groups in any one division differ considerably as is the caw in divisions 0 and 1 then the elements in the sub-groups are quite different chemi- tally from those in the main groups although in general they art3 alike in valency. As the group numbers approach each other in magnitude the elements of the sub-group become chemically much more like those of the main group.This is true of groups 48 and 4R where the group numbers are1 the same and the two groups are practically indistinguishable1 in their general chemical nature. On the outer cylinder of the helix the main groups 1 2 3 become leas positive as the group number increases whilst the correspond- ing sub-groups become more positive. Whenever the atomic volume of a main-group element is large t h a t of the corresponding sub- group element is small and as the atomic volume of the main- group element decreases that of the sub-group increases until the values become about the same in groups 4A and 4R.The metalsof the rare earths are put in the third grouD since their valencp is 3 and since if they are distributed around the table there are not enough known and undiscovered elements together t o go round. Cerium may be classified either with the third or fourth group. A discussion on this point is given in the paper. The elements of the rare earths exclusive of cerium and yttrium decrease in their basic properties as the atomic weight increases which is exactly the opposite of the general rule. I n this case the atomic number increases whilst the valency remains constant. On the other hand,GENERAL AND PHYSICAL CHEMISTRY ii. 243 it seemsprobable that the atomic volume tends t o change normally but this tendency is masked by another tendency which tends to keep the atomic volume constant.The metals of the rare earths lie on the front of the table where the elements in general become less basic as the atomic weight increases so they in this respect as probably they do with the atomic volumes effect a compromise between this tendency and that which seeks t o cause the elements in a single group t o become more basic with increase in atomic weight. The resultant effect is that they become less basic as the atomic number increases but not with anything like1 the rapidity which would be shown if they were to go round the table in the usual manner. I n this sense the rare-earths group constitutes a group of its own but a loop of practically constant valency. The tableshows the relation between the properties of the elements and the nuclear charge and this presumably is equal to the number of external electrons. It is probably the spacing and arrangement (of these electrons which determine the chemical and most of the physical properties of the elements. The graphic representation of the table shows that t.he spiral forms a series of lines which in any part are) very nearly parallel. This is a representation of the fact that the atomic weights increase in a very regular way in any one group and a t about the same1 rate in all the groups. This regu- larity may be explained on the basis of the theory of Harkins and Wilson that the nuclei of the elements are built up from the he'lium and hydrogen nuclei in a regular way according to which the differences in mass in any one group are generally due wholly t o differences in the number of helium nuclei present a t least in the case of the lighter elements. The radioactive elements fit into the system q u i b well. A discussion on the nature of isotopes is entered into. A number of tables and diagrams are included which illimtrate the connexion between the cohesional properties of the elements and the system. Curves are given of melting points with lines of maxima and primary and secondary minima atotmic volumes density cubical-coefficients of expansion compressibility susceptibility atomic frequency elasticity cohesion and hardness. The causes of variations of Lohesion are discussed. J. F. S. The Formation of Molecules in its Dependence on Atomic Structure. W. KOSSEL ( A m . Physik 1916 [iv] 49 229-362).-A theoretical paper in which the author develops the view that the properties of the atoms and in particular the valency are func- tionally related t o the atomic numbers and that the combination of atoms to form molecules is consequently determined by the structure of the atoms in accordance with the at,omic number hypo- thesis. The application of the idea is considered in detail by refer- ence to' elements and groups of varying valency and widely different electrochemical character. H. M. D. Large Fat Extractor. CARL L. A. ~ J c H n m n ( J . Inn. Eng. Chcin. 1916 8 165).-An apparatus suitable f o r extracting the fat from several pounds of material consists of a large distillation flask andii. 244 ABSTRACTS OF CHEMICAL PAPERS. the extractor proper; the latter is a cylindrical vessel 'having a dome-shaped cover which carries a reflux apparatus. A tubulure a t the upper part of the side of the cylinder is connected by a glass tube with the flask this tube allowing the vapour of the1 solvent to pass frosrn the flask to the condenser and the solvent collecting in the cylinder returns t o the flask through a siphon tube extending from a tubulure a t the bottom of the cylinder t o the bottom of the flask. w. I). s.

ISSN:0368-1769    

DOI:10.1039/CA9161005205

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 229 Thrombin and Calcium Chloride in Relation t o Coagulation. JOHN OGLETHORPE WAKELIN BARRATT (Biochem. J. 1915 9 5 11-543).-A given amount of thrombokinase in presence of calcium chloride and prothrombin will produce a definite quantity of thrombin which is indepe'ndent of the concentration of pro- thrombin. The coagulation time is concerned with the action of thrombin (y) on fibrinogen (2) ; when decinmmal calcium chloride is present (0.05 in 5 c.c.) xy=nz where x is the coagulation time and n a constant. I f more calcium chloride is added to snake v0nom thrombin or to a mixture of thrombokinase and prothrom- YOL. CX. i. I?i. 230 ABSTRACTS OF CHEMICAL PAPERS. bin coagulation is retarded. If the coagulation time is plotted against the amount of calcium chloride employed the points up to a critical limiting value lie on a parabola given by the equation w2=ax-b.Of the two constants a is proportional to the amount of thrombokinase and b is a function of a not yet determined. The action of thrombin on fibrinogen takes place according t o the equa- tion w2=p(xy/z-n) where is a constant independent of w zy o r z and p is a function of z not yet determined. Minimal quanti- ties of calcium chloride accelerate thel coagulant activity of the thrombin of the venom of Echis carinatus. W. D. H. The Effect of the Ingestion of Urea Sodium Lactate and Sodium Hydrogen Carbonate on the Reaction of the Blood and the Composition of the Alveolar Air in Man. GORO MOMOSE (Biochem. J . 1915 9 485-491).-These three substances in the doses taken by the mouth produce little1 change in the alveolar carbon dioxide but cause an appreciable increase in the affinity of blood for oxygen in the presence of carbon dioxide which is the result of the increased alkalinity of the blood.Five-gram doses of sodium lactate do not appreciably affect the percentage saturation of the blood with oxygen in the presence of the alveolar pressure of carbon dioxide. W. D. H. The Fixation of Salvarsan and Neo-salvarean by t h e Blcod after Intravenous Injection. WILLIAM JOHN YOUNG (Biochem. J. 1915 9 479-484).-After intravenously injecting goats with these substances the scrum contains arsenic in a form which cannot be separated from the proteins by dialysis and is precipitated with the serum proteins by t'annic acid.Salvarsan and neo-salvarsan therefore behave like atoxyl. No such combination is obtained when inorganic arsenic is injected. This combined arsenic is found in the plasma and in the red blood corpuscles but no trace of it is retained in the fibrin. W D. H. The Influence of Salicylates on the Elimination of Uric Acid and other Waste Products from t h e Blood. W. DENIS ( J . Pharm. expt. Ther. 1915 7 255-262).-From a study of cases of disease izl which salicylates were employed i t is found that the increase of uric acid in the urine is due to a lowered '' threshold " value of the kidney; this probably applies t o other waste products also. I n rheumatism the beneficial effect is ascribed to this circum- stance ; the increase of kidney permeability facilitates a rapid excretion of the unknown toxins which produce rheumatic symp- toms.W. D. H. The Effect of Organ Extracts on Gastric Secretion. JOHN ROGERS JESSIE M. RAHE GEORGE G. FAWCETT and GEORGE S. HACKETT (Amer. J . Physiol. 1916 39 345-353).-Hypodermic injection of the non-coagulable portion of aqueous extracts of thyroid parathyroid thymus spleen and liver stimulate gastric secretion and mobility but those of the pituitary and suprarenalPHYSIOLOGICAL CIlEMISTRY. i. 231 inhibit the Bow. Both tlie coagulable and non-coagulable portions of pancreatic extracts stimulate the flow. All tliese substances appear to act on soiiie peripheral gastric meclianisin in which the iiervous system is an eswiitial part. The Influence of Carbohydrate and Fat on Protein Meta- bolism witn Special Reference to t h e Output of Sulphur.KWANJI TSUJI (Biocliem. J. 1915 9 439-448) .-Three experi- inents on a dog are recorded in which extra nitrogen in the shape of caseinogen egg-albumin and gelatin respectively were super- imposed on a basal diet; nitrogen retention was greater on a carbo- hydrate than on a fat diet The same holds for sulphur except in the caseinogen expesinient. The actual amounts of extra nitrogen and sulphur excreted vary with tlie protein used but the extra sulphur is iiiainly excreted as inorganic sulphate. The partition of the sulphur in the carbohydrate and fat diets is very similar namely nearly equal parts of inoqganic sulphates and (‘ neutral sulphur.” There is no evidence that the protein retained is poor in sulphur.W. D. H. The Use of Phloridzinised Dogs to Determine the Utilkable Carbohydrate i n Foods. The Food Value of Comaercial Glucose. W D. Smsuhi and It. T. WOODYATT ( J . L’iol. C?Lcm. 1916 24 23-30).-The total dextrose which any given food may introduce into the metabolism will depend on (1) the free dextrose i t contains (2) the amount of other carbohydrates capable of con- version into dextrose within the body and (3) protein digestion products. Food analysis alone is often incapable of giving the necessary data. The method suggested is t o give the food to phloridzinised dogs and the extra sugar found in the urine would represent nothing which is either indigestible unabsorbable or unassimilable; nitrogen estimation would give a measure of the sugar derived from protein.I n the present experiments pure dextrose given by the mouth did not appear quantitatively in the urine; some may be destroyed in the bowel by bacteria; this may be excluded by subcutaneous administration and by this means a higher figure (86%) was obtained; with commercial glucose the average figure was 71.3 as compared with 74.6 for the average of the pure dextrose experiments. It is possible some sugar may be burnt in tlie body or elimination by the kidneys may be imperfect. The more freely the kidneys act the more sugar is obtained. W. D. H. W. D. H. The Stability of the Growr h-promoting Substance in Butter- L. FERRY and ALFRED J. WAKEMAN ( J . Biol. Chern. 1916 24 37-40).-Previous work has sllown that this substance in butter- fat (especially abundant in the oil fraction) is unaffected by heat.The present experiments show that storage for some months or even a year in the case of butter-fat has no effect but in the butter-oil gradual deterioration occurred so that its characteristic potency was almost completely lost within a year. fat,. THOMAS R. OBBORNE and LaFAPETTE R. MENDEL [with EDNA W. D. H. 1 2i. 232 ABSTRACTS OF CHEMICAL PAPERS. Ionic Antagonism in Sensory Stimulation. W. J. CROZIER (pmer. J. Physiol. 1916 39 297-302).-The experiments con- sisted in noting the react'ion times in brainless frogs their feet being placed in mixtures of the chlorides of sodium potassium and calcium. Sodium chloride (0.5ill) is a weak but measurable stimu- lant; sea-water does not stimulate.The mixtures of the salts demon- strate antagonism between them. I n normal stimulation the essen- tial step includes the penetration of the surface layer of the receptor by the stimulant. W. D. H. Secretion of the Pituitary by Stimulation of the Superior Cervical Ganglion. V. N. SHAMOFF (Amer. J. Physiol. 1916 39 279-290).-The experiments recorded indicate that stimulation of the superior cervical sympathetic ganglion in the cat leads t o a discharge of pituitary secretio IL which produces diuresis and glycos- uria. The acceleration of the flow of urine is independent of the elevation of blood-pressure. W. D. H. The Effdct of Phloridzin on the Formation of Glycogen in the Liver. ALBERT -4. EPSTPUN and GEORGE BAEHR (J. Biol. Chcnz. 1916 24 17-21).-After removal of the kidneys phloridzin increases the hepatic glycogen.The drug is believed t o stimulate this function of the liver; but if the kidneys are intact the glyco- suric action of phloridzin is so much more powerful that the accumulations of glycogen in the liver are rapidly diminished. On removal of the kidneys however the glycosuric action is eliminated so that the effect on the liver becomes manifest even in a state of starvation. W. D. H. The Action of Pituitary Extracts on Isolated Intestinal Loops. V. N. SHAMOFF (Bnzer. J. PhysioZ. 1916 39 268-278).- Differences were noted in various commercial preparations of pituitary extract (posterior lobe) but some of them are capable of producing relaxation of the isolated intestinal loop (rabbit) and of inhibiting its rhythmic contractions resembling in this respect extracts of the adrenal medulla.The substance responsible for the effect is probably different from that which raises blood pressure and produces diuresis. W. D. H. Salicylaldehyde and Diphenols in the Investigation of the Oxidising Power of Animal Organe. LEOPOLDO L~PEZ-P~REZ (Anal. Fis. Quim. 1915 13 453-460).-The author's experi- mental results indicate the presence in human tissue of a catalyst capable of oxidising catechol quinol and salicylaldehyde its activity being conditioned by the nature of the medium in which the action takes place. A. J. W. The Resistance of Fresh-water Fish to Changes of Osmotic and Chemical Conditions. WALTER E. GARREY (Amer. J. Physiol. 1916 39 313-329).-The fish Notrop's blennius will live for months in St.Louis tap-water which is distinctly alkaline. TheyPHYSIOLOGICAL CHEMISTRY. i. 233 will also live in redistilled water for weeks. Sucrose is directly toxic to them but least so when present in osmotic equilibrium; this toxicity is reduced by salts and alkalis. Chlorides of the following metals are toxic in this order K > Mg > Ca > Na. One chloride (except t h a t of potassium) reduces the toxicity of the others. When three or four are present the solutions become less toxic still. Sea-water diluted to the concentration of the blood (or less) is a perfectly balanced solution f o r these fresh-water fish. Above this concentration death is prompt. W. D. H. The Influence of Fat and Carbohydrate on the Excretion of Endogenous Purines in the Urine of Dog and Man.NOBUYOSHI UMEDA (Biochem. J. 1915 9 421-438).-From experiments on himself i t is clearly shown that the protein-sparing action of carbohydrate is greater than that of fat. A diet rich in carbo- hydrate causes a formation of uric acid as in the dog it increases the allantoin Glycerol is a protein sparer and increases the out- put of endogenous uric acid; the latter effect is also caused by sodium hydrogen carbonate. 111 several experiments the increase of uric acid is associated with a fall in the purine bases excreted. With diets rich in fat butl poor in carbohydrates the uric acid output is decreased. I n dogs sodium lactate raises the output of a1 lan t oin . ROBERT MILNE LANG (Bzochem. J. 1915 9 456-478).-On an ordinary diet the author excreted daily 10-30 mg. of acetone substances. After fasting carbohydrate and t o a less degree protein and glycerol reduce the acidosis but fat increases it. Alcohol has no effect. The amount of acetone substances in the urine of the first few days of starvation depends on the initial carbohydrate storage; when the ratio of the f a t t o carbohydrate present becomes greater than 2 t o 1 these substances appear in abnormal amount and are f o r the most part derived from fat. Some evidence of the formation of carbohydrate from fat in the body is adduced. So-called '' Protective Enzymes." Antitryptic Index and Anaphylaxis. IX. J. BRONFENBRENNER (Proc. SOC. Expt. BioZ Med. New Pork. 1915 13 4243).-The symptoms of eclampsia epilepsy and asthma recall anaphylaxis.There is considered t o be in these conditions a casual relation between the condition of the blood and these diseases. The antitrypsin of the blood is increased; this allows the proteolytic enzyme there to act and results i n auto- digestion of the serum and the production of toxic material. W. D. H. Acidosis. W. D. H. W. D. H. The Output of Craatine in Glycosuria. KWANJI TSUJI (Biocheai. J. 1915 9 449-455).-The injection of adrenaline in a dog caused glycosuria creatinuria and a rise in output of total nitrogen. I n the same' animal ether anzsthesia had similar effects. 111 the estimation of creatine due care was taken not t o confuse i t with acetoacetic acid. TIV. D. H.i. 234 ABSTRACTS OF CHEMICAL PAPERS. Experimental Diabetes after Pancraatectomy. ALBERT A.EPSTEIN and GEORGE BAEHR (J. Biol. Chem. 1916 24 1-16).- I n experimental diabetes after pancreatectomy in cats the volume of the blood alters and this change must be allowed f o r in esti- mating variations in sugar nitrogen and other constituents of that fluid. The hyperglycEmia after the removal of the pancreas mounts progressively in the terminal &ages because the per- meability of the kidney is less; this explains why in diabetic coma the blood-sugar rises so greatly. I f both kidneys are removed the same result ensues; the accumulation of sugar in the blood is largely due to the rnobilisation of carbohydrate from the liver and muscles. W.D. H. Production of Pneum mia b y Intrabronchial Insufflation of Unorganised Substances.B. S. KLIXE and S. J. Mmmm <P?*oc. kqoc. Brpt. Biol. M P ~ . hTew Pork 1915 13 29-30).-Non-virulent pneumococci introduced by insufflation produce pneumonia which macroscopically resembles that caused by virulent organisms. Aleuronat and starch produce pneumonia like that caused by virulent pneumococci ; egg-yolk and lecithin produce pneumonia like that caused by non-virulent cccci. Egg-white has no such effect . W. D. H. Accumulation of Nitrogen in the Tissues in Renal Disease. HELEN DAVIS and NELLIS B. FOSTER (Proc. SOC. Expt. Biol. Med. ,TP?I~ Tori; 1915 13 33-35).-Data of nitrogen-retention in the tissues are given. I n nephritis there is a notable increase in the extractive nitrogen in muscle and liver but when edema was present the results were inconstant.I n other conditions without nephritis for instance pneumonia there was a similar accumula- tion of nitrogen. A Toxic Substance in the Blood of Uremic Patiente. NELLIS B. FOSTER (Proc. SOC. Expt. Biol. Med. New Pork 1915 13 39).-Urzmia blood yields a substance of unknown natMure which is fatal t o guinea-pigs; this is absent in normal blood. W. D. H. W. D. H. Mode of Action of Ultra-violet Radiation on Living Cells especially in the Eye. TV. E. BURGE (Amer. J . Physiol. 1916 39 335-344).-Ultra-violet radiation (especially between 254 and 302pp) affects protoplasm in such a way that certain salts com- bine with it" t o form an insoluble compound o r coagulum. An opacity of the lens can be produced in fishes living in solutions of these salts (calcium chloride sodium silicate) which are greatly increased in human cataract if the eyes are exposed t o radiation from a quartz mercury-vapour burner. Abnormal quantities of these salts in the cells of the eyelids and cornea increase the effectiveness of ultra-violet rays in causing this eye trouble. I n the skin they increase the effectiveness of short wave-lengths in producing sunburn W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 235 The Comparative [Phyeiological] Action of the Stereo- isomerides of Hydroxyhpdrindamin e. YASUO IKEDA ( J . Pharm. expt. Ther. 1915 7 121-124).-The hydroxyhydrindamines have no specific action but are mild general protoplasmic poisons. The d-compound is very slightly more toxic than the Z-compound W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9161000229

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 235 Chemistry of Vegetable Physiology and Agriculture. Rate of Growth of Bacteria. ARTHUR Sr,.irroR (T. 1916 109 a-lO).-It is shown that the rate of growth of bacilli which pro- duce a silky turbidity in the medium can be estimated by com- paring the solutions with suspensions of asbestos in water. The organism employed produces lactic acid and occurs in malt-wort. When an active growth in wort was obtained it was matched against one of the standard asbestos suspensions and then diluted with fresh wort t o dilutions of 1/100 t o 1/100,000. The rate of growth cannot be ascertained from the rate of production of lactic acid as growth is retarded by even small amounts of acid. When however two quantities of wort are seeded the seeding in one case being considerably larger than in the other the develop- ment of acidity in the first case occurs earlier than in the second; the rate of growth is calculated from the difference in time and the ratio of the seedings. Measurements were made a t different temperatures (22-55O) at which growth is possible and in different concentrations of wort.I n the latter experiments it was found the growth was the same when D varied between 1.060 and 1.008. Most of the lactic acid is produced when the development is greatly retarded as even 5*6* acid lowers the rate of growth. N. H. J. 11. Quantitative Investigations on Indole and Tryptophan Decomposition. E. HERZFELD and R. KLINGER (Cent?.. Bnkt. Pay. 1915 i 76 1-12).-The negative indole reaction which is observed in cultures of certain bacteria has been attributed t o their supposed inability t o decompose tryptophan.The authors show that this view is not correct and that when comparatively large quantities of bacteria for example B. typhosus and B. para- typhosus B. are brought into pure tryptophan solution a con- siderable proportion (20-60%) of the compound is destroyed with- out any accumulation of indole. Under similar condit"ions such organisms as B. coli and Vibrio cholercrfe produced up to 55% of indole. The absence of indole from '' indole-negative " cultures is ex- plained in the case of the typhoid and paratyphoid organisms byi. 236 ABSTRACTS OF CHEMICAL PAPERS. the fact that these bacteria have a well-marked capacity of decom- posing indole either in the pure state o r in the presence of small quantities of peptone.The presence of certain sugars or of large quantities of peptonel tends t o decrease1 the production of indole by B. coli and t o prevent tryptophan decomposition by B. typhosus and B. pratyphosus B. H. B. H. The Lipoids of the Blastomycetes. a. AMATO (Centr. Bakt. Par. 1915 ii 42 689-698).-Fixed preparations of Sacchnro- myces ellipsoideus when treated with osmic acid show only a few granules which seduce osmic acid and therefore exhibit black colora- tion whilst the majority of the granules assume a brown colour. On the basis of differential coloration and their behaviour towards fat solvents after being acted on by osmic acid the majority of the granules in the yeast are looked on as belonging t o the class regarded by Bernard and Bigart as labile fats.By comparison with the rate and type of coloration of a number of pure compounds the assumption is made that the majority of the lipoids in yeasts consist of lecithin. Extraction of the washed and dried yeast by means of ether gave a residue which on com- bustion and subsequent extraction with sodium nitrate and sodium carbonate gave the characteristic phosphoric acid precipitate with ammonium molybdate. The behaviour of certain other cell granules towards neutral-red is also' described but no conclusions are drawn as t o their nature and function. H. B. H. Nitrogenous Constituents of Yeast. JAKOB MEISENHEIMER (Chem. Zentr. 1915 ii 1259; from TVoch,. Rrauerei 1915 32 325-326).-The author has investigated the products of the auto- lysis of pure cultures of top and bottom fermentation yeasts in presence of toluene.From the cell residues phytosterol m. p. 156-157O was isolated. The remaining mass was dissolve@ com- pletely in boiling hydrochloric acid and from the solution thus obtained glucosamine hydrochloride was deposited in the crystal- line form. The following amino-acids were detected and their proportions estimated by Fischer's ester process glycine alanine valine leucine proline phenylalanine aspartic and glutamic acids tyrosine and tryptophan; the presence of serine cystine and a n aminobutyric acid was not demonstrated with certainty. The pro- portion of tryptophan from a top yeast containing 6.6% N and 92.4% of dry matter amounted t o 0.30% and that from a bottom yeast containing 6.7% N and 83.4% dry matter t o 0.34% of the dry matter.T. H. P. Action of Ultraviolet Rays on Alcoholic Fermentation. ROMOLO DE FAZI and REMO DE FAZI (Ann. Chim. Appilicata 1915 4 301-329).-A summary is given of the investigations of various authors on the effect of ultraviolet light on micro-organisms. The experiments now described lead to the following conclusions. The action of ultraviolet rays even when exerted for a comparatively long time is favourable to alcoholic fermentation. Beer yeastVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 23'7 undergoes marked increase in activity when exposed t o ultraviolet rays for a definite length of time and is not killed by an exposure lasting for fourteen hours. This action of ultraviolet rays servcs as a means of selection of yeast.These results differ from that of Henri Helbronner and Recklinghausen who found that with an artificial mixture of yeast and sarcina the latter is completely destroyed- by an exposure of thirty seconds t o ultraviolet light whilst the yeast is only attacked after the exposure has lasted thirty minutes. T. H. P. Culture of Aspergillus niger (Sterigmatocystis nigra) in Liquids in which the Zinc is Replaced by Different Elements (Copper Uranium Vanadium). M. JAVILLIER (Chem. Zentr. 1915 ii 1051; from Bull. Sci. Pharmacol. 1914 21 452-463. Compare A. 1913 i 235; 1914 i 119).-When present in sufficient proportion copper produces an appreciable increase in the weight of the mycelium of this organism and is fixed by it the under side assuming a more or less intense blue coloration.The copper also accelerates the formation of conidia and intensifies their colous. This influence of copper on spore formation is also evident when zinc is present in the nutrient solution; the two metals together effect a greater acceleration in the growth of the mould than either separately. Uranium appears to be without appreciable influence on Aspergillus niger. Vanadium increases the yield of mycelium- in o'ne case by more than 40%; this effect may however be due partly t o the sulphur of the vanadium sulphate employed. I n pres- ence of vanadium and zinc together the amount of mycelium forxed is somewhat greater than with zinc alone. Neither copper nor vanadium used in any proportion or for any length of time can accelerate the growth or increase the yield of mycelium t o even approximately the same extent as zinc in proportions between 1 .10-7 and 0.5.10-6. T. H. P. Fluorine in the Vegetable Kingdom. ARAIASD GAUTIEH and PAVL CLAUSMANN (Compt. rend. 1916 162 105-112. Compare A. 1912 ii 681 805 806; 1913 i 677 789 1017).-The authors have determined the percentages of fluorine and phosphorus in a large number of plants o r parts of plants which serve as food for human beings and herbivora with a view to discovering how fluorine passes from the plant to the animal. The results which are set out in detail show that in plants the leaves are the organs which are richest in fluorine the proportion of phosphorus being also generally high as compared with the rest of the plant.The buds as in cauliflowers and asparagus are slightly less rich in fluc,rine although the phosphorus content of asparagus buds is remarkably high. The stems wood and bark are the organs which are poorest both in fluorine and phosphorus. Edible roots such as carrots and radishes contain very variable procportions of fluorine and phosphorus. Soft fruits are moderately rich in fluorine and phosphorus the pulp being poorer in fluorine than the skin. In seeds the fluorine conbnt is mecdium and comparable to that of thei. 238 ABSTRACTS OF CHEMICAL PAPERS. pulp of fruits. I n the case of cereals granitic soils favour an increase of fluorine in the flour. The bran" of wheat is very poor in fluorine' but very rich in phosphorus. The flour from cereals generally resenibles the pulp of fruit in being moderately rich in phosphorus whilst in the seeds of leguminosz the phosphorus con- tent is high. The results do not indicate any particular plant- group where fluorine is particularly abundant and necessary.F o r the different organs of the same plant there is apparently no simple law governing the ratio of fluorine t o phosphorus but they increase and diminish together. W. G. The Displacement by Water of Nitn genous and Mineral Substances Contained in Leaves. G. ANDRB (BdZ. SOC. chim. 1915 [iv] 17 429-441).-For the most part a more detailed account' of work already published (compare A. 1913 i 233). The experiments have been repeated with another year's crop of chestnut leaves somewhat more in detail and the results obtained confirm those already p-ublished (Zoc.cit.). W. G. A New Method for the Preparation of tlie Plant Globulins. GEORGE REEVES (Biochem. J. 1915 9 508-51O).-Sodium chloride solutions are usually employed t o extract the plant globulins but the yield is usually small. Schryver showed that globulins are much more soluble in salt solutions which lower surface tension and this forms the basis of the new method recommended a semi-normal solution of sodium benzoate being the one which gave the b'est results. In this way 130 grams of crude edestin were prepared from 450 grams of hemp seed sifted meal; and 30 grams of excelsin from 250 grams of Brazil-nut meal. Legumin and vicillin were similarly obtained fro'm horse beans and separated by Osborne's method.W. D. H. Evodin. a Crystallised Substance Present in the Fruit of Evodia Rutaecarpa. Y. ASAHINA and M. Ismo (J. Phaim. Chzm. 1916 [vii] 13 5 3 ; from Pakugakuzassi 1915).-The dried fruib of Evodia r u t w a r p possess an aromatic odour and a bitter taste and have long been used in China and Japan in medicine and perfumery. I n 1902 Keimatzu extracted a crystallisable substance from the fruits by means of benzene; the crystals had m. p. 285O were insoluble in water alcohol ether and light petroleum slightly soluble in hot benzene ethyl acetate and chloroform and soluble in acetic acid and in alkali solutions. The authors have further investigated this substance t o which the name evodin has been given. They find that owing to the readiness with which i t oxidises and polymerises i t can be separate& from the fruit as a pure substance only by distillation with steam; it has the formula C,,H,,O,.Besides evodin the fruits contain a considerable quantity of other crystallisable substlances which constitute a complex mixture containing more than 10% of nitrogen. w. P. s.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 239 Chemistry of Heterotrophic Phanerogams. 11. F. l J 7 ~ and J. ZELLNER (Monatslt. 1915 35 1511-1532. Compare Zell- ner A. 1914 i 913).-In extension of the earlier investigation the authors have submitted to chemical examination not only tobacco-plants affected by Orobancke Muteli and Orobanche ramosa but also the parasitic growths themselves and healthy plants. The materials in each case were dried and the analysis was made on the dried substance.In the case of Orobanche Mute& examination was made of the ash the extracts obtained from the dry material with light petroleum ether alcohol and water respectively and the insoluble residue. The roots of healthy and affected plants were examined in a similar manner. The results show that the composition of Orobanche Muteli may vary appreciably with the position of the plant affected but the most notable feature is the relatively high content of Eoluble substances such as potassium salts dextrose and mannitol in the parasite; i t appears probable that the osmotic pressure of these compounds assists in the extraction of sap from the roots of the plants. Nicotine does not pass as such into the parasitic growth. The thickened portion of the stem of the para- site appears t o serve f o r the storage of starch produced from the soluble carbohydrate compounds removed from the parent plant.The affected tobacco root may lose very considerably in weight and shows a reduction in its content of potassium salts starch and to a smaller extent nitrogenous compounds. It is also observed that even with healthy roots the content of soluble substances varies considerably with the season climate and position. It is believed that the food of the parasite is not drawn directly from the root but that the latter merely acts as an organ by which food can pass from the soil and from the1 stem and leaves t o the parasite. Although the root may be affected by this disturbance of its functions i t does not necessarily follow that it will always be very seriously affected.The case of the Orobanche rarnosa was not so closely investigated but €he results indicated a relationship between plant and parasite similar to that described above. D. F. T. Beetroots Attacked by Cercospora beticola sacc. ~ I L E SAILLARD (Compt. rend. 1916 162 47-49).-The beetroot crop of 1915 was attacked by the fungus Cercospora beticola sacc. with the result that the crop was poor in quantity and quality although the sugar content with a few exceptions was as high as in an average year. The juices were less pure and cont'ained momre salts. Reckoned as a percentage of the sugar the beetroots contained more total amino- ammoniacal and injurious nitrogen than in previous years even the dry year of 1911.Further there was decided loss of sugar more remaining in the molasses. The roots contained a dextrorotatory substance other than sucrose which was nct precipitated by lead acetate but which disappeared along with the amino- and ammoniacal nitrogen during the manufactur- ing proem. w. a.i. 240 ABSTRACTS OF CBEMICAL PAPERS. Connection between Absorption and Coagulation and its Influence on the Soil. A. DE DOMINICIS (Chem. Zentr. 1915 ii 1307; from Stuz. sperim. ugrar. ital. 1915 48 525-535. Compare A.. 1915 i 859).-The results of experiments made in conjunction with G. GANGEMI lead t o the following conclusions The recognition of the relation between absorption and coagulation and its bearing on the chemistry of the soil is of considerable importance.The two phenomena proceed together and a change in one is always accom- panied by a simultaneous analogous change in thel other. Thus for instance the coagulating powers of different ions correspond with their degrees of absorption. Absorption effects a retrogression of the colloids a diminution of the difference of electrical potential between the contrasted phases and a rise in the surface tension the phenomenon of coaghatiofn thus making its appearance. T. H. P. Amino-acid Nitrogen of Soil R. S. POTTER and R. S. SNYDER ( J . Ind. Eng. Chem. 1915 7 1049-1053).-The work of Chardet (A. 1915 i 762) who found by the Sorensen method 49-68% of the soil nitrogen t o be amino-acid nitrogen was not confirmed. By the Kober method of estimation (A. 1913 ii 990) no amino- acid nitrogen could be found in the acid extract of soil even if amino-acids were previously added but after one hour's extraction with dilute alkali practically the whole of the amino-acid nitrogen was removed.A typical analysis of a soil containing 0.151% of total nitrogen by the alkali extraction method and estimation according to Kober gave 7.95 parts of amino-acid nitrogen and 31.5 parts of peptide nitrogen per million. From pot experiments with variously treatled soils the conclusion was drawn that these is no tendency for amino-acid nitrogen t'o accumulate in either a limed or an unlimed acid soil whether manured or not and although the heavily manured soils showed a decided decrease in nitrate nitrogen a t first there was a marked increase after from four to six weeks. Amino-acid nitrogen was present in less amount than ammonia nitrogen but it fluctuated in general with the latter. G. F. M. Characterisation of Soils by means of Hydrochloric Acid Extracts and by the Power of Exchanging Bases. ALEXIUS A. J. VON SIGMOND (Bied. Zentr. 1915 44 433-438; from Intern. Mitt. Bode& 1915 5 165).-The classification of soils by means of hydrochloric acid extracts and estimations of the liberated silicic acid dissolved by hot saturated sodium carbonate solutions is discussed (compare Mitscherlich ibid. 1914 4 327). N. H. J. &I.

ISSN:0368-1769    

DOI:10.1039/CA9161000235

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i. 241 Organic Chemistry New Methods of 0 btaining Divinyl Isoprene Pipsrylene and Dimethy lerythrene. I. I. OSTRONISSLENSKI ( J . Russ. Phys. Chent. SOC. 1915 47 1947-1978).-Isoprene may be obtained by the following methods (I) Depolymerisation of natural myrcene CH,:CMe*CH,*CH,*CH:CN.CMe:CN = 2CH2:CMe*CH:CH ; (2) dehydration of B6-di h ydrox y-0-methylbu tam OH*CMe,-CH,-CH,*OH = 2H,O + CH,:CMe*CH:CH ; (3) removal of 2HC1 from fl6-dichloro-fl-methylbutane by means of quinoline o r other aminm CMe,Cl*CH,*CH,Cl= 2HC1+ C€12:CMe*CH:CH ; (4) removal of lHCl from monochloroisoamylenes by means olf sodium stearate CMe,:CH*CH,Cl = HCl + CH,:CMe*CH:CH ; (5) removal of acetic acid from 6-acetoxy-@methyl-Aa-butene CH2:CMe*CH2*CH,*OAc = C,H,O + CH,:CMe-CH:CH ; ( 6 ) depolymerisation of the terpenes dipentene limonene pinene etc.C M e f ~ ~ ~ ~ ~ ~ ~ > C ‘ H * O 1 V l e C H = 2CH,:CDIe*CH:CH ; (7) ac- tion of zinc dust on afly6-tetrabromo-~-methylbutane CH,Br*CMeiBr-CHBr*CH,Br + 2Zn = 2ZnBr + CH,:CMe*CH:CH,. fly-Dimethylerythrene may be obtained by (1) depolymerisation of the cyclic dihexene C M e < ~ ~ ~ ~ - ~ ~ ~ > C J J e*C,Me:C H = 2CH2:CMe*CMe:CH2 ; (2) dehydration of pinacone by means of sulphanilic acid or salts of phosphoric acid OH*CMe,*CM%*OH = 2H20 + CH2:CMe-CMe:CH,. F o r the preparation of piperylene see this vol. A. i 4. Tilden observed that dipentene is depolymerised a t 400-600° into isoprene and the author finds that pyrogenetic decomposition of homolotgues of dipentene yields homologues of isoprene cyclic dibutene being converted into erythrene C,H = 2C,H and cyclic dihexene into by-dime thylerythrene C,,H = 2C,H (compare Lebedev A.1913 i 1285). When heated a t 150-250° limonene is converted into polyterpenes of high boiling point whereas a t 500-600° i t yields isoprene and the increased yield of the latter obtained by Staudinger and Klever (A. 1911 i 731) is due not to dilution of the1 limonene vapour but t o the high temperature a t which this vapour is formed; good results are obtained when the limonene is mixed with benzene toluene xylenel light petroleum etc. The pyrogenetic decomposition of turpentine yields isoprene and also gases and liquid hydrocarbons distilling between 60° and 150O; these hydrocarbons may be used in place of benzene etc. as a diluent. Pyrogenetic decomposition of saturated hydrocarbons and of hydrocarbons containing one double linking yields only erythrene no homologues of the latter being obtained C,H,RR’ = @H,:CH*CH:CH R’H+ RH or C,H,R =CH,:CH*CH:CH + RI-I ; natural myrcene gives isoprene in 60-70% yield.VOL. cx. i. 111.1. 242 ABSTRACTS OP CKEMLCAL PAPERS. The conversion of PG-dichlmo-P-methylbutane into erythrene by the action of an amine takes place only when the basicity of the amine is relatively weak; in the case of primary amines this weakening of the basic properties may be effected by the introduc- tion of radicles into the molecule. I n this reaction quinoline p-chloro- and pbromo-aniline? and tetramethyldiaminobenzophenone are converted into colouring matters of basic charactex which behave as indicators. When heated with quinoline both 6-chloro-P-methyl- Aa-butene and b-chlorocfl-methyl-h~-butene yield isoprene the dimethylallene first formed in the latter case undergoing isomeric change; when the quinoline is replaced by sodium stearate such isomeric change does not take place isoprene being obtained from the first and dimethylallene from the second of th? above chlofro- derivatives. When heated with lime sulphanilic acid o r alkali alkyloxide 6-acetoxy-fl-methyl-Aa-butene gives no trace of isoprene but under the influence of alumina a t 380-450° a yield of 20% of isoprene is obtainable.The dehydration of isoamylene glycol t o isoprene takes place under the same conditions as that of 1 3-iso- butylene glycol; alumina and also phosphoric acid were used as dehydrating agents (compare Lebedev Zoc.cat.). The results obtained on heating hydrocarbons of different types lead t o the following general rule Open-chain hydrocarbons con- taining one ethylenic linking in the molecule or saturated cyclic hydrocarbons lose a t high temperatures mostly saturated hydro- carbons all the carbon atoms being expelled with the exception of four which remain in the form of erythrene. The latter may indeed be obtained from almost any hydrocarbon containing not fewer than four carbon atoms in the molecule thus C,H + C1 = HCl + C,bH27L+lCi ; C,H,,+,Cl= C,H,RCl= HCI + RH + CH,:CH*CH:CH,. T. H. P. Conversion of the cycZoButane Derivatives Bromocyclo- butane and cycZoButano1 into Erythrene. Mechanism of the Remova.1 of Different Rsdicles from the 1- and 4-Positions.I. I. OSTROMISSLENSKI ( J . Rws. Phys. Chem. SOC. 1915 47 1978--1982).-The fact that the action of zinc dust on as-dibromo- AD-butane yields erythrene according to the equations (1) CH-,Br*CH:CH*CH,Br + Zn= ZnBr + CH<gE->?H and (2) CH(:g)”H = { YH*CH2 CH,UHo} = CH,:CH*CH:&3 leads t o the conclusion that reactions yieldiAg cyclobutene should owing to isomerisation of this hydrocarbon give also erythrene. The author has confirmed this conclusion by obtaining erythrene (1) by the scission of hydrogen bromide from bromocyclobutane and (2) by the scission of water from cyclobutanol. Similar results were ob- tained by Willstatter and Schmaedel (A. 1905 i 514) who pre- pared erythrene by the removal of bromine from 1 2-dibromocyclo- butane and obtained a mixture of cyclobutene (about 90%) and erythrene (about 10%) on complete methylation of aminocyclo-ORGANIC CHEMISTRY.i. 243 butane CH,<CH2>CH*NDle,*OH = CH2<CH=>CH + NMe + H,O and by Willstatter and Bruce (A. 1907 i lOlS) who obtained ilay-but-adisne by the reinoval of ammonia from aminocyclobutane. Thus the reactions expressed by the following two equations may be regarded as general methods for the preparation of erythrene (1) CH,<CH2>CHR = R H + CH,:CH*CH:CH and CH2 CH2 CH2 (2) CH2<:2i>CHR’=RH + R’H + CH,:CH*CH:@H,. For instance monosubstituted alkyl- alkoxy- or acetyl-cyclobutane should give erythrene either when heated or when treated with a suitable catalyst ; under similar conditions derivatives of homo- logues of cyclobutane should yield the corresponding homologues of erythrene; thus 1- or 2-methylcyclobutanol should give methyl- er ythrene.Perkin found that when heated cyclobutene-1 2-dicarboxylic acid is converted into the anhydride of an acid the structure of which was not established. According to the above considerations the anhydride thus formed must be that of dimethylenesuccinic acid CH C CO H CH,*C*CO,H C H,*C*CO,H- C H 2 C-CO,H - I - - - - - I \/’ /\I _C H ,*C‘*CO,H-I CH,:C~CO H I I CH,:C* co 1 \o. T. H. P. CH, c. co’ Analysis Purification and Qualitative Reactions of Isoprene. Structure of the Benzene Nucleus. I. I. OSTROMISSLENSKI ( J . Rms. Phys. Chem. SOC. 1915 47 1983-1988).-Ths formation in a reaction of a diolefine with conjugated doable linkings may be detected by shaking 5-10 drops of the products of the reaction f o r a short time wit,h 50 C.C.of mncentrated aqueous sulphurous acid the mixture being then left a t the osdinary temperature in a hermetically sealed vessel. I n the course of two t o thirty hours an abundant colourless amorphous precipitate is formed this consist- ing of a compound of the diolefine with the sulphur dioxide and possessing characteristic properties (compare Badische Anilin- & Soda-Fabrik A. 1911 i 938). Isoprene may be estimated by converting i t into PG-dichloro-B- methylbutane ‘10.49 grams of the latter corresponding with 34.03 grams of isoprene. ‘The procedure is as follows 200 grams of the crude isoprene containing butylenes amylenes benzene etc.are shaken vigorously f o r six hours with 1500 C.C. of fuming hydro- chloric acid. The black opaque upper layer of chloro-compounds is separated by means of a separating funnel washed with aquems sodium chloride solution saturated in the cold again separated after the emulsion formed has divided into two layers dried over calcium chloride and distilled. A t 40-50° only two or three drops of 112 2i. 244 ABS’IRACTS OF CHEMlCAL PAPERS. hydrocar boils usually distil over and the fraction 50-90° contailis butyleiie and amylene chlorides; the fraction 90-130° is collected separately. From 130” the temperature generally rises immediately to 1 4 2 O the boiling point of PG-dichloro-/3-methylbutane. When the crude isoprene has been obtained from turpentine the j3G-dichloro- fi-met81iylbutane~ cannot be distilled but it is found that the residue iii the distilling flask with b.p. beyond 143” consists in spite of its black colour oi almost chemically pure PG-dichloro-j3-methylbutane ; in a vacuum indeed this residue distils completely within 0 * 5 O of the proper temperature. This residue may be filtered through glass wool and the filtrate weighed. The fraction b. p. 90-130° is subjected to careful fractional distillation as it contains /38-dichloro- P-metliylbutane sometimes in considerable quantity. A method is described f o r the purification of crude isoprene con- taining turpeiitine benzene amylenes etc. When heated with sodium chemically pure isoprene yields an abnormal caoutchouc differing considerably in its properties from the sodium-isoprene caoutchouc described first by Matthews and Strange and later by Harries.The author regards the stability of halogen atoms combined with the nucleus of aromatic compounds as due t o the presence in this nucleus of three double linkings the halogen always being attached t o a carbon atom possessing such a linking. On this assumption those chemical agents which react with the halogen of an aromatic nucleus should also react with the halogen of vinyl lialoids. The halogen of bromobenzene reacts readily in presence of ether with either sodium o r magnesium and i t has been shown by Prshebytek (A. 1889 362) that in presence of ether sodium easily removes bromine from P-methylvinyl bromide 2CHMe:CHBr + 2Na = 2NaBr 4- CHMe:CH*CH:CHMe and by Austerweil (A.1912 i 525) that sodium or magnesium acts on vinyl bromide in the same way as on brosmobenzene. The conclusion is drawn that benzene is a hydrocarbon with conjugated linkings and is confirmed by the behaviour of aromatic compounds in various reactions Thus hydrogen unites at the conjugated linking of an open-chain com- pound and also as in the partial hydrogenation of phthalic acids with the benzene nucleus in the 1- and 4-positions. Further pyro- genetic reactions yield erythrene and benzene with almost identical ease and often in identical proportions. With barium peroxide amylenes react with almost explosive violence whereas isoprene is quite passive towards this reagent; this marked stability t o oxidis- ing agents is closely analogous t o that exhibited by aromatic com- pounds.Benzene may be regarded as the cyclic analogue of eehrene l-CTI:CH-’ ’ T. 11. P. CH:CH -CH:CH Transference of the Elements of Halogen Hydracid from One Organic Radicle to Another. Mechanism of the Action of Chlorine on Trimethylethylene [&Methyl-AP-butenel. I. I. OSTROMISSLENSK~ ( J . Russ. Phys. Chem. SOC. 1915 47 1988-1991).-The author shows that the first stage of the actionORGANIC CHEMISTRY. i. 245 of chlorine on P-methyl-AP-butylene (compare Kondakov A. 1885 736; 1886 136) results in the formation of a dichloride of the latter. This dichloride is then converted into chloroisoamylene by loss of the' elements of hydrogen chloride which unite with a further molecule of /3-methyl-AP-butylene (1) C,R + C1 = C,H,,Cl ; (2) C,H,,CI + C5H1o = C5H,Cl + C,H,,CI.Whether the elements of hydrogen chloride are) lost from /3-methyl-Py-dichlorobutane CMe,Cl*CHMeCl or from an unstable dichloro-derivative in which the two chlorine atoms retain their " molecular '' linkings and which may be formed as a transient int'ermediate product is not yet decided. T. H. P. Preparation of Ethyl Bromide. ALFRED HOLT (T. 1916 109 1-2).-1n order to obtain a good yield of ethyl bromide from sodium or potassium bromide i t is necessary t o use a large quantity of a mixture of water alcohol and sulphuric acid and t o distil a t as low a temperature as possible (compare Weston A. 1915 i 1049). The author employs a mixture of 1500 C.C. of concentrated sulphuric acid 900 C.C. of water 1500 C.C. of alcohol and 1200 grams of potassium bromide (or an equivalent of NaBr,2H,O).The ingredients are! mixed carefully in the cold and distilled for eight or nine hours. The yield is 90-96% calculated on the bromine and thel product conhains no hydrogen bromide and is almost free from ether as revealed by a density measurement. J. C. W. Interaction of Tetranitromethane and Potassium Ferro- cyanide. FREDERICK DANIEL CHATTAWAY and JOEIN MALTEIOUSE HARRISON (T. 1916 109 171-174).-A saturated aqueous solu- tion of pot,assium ferrocyanide reacts quietly and quantitatively with tetranitromethane and bromotrinitromethane but not with chloro- or bromo-picrin to form the potassium salt of aci-trinitro- methane thus C(NO,) + 2KiFeC,N = C(NO,),:NO*OK + KNO + 2K3FeC6N and C(NO,),Br + 2K,FeC,N6 = C(NO,),:NO*OK + KBr + 2K3FeC,N,.This affords a safe and easy way of preparing the crci-trinitromethane salt whereas the older method the action of potassium ethoxide on tetranitromethane is very risky (Macbeth A. 1913 i 1146). J. C. W. The Preparation of Anhydrous Ethyl Alcohol. L. W. WINKLER (Zeitsch. angew. Chem. 1916 29 18).-Commercial cal- cium shavings contain appreciable quantities of calcium nitride so t h a t when used for the dehydration of alcohol the latter is liable to cont'ain ammonia. When used as follows however this difficulty is obviated. The shavings are sieved with a fine sieve thus remov- ing most of t'he calcium nitride after which they are washed with dry carbon tetrachloride (or other suitable liquid) to remove traces of petroleum.For every litre of alcohol 20 grams of these cleaned shavings are used. I n order t c remove ammonia from the anhydroas distillate several centigrams of alizarin are dissolved in a litre thereof and 0.5 gram of dry tartaric acid in 10 C.C. The tartaric acid solution is then added slowly to the alcohol coloured by thei. 246 ABSTRACTS OF CHEMICAL PAPERS. alizarin until the reddish-blue colour changes to a pure yellow; a few drops more' of the tartaric acid solution are then added and the whole distilled once1 more care being taken to prevent the access of moisture. T. $3. P. True Homologues of Glycerol ; Heptsuetriol. J. L. HAMONET (Compt. rend. 1916 162 225-226).-A true homologue of glycerol is defined as a substance having &he general formula OH*C"H2*[CH2],:C'H(OH)*[CH2],*CH2*OH and an account is given of the preparation of a8q-heptanetriol where n = 2.y-Iodo-a-methoxypropane OMe*CH,-CH,*CH,I gives a mag- nesium derivative (compare A. 1904 i 467) which when acted on first by ethyl formatlei and then by water yields aq-dimethoxy- heptan-8-01 OMe*[CHJ,*CH(OH)*[CH,],-Ohle b. p. 246-248O ; D18 0.969. This diether can be converted into heptanetriol by two .methods. The first and longest consists in preparing by means of hydrobromic acid in the cold ay-dibromoheptan-&oI o r in the hot ay8-tribromoheptane ; these yield respectively the corresponding diacetin and triacetin which on saponification give the required heptanetriol. The bromo-compounds cannot be converted directly by the action of boiling water into the required glycerol since under the& conditions they yield propyltetrahydrofuran.The second method consists in treating the ay-dimethoxyheptan-6- 01 ih the cold with 2 mols. of anhydrous hydrogen iodide the glycerol being dissolved out with water and obtained on distillation. a?iq-Heptunetriol OH*CH,= [ CH,],*CH(OH)~[CH,],*CH,*OH is a very viscous liquid with a bitter taste b. p. 230-232O/20 mm.; D18 1.075. The met'hod should apparently be general for the pre- paration of other homologtms. W. G. Mercury Mercrsptide Nitrites and tbeir Reactions with t h e Alkyl Iodides. Compounds of t h e Disulphonium Series. PRAFULLA CRANDRA RAY (T. 1916 109 131-138).-1n a preliminary note (P. 1914 30 140) it was shown that mercuric nitrite readily reacts with mercaptans t o form mercury mercaptide nitrites of the type R*S*HgNO,.The methyl and ethyl members of this series have now been more thoroughly examined particularly with regard to the action of alkyl iodides on them. This reaction is lound to proceed as represented by the scheme 2R*S*HgNO + 2RI = R,S + Hg,I + 2R*NO but this is immediately complicated by other changes. Instead of mercurous iodide the mercuric salt is formed probably by the abstraction of iodine from some more of the alkyl iodide but the most interesting result is the production of complex salts of the type R,S2,HgI,,R'I. These are regarded as sulphonium salts in which the two1 bivalent atoms in ethyl sulphide have become quadrivalent thus SRR'I-SRI*Hg'I. Mercury methyl- and ethyl-mercaptide nitrites are obtained by adding dilute alcoholic solutions of the mercaptans to an excess of concentrated mercuric nitrite solution.Nitrous fumes are evolved and the product8 separate as almost white crystalline nacreous precipitates.ORGANIC CHEMISTRY. i. 247 The reaction with alkyl iodides is brought about by warming the mercury mercaptide nitrite with an excess of the iodide on the water-bath until the mixture separates into two or three distinct layers. Besides volatile producte it is recognised that other com- plex substances are formed as well as the disulphonium compounds but these are usually separated by fractional crystallisation from acetone. Ethyldisulphon~~~m-mercuri-iodide SEt$*SEtI*HgI forms yellow crystals m. p. 1 1 2 O ; the compound Me,S,,HgI,,EtI from mercury methyl mercaptide nitrite and ethyl iodide has m.p. 69-71O ; the! compound E~S,,HgI,,PrI from It-propyl iodide forms dark brown shining crystals m. p. 75-78O; and the1 com- pound Me,S,,Hg12,PrI is a yellow mealy substance m. p. An alcoholic solution of ethyl disulphide also reacts with mercuric nitrite nitrous fumes being evolved and a compound Et2S2,Hg(N02)2,Hg0 being precipitated in microscopic needles. The formation of the latter is interesting as i t throws some light on the constitution of the above complexes. It is assumed that the sulphur atoms first add mercuric nitrite and then nitrogen trioxide is eliminated thus 99-102'. I F N 0 2 I E t S-- SRt + EtS- SEt . Preparation of Ethyl Acetate from Acetaldehyde. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (Eng.Pat. 1915 1288; from J . Soc. Chem. Id. 1916 35 141).-Ethyl acetate is produced in 85% yield when 400 parts of acetaldehyde are gradually stirred into a filtered solution of 16-20 parts of aluminium ethoxide in 45 parts of dry solvent naphtha or other organic solvent of high boiling point such as nitrobenzene or xylene the temperature being main- tained a t 0-15O by thorough cooling. After keeping for twenty- four hours the product is fractionally distilled and the first run- nings of acetaldehyde used again. Ethyl amtab forms the inter- mediate fraction and from the residue the naphtha is recovered by steam distillation. G. F. M. Preparation of Esters of Unsaturated Alcohols from Aldole. I. I. OSTROMISSLENSKT ( J . Russ. Phys. Chem. SOG. 1915 47 1991-1993).-The action of magnesium amalgam on aldol yields the acetyl derivative of crotonyl alcohol OH*CHMe-CH,-CHO = 2CH3*CH0.OH*CHMe*CH2*CH0 + CH,*(YRO = OH*CHMe*CH,-CH,*OAc = H20 + CHMe:CH*C'H,*OAc. When treated with alumina this ester is readily converted into erythrene and acetic acid (this vol. i 4). If analogous and homo- logous aldols exhibit similar behaviour towards magnesium amal- gam this reaction would represent a new method f o r obtaining esters of unsaturated alcohols. T. H. P.i. 248 ABSTRACTS OF CHEMICAL PAPERS Hydrogenation of Oils. L. HAMBURGER (Chem. Weekblad. 1916 13 2-13).-An account of results obtained in thel hydrogen- atlion of oils by Sabatier’s method under pressures up to 200 atmospheres. A. J. W. H. ScHiiN- FELD (Zeitsch.nngew. Chem. 1916 29 3940).-TheI author dis- putes the statement of Bosshard and Fischli (A. 1915 ii 788) that the catalytic hydrogenation of oils in presence of nickel borate is con- ditioned by tlhe previous decomposition of the salt; the reverse in fact is the case f o r with increasing decomposition of the borate owing t o the! action oC the free oleic acid used in Bosshard’s experi- ment the activity of the catalyst diminishes. The relatively high nickel content of the oleic acid hardened in presence of nickel borate is likewise to be attributed to the decomposition of the salt by the free fatty acid. Hardening of Oils i n Presenceof Nickel Borate. G. F. M. Oxidation of Aa-Hypogaeic Acid by Alkaline Permanganate Solution and by Caro’s Rectgent. N. ZINOVSKI ( J .Rziss. Phys. Chem. SOC. 1915 47 2121-2124).-Oxidation of Aa-hypogzeic acid m. p. 47-49O solidifying point 44-43O (compare Ponzio A 1905 i 405) by means of alkaline permanganate solution yields an afl-dihydroxyplmitic acid CO,H*CH( OH) *CH(OH) [CH,],,*cH which crystallises in needles m. p. 125-127O solidifying point 123-121O; 1.43 parts dissolve in 100 parts of alcohol1 at 19O and 0.15 part in 100 pasts of ethyl ether at 1 8 O . Oxidation of Aa-hypogaeic acid by means of Care's reagent in the conditions employed by Albitzki (A. 1903 i 288) yields a dihydroxy- pnlmitic acid Ci6H3,04 m. p. 105-106*5° solidifying point 102.5-100°; 7.94 parts dissolve in 100 parts of alcohol a t 19O and 1-39 parts in 100 parts of ether a t 18O. T. H. P. Oxidation of AS-Oleic and A<-Elaidic Acids by Alkaline Permanganate Solution and by Caro’s Reagent.T. AFANASIEVSKI ( J . Russ. Phys. Chem. SOC. 1915 47 2124-2127).- Oxidation of petroselic acid (compare Vongerichten and Kohler A. 1909 i 454) by means of Caro’s reagent under the conditions indicated by Albitzki (A. 1903 i 228) yields a ec-dihydroxystearic mid C0,H*[CH,]4*CH(0H)*CH(OH)*[CH2],,*CH3 m p. 96-99O solidifying point 92-90° which is stereoisomeric with the acid m. p. 122O obtained when the oxidation is effected by permanganate (Vongerichten and Kohler Zoc. cit.). Oxidation of A{-elaidic acid m. p. 52-5407 by alkaline permanganate gives a dihydroxystearic acid C,,H,O having the same melting point 96-99O as that described above. An isomeric acid m. p. 120-123° solidifying point llG-114° is obtained by oxidising Ac-elaidic acid by means of Caro’s reagent.T. H. P. Glycerides of Linoleic Acid. AD. GRUN and H. SCHONFELD (Zeitsch. angew. Chem. 1916 29 37-39).-aa-Diliitolein was obtained by the’ action of potassium linoleate on aa-dichlorohydrin,ORaANlC CHEMISTRY. i. 249 and in better yield by the elimination of bromine by means of potassium iodide in ethyl acetoacetate solution from aa-di-tetra- bromostearin which was prepared in good yield by the action of potassium tetrabromostearate on aa-dichlorohydrin. aa-Dilinoleiii formed a clear oil of neutral reaction and gave on bromiiiation j i i carbon tetrachloride a small quantity of the above di-tetrubrwuo- stenrin rn. p. 71O. From glyceryl tribromide and potassium lino- leate only a poor yield of trilinolein was obtained.Mixed tri- glycerides could not be obtained by the usual methods but lino- leodistearin and linoleodipalmitin welre successfully prepared from distearin and dipalmitin by esterification with linoleic anhydride according to1 the method of Grun and Schacht (A. 1907 i 462). These mixed glycerides are more soluble in the various fat solvents and have lower melting points than the saturated glycerides and the symmetrical compounds are less fusible than the asymmetric. s-Lin oleodiplmitin has m. p. 28-29O as-linoleodipalmitin m. p.. 1 1.5-1307 s-linoleodisteam’n m. p. 42O and 36O and as-linoleode- stearin m. p. 34O. G. F. M. Glutaconic Acid. I. P. E. VERKADE (Proc. K. Akacl. TVetensch. Amsterdam 1916? 18 981-992).-1n this and in subsequent co’m- munications the author supports J.F. Thorpe’s views on the con- stitution of glutaconic acid with evidence chiefly of a physico- chemical nature. In the first place it is shown t h a t the glutaconic acid prepared by widely differing methods is always the same. These methods are reviewed and i t is pointed o n t t h a t (1) Conrad and Guthzeit’s method starting with ethyl sodiomalonate and chloroform is the quickest but costly; (2) von Pechmann and Blake’s method start- ing with acetonedicarboxylic acid is very good ; Morgenstern and Zerner’s method (A.? 1910 i 656) starting with dichlorohydrin and potassium cyanide is the best for large-scale operations; and that Buchner’s method which involves as a preliminary the con- densation of methyl acrylate with ethyl diazoacetate results in the production of a mixture of glutaconic acid and cis- and trans-tri- methylenedicarboxylic acids which can be separated by fractional crystallisation from water ether and ethyl acetate.The specimens of glutaconic acid obtained had m. p. 136-138O and all had the usual properties. The author emphasises the point that this ordinary form of glutaconic acid is superior in stability to the other two’ possible isomerides. It will be shown t h a t it has neither all the properties of a cis-acid nor all those of a trans-acid and t h a t the speed a t which i t is reduced by hydrogen and a platinum catalyst is different from the rate a t which an acid with a fixed double linking is reduced and the course of the hydrolysis of the hydroxy- anhydride will be studied by physico-chemical means. All the evidence points t o the presence’ of a ‘ I floating ” double bond.An attempt was made to effect a new synthesis of glutaconic acid by the hydrolysis of ethyl a-cyanoglutaconate.” This was prepared by condensing ethyl sodiof ormylacetab with ethyl cyanoacetate but m+i. 250 ABSTRACTS OF CHEMICAL PAPERS. as Guthzeit and Eyssen have found (A. 1909 i 674) it yields no glutaconic acid or pyridine derivatives on hydrolysis which might have been expected from the hydrolysis of ethyl a-cyano-#I-methyl- glutaconate (Thorpe and Rogerson T. 1905 87 1685). Probably C,W I3 t ) C N H J. C. W. the ester has the structure CH/ >o \CH==U.OEt Oxidation of Unsaturated Fatty Oils and Unsaturated Fatty Acids.I. Formation of Acraldehyde by the Oxida- tion of Linseed Oil and Linolsnic Acid. ARTHURT'IENRY SALWAY (T. 1916 109 138-145).-A satisfactory explanation of the chemical processes involved in the " drying" of linseed oil would seem t o be impossible until the oxidatibn of the constituent unsatur- ated glycerides is understood. Since it is extremely difficult to obtain the pure glycerides of linolenic lindeic and oleic acids however and since it can be shown that the glycerol plays no part in the reactions the author has commenced a study of the action of air o r oxygen on the free acids. He has shaken linseed oil the mixture of acids from saponified linseed oil linolenic acid and oleic acids with oxygen in a bulbed tube immersed in water a t looo and connected on the one hand to a manometer and gas cylinder and on the other t o a wash-bottllel containing water and he has found that except in the case of oleic acid (and also pure glycerol) acraldehyde is onel of the volatile products.The literature of the subject is not very extensive but contains references which are interwting in the light of the above. Thus nunlop and Shenk (J. Amer. Chem. SOC. 1903 25 826) noticed an odour of acraldehyde about " drying '' linseed oil; Baly (A. 1912 i 533) attribubd the toxicity of the vapours of fresh paint t o unsaturated aldehydes; and Gardner (A. 1914 i 380) and King (A. 1915 i 645) observed the production of carbon monoxide and carbon dioxide. An explanation of the mechanism of the processes which would account for the formation of these substances but however would involve a new conception of the structure of linolenic acid is given and the interesting suggestion is made that the (' dry " oil contains the polymerides of acraldehyde and glyoxal.J. C. W. Composition of the Hydrochlorides obtained from Formald- oxime. C. H. SLUITER (Proc. E. Akad. Wetemch. Amsterdam 1916 18 1007-1012).-Scholl (A. 1891 i 663) stated that the oomposition of f ormaldoxime hydrochloride varies owing to a pro- gressive change which takes place during the formation of the salt but Dunstan and Bossi (T. 1898 73 353) assigned the definite formula (CH,".-OH),,HCl t o the only substance which they could isolate in a pure state. The author has reinve&gated these salts and finds that Scholl's opinion was correct.The freshly prepared salt crystallised once from methyl alc'ohol and then from ether and dried in a current of dry hydrogen chloride contains about 1 molecule of the acid toORGANIC! OHEMISTRY. i. 251 1 of the airnple oxime CH&N*OH; in a vacuum this salt quiakly cbangw into o w oontaiaing lHCX to 2CH2:N*OH and after repeatscl aryzltallisations and long drying this gives Dunstan’s salt lHCl to 3CH,:N*OH. It is assumed therefore that the oxime molecule changesl in structure and the strength of the bases present a t the various stages has been measured by t?neir catalytic effect on the hydrolysis of ethyl acetate and sucrose. The facts are best explained by assuming a cyclic arrangement of three molecules of the oxime and will be dealt with more fully in another paper (Bee. trav.d i m . ) . J. C. W. Some Properties of Sfarch Gonsidered from a Golloid- Chemical Point of View. W. HARRISON ( J . Xoc. Dyers 1916 32 4043).-Experimenh are dsscribed which show that starch granules contain no starch which is really soluble in water and that the outer portions of starch granules do not; differ chemically from the inner portions. Such variations as are flound in the &arch granules are attributable to differencm in the physical condition of the starch the appearance of the granules under polarised light indicating a considerable degree of compression. The differences in size ahape and rwistaaoe to the action of hydrolytic agents which are shown by various kinds of starch grandee are probably due to differences in the methdd and rapidity of deposition of the starch.Observations on the precipitation of starch solutions by alcohol indicate that the precipitation is oonnwtd with the prwence of inorganic d t s . By the fractional separation of the mineral con- stituents of ordinary starch by mean8 of alcohol purer varieties of starch have been prepared. Solutions of mch relatively pure starch are found to deposit granula in contact with the glass of the containing vessel and it is suggested that this is due to the coagu- lating influence of salts dissolved from the glass. The precipitation of starch by inorganic substances hae also been examined. The resulte show that the coagulating powers of the metals depend on the valenay a& shown by the following mriw of relative numbers hydrogen 1 ; sodium 1 ; barium 4 ; magnwium.4; aluminium 16. The precipitating action of barium hydroxide has been supposed to be due to the formation of a definite com- pound; the author’s experiments Bhow that this is not the case but that the composition of the precipitate varies with the concen- tration of the solution in accordance with the adsorption formula. H. M. D. Preparation of Diethylamine. WILLIAM EDWARD GARNER and DANIEL TYRER (T. 1916 109 174-175).-A mixture of mono- di- and tri-ethylamine can easily be separated by fractionating with a 10-bulb column and the authors have therefore been able to make diethylamine on a large scale in the laboratory star4;ing with ethyl bromide and ammonia. J. C. W. m* 2i. 252 ABSTRACTS OF CHEMICAL PAPERS. Preparation of a Compound of Silver Glycocholate Readily Soluble in Water.FARBWERKE VORM. MEISTER LUCIUS KZ BRUNING (U.S. Pat. 1161867; from J . SOC. Chem. Ind. 1916 35 141).-Hexamethylenetetramine-silver glycocholate is obtained as a colourless compound soluble in water in 90% alcohol and in methyl alcohol but almost insoluble in light petroleum by treating silver glycocholate with a solution of hexamethylenetetramine. The aqueous solution of the compound is decomposed by hydrochloric acid into hexametliyleiietetramine hydrochloride silver chloride and glycocholic acid. G. F. M. Heptamethylenebis a-imino-acids and the Stereoisomerism of their Copper Salts. N. A. SCHLEZINGER ( J . Rzsss. Phys. Chem. SOC. 1915 47 1811-1819).-As is the case with the copper salts of other organic and inorganic acids the copper salts of the majority of kisimino-acids are known only in one modification.The results obtained wi t<h the' copper salts of as-pentamethylenebisiminoiso- butyric acid (A. 1915 i 945) indicate that these salts are capable of exhibiting cis-trans isomerism but only the less soluble isomeride could be isolated in the pure state. From the structural formulze of the copper salts of aa-polymethylenebisimino-acids i t is evident that the cis-salts should be the more stable when the number of methylene groups is small and the tram-salts when more methylene groups are present. It is therefore clear why with ab-ethylene- and ay-trimethylenebisimino-acids the blue copper salt is alone observed whilst only with the pentamethylene-acid does the second violet form appear although in this case also the blue form exhibits almost perfect stability.With the corresponding heptaniethylene-acids for instance ay-lieptamethylenedi-iminodiisobutyric acid both copper salts are obtlainable in the pure crystalline anhydrous condition ; the stable violet form exhibits normal molecular weight in freezing phenol but no suitable solvent could be found for the labile blue modification. ay-he pitame t ?i yl e nedi-iminodiiso b 11. tyro ni trile C,H,,(NH*CMek*CN) prepared from heptamethylenediamine potassium cyanide and acetone forms an almost colourless oil and its hydrochloride +2HC1 when rapidly heated in a sealed capillary has m. p. about 129O (decomp.). 'The corresponding acid C,,H,O,N forms anhy- drous crystals aqd does not melt even a t 3 1 0 O .The violet-red copper salt which is probably the trans-isomeride is obtained by mixing the theoretical amount of cupric hydroxide with an am- moniacal solution of thel acid and evaporating the solution. The blue cis( ?)-modification is obtained by dissolving the violet salt in fused phenol shaking the sollltion with much water t o dissolve Eart of the phenol and dissolving the rest of the latter in alcohol; the colour of this liquid gradually changes t o blue and extraction with ether then yields the blue salt; the latter is converted into the violet4 form slowly by boiling alcohol or rapidly by hot water but the) dry salt' is not changed by prolonged heating a t 90*.ORGANIC CHEMISTRY. i. 253 ar]-Heptarnethylen edi-imin odiphenyldiace tonif rile C7Hl (NH CHP h*CN) prepared from heptainethylenediamine potassium cyanide and benzaldehyde is an oil aiid its ?~ydroc?doride has m.p. 144O (decornp.) in a sealed capillary. The corresponding acid C23H,,0,N decomposes a t about 2 3 1 O in a sealed capillary; its hydrochlomd? +H,O was prepared and its methyl ester C,jH3104N2 forms a viscous oil DY 1.0851 ??Eo 1.5293; the b l u e copper salt was obtained as above. T. H. P. Preparation of a Derivative of a-Bromoisovaleramide. KNOLL & Co. (D.R.-P. 287017; from J . Soc. Chem. Ind. 1916 35 142). -a-Bromoisovaleramide reacts with oxalyl chloride according to the equation 2NH2*CO*CHBr*CHMe + C20,C12 = The derivative produced has sedative and hypnotic properties and also serves as the starting point f o r the preparation of a-bromo- isovalerylcarbamide. G.F. M. Preparation of Carbamide and of Ammonium Carbonate for Use in its Preparation. RADISCHE ANILIN- st SODA-FABRIK. (Eng. Pat. 19-14 23939; from t7. SOC. Chem. 1)7d. 1916 35 141).- Ammonium carbonate is prepared by the direct union of ammonia and carbon dioxide in suitable proportions under pressure with o r without cooling. The reaction is carried out in a lead- or silver- lined autoclave and if instead of allowing the vessel to cool and t h e ammonium carbonate t o solidify it is only cooled sufficiently to keep the preesure below 50 atm. during the reaction and subse- quently the temperature is maintained a t 130-140° carbamide is formed. G. F. M. CO(NH*CO*CHBr*CHMe,)2 + 2HC1+ CO. Constitution of the Fulminuric Acids.VIII. Metafulmin- uric Acid. C. ULPIANI (Gnxxetta 1916 46 i 1-45. Compare A 1912 i 611).-The work of Ehreiiberg (A. 1884 419; 1885 1192) Scholvien (A. 1885 39; 1886 137) Nef (A. 1895 i 9) Palazzo and Tamburello (A. 1907 i 298) and Wieland and Hew (A. 1909 i 369) is discussed. The author finds t h a t the trans- formation 3f metafulminuric acid into osiminocyanoacetohydrox- nmic acid takes place not only under the influence of alkali b u t also spontaneously and occupies a few hours or a few months according to the conditions; the change is greatly accelerated by heat or alkali. I n a desiccator oximinocyanoacetohydroxamic acid undergoes no further appreciable alteration but under other con- ditions f o r instance in a closed paraffined vessel o r in an open vessel i t is transformed completely int40 isofulminuric acid in a few weeks.Marked discrepancies occur between the properties found by the author for oximinocyanoacetohydroxamic acid and those ascribed t o i t by Nef and by Wieland and Hess and the author shows t h a t these are due to the fact t h a t this acid undergoes change in different directions according t o the conditions in which it is kept. (1) I n solution in water or an organic solvent i t is trans-i. 254 ABSTRACTS OF CHEMICAL PAPERS. formed into an uncrystallisable syrup tlhe syrupy fulminuric acid of Ehrenberg and this has not yet been purified but is still under investigation. (2) When heated for about thirty minu+ at 70° the anhydrous form of oximinocyanoacetohydroxamic acid is con- verted into 4-nitro-5-aminoiso- .Is :c N:CH oxazole (annexed formula) (A.I 1912 i 611). The transformation C:NOH 1 L'NO of the group / I HO*b:NOH O*C:.NH *C( :NOH)*C( :NOH)* into -C(NO,):C(NH,)* here taking place is in accord with the general law that a substance corre- sponding with a form of intermediate oxidation tends to decom- pose in two senses namely into the forms of lowest and highest oxidatlion. (3) The most typical change of oximino- cyanoacetohydroxamic acid is however that into isofulmin- uric acid or hydroxyf urazancarbonamide which the author explains by the scheme C:NOH + [ -+ C:N This reaction evidently requires the presence of only a minimal amount of moisture but cannot take place in a desiccator. To oximinocyanoacetohydrolxamic acid (I) and the orange acid (11) obtained from it by the action of sodium hydroxide and t o the two amidines (I11 and IV) obtained by the action of dilute or concentrated ammonia solution on acid (I) the following stereo- isomeric f ormulz are assigned CN CO*NH CO*N€i I I HO*&:N >*- HO&NOH H0.C NO 1-1 CN I (I.) ( Syn.) (11).(Amphi.) (111.) (White amphi.) (IV.) (Yellow anti.) The1 author adopts the structure proposed by Wieland and Hess (Zoc. c i t . ) f o r metafulminuric acid. The furazanio formula is also discussed in view of the fact that ' x:yH O<,U :C*C(OH) NOH' \ I f urazancazboxylic acid when converted into its salts undergoes transformation into oximinocyanoacetic acid ; since however sodium nitrite acts rapidly on oximinocyanoacetohydroxamic acid giving immediabe and copious evolution of nitrous oxide and formation of oximinocyanoacetic acid whereas with f ulminuric acid this reaction takes place only with extreme slowness t'he conclusion is drawn that the hvdroxamic acid group in metafulminuric acid is not free but .I >O for metafulminuric acid C$Q:NH(OH) bound.Thel structure> HO* C==N is also considered.ORQANIC CHEMISTRY i. 255 Metafulminuric acid has m. p. 8 6 O (+ 2H,O) or 102O (anhydrous) t iic anhydrous form being non-explosive. Osimiiiocyanoacetohydroxamic acid C,H,O,N + 3H20 softens a t about 4 5 O and is completely liquid a t about 80°; with $H,O it has in. p. 1 0 5 O . With ferric chloride its aqueous solution gives an intense seddish-violet coloration which unlike the colour given with rnetafulminuric acid is stable on addition of a few drops of dilute hydrochloric acid. Its ucetyl derivative C,H,0,N3 + H20 m.p. about 9 9 O and triacetyl derivative C,H,O,N m. p. 55-57O were prepared. The m ono-am m onium salt of oximinocyanoacet o hydroxaniic acid C3H,0,N3,XH3 forms yellow needles m. p. 1 1 5 O (violent decomp.). The diamnzomum salt C3H,03N3,2NH wrongly described by Schol- vien (Zoc. cit.) as the diammonium salt of metafulminuric acid forms microscopic crystals ni. p. 1 2 5 O (decomp.). The corresponding amphi-antidine (vide supra) C3H603N4 obtained when an aqueous solution of either ammonium salt is left in an open vessel and described by Scholvien (LOC. c2t.) as the ammonium salt of metaful- minuric acid forms white crystals and begins to contract and turn brown a t about 170° becoming completely charred a t 1 8 5 O ; the nitrate m. p.119-120° and the sulphate m. p. 1 5 3 O (decomp.) were prepared. When converted into salts by treatment with mineral acids the stable amphi-amidine is transformed into salts of the labile yellow symmodification which undergoes spontaneous change into the amphi-form when suspended in water. The isomeric anti-amidinc. obtained on gradual evaporation of a solution of the diaminonium salt of oximinocyanoacetohydroxamic acid in concen- trated ammonia solution forms intensely yellow slender needles ; its nitrate m. p. 120° and szdphate m. p. 145' (decomp.) were prepared. The action of sodium nitrate on salts of the above anti-amidine NH,*C:NH NH;C:NH &N,OT-I I I UO,H CO H (1.1 (11.) ferric chloride and an intense blue yields the amidine of anti- oximinocyanoacetic acid (an- nexed formula I) which forms microscopic needles charring a t above 200° and gives a faint Marsala-yellow coloration with coloration with ferrous sulphat'e and a trace of potassium hydroxide or ammonia solution.The action of sodium nitrite on salts of the syn-amidine of oximinocyano- acettohydroxamic acid yields the amidine (I) just described and also t h a t of sy iz-oximinocyanoacetic acid (annexed formula II) which forms microscopic needles carbonising a t about 300° and gives a Marsala coloration with ferric chloride and an intense blue colora- tion with ferrous sulphate mixed with either sodium acetate or potassium hydroxide o r ammonia solution ; the formation of the two isomeric amidines in this case is due to the spontaneous transf'orma- tion in solution of the labile yellow Syn-amidine of oxim'nocyano- ncetohydroxamic acid into the stable white amphi-isomerlde.By prolonged heating on the water-bath with dilute hydrochloric acid the amidine of mati-oximinocyanoacetic acid is transformed into thei. 256 ABSTRACTS OF CHEMICAL PAPERS. isomeric syn-compound. Reasons are given for regarding these two pairs of amidines as stereoisomerides and not structural isomerides (compare Wieland and Hess Zoc. cat.). I n presence of 1 equivalent of sodium ethoxide metafulminuric acid gives sis0 successively to the following monosodium salts of oxiainocyanoacetohydroxamic acid yellow C3H203N3Na red (+ l&H,O) and black (+ 1$H20) these corresponding respectively with the following modifications of the hydroxamic acid white crystalline ; orange insoluble ; and green which could not be eepa- rated from eolution. The action of two equivalents of sodium ethoxidel on either metafulminuric o r oximinocyanoacetohydroxamic acid yields die amorphous yellow disodium salt of the latter acid C31€03N,Na + 3H,O then the bright yelIow disodium salt of the isomeric orange acid (+2H,O) and finally the disodium salt of isofulminuric acid.T. H. P. Some PointrJ Connected with the Representation of the Benzene Formula. GERVAISE LE BAS (Chem. News 1916 113 73-74).-The formula for benzene suggested in a previous paper (ibid. 1914 110 37) may be combined with the centric formula t o yield a combination formula which is said t o include the Kekul6 formula.On the assumption of vibrating valencies and directive forces f o r positive and negative valencies i t is found that the centric formula may be regarded as a transition phase with the two alternative Kekul6 formulE as the limiting phases. H. M. D. Preparation of 1 4-Dichloronaphthalene. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 286489; from J . SOC. Chem. Znd. 1916 35 107).-Dichloronaphthalenes of which the 1 4-iso- meridel is the main product are exclusively formed by the action *of the calculated quantit'y of sulphuryl chloride on naphthalene a t telmperatures above looo. They are used as intermediate products for the production of dyes. G. F. M. Polymorphism in Halogen-substituted Anilides.FREDERICK DANIEL C'HATTAWAY and GEORGE ROGER CLEMO (T. 1916 109 59-105. Compare this vol. i 140).-some 2 4-dihalogenoacet- anilides and -nitrobenzanilides have been obtained in two crystal- line forms and a large number of other derivatives of halogeno- anilines have been prepared. 2 4-Dibrommniline is conveniently obtained by heating aceto- pbromoanilidel with bromine in t'he presence of glacial acetic acid and sodium acetate followed by hydrolysis. 2-Chloro-4-brompaniline is obtained by the action of chlorine on aceto-p-bromoanilide and 4-chloro-2-bromoaniline by heating aceto-pchloroanilide with brominel the products being subsequently hydrolysed. Aceto-2-chloro-4-bromoanilide and aceto-4-chIoro-2-bromoanilide crystallise from well-boiled solutions in glacial acetic acid on cooling slowlv in tufts of slender needles which sooner o r later give place t o compactl crystals.n-Rz1t,~ro-2-cAZor0-4-bromonnilide C,H,ClBr*NH*CO*C,H formsORGA4NIC CHEMISTRY. i. 257 long colourless needles m. p. l l O o extinction 21° and the -4-chloro- 2-bromomilide has m. p. 111*5O extinction 3 1 O . Phenylaceto-2- c hloro-4- b ro m oa n ilid e C,H,ClBr NH*CO*CH,Pli f oms colourless needles m. p. 150° extinction * variable; the -4-chloro-2-bromo- n d i d e has m. p. 148O; the -2:4-dibromoanilide has m. p. 160O. o-Nilro b eii zo-2-chloro-4-6 romoa 12 ilide C6H3C1Br*NH-CO-C,H4~-NO forms colourless needles m. p. 165O extinction 25O; the -2:4-di- bromoanilide crystallises in pale yellow plates m. p. 178O extinction 24O ; the -4-chloro-2-bromoanilide forms colourless plates m.p. 166O extinction 1 8 O ; the -2 4-dichloroanilide has m. p. 153*53. m-Nitro- benao-2-chloro-4-bromoa?ailide separates in long needles m. p. 191O ; the -2 4-dibromoanilide has m. p. 165O extinction variable; the -4-chloro-2-bromoanilide forms flattened platea m. p. 167*5O which show a small positive biaxial figure' in convergent light; the -2 4-di- chloroanilide has m. p. 183O extinction straight. p-Ndtrobenzo-2- chloro-4-bromoanilide separates when a concentrated alcoholic solu- tion is rapidly cooled as a felt-like mass of almost colourless fila- ments but these soon give place to pale yellow hexagonal plates m. p. 199O extinction straight; the -2 :4-dibromoanilide m. p. 194O crystallises in very similar forms; the -4-chdoro-2-bromoanilide sepa- rates in very slender needles with straight extinction which change slowly into pale yellow stout six-sided rhombic plates with diagonal extinction m.p. 174O ; the -2 4-dichloroanilide forms very slender needles which change in the course of a few weeks into st'out six-sided prisms with domed ends m. p. 174O. The 2 4-dihalogenoanilines were also condensed with phthalic anhydride at 1 8 0 O . Phthalo-2-chloro-4-bromoanil c,H,<~~>Fc,H,c~ R ~ m. p. 165O the -4-chloro-2-bromoanil m. p. 140° the -2 4-dichloro- mil m. p . 155O and the -2 :4-dibromoanil m. p. 153*5O all crystal- lise in colourless prisms with straight extinction. The anilines were also treated with methyl o r ethyl chloroformate in pyridine and ether.Methyl 2-ch loro-4-hromocar6ana'late C,H,ClBr-NH~CO,nTe forms colourless ne'edles m. p. 76*5O extinc- tion 42O; the ethyl ester has m. p. 96O extinction 38O. Methyl and ethyl 2 4-dibromocarbanilates had already been obtained by less suitable means (Fromm and Heyder A. 1909 i 911). Methyl 4-chloro-2-bromocnrbanilate has m. p. 87.5O and the ethyl ester m. p. 90°. Methyl 2 4-dichlorocarbnnilate crystallises in needles m. p. 70-5O and the ethgl ester has rn. p. 89O. s-Ris-dihalogenophenylcarbamides were obtained by heating the anilines with an excess of carbamide a t 180° for forty hours. s-2 2/-nichloro-4 4r-dihromodinheng~carbamide CO (NH*C,R,Cl B r ) I! separates from nitrobenzene in hair-like needles with oblique extinc- tion m. p. 279O whilst the very similar s4 4'-dichloro-2 2ldihromo- diphr:n?yZcarbamide has m.p. 2 7 4 O and extinction 40°. The anilines were also heated with an excess of ethyl oxalate a t 220° when the oxanilah and small quantities of the oxanilidesi. 258 ABSTRACTS OF CHEMICAL PAPERS were formed. were prepared from the esters. forms colourless needles m. p. 124O; the free acid C,H,ClBr*NH*CO*CO,H has m. p. 131O (decomp.) ; s-2 2/-dichloro-4 4/-dibromo-oxanilide crystallises from nitrobenzene in colourless needles m. p. 285O ; 2-chloro-4-bromo-oxanilarnide C,H3C1Br*NH*CO*CO*NH2 has m. p. 243O. Ethyl 4-chloro-2-bromo-oxanilate has m. p. 1 2 1 O ; the acid crystallises from benzene in colourleas needles m. p. 126-127O (decomp.) o r from water with 1H20; the oxanilide has m.p. 2 9 5 O ; the oxanilamide has m. p. 2 3 6 O . Ethyl 2 :4-di- bromo-oxanilate forms curved hair-like crystals m. p. 130° ; the acid crystallises from benzene in needles m. p. 138O (decomp.) and from water with 1H20 ; 2 4 2/ 4~-tetrabromo-oxanilide has m. p. 298O straight extlinction; and the oxanilamide has m. p. 250O. Similar compounds were obtained from ethyl malonate (compare T. 1910 97 339). 2 2/-Diehloro-4 4fdibromomalonanilide CH2(CO*NH*C,H,C1Br) forms colourless needles with straight extinct'icn m. p. 214O. Ethyl 2-chloro4-bromomalonanilate C,H3ClBr-NH~C'O*CH2*C02E~ crystallises in colourless prismatic plates with straight extinction m. p. 81.5O; the free acid forms long slender prisms which melt and change into aceto-2-chloro-4- bromoanilide a t 1 6 5 O ; the amide C6.H3C1Br*NH*CO*CH2*C0.NH has m.p. 149O. 4 41-Dich10ro-2 2~-dabromomaEonanilide crystallises in colourless prisms m. p. 221° straight extinction. Ethyl 4-chloro- 2-bromcmalonanilate separates from alcohol in prismatic plates m. p. 8 3 . 5 O ; the acid forms long prisms m. p. 1 6 1 O (changing into aceto-4-chloro-2-bromoanilide ; the amide crystallises in long slender needles m. p. 159O. 2 4-Dibromomalo~~anilamide forms slender needles m. p. 1 6 4 O . Various sulphonanilides were obtained by adding an ethereal solution of the sulphonyl chloride to a solution of the aniline and pyridine in ether and these1 were converted into N-chlorides by means of hypochlorous acid. Benzenesulphon-2-chloro-4-bromo- anilide C,H,ClBr*NB*SO,Ph forms striated colourless flat prisms with straight extinctiosn m.p. 122O and benzeneaulphon-2-chloro- 4-bromophenyZchZoroumide C,H3C1Br*NC1*S0,Ph crystallises in stout prisms m. ?. 111-1 120. Benzenesulphow,-4-chloro-2-bromo- anilide crystallises in flat prisms terminated by domes with straight extinction m. p. 1 2 8 O and the -phevyZchloroumide forms stout prisms m. p. 123O. p-Toluenes~ilphon-2-rhZoro-~-bromoan~l~de C,H3C1Br*NH*SO2*CAHqMe forms colowless pIates m. p. 12l0 and the -phenylchZoroamide separates from chloroform in stout prisms m. p. 780. p-~luenefiulphon-2 4dihrornonnilidP crystallises in plates with straight extinctions m. p. 1 3 4 O and the -phenylchloro- nmide in stout prisms m. p. 7 8 O . p-Tolucnesiclphon-4-chloro-2- brromoanilide forms plates m. p. 126*5O and the -pli Pndchloronmida stout prisms.m. p. 7 7 O . p-Nitrotolircize-o-.czllp~t oiz-2-cAloro-4-hro:z~- n I? ilide C,H,ClBr*NH*SO,*C,H,Me*NO crvstallises in very pale yellow obliqixeily terminated prisms extinction 25O rn. p. 164.Fj0 The corresponding oxanilic acids and oxanilamides Ethyl 2-chEoro-4-b~omo-oxan~late C,,I-I,02N,C12Br,,i. 259 ORGANIC OHEMlSTRYb and the -phenylchloroamide in prisms m p. 123-124O. p-Nitro- toluene-o-sulpho~4-chloro-2-bromoanilide forms very pale yellow flattened prisms istraight extinction m. p. 165O and the -phenyl- chl6roclmi.de colourlees prisms m. p 122O. p-nitro toluene-clsdphor- 2 4dibromoanilide crystallism in flat prisms with straight extinc- tion m. p. 173O and the -phenylchZoroamide in colourless prisms m. p. 124-125O.Am-dyes with B-naphthol were found to be characteristic deriv- ativea of the several anilines. 2-Chloro-4-bromo b enzeneazo-S-nu& thol C6H3C1Br*N,*C,,H6*OH crystallises in plates m. p. 210° which have- a beetlegreen colour by reflected light and a red colour by transmitted light. 4-Chloro-2-bromobenzeneazo-~~phthol forms brilliant sharply pleochroic red plates with straight extinction m. p. 193O. 2 4-Dibromobenzeneazo-/3-naphthol (compare Hantzsch and Schmiedel A. 1897 i 185) forms flat brick-red prisms m. p. 203O with straight extinction. J. C. W. Imino-acids. G . L. STADNIKOV (J. Russ. Phys. Chem. SOC. 1915 47 1792-1796).-The author replies to Schlezinger’s criticiams (A. 1915 i 959) of his views concerning the increasing instability of imineacids with increw of the molecular weight.Against Schlezinger’s conclusions the following facts are cited (1) the nitrilu-ester of iminophenyldiaaetic acid does not decompose a t the imino-group when boiled with 20% hydrochloric acid and thus resembles nitrile9 of the lower aliphatic imino-acids; (2) under the same conditions the nitrilo-ester of phenylmethyliminodiacetic acid partly decomposes a t the imino-group and thus occupiesi an inter- mediate position ; and (3) the nitrilo-ester of cycloheptaneimino- propionic add is readily resolved a t the imino-group by 20% hydro- chloric acid. Schlezinger’s views are also inapplicable to the case of the aliphatic imino-acid obtained by Erlenmeyer and Sigel (A. 1874 981) from heptaldehydeammonia the nitrile of this acid being aW0mp-d a t the imino-group by 20% hydrochloric acid.These and other observations are regarded as confirmation of the view that the stability of derivatives of imino-acids diminishes as the molecular weight increases although the author does not deny the influence exerted by acidifying groups in organic compounds in general and in imino-acids in pasticular. Various instances are quoted to show that the =me rule holds for the imino-acids them- selves. T. H. P. Reaction of Esters with Organo-magnesium Compounds. 11. G. L. STADNIKOV (J. Russ. Phys. Chern. Soc. 1915 47 2037-2044. Compare A. 1914 i 954).-Further complicati6ns are encountered in the interaction of esters and organo-magnesium .com- pounds when heavy radicles take part in the reaction (compare A. 1915 i 957 975). When a methyl or ethyl ester is used the iodo- magnwium sec.- or tert.-alkyloxide formed reacts with the un- changed initial ester giving an ester corresponding with the alcohol synthesised.In some cases this ester will react with magnesium iodide giving the iodide corresponding with thO alcohol synthesid.i. 260 ABSTRACTS OF CHEMICAL PAPERS. This iodide may then (1) react with the iodomagnesium alkyloxide of the alcohol synthesised giving the simple ether of such alcohol; (2) react with the iodomagnesium methoxidel (or ethoxideJ present forming a mixed ether of the synthesised alcohol; (3) react with magnesium alkyl iodide yielding a hydrocarbon (tri- or tetra-alkyl- met’hane). Two conditions absolutely necessary f o r the reaction to proceed in the above directions are a high temperature and the presence of a sufficient.proportion of the initial ester. The condi- tions employed were as follows t o the organo-magnesium compound cooled by means of tap-water the ester is added as far as possible atl one’ time and not in small portions; if the mixture begins t o boil the vessel is kept in water until the boiling is allayed and is then heated on a bath t o the boiling point of the ether f o r six to ten hours. Under conditions such as these magnesium phenyl bromide and methyl benzoate yield considerable’ proportions of triphenylmethyl methyl ether and triphenylcarbinol. With magnesium phenyl bromide and benzyl benzoate a relatively small yield of triphenylmethyl benzyl ether is obtained the reaction virtually stopping a t the first stage namely the formation of iodomagnesium tert.-alkyloxide.T. H. P. Reaction of Esters with Organo-magnes’um Compounds. 111. 0. L. STADNIKOV ( J . Rz~ss. Phys. Chem. SOC. 1915 47 21 15-2120. Compare preceding abstract).-In those cases where the tert.-alkyl bromide or iodide in presence! of haloidomagnesium alkyloxide gives an unsaturated hydrocarbon (A. 1914 i 954) the whole cycle of reactions between an ester and a magnesium alkyl haloid is expressed by the following equations (1) C’R,R-CO,Et + 2MgR’X = CH,R*CR,’*O*MgX + OEt-MgX ; (2) CH2R*C0,Et + CH,R*CR’,*O*MgX = OEtoMgX + CH2R*C0,*CR2’*CHvR ; (3) CHzR*COz.CR2’*CH2R + MgI = CH,R*CO,*MgI + CH2R*CR2’I ; (4) CH2R*CR’,I + CEtaMgX = Et-OH + MgXI + CR’,:CHR. The re- sults obtained under different conditions are as follows (a) If the ethyl ester acts on the magnesium alkyl haloid in the cold and the ester is added in drops and the mixture energetically shaken mean- while the tertiary alcohol is obtained.( b ) If the whole of the ester taken in excess is introduced a t once into1 the solution of the magnesium alkyl haloid and the reacting mixture is then heated a t the boiling point the ethylenic hydrocarbon corresponding with the tertiary alcohol is obtained. ( c ) I f the conditions are as under ( b ) but a benzyl est’er is used both the tertiary alcohol and the corresponding ethylenic hydrocarbon are1 obtained ; thus from benzyl acetate and magnesium phenyl bromide under these condi- tions diphenylmethylcarbinol and as.-diphenylethylene are formed.T. H. P. Combination of Hydrogen with Acetvlene Derivatives. VI. Hvdrogeaation of an Acetvlmic Alcohol. J. S. ZALHIND (J. Russ. Phys. Chem. SOC. 1915 47 2045-2050. Compare A. 1915 i 640).-Atl the ordinary temperature the hydrogenation ofORGANIC! CHEMISTRY. i. 261 6 - phenyl - B - methyl - A7 - butinen-P-ol OH*CMe,*CiCPh (compare Iocitsch A 1914 i 401) in anhydrous alcoholic solution and in presence of colloidal palladium proceeds uninterruptedly no arrest occurring when two atoms of hydrogen have been taken up pel molecule of the alcohol. ~ - I - ’ k e i a y l e t ~ ~ l d i r n e t ~ ~ l ~ ~ r ~ ~ t z o l CH,Ph*C€12*CMe2=OH obtained in the above reaction is a viscous liquid with a pleasant smell b. p. 144O/85 mm. D,“ 0.9778 Di”7 0.9626 9z;p7 1.50775.Its acetyl deriv- ative Cl3Hl&& is a colourless viscous liquid b. p. 131°/17 mm. D’j 0.9987 D 0.9831 n:’7 1.48820. T. H. P. Cholesterol and Coprasterol. 111. The Ozonides of Chole- sterol. IV. Action of Bromine on Gholesteryl Benzoate. CHARLES D O R ~ E and LIONEL ORANGE (T. 1916 109 46-55).-The application of ozone to the determination of ethylene linkings in cholesterol and its derivatives has given very different results in the hands of various workers. Many of the pitfalls have now been recognised. Not only is i t important when aiming a t a pure ozonide t o use pure ozone washed free from oxozone but chloro- form must be abandoned as a solvent and a weak ozone of only 1-2% concentration should be employed. The authors have there- fore treated cholesterol and the acid C27H4404 (Diels A.1903 i 819) with pure and (‘ crude” ozone in glacial acetic acid or acetone and have purified the products by frequent precipitation by light petroleum from ethereal soluticjns followed by exposure to a high vacuum for some days. They find that cholesterol combines with a maximum of six atoms of oxygen when treated with pure ozone whilst seven atoms are absorbed when “crude” ozone is used whereas the acid combines with 7 and 8 atoms respectively. The first st’age defined roughly as the point a t which the cholesterol dissolves as an ozonide suggests t8hel formation of an ozonide + 03 with washed ozone but the addition of 0 with the crude ozone. All the products were brittle solids m. p. 85-95O decomp. above looo which were dextrorotatory and gave resinous acids and neutral substances on decomposition.The authors believe that the second unsaturated linking which is involved in the reaction is not pre- existent but is developed by the breaking down of a bridged ring system. Cholesterol was also heated with sulphur for several hours a t 160-165O a t which point the element is supposed to exist as active S molecules analogous to ozone (Erdmann A. 1908 ii 830). A dark red brittle solid was isolated which is probably a (( mono- t IL io-ozo nide ,” C,,H,,0S3. Cholesteryl benzoate and nitrobenzostes behave towards bromine in a somewhat different manner from the other esters. I n cold carbon disulphide solution no reaction seems t o take1 place until a few minutes have elapsed but then substitution and also addition set in rapidly.Bromocholesteryl benzoate narrow six-sided prisms m. p. 140-142O (compare Obermuller A. 1891 299) and chole- steryl h f i t m a t e dibromide C38H5002Br large hexagonal tablets m. p. 168-16W were isolated in the case of the benzoate. Chole-i. 262 ABSTRACTS OF CHEMICAL PAPERS. steryl m-nitrobenzoate m. p. 137O (turbid clear at 170O) and the p-nitrobenzoate glistening plates m. p. 185O (tarbid clear a t 250°) show a characteristic play of colours violet green and red on cooling. Bromocholesteryl m-nitrob enzoate cr-.stallises in leaflets m. p. 149O. J. C. W. Mechanism of Perkin's Reaction. M. BAKUNIN and GI FISCEMAN (Gazzetta 1916 46 i 77-103).-The authors have made a number of experimenh with the object of elucidating the behaviour of the various types of compounds characterising Perkin's synthesis.Between sodium acetate and phenylacetic anhydride or between sodium phenylacetate and acetic anhydride a reversible reaction takes place 2CH2Ph*C0,Na -I- (CH,*CO),O Z 2CH3*C0,Na + (CM,Ph*CO),O such a reaction also occurring when the radicles of the anhydride and salt are identical. Acetic anhydride alone does not react with aldehydes except that with pnitrobenzaldehyde it yields a little pnitrocinnamic acid reaction in general being det'ermined by the presence of acetate. Phenylacetic anhydride is decidedly more reactive and with aldehydes forms unsaturated acids but the percentage yiellds of the latter are greatly increased by addition of sodium acetate or t o a less extent sodium phenylacetate.The sole purpose of increasing the1 yield is served by adding acetic anhydride which is a dehydrating agent capable of dissolving salts anhydrides and aldehydes and therefore of rendering possible the intimate contact otherwise unattainable. It is advantageous but not indis- pensable that one of the compounds taking part in the double decomposition should be an anhydride unsaturated acids being also obtained if the anhydride is replaced by an acid. The question of the formation of intermediate compounds in the reaction is discussed. T. H. P. Derivatives of Cinnamic Acid Syntheses of P-Phenyl- a-ethylcinnamic and P-Hydroxy-PP-diphenyl-a-etbylpropionic Acid. R. DE FAZI (Attz R. Accad. Lincez 1916 [v] 25 i 92-99). -&Hydro zy/3fl-&phenpl-a-e t hylprop.0 nic acid OH*CPh,*CHEt*CO,H obtained from the corresponding ethyl ester (A.1915 i 1063) forms slender white needles m. p. 179-180° and gives an emerald- green coloration with cold concentrated sulphusic acid which con- verts it into 3-phenyl-2-ethylindone. Ethyl P-phenyl-a-e thylcinnama te CPh,:CEt*CO,Et prepared by the action of pholsphoric oxide on ethyl fl-hydroxy-BB-diphenyl- a-ethylpropionate forms large shining colourless prisms m. p. 88-89O and gives an emerald-green coloration with cold concen- ttrated sulphuric acid which converts i t into 3-phenyl-2-ethylindone. The corresponding acid CPh,:CEt*C'O,H forms slender white needles m. p. 159-160° and behaves like its wter towards sulphuric acid.ORGANIC CHEMISTRY. i. .263 PP-Dzpheizyla-ethyEpropionic acid CHPh,*CHEt.CO,H obtained by reducing the preceding acid by means of sodium amalgam forms slender white needles m.p. 167-168O and gives no coloration in the cold with concentrated sulphuric acid. Ethyl /3-phenyl-a-met h ylcinnamat e CPh, CMw CO,Et prepared by the action of phosphoric oxide on ethyl P-hydroxy-Bjl-di- phenyl-a-methylpropionate forms shining colourless prisms m. p. 87-88O and gives in the cold an emerald-green coloration with concentrated sulphuric acid which converts it into 3-phenyl-2- methylindone. The corresponding acid was prepared by Rupe Stleiger and Fiedler (A. 1914 i 281). PP-Diphsnyl-a-methylpropior,ic acid CHPh,*CHMe*CO,H forms slender white needles m. p. 164-165O and gives no coloration with concentratd sulphuric acid.B. L. VANZETTI (Atti R. Accad. Lkncei 1915 Lv] 24 ii 533-536).-The electrolysis of phenylpropiolic acid has been investigated in order to ascertain whether the marked facility f o r decomposition shown by acety3ensdicarboxylic acid (A. 1915 i 494) evidently due to the presence of the triple linking is repeated in the simplest acetylenic acid of the aromatic series; 28% solutions of potassium phenyl- propiolate were electrolysed a t various temperatures and under various current densities. The products consist of hydrogen oxygen and increasing proportions of carbon dioxide a t temperatures above 50° but in no case was the formation of carbon monoxide observed. No acetylene was formed but minute proportions of unsaturated compounds were obtained a t tempmatures above 70°.During the first hours of the electrolysis a pronounced odour of acetophenone is notice<d probably as the rmult of a reaction analogous t o that occurring when phenylpropiolic acid is heated with water a t 120° CPhiC*CO,H + CPhiCH -+ Ph-COMe. Notwithstanding the presence of the triple linking phenyl- propiolic acid presents theref ore considerable stability towards electrolysis and khus bears a marked resemblance to benzoic acid with which it has many other properties in common. T. H. P. Electrolysis of Organic Acids Paenylpropiolic Acid. T. H. P. Bilvmuth Acetylsalicylate [o-Acetoxybenaoate]. L. VANINO and FR. MUSSGNUG (Arch. Pharm. 1916 253 511-512).-Bis- muth 0-acetoxybnzoate is precipitated when a concentrated aqueous solution of bismuth nitrate (16 grams) and mannitol (6 grams). is added to a solution of sodium o-acetoxybenzoate (20 grams).Its physiological action is not different from that of known o-acetoxy- b enzoates. c. s. Saponification of Beneoylated Cyanohydrins by Acetic Acid in Presence of Metallic Salts. J. ALOE' and CH. RARAUT (BulZ. SOC. chim. 1916 [iv] 19 44-46).-The benzoylated cyanohydrins of the aldehydes and ketones already described (compare A. 1913 i 620 728) can be readily hydrolysed by gently boiling 4 grams of the cyanohydrin with 25 C.C. of acetic acid (4 vols. of the glaeiali. 264 ABSTRACTS OF CHEMLCAL PAPERS. acid to 1 vol. of water) and 1 grain of ziiic oxide for two liours an\l then pouring the liquid into water when the corresponding amide separates and can be purified by crystallisatdon.I n place of the oxide the metal or its acetate can be used and the amount of oxide used can be reduced if the duration of boiling is lengthened. The oxide’ of zinc can be replaced by the oxides of mercury silver nickel cobalt and copper but hydrolysis does not occur in the presence of the oxides of lead cadmium aluminium iron chromium thorium o r of the alkali or alkaline-earth metals. Manganese oxide exerts a slight favourable action. The sulphates of zinc and copper also give good yields but cobalt chloride is without action. The benzoylated cyanohydrin from anisaldehyde yields the amide O&le*C,H4*CH(OBz)*CO*NH2 m. I). 155O. W. G. Preparation of Hydroxytriphenylmethanscarboxylic Acide. FARBENFABRIK VORM. F. BAYER & Co. (D.R.-P.286744; from J . SOC. Chern. I72d. 1916 35 107).-Carboxyl groups are introduced into hydroxytriphenylmethanes by the action of carbon dioxide in the usual manner. The products such as 2-chloro-4/ 4//-dihydroxy- 3/ 3’/-dimetlhyltriphenylmethane-5/ 5N-dicarboxylic acid and 4’ 4//- bisdimethylamino-3-hydroxytriphenylmethane~4-carboxylic acid are used in the preparation of dyes. G. F. M. Lichens and their Characteristic Constituents. XIII. 0. HESSE ( J . pr. Chem. 1915 [ii] 92 425-466. Compare A. 1911 i 208).-The inactive erythritol which has been noted in many Bocellas has recently received the correct designation (‘ meso- erythritol.” The author suggests that the old name should be retained however and that the d- and 1- and dl-isomerides should receive the systematic name tetritol.” The occurrence of erythritol or erythrin has been noted in two algze Yrotococcus vulgaris and Chroolepus (Trentepohlia) Jolithus and also in the fungus Ustilago Maidis so that their production in nature is not peculiar to lichens.14sp-cdia calcarea (L.) Xbr. (var. farinosa) collected in the rock gardens a t Besigheim (Wurtt.) contained 0.11% erythrin and 0.23% erythritol. Bvernia pv-ibiaastri (L.) contains atranorin and everiiic acid when grown on birch limes beech or sand-stone but usnic acid in addition when found on oak. The following derivatives of evernic acid are described potassium sodium barium calcium copper lead and silver salts and diacetyl derivative C,,H,,O,Ac a crystal- line powder m. p. 144O. The evernic acid from this lichen has also been converted into everninic acid and this has been identified with the acid synthesised by Fischer and Hoesch (A 1912 i 860). The following derivatives of everninic acid have been prepared acetyleverninic acid C,H,O,Ac colourless short prisms m.p. 111’ ; nitroeverniizic acid small orange-red needles m. p. 1 9 5 O ; dinitro- everninic acid C,H,04(N02),,H,0 golden-yellow needles m. p. 87’ (potassium salt very explosive yellow needles). A well-developed form of Euernk furfuracea (L.) (var. isidio- phora) was said by Zopf (1903) to contain “isidic acid.” Some ofORGANIC CHEMISTRY. i. 265 this lichen has beea collected from birches and found t o contain atranorin evernuric acid and physodylic acid which agreed with Zopf’s description of (‘ isidic acid.” It is again found that Parmelia caperata (L.) when growing on limes rocks o r walls contains d-usnic capraric and caperatic acids whilst specimens collected from oaks contained caperin and caperidin in addition.Soloriiza crocea (L.) .4 ch. collected in the Engadine district has been extracted in the usual way with ether and then acetone and solorinic and soloric acids and hydrosolorinol isolated from the former extract and mannitol (1%) from the latter. Zopf (A. 1909 i 238) found solorinic acid and mannitol and a trace of solorinin,” which the author thinks might. have contained soloric acid. Solorinic acid C,,H,,O,*OMe forms microscopic red leaflets and yields an acetyl derivative C,,H,,O,Ac (;bid.) and a be71 zoyl derivative C,,HBIOsBz yellowish-brown needles m.p. 153O. The yellowish-red solutions of the acid in acetic acid become pale on treatment with zinc dust and solorinol C,,H,,O may then be isolated as a brownish-yellow crystalline powder m. p. 162O. When boiled with hydriodic acid i t not only loses methoxyl but is degraded to a much simpler compound soloro! C,,H,,O which forms yellowish- brown microscopic leaflets m. p. 216O. This substance yields a hepta-acetate yellowish-brown needles m. p. 215O which may be cxidised by chromic acid t o “ hexa-acetylsoloron,” C H 0 Ace well- developed yellowish-brown needles m. p. 197;; (‘Soloron,” C,5H12089 forms scarlet needles m. p. 280° like rhodocladonic acid. fIydrosolori~zol C,,H,,O occurs especially in the apothecia of the lichen and i t is best to pick these off separately in order to isolate the compound.It forms a dark violet almost black crystalline powder. Soloric acid C36H3C,0,4 crystallisees in colourless soft needles m. p. 205O yields methyl betorcinolcarboxylate on methyla- tion (A. 1898 i 534) and is a homologue of gyrophoric acid. Clndoizin rnncileiztn (Ehrh .) Hoff m. contains coccellic acid (0.4%) and thamnolic acid (O-l?!,) in the podetia and rhodocladonic acid in the apotliecia. The latter acid may be reduced by adding zinc dust to a hot solution in glacial acetic acid the product being hydrorhodoclndonic acid C,,H,,Os a bluish-black crystalline powder . Cladonin tentcis FlowFe contains fumarprotocetraric acid and d-usnic acid m. p. 196O [a];+494*l0. Clndonin fimbrintn ( L . ) var. cor?iuto-mdintn was said by Zopf t o contain fumarprotocetraric acid but’ this cannot be confirmed.It probably contains nemoxynic acid which Zopf first found in (7. nemoxyna (Chem. Zentr. 1908 ii 2183). Cladonia crisputa ( A ch.) var. qracilesceizs (Rnbenhorst) is found t o contain squamatic acid (Zopf A. 1907 i 219) and cYadonin C3nH4805 a white granular powder m. p. 228O. Cladonia coiidensnta (Flowke) Zopf contains I-usnic acid (0*5%) [a) - 494*3O and cornic7,Ynrin C,,H,,O which forms microscopic granules m. p. 229-230°. Pycnothelia pp7lrrria (nu f o u r ) var. molariforrnis (Hoffm.)i. 266 ABSTRACTS OF CHEMICAL PAPERS. [Cladonia papdlaria (Ehrh.) var. molariformis (Hoffm.)] is found to contain ahranorin (0*04%) cladonin and proto-a-lichestearic acid satin-like leaflets m. p.113-114° [u] + 2 2 . 3 O (alcohol) 23*9O (chloroform). CorsLicularia aculeata var. stuppea Fw. has been examined again (loc. cit.). The constituent cornicularin C28H4405 when . pure does not give a colour with ferric chloride as was first supposed. The sweet substancel C12H26011 previously reported in Corni- cularia aculeata var. acanthella A ch. has crystallised in the course of time and is recognised as dimannitol. It forms long colourless needles. Pertusaria ocellata uariolosa Fw. contains atranorin and gyro- phoric acid which according t o an ebullioscopic determination of the molecular weight has tlhel formula C,,H,80,4. J. C. W. Preparation of o-Aldehydophenylglycine. W. GLUUD (D.R.-P. 286761; from J . Soc. Chem. Znd. 1916 35 106).-o-Aldehydo- phenylglycine may be obtained as the bisulphite compound by decom- posing the corresponding oxime with sulphurous acid or its salts.The method is also applicable1 t o derivatives of the oxime in which the carboxyl oximino- o r imino-group is substituted. G. F. M. Preparation of Condensation Products of o-Aldehydophenyl- glycine Oxime and its Derivatives Substituted in the Carboxyl Group. W. GLUUD (U.R.-P. 286762; from J. SOC. Chena. Ind. 1916 35 106).-The oxime u s its derivative is treated for a short time a t a high temperature with an aldehyde under such conditions that the oximino-group is not removed. Thus with formaldehyde the reaction is apparently as follows NiiOH O>CH2 -+ <CH:N*OH HCHO CH:N-- 6 4 NH*CH,*CO*NH -+ ' 6 ~ 4 ' ~ (CH,* co* NH2) CHX--- 0 C,H,<N(CH,*CO,H)>CHt.The products are intended f o r dyes medicinal preparations and starting materials for the preparation of indoles. G. F. M. Additive Molecular Compounds in Organic Ghemiatry. MICHELE GIUA (Atti R. Accad. Lincei 1916 [v] 25 i 99-105).- The author discusses briefly the relations of complex inorganic compounds intermetallic compounds and organic additive mole- cular compounds t o the theory of valency. Cryoscopic investiga- tion of the system 2 4 6-trinitrotoluene-paminophenyl methyl ketone indicates the formation of the compound C6H,Me(N02)3,NH2*C6H~*COMe which forms shining red prisms m. p. 94O and gives a garnebred coloration with acetone and ammonia. The eutactic betweenORGANIC CHEMISTRY. i. 267 trinitrotoluene and this compound melts a t 73O and that between the compound and the' amino-ketone a t 85O.Picric acid and p-aminophenyl methyl ketone form the compound which forms yellow ne,edles m. p. 130-131O. C,H (NO,),*OH,C,H,ON T. H. P. 3-Allylmenthanol 3-Allyl-A3-menthene and 1 -Methyl-3-allyl- A3-cyclohexene. M. ZA~JCEV ( J . Russ. Phys. Chenc. SOC. 191 5 47 2127-2129. Compare A. 1913 i 1370).-When treated with allyl iodide and zinc (1) I-menthone [a] -27*46O obtained by the oxidation of menthol yields 3-aZlyZmenthnnol b. p. 125-129O/ 18 mm. D," 0.9058 [a] - 3*09O and (2) d-menthone [a] + 26*85O gives the same compound b. p. 121-124°/!4 mm. DY' 0.9061 [a] -2.88O. Saturation of these alcohols in the cold with hydrogen chloride gives the corresponding chlorides which are transparent liquids and distil undecomposed under diminished prelssure. Treat- ment of the chlorides with either silver carbonate or nickel carbonate yields 3-aZZyl-~3-menthe,zef b.p. 214-217O or 97-100°/17 mm. the two preparations having the properties (1) DY 0.8551 [aID +50*86O and (2) DYJ 0.8552 [a] + 45.06O; oxidation of the hydrocarbon by permanganate in neutral solution gives a polyhydric alcohol acetone and acetic iso- butyric and P-methyladipic acids. Oxidation of 3-allylmenthanol by means of potassium dichromate and sulphuric acid yields acetone and acetic isobutyric and P-methyladipic acids and that of 3-methyl-3-allylcyclohexano1 acetic and niethyladipic acids. l-~ethy~-3-a~Zyl-A3-c~cloh ~ X P ~ L P obtained by converting thel inac- tive 3-methyl-1-allylcyclohexanol into the corresponding chloride and treating the latter with silver carbonate is a liquid b.p. 171-173O I)? 0.8361 [a] +52*84O and yields a polyhydric alcohol and fl-methyladipic acid when oxidised by permanganah. I n the preparation of the above alcohols from ketones by means of zinc and allyl iodide the resultant product was decomposed by water and distilled in a current of steam the addition of sulphuric acid being avoided in order to preserve the stereochemical structure of the ketone from secondary influences. 'The results obtained which are t o be described more in detail later support Beckmann's view t h a t d- and I-menthones are not mirror-images. T. H. P. Reduction and Oxidation Processes in the Twpene Grout-. GUIDO CUSMANO ( A t t i R. Accnd. L i n c e i 1915 Lv1 24 ii 520-527).-It has been shown (A. 1914 i 303 556) that on direct brominatdon. menthone and tetrahydrocarvone yield respectively compounds (I) and (11) and that each of these gives buchu-camphori. 265 ABSTRACTS OF CHEMICAL PAPERS. (VI) when treated with dilute alkali hydroxide solution. suggested that tdiese changes take place according to the scheme It is The present work was carried out with the object of testing the accuracy of this interpretation especially as regards the conversion of the unsaturated alcohols (111) and (IV) into the saturated kettone (V). Attempts have been made t o eliminate halogens from halogenated terpenic ketones by the action of alkali and thus to obtain compounds containing a secondary carbinol group and a doublel linking in one and the same nucleus as in (111) and (IV).The first compound t o be employed is the tribromotetrahydro- carvone obtained by Wallach (A. 1895 i 621) from 1 :8-dibromo- tetrahydrocarvone and regarded as the 1 3 8-compound and con- sequently a derivative of compound 11. I n contact with 2.5% aqueous alkali hydroxide solution this compound reacts quantita- tively in the cold thus C,,H,,OBr f. 4NaOH r= C,,H,,O,Na + 3NaBr+ H,O. The product thus formed is the sodium salt of an aliphatic monocarboxylic acid containing a double linking and two hydroxyl groups and when treated in dilute acetic acid solution with lead peroxide yields carbon dioxide' and 3-methyl-Ae-hepten-P- one CMe,:CH*CH2*C€€,*COMe the latter being given in quanti- tative yield when the sodium salt is heated a t above 250O.I n aqueous solution and in presence of platinum-black this sodium salt absorbs two' atoms of hydrogen and the new salt thus formed furnishes (-methylheptan-fl-one quantitatively when heated. The conclusion is drawn that the acid C1,HI8O4 is an afl-dihydroxy- citronellic acid CMe2:CH*C'R2*CH,*CMe(0H)*CH(0H)~C0,H. The first step in the formation of this acid by the action of alkali on 1 3 8-tribroniotetrahydrocarvone is represented thus :ORGANIC CHEMISTRY. i. 269 The latter then either (1) undergoes hydrolysis between carbon atoms 3 and 4 giving the hydrated aldehyde Cnlle2:CH*CH,*C~,*CMe(OH)*~0.CH(OH)2 which changes into the dihydroxycitronellic acid by reciprocal reduction and oxidation of the carbonylic and aldehydic groups or (2) undergoes hydration and subsequent dehydration giving the tautomeric compound OH*CMe<'H('H)*Gu>I dH 2--LH2 :CM+*2 which then undergoes hydrolysis between carbon atoms 3 and 4.Scheme (2) is the more in accord with the mobility of terpene molecules. I n the preparation of tribromotetrahydrocarvone the latter is accompanied by a liquid which under the action of sodium hydr- oxide gives (1) the sodium salt C10Hli04Na (2) a compound C,,H1402 which forms shining white needles m. p. 76O has a phenolic odour and gives a violebblack coloration with aqueous ferric chloride. The sodium sodium hydrogen barium (+ 2H,O) and silver salts of dihydroxycitronellic acid were prepared and the sodium and silver salts of the acid C10H2,04 obtained on reduction. T. H.P. Bromocamphorsulphonic Acid and Oxonium Gompounde. D. MCINTOSH (Trans. Roy. Soc. Canada 1915 [iii] 9 (3) 85-86). -The author has unsuccessfully attempted t'o resolve the additive compounds of methyl ethyl ether with halogen hydracids into the corresponding dextro- and lzvo-stereoisomerides by the crystallisa- tion of a supersaturated ethereal solution a t low temperature. Bromocamphorsulphonic acid might be expected to produce more stable oxcnium compounds with alcohols and ethers than do the halogen hydracids but unfortunat'ely no indication of the forma- tion of oxonium compounds bet'ween this acid and alcohol or ether was observed. I n the opinion of the author the compounds formed by dimetliyl- pyrone with Iialggen acids are not oxonium salts but molecular compounds contzin71:ng acid of crystallisation and therefore do not contain asymmetric oxyge8n. Fenchone Derivatives.D. 3'. T. S. S. NAMETKIN ( J . Bziss. Pliys. C/icm. SOC. 1915 47 1590-1606).-Various authors have prepared saturated Eicyclic hydrocarbons Cl0Hl8 to which the name fenchane has been given their properties being as follows (1) b. p. 1G2.5-163*5°/751 mm. DY 0.8550 n 2 0 1.4560 [aID - 8O16' (Zelin- ski ,7. Russ. Phys. Chem. Soc. 1904 36 770); (2) b. p. 151.5'1 763 mni. D;O 0.8325 n 2 0 1.4463 [aIn -16.53O (Kishner and Prosk- urjakov A 1911 i 680); (3) b. p. 149O/750 mm. DT 0.8316 n 2 0 1.4462 [aID - 18.1O (Wolff and Nolte A. 1912 i 988) ; (4) b. p. 162-163O/737*8 mm. D20 0.8733 n17 1.4541 [a] - 19-83O (Ipatiev and Matov A. 1913 i 65). It. is evident that the name fenchane has been given t o a t least two different hydrocarbons and this name should bel retained only where the bicyclic system of the compound is identical with that of fenchone.Such may be assumed t o be the case with the hydrocarbons (2) and (3) which are obtainedi 270 ABSTRACTS OF CHENICAL PAPERS. from the ketone in conditions under which no rearrangement has yet been observed. I n the case of compounds (1) and (4) however their preparation is undoubtedly accompanied by isomerisation of the bicyclic system of fenchyl alcohol; that this is so follows from the analogous transformations of borneol from which Zelinski and Celikov (A. 1902 i 2) obtained “liquid camphene” instead of bornylene and Ipatiev and Matov (Zoc. cit.) isocamphane instead of camphane.Further proof of these relations is advanced in the present paper. Assuming Semmler’s formula for f enchone the corresponding saturated bicyclic hydrocarbon (annexed formula) should from analogy with similar cams (A. 1915 i 698 699 700 701) give only a secondary nitro-com- Cd1‘OMe2 pound when treated with dilute nitric acid in a sealed tube; no tertiary nitro-product should be formed since the only tertiary hydrogen at’om being united to replaced by a nitro-group under the condit’ions of Konovalov’s reaction. This is actually found t o be the case with the hydrocybon prepared from fenchone by Kishner’s method the neutral products of the nitration containing only secondary nitro- compounds and a ket’one. J u s t as was found with camphenilane (A.1915 i 699 701) the action of nitric acid on fenchane is directed simultaneously and independently towards both rings the products being nitro .compounds corresponding with the initial f enchone and with isof enchone respectively. Thesel two nitro-compounds have not been isolabed in the pure statei but the ketones prepared from them dfenclione and I-isofenchone have been investigated. I n this way is established the identity of the three bicyclic systems Kishner and Proskurjakov’s f enchane natural fenchone and Ber- tram and Ilelle’s isofenchone (A. 1900 i 398). The acid layer from the nitration of f enchane yields crystalline isof enchocamphoric acid ; Ihe formation of this acid which is 1 3 S-trimethylcyclo- pentanedicarboxylic acid from fenchane renders possible the simpli- fication of its name t o fenchocamphoric acid.The examination of Zelinski’s hydrocarbon is not yOtt complete but the’ results now obtained indicate the pesence of a bicyclic system quite different from that of fenchone. Th0 principal product of the nitration with dilute nitric acid is in this case a typical tertiary nitro-compound whilst the acid layer contains apocam- phoric acid (annexed formula I). From this i t is evident that Zelinski’s dihydrofenchene is 2 7 ‘I-trimethyl-[l 2 21-bicyclopen- tane and may be called shortly ‘‘ isobornylane ” (annexed formula CH a carbon atom common to both rings should not be 11) CH,-CH*CO,H CH,-CK-CKMe CH,~H-C ;M~-NO C H,* CH CO,H C H,-CH-C H CH,*CH-CH I I I CMe 1 I I (1. ) (11.) (111.) By analogy from the behaviour of isocamphane secondary pro-ORGANlC CHEMlSTRY.i. 371 msses combined with the formation of a hemicyclic double linking might be expected to accompany the formation of the tertiary nitro-compound (111). Since experiment does not confirm such expectation this coinplication of Konovalov's reaction cannot be regarded as general f o r saturated bicyclic hydrocarbons. By oxidising a mixture of fenchenes with permanganate Wallach obtained tKo a-hydroxy-acids in p. 152-153O and 138-139O. Further oxidatioq of the latter yields a fenchocamphorone m. p. 62-63O and treatment of this with nitric acid (D 1.25) appears to give only dimethylsuccinic acid. For the corresponding fenchene termed isofenchene Semmler (" Aetherische CJfe2*CH-CH2 Ole," 111 550) suggests the annexed formula I from which it follows that this second cam- I cH2 I I phorone should be identical with Hintikka and UH,-G€i-c;:CH Komppa's a-isocaniphenilone (A.1912 i 278) whereas actually these two ketones show marked differences in all their properties. If indeed this fenchocamphorone has the structure of 5 6-dimethyl-[l 2 2]-bicycZoheptan-2-one its oxidation should yield not dimethylsuccinic acid but npofencho- camphoric acid (A 1915 i 701). It i:. evident therefore that Wallach's second f enchocamphorone and the corresponding hemi- cyclic fenchene cannot have the structures assigned to them by Semmler and his school (compare Bartelt " Die Terpene und Cam- pherarten," 1908 95). Since further this felnchocamphorone is not identical with either of the two other known 5 5-dimethyl-[l 2 21- bicycloheptanones namely camphenilone and /3-isocamphenilone ( A 1915 i 701) the only possible structures for it and the corre- spondinc fenchene are the Lnnexedvones the assumption CMe2*CH-CH2 bping made that the 5 5-di- methyl - [l 2 21 - bicyclohep- CH,-&H-CH2 them.tanone grouping persists in I 1 O:CH I [With (MLLES.) V. S. MANU- ILOVA and T. I. MACEEVSKAJA.]-T~~ two nitro-derivatives C,,H,*NO obtained by the action of nitric acid (D 1'075) on Kishner and Proskurjakov's hydrocarbon have the properties (1) b. p. 84-85O/1'3 mm. D$ 1.0396 ?L 1.4759 [aID +15-5O (in alcohol); this consists of a mixture of a t least two isomeridw 2-nitrof enchane corresponding with f enchone and 6-nitrofenchane corresponding with isofenchone ; (2) b.p. 139*5-140°/40 mm. DF 1.0351 12;' 1.4742 [ a ] -12.48O; since oxidation with alkaline permanganate gives a ketone corresponding in properties with iso- f enchone and yielding fenchocamphoric acid on further oxidation this nitro-contpound represenk one of the stereoisomeric 6-nitro- fenchanes. The dibasic acid CJ31604 also formed in this action consists of a mixture of cis- and trans-feiichocamphoric acids the former pre- dominating (compare Sandelin A.; 1913 i 469) ; the cis-Z-acid was separated by means of its anhydride. The ketonic products consist of a mixture of d-fenchone and I-isofenchone.i. 272 ABS'PRACI'S OP CHKBIlCAL PAPERY. [Wit'h (B~LLE.) L. N. A B A K U M O V S K A J A ] . - ~ S O B ~ ~ ~ ~ ~ ~ ~ ~ was ob- tained as follows Fenchone was reduced by means of sodium in alcoholic solution t o fenchyl alcohol m.p. 45O [alp -11.18O (in alcohol) which when heated a t 265O with phthalic acid gave fenchene CiOHl6 b. p. 152-157O/750 min. D,"' 0.8616 n 1'4642 [a] -4*51°. Hydrogenation of the fenchene a t 165O by Sabatier and Senderens' method gave isobornylane CIOH18 b. p. 163*5-164*5O/753 mm. I):' 0.8579 nio 1.4590 l a ] - 12*36O with a faint odour recalling that of isocamphane. When heated with nitric acid (D 1.075) a t 130-135° isobornylane yields (1) the tertiary nitro-compound (formula 111 above) which is a colourless oil b. p. 113-11d0/ 1 2 mm. Di0 1.0575 nEo 1.4813 [a] - 26.720 (in alcohol). On reduction it gives the corresponding arnine C,,H,,*NH which is a colourless liquid b. p.199-199*5O/756 mm. DY 0.9171 ?a:' 1.4800 [a] -6'24O (in alcohol) with the character- istic odour of aliphatic amines and absorbs carbon dioxide with avidity ; its henzoyl derivative CioHi,*NHBz forms crystals m. p. 134-135O. (2) apocamphoric acid (wide supra). T. H. P. L. FRANCESCONI and E. SERNAGIOTTO (Gcuxetta 1916 46 i 119-127).-The essential oil of Buplez~rzcm fruticosum gives a nitrosochloride of almost constant specific rotation but in a yield which increases with diminution of the specific rotation of the fraction of the oil employed. Since a-phellandrene does not form a nitrosochloride under the same experimental conditions as the p-isomeride it seemed probable that the specific rotatdon of the latter has a value about equal to those given by Pesci (A.1886 1038) Wallach (A. 1904 i 1035) and Schimmel namely +14*45O t o +18*54O. and that a second terpene probably a-phellandrene is also present in considerable proportions in the more highly dextro- rotatory fractions of the oil. It is found however that the yield of nitrosite and also its specific rotation are constant with the different fractions of the essential oil. The conclusion is therefore drawn that the specific rotation of /3-phellandrene is atl least 65*02O which is the maximum observed value for the oil and that the fractions exhibiting lower activity are mixtures of the two optical antipodes with the dextrorotatory form always preponderating. This view is supported by the fact that identical products namely tetrahydrocuminaldehyde and P-isopropyladipic acid are obtained on oxidising two fractions of the oil with specific rotations of + 65O and + 19O respectively by means of permanganate under the conditions employed by Wallach (Zoc.cit.). The Essential Oil of Eucalyptus Smithii from Various Forms of Growth. HENRY G. SMITH (J. Roy. SOC. New South TVaZes 1915 49 158-168 with 14 plates).-As the time seems to be approaching when a choice will have to be made of the best species of eucalypts for cultivation attention is called to E. Smithii the lelaves of which produce one of the best cineol-pinene eucalyptus oils yet examineld. The tree is valueless for timber but is rernark- ably virile and seems t o flourish after repeated loppings. Indeed i t is best t o cultivate the "suckers " which rapidlv grow out of the /3-Phellandrene.T. H. P.ORGANIC CEEMISTRP. i. 273 stumps of the felled mature trees as these produce more leavee and are more easily harvested. The oil contains a very high percentage of cineole also pinene a phenol d-eudesmol m. p. 79O a paraffin m. p. 64O a small quantity of esters aiid of a sesquiterpene and a small amount of volatile aldehydes which soon disappear and change into agreeable sweet- briar-like perfumes. The oil is almost free from objectionable con- stituents and may be purified without distillation merely by shak- ing i t with very dilute sulphuric acid for some hours and then with anhydrous sodium carbonate. From an evaluation of oils obtained from varioas growths it may be accepted that the cultivated trees can be profitably cut a t three years old and then every two years.J. C. W. Gynocardia and Chaulmoogra Oils and Gynocardic and Chaulmoogric Acids. M. A. RAKUZIN and G. D. FLIER (J. Russ. Phys. Chem. SOC. 1915 47 1848-1851).-0stromisslenski and Bergman (A. 1915 i 646) refer to gynocardia oil and chaulmoogra oil as identical. These oils have indeed often been confused and investigation of products sold as gynocardia oil and gynocardic acid showed that these were actually chaulmoogra oil .and chaul- moogric acid respectively ; thO latter have the respective specific rotations + 51'8O and + 55*5O whereas the Gynocardia products are optically inactive. The healing properties in cases of leprosy probably belong to chaulmoogric and not t o gynocardic acid. T. H. P. New Syntheses of Caoutchouc and its Homologues.I. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1910-1915).-Much of the work published since 1911 on the poly- merisation of t#he diolefines is inaccurate and many of the patents are useless. I n the succeeding papers the author describes (1) pecu- liar processes of isomerisation of two different forms of isoprene caoutchouc and (2) methods for the catalytic polymerisation of diolefipes to both normal and abnormal caoutchoucs; these methods give nearly or quite quantitative yields. T. El. P. Synthesis of the s-Bromide of Erythrene Caoutchouc of the Caoutchouc itself and of Caouprene. I. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1915-1927).-Caouprene bromide is shown to be identical with the s-bromide of erythrene caoutchouc.Removal of hydrogen bromide from either caouprene bromide or the as-bro1rnid.e of erythrene caoutchouc yields dehydro- caouprene C32H48Br16.- 16HBr = C32H32 and a homologous com- pound C32H24Me8 is similarly obtained from the bromide of natural Para caoutchouc C3?H4,,Me8Br16. Cryoscopic determination of the molecular weight of the readily soluble modification of caouprene bromide (a) in ethylene bromide gives the value 1809 in agreement with the above formula. When forced through a capillary dipping into alcohol or glacial acetic acid the asymmetric bromide of erythrene caoutchouc or caouprene bromide in concentrated solution VOL. CX. i. 31i. 274 ABSTRACTS OF CHEMICAL PAPERS. is precipitated as a continuous white thread but this e'xhibits little strength and no silky lustre.Caouprene bromide is regarded as FHBr*[CH,*C€lBr],*QH having the structure CH,-[CHBr-CH2l7-CHBr ' Reduction of caouprene bromide by means of zinc dust yields erythrene caoutchouc and in greater or less proportion the isomeric eaouprene C32H48 which has one of the constitutions CH,:9-CH,-QH*CH2*~H. . . . *QH*CH,*QH CH,*CH,-CH*CH,*CH* . . . 'CH*CH,*C:CH,' or gMe*CH,*yH*CH,*yH* . . *YH*CH,*EH CH-CH,-CH*CH,*Cti- . . . *CH*CH,*CMe' Caouprene is transparent and forms either a viscous liquid or an amolrphous elastic mass; on dry distillation it yields carbon and hydrogen almost quantitatively and when heated a t 60-70° with benzoyl peroxide is converteld into normal erythrene caoutchouc. It was ozonised in chlorof orm solution but decomposition of the ozonidel by water gave no definite product; it's tetrabromide and dihydrochloride were prepared.The action of zinc dust on the asymmetric bromide of natural or synthetic caoutchouc in presence of alcohol gives the free caout- chouc C,,H,,Br + 8Zn = 8ZnBr2 t C32H48. This reaction has been used for the recovery of rubber irom the bromide of Para caout- chouc. T. H. P. Synthesis of Natural Caoutchouc by W a y of /3-Mgrcene. I. I. OSTROMISSLENSKI and F. F. KOSCHELEV ( J . Russ. Phys. Chem. SOC. 1915 47 1928-1931).-When cautiously heated a t 80-90° isoprenel yields an open-chain myrcene-like hydrocarbon C10HIG7 which contains three double linkings two of them in conjugated positions and is termed P-niyrcem. The latter is a colourless mobile liquid b. p. 63-63*5O/20 mm.58O/13 mm. Di0 0.8472 nz 1.53681. When heate'd a t 60-70° with barium peroxide and sodium /3-myrcene is converted quantitatively into normal isoprene caoutchouc whereas under similar conditions isoprene gives an abnormal caoutchouc. The most probable constitution of 6-myrcene is CH,:CH-CMe~:CH*CH,-CH,*CMe:CH,. Unsuccessful attempts were made to avoid the usel of isoprene and to prepare the hydro- carbon by dehydration of the corresponding alcohols of the terpene series. T. H. P. Structure of Caoutchoucs. 1. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1932-1936).-The bromide of natural caoutchouc being hom6logous with caouprene bromide has a uni- cyclic structure [-CH2*CH2*CMe~Br*CHBr.l and since under the action of zinc dust it is converted readily and quantitatively intoORGANIC CHEMISTRY.i. 275 the free caoutchouc the latter will also possess a unicyclic structure namely [*CH,*CH,*CMe:CH*]z (compare Pickles T. 1910 97 1085) ; the positions of the methyl groups and double linkings in this formula are established by the products of decomposition namely laevulinaldehyde and lzvulic acid. I n the case of normal isoprene caoutchouc prepared by direct heating of isoprene the grouping of the1 methyl radicles and ethylenic linkings must be different from t h a t given above since decomposition of the corresponding ozonide bx meam of water yields notl only lzvulinaldehyde and lzvulic acid but also succinic acid and acetonylacetone. M7illstatter has shown that multiple-membered unicyclic groupings of unsatur- ated hydrocarbons are readily transformed into polycyclic group- ings and Harries has proposed for natural caoutchouc a structure in which such isomerisation is assumed.That both free caoutchouc and also its halogenides and hydrohalogenides possess however uni- cyclic structures and are not polymerides of the corresponding cyclooctadiene is however shown by the following facts (1) Caout- chouc bromide and hydrobromide have! t'he respective compositions C?3,H40Me8Br and C,2H40Me8( HBr)8 and not C32H40Me8Br4 and C32H4,Me8(HBr)2. The action of halogens on caoutchouc is not accompanied by depolymerisation of the1 molecule since erythrene caoutchouc bromide has the molecular weight 1809 corresponding with the formula C32H48Br16 and readily regenerates the free caout- chouc when treated with zinc dust.(2) Dimethylcyclooctadiene tstrabromide described by Willst'atter is a crystalline compound with a sharp melting point and has no properties comparable with those of caoutchouc bromide. (3) Polymerisation of cyclooctadiene occurs with almost explosive readiness and yields crystalline and horny compounds but no trace of caoutchouc. On the other hand in no case does the depolymerisation of caoutchoucs or any of their other reactions give rise to cyclooctadiene derivatives. T. H. P. Polymerisation of Ethylenic Compounds and Mechanism of the Conversion of Vinyl Bromide into the Bromide of Erythrene Caoutchouc. I. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1937-1941).-Tlie conversion of unsaturated compounds into ring compounds is completely analogous t o the process of poly- merisation the molecule first undergoing decomposition into a hydrogen atom and a free radicle the affinities of which are imme- diately satisfied by the double linking of the same molecule. Thus the cyclisation of unsaturated compounds may be regarded as a process of intramolecular polymerisation.At the moment when the trimeride appears the polymerisation of vinyl bromide pro- ceeds in two directions (1) A small part of the trimeride undergoes intramolecular polymerisation with formation of the stable six- membered ring compound 1 3 5-tribromocgclohexane which is an oily liquid b. p. i54-158O/13 mm. and is converted into benzene when heated with quinoline. (2) The remainder of the trimeride unites with unchanged monomeride until a 32-mem- r n ?i.2'76 ABSTRACTS OF CEEMICAL PAPERS. bered chain of carbon atoms is formed this then undergoing cyclisation t o form the symmetrical bromide of erythrene caout- chouc. T. H. P. Mechanism of the Conversion of Isoprene into Caoutchouc and Conversion of P-Myrcene into Caoutchouc. I. I. OSTROMISS- LENSKI (J. BUSS. Phys. Chem. SOC. 1915 47 1941-1947).-The dis- copery by the author and Koschelev (this vol. i 274) of the forma- tion of P-myrcene in the process of conversion of isoprene into caout- chouc throws light on the mechanism of this process. I n the first place the hydrogen atom and the residual radicle from a molecule of isoprene combine a t the ethylene linking of a second molecule giving the dimeride 6-myroene.The latter is then converted into thO tsimeride and so on until the octameride is formed this then undergoing " intramolecular polymerisation " or cyclisation t o isoprene caoutchouc. As was shown by Steimmig (A. 1914 i 307) all the poljmerides of isoprene yet obtained differ from natural Para caoutchouc since the decomposition of their ozonides by water yields acetonylacetone and succinic acid in addition tn lzvulin- aldehyde and laevulic acid. Theoretically P-myrcene may like isoprene dissociate into a hydrogen atom and a radicle in different ways and experiment shows that under the action of barium peroxide and sodium pure P-myrcene is converted quantitatively into normal isoprene caoutchouc which has an elasticity point con- siderably below Oo and coincident with that of natural caoutchouc; on the other hand a mixture of 90% of isoprene with 10% of P-myrcene gives under the same conditions a quantitative yield of an isomeric abnormal caoutchouc the elasticity point of which is + l l O o .This polymerisation of chemically pure P-myrcene may possibly represent the only synthesis of natural caoutchouc that is of a substance perfectly identical with Para caoutchouc both in the general structure of its nucleus and also in the positions of the methyl groups and double linkings of the molecule. There is reason t o believe that tropical plants synthesise caout- chouc by means of P-myrcene o r myrcene-like hydrocarbons or their dimerides and not by the polymerisation of isoprene. Thus the sap of plants frequently contains compounds with an atom-grouping lik0 that of myrcene such as geraniol linalool nerol etc.and simple dehydration of these unsaturated alcohols would lead imme- diately t'o the corresponding myrcenes. A very close analogy exists between the polymerisation of isoprene and t h a t of vinyl bromide). Each gives cyclic compounds of two types onel 6-membered and the other 32-membered ; the former are dipentene and tribromocyclohexane respectively and the latter caoutchouc and the bromide of erythrene caoutchouc. T. H. P. Cold Vulcanisation of Caoutchouc by Means of Sulphur or Trinitrobenzene or Benzoyl Peroxide. I . I. OSTROMISSLENSKI (J. Rzcss. Phys. Chem. SOC. 1915 47 1885-1892).-It has been previ- ously shown (ibid. 1915 47 1441) that a mixt,ure of a primary or secondary aliphatic amine with a metallic oxide either acceleratesORGANIC CHEMISTRY.i. 277 the vulcanisation of natural and synthetic caoutchoucs or consider- ably lowers the temperature of vulcanisation. It is now found that in presence of such niixtures vulcanisation takes place a t the ordinary temperature this process being especially rapid with chemi- cally pure caoutchoucs such as normal erythrene o r normal isoprene caoutchouc obtained synthetically; with natural caoutchoucs the vulcanisation requires two t o six months. I n either case tho change is greatly accelerated by preliminary heating of the mixture a t 40-60° f o r ten to forty minutes vulcaiiisation then being com- pleted in ten to fortyeight hours. Since the volume changes either not a t all o r but negligibly a t the ordinary temperature the use of special metallic moulds is rendered unnecessary.Vulcanisation by means of 1 3 5-trinitrobenzene o r benzoyl peroxide also takes place a t the ordinary temperature no special catalyst being required. Oxides of zinc niagnesi-am and particularly lead accelerate the action when the nitro-compound is used but these1 oxides retard cold vulcanisation by benzoyl peroxide and diminish the value of the vulcanised product. T. H. P. Mechanism of the Action of Aminels and Metallic Oxides on the Vulcanisation of Caoutchouc. I. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1892-1898).-With a mixture of caoutchouc sulphur amine and metallic oxide the sulphur and the amine first react with formation of the corresponding thi- ozonide R*NH + 45 = NHR*S*S*S*NHR + H,S this reaction pro- ceeding onlv in presence of a catalyst such as an oxide.The unstable thiozonide then transmits its sulphur t o the caoutchouc the amine being regenerated o r the aminic residue under the influence of the oxide uniting with a fresh portion of sulphur t o give thiozonide. Thus the process is one of double catalysis the meltallic oxide catalyses the formation of the thiozonide of the amine which in its turn accelerates the formation of the caout- chouc thiozonide and so catalyses the1 vulcanisation. Only primary and secondary aniines give thiozonides and these are the only amines which catalyse the vulcanisation of caoutchouc. Thiozonides of aromatic amines which are formed according to the equations (1) 2NH,Ph + 4s =NHPh*S-S*S*NHPh + H,S and (2) NHPh*S*S*S*NHPh = NH,*~~H,*S*S*S*C',R4"R are relatively stable compoundP and should therefore be incapable of functioning as sulphur-carriers ; an explanation is thus afforded of the observation that aromatic amines have practically no catalys- in? action on the vulcanisation of caoutchouc.From Bernstein's observation that the ordinary vulcanisation of caoutchouc nroceeds at. the ordinarv temperature under the action of ultraviolet li&t (A. 1913 i 638 746) the conclusion is drawn that in absence of air thiq l i ~ h t activates sulnhnr by convertinq i t into thiozone S,; the vnlcanisation is then effected partly hv the 1att"er and partly by the ozone formed simultaneously. It is shown experi- mentally t h a t .thiozone is also formed when ordinary sulphur is dissolved in a primary or secondary aliphatic amine such as piper- idine with a side-chain and the solution either heated for twenty t oi.278 ABSTRACTS OF CHEMICAL PAPERS. fifty minutes with lead oxide in a reflux apparatus on a water-bath or left a t the room temperature. I f as Erdmann supposes (A. 1908 ii 830) sulphur dyes are either stable thiozonides or products of their decomposition condensation etc. the presence of a mixture of amine and oxide should lower the temperature of formation of these dyes aliiiost to the ordinary temperature or should accelerate their formation a t higher temperatures. Such a mixture should cheapen and simplify the1 production of some of these dyes and should lead to the isolation of a new series of ozonides unobtainable at the higher temperatures and with prolonged heating.T. H. P. Vulcanisation of Caoutchouc by Means of Halogenated Compounds. Mechanism of Vulcanisation. I. I. OSTROMISSLENSKI ( J . Buss. Phys. Chem. SOC. 1915 47 1898-1904).-1n the forma- tion of vulcanite-like substances by the action of bromine iodine or iodine bromide on caoutchouc the first phase of the change undoubtedly consists in the1 formation of the caoutchouc halogenide the1 unchanged caoutchouc then either adsorbing th’is new compound o r swelling into it. Itl is indeed found that this process may also be carried out by tseatment of the caoutchouc with its halogenide the latter acting when either freshly prepared or old. All three halogenides of either natural o r synthetic caoutchouc may be em- ployed.It is found further that caouprene chloride or bromide exerts a similar action in caoutchouc the products obtained from the chloride being especially valuable in view of their great stability and relatively low elastic point and of the fact that they are usually obtained in chemically pure condition. The amount of caoutchouc used need not exceed 7-10 parts per 100 parts of caouprene chloride the cost of the ebonite obtained being thus considerably reduced. Similar vulcanisation is effected by the action of the hydrochloride of natural caout.chouc but not by that of aluminium chloride. The products obtained by the above method have the black colour of ordinary ebonite are electrical non-conductors may be scratched with the nail keep well even in moist air and take a high polish.Vulcanisation of Caoutchouc by MoIecular Oxygen Ozone or Ozonides of Organic Compounds. I. I. OSTROMISSLENSKI ( J . Russ. Phys. Chem. SOC. 1915 47 1904-1909).-The action of ozone1 in vulcanising caoutchouc rests on the preliminary formation of the ozonide of the caoutchouc. The ready-formed ozonide has indeed an effect similar to that. of ozone both soft and horny resins being formed; the course of the process is debrmined most of all by the concentration of the vulcanising compound. When caoutchouc is exposed in an atmosphere of dry air to the ultraviolet rays of a quartz mercury lamp it undergoes gradual vulcanisation increasing in weight a t the expense of the oxygen; a t 40-80° this process takes place fairly rapidly but atl 120° no vulcanisation occurs.Vulcanisation of caoutchouc by means of its ozonide takes place under the same conditions as vulcanisation by benzoyl peroxide. T. H. P.ORGANIC CHEMISTRY. i. 279 I n pmsence of moisture chemically pure caoutchouc activates molecular oxygen and thus behaves like most of the terpenes. Thus moist isoprene (or erythrene) caoutchouc of the normal series when left in the air a t the ordinary temperature gradually becomes covered with a layer of new less elastic substance this process being analogous to the drying of vegetable oils. If normal erythrene caoutchouc coated in this way is passed between cold rolls t o render it as homogeneous as possible and then heated in the ordinary way in absence of air the unchanged caoutchouc undergoes vulcanisation ; if however this surface is first removed vulcanisa- tion does not take place.It is evident that this layer consisting of a product of the action of atmospheric oxygen on the caoutchouc constitutes the vulcanising substance. The vulcanisation of caoutchouc by its halogenides or ozonides is a purely physical process and is comparable with the formation of celluloid ; the latter process may indeed be regarded as vulcanisa- tion of cellulose esters by camphor etc. The large number of known vulcanising agents indicates that the chemical nature of these1 plays no determining part. All these agents form colloids with the caoutchouc and it is by these colloids that vulcanisation is effected. T. H. P. Preparation of Vulcanised Caoutchouc Goloured with Organic Pigmenta.I. I. OSTROMISSLENSKI (J. Russ. Phys. Chem. SOC. 1915 47 1993-1995).-Since organic pigments readily decompose a t a high temperature especially in presence of sulphur the author’s method of vulcanising at the ordinary temperature in presence of sulphur an amine and an oxide (this vol. i 277) is of especial value in the manufacture of caoutchouc articles coloured with such pigments. Some of the latter are not decomposed when heated edther at a comparatively low temperature or even at the temperature of ordinary vulcanisation provided that this is main- tained for only a short time; in such cases the author’s process permits of the acceleration of the vulcanisation o r of the lowering of the temperature employed.Experiments were made with eosin erythrosin alkali-blue and cinnamylidenefluorene. T. H. P. . The Theory of the Acid Dye-bath. M. FORT ( J . SOC. Dyers 1916 32 33-39).-1t has been frequently assumed that the dyeing of wool by acid dyes is dependent on the liberation of the colour acid by the action of sulphuric acid on the sodium or other salt of the colour acid. Evidence is adduced in support of the view that this displacement’ of the colour acid from its salts plays no essential part in the process of dyeing by means of such acid dyes. I n the author’s opinion the action of acids on wool results in the formatlion of salt-like compounds in which hydrolytic amino- products play the part of ths base. These salts which in the ordinary practice of the acid dyebath consist of sulphates react with the colour acid or its sodium salts in accordance with the equation wool base H,SO + colour acid wool base colour acid + H,SO ; or wool base H,SO + colour acid Na Z wool base colouri.280 ABSTRACTS OF CHEMICAL PAPERS. acid + Na,SO the reactions in both cases being reversible. Quau- titative experiments are described which are said to furnish evidence in support of this theory of acid dyeing. The fact that i t is much more difficult to dye cotton with acid dyes is well known but by mordanting cotton with benzidine so as to give i t a sufficiently pronounced basic character i t has been found possible to fix acid dyes on cotton with comparative ease. The attachment of the1 benzidiiie to the fibre is purely mechanical but by the use of tannin-mordanted cotton which readily takes up benzidine from a strong hot solution of the hydrochloride very much better results have been obtained.H. M. D. ColouriDg Matter of Cotton Flowers. 111. ARTHUR GEORGE PERKIN (T. 1916 109 145-154. Compare T. 1909 95 2181; 1913 103 650).-The author has examined the Egyptian and ordinary Indian yellow cotton flowers Gossyp*um 11 erbaceum in order t o ascertain whether they are chemically different and whether the red pink and colourless petals of other varieties have any outstanding chemical characteristics. It is found that the red flowers G. arboreurn Li?ati. contain isoquercitrin but no other flavone glucoside differing theref ore from the yellow flowers which also contain quercimeritrin and gossypitrin. The point has also been investigated whether the particular red pigment is an oxidation product of gossy-petin or its glucoside but the evidence obtained is inconclusive.The yellow flowers G. negZectum,efrom India and also the ordinary yellow Indian flowers G. herbaceum are found to contain gossypitrin and isoquercitrin but practically no quercimeritrin which is an important constituent of the Egyptian flowers. Gossy- pitrin exists in two forms; if boiled with acetone or alcohol it has m. p. 200-202° but after boiling with water i t has m. p. 239-242O. The acetyl derivative C,,H,,0,3Ac forms colourless needles m. p. The white flowers G. n,egZectzcm or rossriCm and the pink G. sanguineurn are practically devoid of tinctorial properties. Gossypitrin has been oxidised by alcoholic p-benzoquinone to the q uinone gossypitron e C,,H which forms maroon-coloured needles m.p. about 255-259O and dyes aluminium mordanted calico green shades and mordanted wool the saxe shades as gossy- pitrin. J. C. W. Mechaniem of the Formation of the Colouring Matter of Bile from the Ferruginous Components of the Colouring Matter of Blood. WILLIAM KUSTER (Arch. Phnrm. 192 6 253 457-497) -A historical survey of the chemistry of hzemin and of bilirubin. Although i t is almost a matter of certainty that bilirubin the colouring matter of bile is produced from thO hzematin of the blood the mechanism whereby the liver cells effect the change is still a myetery and can only be thoroughly understood when the constitutions of the two substances are known. With the informa- 226-228".ORGANIC CHEMISTRY.i. 281 tion a t preBent available however it is possible to trace paths along which the change may proceed. The author therefore discusses in some detail the investigations instituted since 1847 t o throw light on t'he constitution of hzemin. The importance of haematic acid hzmo- crypto- and phyllo-pyrroles and their carboxylic acids and other fragments of the haemin molecule is emphasised and the way is indicate'd whereby from the known constitutions of these substances a formula for haemin such as that of Piloty can be built up. Bilirubin and its fragments are treated in the same way and formulae for the colourless ( ?) orange and reddish-brown modi- fications of bilirubin are built up. A comparison of these formuke with t h a t of hzemin indicates that bilirubin may be produced from liaeemin by a fairly simple1 process of oxidation.A full list of references to the literature is given a t the end of Valency of the Elements. IV. G. POVARNIN ( J . Rzw. Phys. Chem. Soc. 1915 47 2073-2115).-The author criticises Fahrion's oxidation theory of tanning (Zeitsck. ccngew. Chjem. 1909 22 2083 2135 2187) and advances a theory based on the presence in all organic tanning materials of an active carbonyl group. the paper. c . s. T. H. P. A Synthesis of Flavones. BROJENDRA NATH GHOSH (T 1916 109 105-122. Compare A. 1915 i 831 832).-Instead of using the esters of acetoacetic acids in the condensations with phenols the nitriles have been employed. These react best with phenols con- taining methyl or hydroxyl substituents giving imines which can be1 hydrolysed to the flavones. Condensations with Acetylphenylncetonitri1e.-When mixed with resorcinol and concentrated sulphuric acid the nitrile gradually deposited 4-imino-7-h ydroxy-3-phenyl-2-me thyl- y-b enzopyra n [4-mnim- 7-hydrdxy - 3 - phenyl-2-methyl-y-benzopyrylitcm] szilphate (annexed formula) in short yellow HYO (3 needles m. D.246O. The free base. W 1 3 5 O and a ben * I C,,H,30,N,3H,O formed brown prisms m. p. 2 2 1 O (decomp.) and yielded a picrate orange-ye'llow needles m. p. 2 2 7 O a perchlorate yellow needles an acetyl derivative +H,O very pale yellow needles m. p. zoyl derivative +H,O colourless needlea m. p. 178-179O. The constitution of the imine was proved by boiling the sulphate with 10% sulphuric acid when 7-hydroxy-3-phenyl-2- methyl-y-benzopyrone (Zoc.c i t . ) was produced. The nitrile was also condeased with pyrogallol with the forma- tion of 4-imino - 7 8 - dihydroxy - 3 - phenyl-2-methyl-y-benzoppan C,H2(OH),<c(:NH).~ph in dark brown prisms with 4H20 m. p. 0- C N e 142O (decomp.) This yielded an acetyl derivative pale yellow needles m. p. 194* and was hydrolysed t o 7 8-dihydroxy-3-phenyl- 2-meth yl-y-benzopyrone. n*i. 282 ABSTRACTS OF CHEMICAL PAPERS. Condeiisation with a-naphthol gave rise to 4-amino-3-phe~~yl-2- niethyl-1 4-a-?zayh thupgrylizcm sulphate C,,H,,ON,H,SO which crystallised in bright orange needles m. p. 174O (clecomp.). The free base formed palel brown prisms with $H20 m. p. 162O and 3-phenyl-2-methyl-1 4-a-naphthapyrone was obtained on hydrolysis.m-Cresol gave a small yield of 4-amino-3-phenyl-2 7-dimethyl-y- berzzop?/ryZium szilphate C,iH,,0N,H2S0 yellow prisms m. p. 122O which was converted into the free base short colourless needles m. p. 89O and into 3-phenyl-2 7-dimethyl-2-benzopyrone C,H3Me<C0.~Ph' colourless needles m. p. 1 5 5 O . CoiLdensatioms with Formy1pheerLylacetonitrile.-Formylphenyl- acetonitrilel was prepared by the addition of ethyl formate to a well- cooled solution of phenylacetonitrile and sodium in alcohol. It condensed with resorcinol under the1 influence of phosphoryl chloride with the formation of 4-am~no-7-hydroxy-3-phe?zyl-y-benzopyryl- 0-CMe OCl--E H iicm chloride OH-C H < which crystallised with <C(NHL*CPh' lH,O in short dull yellow nkedl;; m.p. 215O (decomp.). The free base Cl,H,,0,N,H20 fosmed bright yellow needles m. p. 226O and yielded an acetate Cl,Hl,03N colourless needles m. p. 186O (decomp.) a benzoate C2,H,,03N,H20 m. p. 136O and a per- chlornte bright yellow needles. The hydrochloride was also con- verted into' 7-hydroxy-3-plienyl-y-benzopyrone by hydrolysis. Under similar conditions the nitrile condensed with pyrogallol t o form 4-imii2 0-7 8-dihydroxy-S-ph eny 1- y-b en zopyra 12 yellow needles m. p. 220° which gave an acetyl derivative colour- less needles with 1H,O in. p. 171° and on hydrolysis yielded 7 8-dihydroxy-3-phen yl- y-beiazopyrone Cl,Hlo0,,2H,O pale yellow needles m. p. 215O (ncetyl derivative with lH,O m. p. 184O). I n the same way orcinol gave rise t o 4-imino-7-hydroxy-3-phenyl- 5-m~fh?/Z-y-be?azop~.1.nn C16Hl,02N,H20 bright yellow needles m.p. 235O decomp. 241° which was hydrolysed to 7-hydroxy-3-phenyl- 5-?n~thyZ-y-benzop.1~ror7e OH*C,H,Me<'-gH pale yellow needles with 2H20 m. p. 224O. a-Naphthol was condensed with the nitrile under the influence of hydrogen chloride giving 4-amino-3-phen yl-1 4-a-naph thapyryl- iicm chloride C,gH,,0N,HCl,H20 yellow needles m. p. 135O (decomp.) from which the free base dull yellow prisms with lH,O decomp. 115-1 30° and 3-phenyl-1 4-a-naphthapyrone pale yelllow needles m. p. 169-170° were prepared. Condensatio ?i s with Be 17 zoylph enyla ce t o nitril e .-The nit'rile was prepareld by adding ethyl benzoate to a solution of phenylaceto- nitrile and sodium in alcohol.It condensed with resorcinol under the influence of hydrogen cliloride to form 4-amino-7-hydrory-2 3- diph e n yl-y-henzopyry7iirrn chloride C21H,,02N,HCI,H20 which C1,H1,03N,H20 CO*CPh C19H1202,?tH20,ORGANIC CHEMISTRY. i. 283 separated in pink needles m. p. 286O. The free base crystalliseed in yellow needles ni. p. 290° the cscetyl derivative C,,H,70,N,~H20 formed colourless needles m. p. 2 1 5 O and the product of hydrolysis U-I,;'Yh CO-CPh ' namely 7-hydroxy-2 3-cliphetryl-y-Z etuopyroize OH*C,H3< separated in colourless needles m. p. 288O (cxcetyl derivative colour- less leafl6ts with 1H20 m. p. 222O). The constitution of the pyrone was proved by decomposition with concentrated potassium liydr- oxide when deoxybenzoin resorcinol and /3-resorcylic acid were isolatled from the products.An attempt was rnade t o bring about the original condensation with the aid of concentrated sulphuric acid but the nitrile was merely hydrolysed to the amide. Pyrogallol condensed with benzoylphenylacetonitrile to form 4-imino-7 8-dihydroxy-2 3-d~~?~eizyl-y-benzo~~ralz C2,H,,O3N,~H,O yellow needlm m. p. 179-180° which was liydrolysed to 7:8-di- hydroxy-2 3-diphenyl-y-beizzopyrone C,,H,,O colourless needles m. p. 1 8 5 O . Condensations with BeizzoyZacetoizitrile.-This nitrile condensed with resorcinol in the presence of concentrated sulphuric acid to f orrn 4-%mino-7-hydroxy-2-phenyF y-b enzopyra I$ C,,H,,O,N,+H,O yellowish-brown prisms decornp. 185-235O which yielded a picrate orange needles m. p. 238O and gave 7-hydroxy-Z-phenyl-y- benzopyrone (Emilewicz and Kostanecki A. 1898 i 369) on liydro- lysis with 5% sodium hydroxide and acetophenone resorcinol and P-resorcylic acid when boiled with concentrated potassium hydr- oxide. Similarly a-naphthol yielded 4-ami?zo-2-phe,~yl-l 4-a-napht hapyr- ylium sulphate C,9H,,0N,H,S0 prisms decomp.185-215O ; free base pale brown prisms decomp. 138-148O ; picrate orange needlm m. p. 274O (decomp.). On boiling with 5% sodium hydr- oxide thel amine gavel a small yield of 2-phenyl-1 4-a-naphtliapyrone (Kostanecki A. 1898 i 374). Pyrogallol gave rise to 4-imino-7 8-dihydroxy-2-phenyZ- y-71 ~ n z o - p y r c i t t C,,H,,0,N,H20 brown prisms decornp. 145-1 6 5 O . J. C. IT7. Synthesis of Ketoindopyranols. SOSALE GARALAPURY SASTRT and BROJENDRA NATH GHOSH (T.1916 109 175-180).-1t has been shown that diketohydrindene suffers condensation with o-hydroxyaldehydes in the presence of an alkali (A. 1915 i 1067). It does not react with diket'ones like acetylacetone in an alkaline medium but condensation takes place in the presence of hydrogen chloride. The ketones probably react in their enolic forms for diketohydrindene also condenses under the same conditions with ketonitriles behavin 3 therefore like a phenol (compare preceding abstract). Diketohydrindene condensed with acetylacetone in niethyl-alco- liolic hydrogen cliloridel t o form 4f-keto-6-rn~th?/l-4-?)zet?~yZe?a~-2 3- i H c?u n o pyrn n ( 1 4) h y dr o ch 1 orid e [ 5 -k c t 0-2 $-dim P t hpl-fl y-i I I de 11 o pyr- n 2i. 284 ABSTRACTS OF CHEMICAL PAPERS.yliunz chloride] (I) brown needles m. p. 120° from which the free base (11) was obtained in brown prisms m. p. 1 8 2 O by the action of sodium acetate. Similarly benzoylacetone yielded 5-keto- 0 Y1 0 EM^ + f)-g/\Ebfe \ / \ / C \ P H I 1 8 UO CMe CH (1.) (11.1 2-ph etLyl-4-me t ?L yle tLe-Py-ind e riopyra n brown prisms m. p. 2 19' (decomp.) and its heydroc?doTide brown prisms m. p. 190-200°. Acetylphenylacetonitrile gave rise to 4-imino-4f-keto-5-p?be?ayl-6- methyl - 2 3 - indenopyran,(1; 4 ) ?hydrochloride [4-amino - 5 - keto-3- p?~enyl-2-met?~yl-P y-i?zdenopyryliurn chloride] dark red needles m. p. 210° (decomp.) from which the base (111) was isolated in brown prisms in. p. 222O (decomp.). The product' was hydrolysed by boiling 10% sulphuric acid t o 4 ; 5f-diketo-3-phenyl-2-rnethyl-Py- iizdenopyran(1 4 ) (IV) pale yellow needles m.p. 256' 0 0 The Alkaloids of the Calabar Bean. V. Action of Phengl- carbimide Phenyl Homologuss of Eserine and Geneserine. MAX POLONOVSKI (13~71. Soc. chim. 1916 Liv] 19 46-59. Com- pare A. 1915 i 891 892 987; this vol. i 221).-Phenylcarbimide condenses with eseroline and geneseroline in much the same way as does methylcarbimide and the methods employed have been the same as those' previously used in the latter case (Zoc. cit.). When t'o eseroline (1 mol.) in ethereal solution in the presence of a trace of sodium phenylcarbimide (1 mol.) is added in benzene solution and the solvent allowed to evaporate1 slowly a crystalline compound which the author calls phenesem'ne is obtained in colour- less prisms m.p. 150O; [a]= -;80° in absolute alcohol. Its solutions are alkaline b u t it does not give crystalline salts except in the case of its methiodide needles m. p. 1 9 8 O ; [a] -92.8'. Phen- eserine is insoluble in cold dilute alkalis but is decomposed by hot alkalis giving eseroline aniline and carbon dioxide. Analysis and estimation of the carbon dioxide thus liberated show t h a t it has the composition C,,H,,N,*O*CO-NHPh. I f eseroline is heated with an excess of phenylcarbimide in benzene solutlion in a sealed tube a t 100' for foar hours i t yield dipheneseriirp small needles m. p. 184';ORGANIC CHEMISTRY. i. 285 [aID -244O. Its solutions are neutral and i t is soluble in warm concentrated acids being reprecipitated by the addition of water.I t s constitution is represented by NHPh-CO*N*C,,H,,N*O*CO*NHPh. Pheneserine can be converted into dipheneserine by the further action of phenylcarbimide. If the above condensations are carried out in neutral solution in anhydrous ether and the first crop of crystals rapidly filtered off these crystals are found to be eseroline- phenylcarbimide C,,H,,ON,,PhCON m. p. 115-120° which is very strongly alkaline and is rapidly saponified by alkalis. It is readily converted into dipheneserine and pheneserine by shaking its ethereal solution with aqueous sodium hydroxide. Geneseroline under similar conditions only gives one compound with phenylcarbimide namely phenegeneserine C,,H,,ON,*O-CO-NHPh in. p. 164O; [aID -125*5O in chloroform solution; i t forms a p*crate m. p.172O. When reduced with zinc and acetic acid phenegen- eserine is readily converted into pheneserine. When eserine is condensed in neutral ethereal solution with phenylcarbimide an oily product is obtained. If the two substances are heated together without a solvent in the presence of a trace of sodium acetate in a sealed tube at 10Qo f o r two hours from the product dicarba~ziZi~oe.seri,ze m. p. looo [a]= -230° can be iso- lated. Eserethol behaves similarly giving an oily product from which a little dicarbn?,ilidoeseretizoZ [alD about - 235O is isolated. Geneserine and geneserethol do not react with phenykarbimide. W. G. Scopoline. ERNST SCHMIDT (Awh. Phciwn. 1916,253 497-504). -Mainly an account of work already published (A. 1906 i 104; 1909 i 173).The methylpiperidinedicarboxylic acid obtained by the oxidation of hydroscopolinel (Zoc. cit.) forms a dimethyl ester the methiodide C,H,,N(CO,Me),,&feI of which m. p. 175-17607 crystallises in anhydrous prisms (the corresponding aurichloride CT,H,,NMerCO,Me],,AuCl yellow crystals has m. p. 124-125O). Although Willstatter and Lessing record 167-168O as the m. p. of the methiodide of methyl 1-methylpiperidine-2 6-dicarboxylate the identity of the oxidation product of hydro- CH;CH--CH*OH scopoline with 1-methylpiperidine-2 6-dicarb- " - - YH,,Me I oxylic acid has been proved by direct com- CIH,. H-CH.OH parison with the latter synthetically prepared acid. Hydroscopoline the,ref ore has very probably the annexed formula. c. s. Degradation of Scopoline.Scopoline + Hydroscopoline + Scopolic Acid. KURT HESS and A. SUCHIER (Ber. 1915 48 2057-2067. Compare this vol. i 74).-The present knowledge of the constJtution of scopoline may be summed up in the scheme C,H,30,N = C,H,,NMe,OH,O:. The authors have now attempted to throw some1 light on the constitution of the residue C,H byi. 286 ABSTRACTS OF CHEMICAL PAPERS. investigating the oxidation of scopolines and its derivatives in the hope of obtaining amino-acids of cyclic bases which might be known Scopoline itself was found t o be unsuitable' for such a purpose. It was therefore! hoped that norscopoline would furnish a suitable amino-ketone on oxidation with formaldehyde' (a new oxidation method this vol. i 67) but the base was merely reconverted into scopoline.This point will be discussed later as it probably means that the hydroxyl group in scopoline' is a tertiary one. Scopolyl chloride (Willstatter and He'dley A. 1912 i 577) was likewise unsuitable. It has been found however that by heating scopoline with a solut'ion of hydrogen bromide in glacial acetic acid a t 115-120° in a sealed tube it gives the hydrobromide of an additive compound which is easily reduced t o a hydroscopoline by means of zinc and an acid. The latter base gives an acid on oxidation with chromic acid which is identical with the 1-methylpiperidine-2 6-dicarboxylic acid recently synthesised from lutidine (this vol. i 74) and now desig- nated scopolic acid. The positions of all the carbon atoms in scopo- line are therefore revealed and the alkaloid is proved to belong t o the piperidinel series.The addition of hydrogen bromide in acetic acid gave two products namely the hydrobromide of the additive compound C,H,,O,NBr,HBr long rectangular prisms m. p. 210-211O (decomp.) and the corresponding hydrobromide of the diacetate triclinic pyramids m. p. 283-285O (decomp.) the latter being easily removed by reason of its ready solubility in methyl alcohol. The hydroscopoline C,H,,O,N formed indefinite crystals quite unlike scopoline m. p. 165O reduced ammoniacal silver solutions absorbed bromine readily and yielded a hydrobromide m. p. 260° (decomp.) a picrate m. p. 232O a very soluble1 aurichlordde m. p. 2000 and an extremely characteristic double salt with zinc bromide C,H,,ON,HBr,~ZnBr which crystallised from glacial acetic acid in massive spikes often a centimetre long m.p. 215-216O. J. C. W. Yohimbine. 111. Constitution of Yohimbine and its 'Relationehip to Yohimboaic Acid. Mesoyohimbine a New Yohimbehe Alkaloid. L. SPIEGEL (Ber. 1915 48 2077-2083\.- The researches and analyses published in earlier papers (compare A. 1904 i 521) were regarded by the author as demonstrating t h a t yohimbinei is the N-methylated methyl ester of yohimboaic acid that is i t differs by C,H thus C,,H,,O,N and C,,H,,O,N,. Recently however Fourneau and Page (A. 1914 i 862) who thought to have proved that yohimbine is identical with quebra- chine (compare following abstract) suggested thatl the author's analyses might be inte'rpreted in favour of C,,H,,O,N the accepted formula of quebrachine.The author now shows that Fourneau's own material contained a new ingredient mesoyohim- bine. Barger and Field on the other hand (A. 1915 i 835) agreed with the formula C,,H,,OpN f o r yohimbine but proposed C,,H,,O,N for yohimboaic acid. The author points out that theORGANIC CHEMISTRY. i. 287 barium salt which these workers analysed is scarcely a trustworthy material for such a purpose. Considerable light is now thrown on the subject by the isolation of an intermediat’e compound C,,H,,O,N which should be called ‘’ noryohimbine,” but as this name was originally given t o yohirn- boaic acid the new bass is designated ~nesoyohimbi~ie. It is met with in technical yohimbine and can be isolated from this by crystallisation from 50% alcohol in which it is the more soluble.It can be obtained from pure yohimbine by heating this with dilute alcoholic potassium hydroxide’ (+ mol.) and can be converted into yohimboaic acid on further hydrolysis. It crystallises in needles m. p. 247O (yohimbine has m. p. 234’5O) is dextrorotatory gives a cryst’alline hydrochloride and contains a methoxyl group. J. C. W. Yohimbine. IV. The Supposed Identity of Yohimbine and Quebrachine. L. SPIEGEL (Bey. 1915 48 2084-2087. Compare Fourneau and Page A. 1914 i 862 and preceding abstract).- Fourneau and Page compared yohimbine with a specimen of “que- brachine” from Merck & Co. but the author has found t h a t this preparation consists really of yohimbine and mesoyohimbine. Com- paring the properties of yohimbine with those originally assigned by Hesse to his “quebrachine” (A.1882 742) i t is doubtful whether Hesse’s alkaloid was really yohimbine itself. Hesse after examining what remains of his original preparation inclines to the view t h a t his ‘‘ quebrachine” was yohimbine. Probably it was a mixture of related alkaloids. One thing is certain that the alkaloid is only a casual constituent of Quebracho blanco (compare Ewins T. 1914 105 2738). J. C. W. Relation between Absorption and Structure. 11. Chromo- isomerism and Chromotropy with Acid Additive Products of Aldamines. V. A. IZMAILSKI ( J . RUSS. Phys. Chem SOC. 1915 47 1626-1643. Compare A. 1915 ii 198).-The author advances the view t h a t the cause of chromo-isomerism in the so-called cyclammon- ium (pyridinium quinolinium acridinium) salts is t o be sought partly in the presence of azomethine groups.Attention is drawn to the structural similarity of the alkylideneamines or aldamines t o the auramines and the so-called pyridine colouring matters and the conclusion drawn that the simplest azomethine compounds may be obtainable in chromoisomeric and chromotropic forms. This con- clusion is confirmed experimentally. Further modification is required of Decker and Remfry’s view (A. 1909 i 408) t h a t exist- ence in differently coloured forms is confined to those “ ammonium ’’ salts particularly the iodides in which the nitrogen belongs to the ring since this phenomenon is observed also in cases where the nitrogen belongs to an azomethinic group of an open chain. These salts exhibit the following characteristics in the existence of the differently coloured salts the temperature and t h s solvent play an impo’rtant part; the colour of the salt depends largely on thoi.288 ABSTRACTS OF CHEMICAL PAPERS. anion ; when treated with alkali the salts form carbinols o r pseudo- bases which readily lose watler and are converted into anhydro- bases. The latter decompose more o r less readily into carbonyl and amine components the simplest members of this class being sensitive t o traces of water o r alcohol. The sensitiveness towards water may be diminished considerably by intensifying the basic properties of the chromo-radicles for instance by introduction of the aminegroup. The only solvent with the help of which the two forms are obtainable is acetic anhydride and in most cases only a mixture of the two is formed; the morel intensely coloured modifica- tion is always the more soluble.Special consideration is given t o the case of benzylideneaniline which exhibits isomeric additive products. With aIdamines contain- ing an auxochrome group in the para- or ortho-position t o the azoinethine group there may be quinonoid re-grouping but with benzylideneaniline the only possible interpretation is that the chromoisomerism is similar t o that of triphenylcarbinol salts. The anhydro-bases of a number of analogous compounds were investi- gated. The parallelism t o triphenylmethyl salts is emphasised by the ability of certain of these bromides and iodides to form with stannic bromide and iodide strongly absorbent salts.The chromoisomerism of the so-called pyridine dyes should un- doubtedly be considered from the same point of view (compare Kanig A. 1913 i l082) since such dyes represent amino-substi- tuted alkylideneimines and belong therefore t o the group of azo- methine salts. To the latter are related also1 the auramines with which i t is possible t o obtain additive products in chromoisomeric forms (compare Semper A. 1913 i 577; Graebe A. 1902 i 683). With various carbonylic compounds such as distyryl ketone the additive products exist in colourless and also coloured forms. Chromoisomeric additive products are found also with azo-com- pounds pa minoazobenzene f o r example giving two hydrochlorides. As regards the nomenclature of the adducts the author prefers the name ‘ I hydrogenochloride,” etc.t o “ hydrochloride,” etc. of an amine; or imine the latter being suitable in cases where the formation of the additive product is accompanied by scission of water. The hydrogen-iodide additive products of benzylideneaniline exis& in the three chromotropic forms (1) dark red needles decom- posing at about 1 5 7 O ; (2) orange hexagonal plates which may poasibly be mixed crystlals of (1) and (3); (3) yellow leaflets or scales. Additive products of henzvlidene-piodoaniline benzylidene- P-naphthylamine cinnamylidenephenylamine and diphenylmethyl- idenephenylamine (also termed phenyliminobenzophenone benzo- phenoneanilide etc.) are also considered. The last of these com- pounds forms a hydrogenobromide which gives a dark red solution with stannic bromide.T. H. P. Preparation of Indole. W. GLUUD (D.R.-P. 278282 ; from i7. Soc. Chem. Znd. 1916 35 106).-The elimination of carbon dioxide and water from o-aldehydophenylglycine by warming withONGANIC CHEMISTRY. i. 289 acetic anhydride preferably with the addition of fused sodium acetate results in the formation of indole. G. F. M. Oxidation 01 Thiodiphenylamine. L. PESCI (Gazzetta 19 16 46 i 103-1 18).-Oxidation of thiodiphenylamine by means of mercury acetamide (compare Forster T. 1898 73 793) proceeds according to the equation 2S<$E:>NH + Hg(NHAc) = Hg +- 2NH2Ac+ S<3E4>N *N<%:i>S ; a similar oxidation is effected by means of yellow mercuric oxide. o-Dithiotetraphenylhydrazine C,,H,,N,S thus obtained forms an almost white amorphous powder and decomposes without melting ; i t remains unchanged when treated with zinc and acetic acid and like t'etraphenylhydr- azine i t does not reduce Fehling's solution.I n concentrated sul- phuric acid it gives a red solution which turns green on addition of a small proportion of a nitrate or nit'rite but with et'hereal hydrochloric acid it gives no coloration (compare Wieland and Gambarjan A. 1906 i 453). o o-Thiodiphenoquinoneanil (annexed S formula) obtained together with di- t hiotetraphenylhydrazine etc. when a I I-\-/ mixture of thiodiphenylamine and aniline is oxidise'd by means of yellow mercuric oxide forms shining reddish- yellow lamin= with metallic lustre m. p. 1 5 0 O . Its hydrochloride C,sH,iONS,HC1 forms dark green needles with metallic lustre and in hot aqueous solution dyes wool and silk a bright bluish-green which withstands washing with water and is changed to violet-red by the action of a base.The xinci- c hlom'de ( C,,H,,0NS,HC1)2,ZnC12 forms dark green needles with the lustre of copper. Reduction of the base by means of ammonium sulphide in pyridine solution yields the Zeuco-base Cl8Hl30NS which is obtained in pale red crystals and is rapidly oxidised in the air especially in presence of moisture o r ammonia or potassium hydroxide solutdon. The unilide of the base C,,H,,ON,S crystal- lises in small cantharides-green lamin% m. p. 215O and forms ail ncetcrte C2,H,,0N2S,C,H,02 m. p. 1 2 7 O and a hydrochloride C,,H,,ON,S,IICl which decomposes withoutl melting. The action of methyl iodide on the anilide in methyl-alcoholic solution yields tlhe compoztn.d C,,H,,ON,S which crystallises in shining cantharides- green needles decomposing a t about 210° ; by ammonium sulphide in acetone solution i t is converted into the Zeuco-base C,,Hj8ON,S which forms straw-yellow needles turning brown a t about 200° m.p. 225O and oxidises rapidly in moist air. Indophenol also yields ail a d i d e NHPh (annexed formula) which crystallises in NMe,(-\ .N. /=\.o rhombohedra o r needles m. p. 196-197O \-/ * \ - / * and forms violet-blue' solutions in ace- /-\ tone pyridine ether alcohol or light \-/ petroleum ; the hydrochloride 6 4 /\/\/\-/=\ i \/\/\/ x C&2 ON 2H (21,i. 290 ABSTRACTS OF CHEMICAL PAPERS was prepared. Hydrolysis of the anilide by means of hydrochloric acid in the cold yields 2-anilinonaphtliaquinone and p-aminodi- met8hylaniline whilst in the hot paminodimethylaniline aniline and 2-liydroxynaphthaquinone are formed.T. H. P. Reduction of Indigotin by means of Triethylphosphine. N. KISHNER ( J . Russ. Phys. Chem. SOC. 1915 47 2129-2132).- Indigotln which is stable towards oxygen is oxidised by the latter in presence of triethylphosphine this being converted into the unstable triethylphosphine peroxide PEt3 <? * the indigotin then takes partl of the ocxygen of this peroxide which is transformed into the corresponding oxide. Triethylphosphine also exerts how- ever a reducing action on indigotinsulphonic acid which i t converts int'o the white1 lenco-compound. This reduction proce,eds even in presence of atmospheric oxygen and precedes the oxidation referred t o above.0 ' It is expressed by the equations it may be. carried out so as to serve as a striking lecture) experiment. T. H. P. Action of Eydrazine on Dibenzglideneacetone [ Distyryl Ketone]. Conversion into Derivatives of cycZoPropane and cycZoPentane. N. KISHNER (J. Russ. Phys. Chenz. SOC. 1915 47 1819-1848).-Thel struct,ural similarity between phorone and distyryl ketong suggests t'he possibility of converting the latter by the action of hydrazinel into a pyrazoline derivative capable of decomposing into1 nitlrogen and a derivative' of cyclopropane (com- pare A. 1913 i 1163); this expectation is not however confirmed experimentally. The1 nature of the final product' obtained varies with the proportions of the reacting compounds (1) when not more than 1 mol.of hydrazine is used per mol. of distyryl ketone ? is formed; 5-phenyl-3-s tyrylp yrazoline CHP h CH C< CH,*y HPh N--N H (2) when however excess of hydrazine is present 2 molecules of the above pyrazolinel base unit-e with 1 molecule of hydrazine N giving the compound fornation of which is completely analogous tol the union of hydroxyl- aminel with distyryl ketoneoxime a t the double linking. When heated 5-phenyl-3-styrylpyrazoline decomposes without the inter- vention of a catlalyst giving 3 4 - diphenylcyclopentene,ORCIANIC CHEMISTRY. i. 291 vHPh*CH2>CH. When heated with hydrochloric acid compound CHPh-CH (I) (vide supra) yields the hydrochlorides of hydrazine and 5-phenyl- 3-styrylpyrazoline but when heated alone i t decomposes in two directions (1) part gives liydrazine and 5-phenyl-3-styrylpyrazoline the latter then undergoing change into nitrogen and 3 4-diphenyl- c!iclopentene; (2) the other part undergoes scission a t the liydrazine residue losing nitrogen and giving 5-phenyl-3-~-phenyletliylpyr- azoline CH,Pli~CH,*C<N-NH CH2* 7 Hph ; this compound when heated in presence of potassium hydroxide and platinised porous tile loses nitrogen forming l-phenyl-2-~-phenylethylcycZopropane. The compound C3HsNF formula (I) farms white acicular crystals m.p. 55-60° and could not be recrystallised on account of its inst'ability; in a vacuum over sulphuric acid it may be kept for a long time unchanged. 5-Pheiz?lZ-3-styrylpyruzolilze C17H,,N2 forms lemon-yellow aci- cular crystals m.p. 77-78O (decomp.). Its hydrochloride C,,H,,N,,Ha forms elongated hexagonal yellow plates m. p. 1 69-170° (decomp.) and its 1-nitroso-derivative forms pale yellow needles m. p. 151° and forms a compound (C17H150N3)2,C6HG in golden-yellow needles. With phenylthiocarbimide it gives the compound C2,H2,N,S m. p. 160'5O. When the hydrochloride is heated loss of hydrogen chloride is accompanied by isomerisation of the free basel into the dipyrazoline base CH-C-CH + !I ! I Ph*CH NH-CHPh /\ H C1 /\ H C1 the formation of the second pyrazoline ring being essentially similar t o the formation of the first ring in the action of hydrazinel on distyryl ketone. The d@mpazoZiIte base forms rectangular plates m. p. 97*5O b. p. 255O/10 mm.or 424O/737 mm. and exhibits only feeble basic properties; in acetic acid its cryoscopic behaviour is normal but in freezing benzene the molecular weight increases from 416 (1.4276 solution) to 594 (5*47%) ths value 496 corresponding with the doubled formula; its hydrochloride m. p. 202-204O was prepared. 3 4-Diphenylcyclopenten e CI7Hl6 is a colourless odourless liquid b. p. 321*5O/747 mm. Di0 1.0360 17; 1.5881 and is rapidly oxidised by permanganate in the cold. 3 4-Dibromo-1 2-diphenylcyclopen- tune Cl7Hl,Br2 forms colourless rhombic plates rn. p. 119O has the normal molecular weight in freezing benzene and is converted by zinc dustl and alcohol into 3 4-diphenylcy~lopentene~; the latter is therefore more simply obtained by means of this dibromo-deriv- ative the preparation of 5-phenyl-3-styrylpyrazoline in the pure state being avoided.Oxidation of 3 4-diphenylcyclopentene byi. 292 ABSTRACTS OF CLIEMICAL PAPERS. potassium permanganate yields benzoic and ap-diphenylglutaric acids. The latter acid (compare Avery and McDole A 1908 i 343; Borsche A. 1910 i 35) exists in (1) a maleinoid modification m. p. 200-201° which forms a methyl est'er m. p. 87O and an ethyl ester m. p. 75-76O and (2) a fumaroid form m. p. 220-221° which gives a meth,yl ester m. p. 140*5O and an ethyl ester m. p. 95-96O. I n ethereal solution and in presence of platinum-black 3 4-diphenylcyc7opentene readily undergoes hydrogenation t o 1 2-diphenylcyclopentane m. p. 65*5O b. p. 321*5O/735 mm. identi- cal with the hydrocarbon obtained by reducing diphenylcyclobutyl- idenemethane with hydrogen iodide (compare Kishner A.1911 i 43). 5-Pheii~l-3-P-pheiaylethyll~yrazolin e C,,H,,N is a colourless viscous liquid b. p. 222O/10 mm. D:" 1*0625! $ 1.5874 and forms a viscous hgdrochloride which turns violet in the air. l-l'kenyl-2-P-phenylet hylcyclop~opar? e CH,< CHPh I CH*CH,*CH2P11' is colourless odourless liquid b. p. 204*5O/ 28 mm. Di5 0.9995 12 1.5666 optical exaltation 0.84; i t exhibits a saturated char- acter towards permanganate and in chloroform solution combines slowly with bromine. With hydrogen bromide it gives a compound which when boiled with aqueous alcoholic potassium hydroxide yields an unsaturated hydrocarbon probably as-diphetzyl-Ap-pentene CH,Ph*CH:CH*CH,*CH,Ph b. p. 328O/ 746 mm.180°/18 mm. 1 7 2 O / 8 mm. J3:O 1.0226 nEo 1.5872; this hydrocarbon is oxidised by permanganate and combines with two atoms of bromine. T. H. P. Behaviour of Certain Metallic Oxides towards Phenyl- hydrazine. ERNESTO PUXEDDU (Gazzctta 1916 46 i '71-7'6)- I n the absence of solvent the' various oxides of mercury react vigorously with phenylhydrazine with marked rise of temperature ; the action is less energetic with the red crystalline oxide or with old yellow oxide than with freshly prepared yellow oxide but when finely powdered the red oxide reacts immediately. Yellow or red mercuric oxide is reduced by phenylhydrazine in ethereal solution the1 mercury being precipitated in a bluish-grey pulverulent form and mercury diphenyl formed (compare Fischer A. 1880 234).I n one instance a sample of the yellow oxide which had been prepared some months gave with ethereal phenylhydrazine the pulverulent mercury mixed with a white compound forming nacreous scales m. p. about 250O. Mercurous oxide is also energetically reduced t o mercury by phenylhydrazine. Lead peroxide relacts instantaneously and vigorously with phenylhydrazine yielding lead and its oxide and suboxide. Triplumbic tetroxide reacts with phenylhydrazine when gently heated the resulting products being similar to those obtained with lead peroxide. ERNESTO PUXEDDU (Gazzetta 1916 46 i 62-70).-The author gives a summary of the literature referring t o phenylhydrazine as a reducing agent and T. H. P. Reducing Properties of Phenylhydraeine.ORGANIC CHEMISTRY i. 293 describes the results obtained by himself by the reduction in this w-ay (1) of various metallic oxides (preceding abstract) and ( 2 ) of bisazo-compounds with the view of showing that the latter may give rise to either diaminophenolsi o r aminohydroxyazo-compounds according to the extent to which the reduction proceeds.With bisazocarvacrol the reduction is complete the product being diaminocarvacrol [OH Me P r (NH&,= 2 1 4 3 51 which is a highly unstable compound and is easily transf osmed by concentrated ferric chloride solution into hydroxythymoquinone ; bisazothymol behaves similarly. Other bisazo-compounds prepared according t o Nolting and Kohn’s indications (A. 1884 900) give however under certain conditions compounds which appear t o be amino- hydroxyazo-compounds and are under investigation.Phenyl- Iiydrazine also reduces azo-derivatives of aromatic hydroxy-alde- hydes the azo-group being reduced as with the hydroxyazo-com- pounds except that the presence of the aldehyde group leads to the formation of the hydrazone. Thus the azo-derivative of salicyl- aldehyde yields 5-amino-2-hydroxybenzaldehydephenylhydrazone. The advantages of phenylhydrazine as a reducing agent for hydroxyazo-compounds are (1) the rapidity of the action either in the cold or with gentle heating; (2) the amino-compound may often be separated in crystals by addition t o the products of the reaction of a suitable solyent; (3) good yields of highly pure products; and (4) the general character of the reaction. T. H. P. Bisulphite Compounds of Hydroxyazo-colouriog Matters.11. N. N. VOROSHCOV ( J . Buss. Phys. Chem. SOC. 1915 47,1669-1737 Compare A. 1911 i 8T9).-The colmpounds obtained by the action of sodium hydrogen sulphite on sodium 1 :5- and 1 8-naphthol- sulphonates represent anhydrous esters SO,Na*O*C,,H,*SO,Na whereas those obtained from 1 5- and 1 8-aminonaphthols which are separable only with the hydrogen unsubstituted and not as salts contain an extra molecule of water NH,*C,,H,*OH + H,SO,. The stability of the latter compounds indicates that this molecule of water is constitutional and the! conclusion is drawn that the naphtholic nucleus is first converted into the ketonic form to which the sulphurous acid is then added OH O*SO,H \/ OH co C It may indeed be assumed that similar transformations take place with the naphtliolsulphonates the products thus formed then losing 1 mol.of water. There is no reason t o expect that diazotisation should produce any change in the ring not containing the amino- group and this is confirmed by analysis of the compound obtained by coupling t,he diazotised sodium hydrogen sulphit’e derivative of 1 5-aminonapht.ho1 with phenol the final product stmill containingi. 294 ABSTRACTS OF CEEMICAL PAPERS the additional molecule of water ; thus such colouring matters cannot have the ordinary ester structures assigned to them by Bucherer (A. 1904 i 309; 1905 i 48) and others (compare Lebedev UISS. Llresdeih 1914). a-Naphthylamineazo-2-aminobenzoic acid yields the same com- pound with sodium hydrogen sulphite as does a-naphtholazo-2-amino- benzoic acid the resulting colouring matter having after hydrolysis a hydroxyl group in its naphthalene1 component.Similar replace- ment of the amino-group by hydroxyl takes plsce in the action of sodium hydrogen sulphite on 6-naphthylamineazo-4-aminobenzene- sulphonic acid and on paminophenol-azo-8-naphtliyiamine. The structure given above for the compounds obtained by the action of sodium hydrogen sulphite is confirmed in a number of other cases. [With A. I>OMKE.]-T~~ sodium hydrogen sulphite compound of 1 4-naphtholsulphonic acid C,H <o~so,xa~ C H forms colourlew hygroscopic crystals but was not obtained free from mineral salt. Descriptions are given of the compounds obtained by treatment of 1 5- and 1 8-aminonaphthols with sodium hydrogen sulphite followed by diazotisation and coupling with phenol or a- or 8-naphthol. [With A.PoRTNER.]-T~~ relations towards sodium hydrogen sulphite of azo-colouring matters derived from the three diazotised monosulphonic acids of aniline and the monoamino- o r mono- hydroxy-derivative of naphthalene S O,H* C,H,* N N* C loH,*A ux (OH o r NH,) . The cases investigated comprise SO,H in the ortho-position; Aux in the (1) a- (2) &position; S0,H in tlhe meta-position Aux in the (3) a- (4) !-position; SO,H in the para-position Aux in the (5) a- (6) P-positlion. (Aux= auxochromel.) [With I. ARoNsCHTAM.]-Similarly the behaviour towards sodium hydrogen sulphite of the twelve azo-cotlouring matters represented by the schemel C0,H*C6H,*N:N*CloH6*Aux(OH or NH,) has been stludield. [With ST.RATS CHINSKI .]-similar investigations have been made on the colouring matters derived from diazotised paminoplienol and a- o r @-amino- or hydroxy-naphthalene. The1 action of sodium hydrogen sulphite on a-naphtholbisazo- benzene l-naphthol-2-azobenzene and 1-naphthol-2-azobenzene-4- sulphonic acid has also beten studied. When treated with sodium hydrogen sulphite! pdimethylamino- azobenzene pdiefhylaminoazobenzene and pnitrobenzenediazodi- phenylaminel first unde'rgo scission. I n the1 base of 1-benzeneazo-4- C(OH)(O*SU,Na)*(jHI methoxynaphf8halene the methoxy-group is replaced by hydroxyl. T. H. P. Non-aromatic Diazonium Salts. V. Diazo-derivatives of Aminotriazoles. GIL~ERT T. MORGAN and JOSEPH REILLY (T. 1916 109 155-160).-Thiele and Manchot (A. 1899 i 167)ORGANIC CHEMISTRY.i. 295 found that aminotriazoles in hydrochloric acid solution yield diazon- ium salts which couple with bases like P-naphthylamine. They noticed however that the diazo-compounds are very unstable in the presence of hydrochloric acid the diazo-nitrogen being evolved with the production of chlorotriazoles. The present authors have found that the diazo-compounds are stable however in the presence of an oxy-acid and have obtained characteristic derivatives of them. 5-Amino-3-methyl-1 2 4-tsiazolef was prepared from aminoguan- idine nitrate through the acetylaminoguanidine nitrate and treated with sodium nitrite in the presence of dilute nitric acid. The diazo-compound was isolated as 5-diazo-3-methyl-1 2 4-triaxoZ~ nurichloride C,H3N,,H,0,AuC13 a heavy precipitate of rosettes of small bright yellow prisms and condensed with alcoholic P-naphthol t o form 3-methyl-1 2 4-friaxole-5-ctzo-P-naphtko1 CI3HllON5 dark mange-brown plat’es and flattened needles m.p. 213-215O. When a solution of the diazonium nitrate obtained by the action of ethyl nitrite is evaporated t o dryness over potassium hydroxide a t the ordinary temperature 3-methyl-1 2 4-trinzole-5-isodiazohydroxide is obtained a s a colourless residue which crystallises from alcohol in prismatic needles C3H,0N,,EtOH. This does not. couple with P-naphthol unless i t is first dissolved in moderately concentrated nitric o r sulphuric acid. 5-Amino-1 2 4-triazole was obtained from formylaminoguanidine nitrate and diazotised as above.5-Dicrzo-1 2 4-triazole aurichloride C,HN,,AuCl forms opaque yellow granules; 1 2 4-triazole-5-azo- P-?/aphthol C,,H,ON forms acicular orange crystals m. p. 252-255O ; 1 2 4-triazole-5-nzo-P-)zap~t~~lami?~e crystallises in dark brownish-red plates m. p. 243-245O. 1 2 4-Triazole-5-isodiazo- hydroxide was not isolatled in as pure a condition as the homologue. The above azo-dyes are soluble in dilute potassium hydroxide which is doubtless due to’ the imino-group in the triazole ring. J. C . W. Composition and Properties of Nutrose. M. A. RAKUZIN and (MLLE.) EK. MAKS. BRAUDO ( J . Rziss. Phtys. Chem. Soc. 1915 47 1852-1853).-“ Nutrose ” is sold as a tasteless powder neutral to phenolphthalein and like casein shows all the colour reactions of the proteins with the exception of Liebermann’s reaction.It has [a] -145’45O and its ash-content (Na2C03) is 4*63:6. All these properties 81-43 in agreement with those of sodium caseinate. The method employe3 to manufacture this preparation in large quanti- ties and in the form of a powder remains a secret. The authors have prepase’d a number of coloured caseinates wit,h salts of the heavy metals. T. B. P. The Influence of Temperature and Poisons on Enzyme Action Fermentation and Growth. OTTO RAHN (Biochenz. Z ~ i f s r h . 1916 72 351-377).-A theoretical paper in which Tam- mann’s theory of enzyme action is applied t o explain various actions of ferments and poisons. Two main actions in the case of thei. 296 ABSTRACTS OF CHEMICAL PAPERS.enzymes are coiisidered namely the action of the enzyme on the substsate and the rate of destruction of the enzyme. The equations f o r a unimolecular reaction and the equation of Arrhenius con- necting the reaction constant with tha temperature are applied. The conclusions drawn in the case of the action of emulsin are as follows The action of the ferment on the substrate has a normal temperature-coefficient ; the higher the temperature the greater the activity. At the higher temperatures however the amount of enzyme rapidly diminishes and the increased activity acts in opposition t o the destruction of the ferment. The rate of change of the latter process is greater than its increased activity with rise of temperature. A t high temperatures itl is therefore possible t o observe a great initial rate of action which after a few minutes or even seconds comes to a standstill.There is no “optimal ” hm- peratusel for ferment action. Ferment actions are generally incom- plete actions which can approach completion a t the lower tempera- tures and the end-point recedes with higher temperatures. I n a fermentation system (for example’ with yeast cells) the enzymes are inside the cells as well as outside. The living cell however pro- duces continually new quantities of enzyme to replace those destroyed. As the temperature-coefficient of cell destruction is high a point is reached a t which the part destroyed is no longer replaced eatirely by that newly formed. As a consequence thO rate of fermentation which at the start is very rapid quickly falls off.I n fermentation produced by a living cell there is true optimal temperature and i t is that a t which the1 ratel of production of new enzyme quantities is equal t o the rate of destruction. Similar considerations can be applied to growth. Poisons accelerat’e both the rate of action and rate of destruction of ferments. The actions can be subjected to a theoretical tmat- ment similar t o that applied t o the consideration of the influence of temperature. S. B. S. The Hydrolysis of Vegetable Proteins by Papain. N. T. DELEANU (BziZZ. Sci. Acad. Rournaa’ne 1915-19’16 4 207-216).- Various vegetable1 proteins when heated rapidly with papain are Iiydrolysed and yield proteose peptones a’nd amino-acids. Some of the proteins can be’ degraded into amino-acids at any tempera- ture whereas in the caw of others the hydrolysis only takes place a t medium temperatures not exceeding 4 5 O . Coagulated proteins are attacked with greater difficulty than the uncoagulated; but the products of degradation are the same in both cases. Animal proteins either coagulated or dried are no€ attacked by papain. The proteins of seeds of lupines when treated with papain do not yield arginine as they do on autolysis o r germination. S. B. S. Enzymes. X. Attempts to Sgmthesise Disaccharides by means of Enzymes. WALTHER LOB (Biochem. Zeitsch. 191 6 72 392-415).-An account is given of numerous attempts t o synthesis0 sucrose from hexoses by means of invertase obtained from sugar beet yeast pancreas and kephir. Under the conditionsPHYSIOLOGICAL CHEMlSTRY. i. 297 of the experiments selected no evidence of synthetic action of the ferment could be obtained. S. B. S. Preparation of a Hexa-aminoarsenobenzene. C. F. BOEHRINGXR & SOHNE (D.R.-P. 286854 and 286855; from J . SOC. Chem. Ind. 1916 35 142).-3 5-Dinitro-4-aminophenylarsinic acid is reduced to the corresponding triaminokcompound with the calculated amount of sodium hyposulphite and this is further reduced with hypo- phosphorous acid to 3 4 5 3’ 4f 5/-hexa-aminoarsenobenzene o r the operations may be reversed in order with the intermediate production of a nitroarwnobenzene. I n the second patent’ 3 5-di- nitro-4-aminoplienylarsinic acid is reduced in one operation with a quantity of sodium hyposulphite sufficient to reduce both the nitro-groups and the arsinic acid group and the resulting sulpliur- containing compound on decomposition with acids yields sulphur dioxide and a salt of hexa-aminoarsenobenzene. This compound is cliaracterised by it”s slight toxicity and has valuable therapeutic properties on account of its powerful spirillocidal action. G. F. M. Preparation of a Tetra-aminodimethylaminoarsenobenzene. C. F. BOEHRINGER & SOHNE (D.R.-P. 286667 and 286668 additions to D.R.-P. 285572 see A. 1914 i 1101; from .7. SOC. Chem. Ind. 1916 35 141-142).-Instead of using tin and hydrochloric acid for the reduction of dinitromethylnitroaminophenylarsinic acid as prescribed in the chief patent stannous chloride with hydrochloric acid o r with hydrochloric and acetic acids zinc with concentrated hydrochloric or acetic acid or iron and hydrochloric acid may be used. To avoid formation of arsine the reaction mixture is heated only until a clear solution is obtained. Reduction of the above nitro- arsinic acid may also be effected in stages; thus reduction of 3 5-di- nitro-4-methvlaminophenylarsinic acid is brought about by mercury and sulphuric acid and sodium hyposulphite further reduces this to tetra-aminodimethylaminoarsenobenzene. On the other hand tetra-aminodimethylhydrazinoarsenobenzene may be first formed (this vol. i 175) and then further reduced or reduction may be effected by means of phosphorus o r hypophosphorous acid t o tetra- nitrodimethvlaminoarsenobenzene and this subsequently reduced to the tetra-amino-compound with tin and hydrochloric acid. G. F. M.

ISSN:0368-1769    

DOI:10.1039/CA9161000241

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 244 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. The Solubility of Hydrogen in the Solid AIloys of Palladium with Gold Silver and Platinum. A. SIEVERTS E. JURISCII and A. METZ (Zeitsch. anorg. Chem. 1915 92 329-362).-Except f o r a few isolated measurements by Graham the only determinations olf the solubility of gases in solid alloys are those by Berry (T. 1911 99 463) according t o which the1 solubility of hydrogen in alloys of palladium and gold decreases regularly with increasing gold becoming zero a t 80% Au. I n the present experiments the alloys are warmed t o a constant temperature in an atmosphere of hydrogen a t a given pressure. The measurements are made in the same way as with pure palladium (A. 1914 ii 626). The range employed is from 138O to 820° and from 1 atmosphere pressure downwards.I n all cases the solubility is proportional to the square root of the pressure and except in the platinum series diminishes with increasing temperature. The addition of gold to silver first increases and then diminishes the solubility of hydrogen the maxi- mum occurring a t lower concentrations of gold the higher the temperature until atl 827O any addition of gold lowers the solu- bility. The isotherms of relative solubility also pass through a maximum a t temperatures below 600O. Although hydrogen is insoluble in pure silver thel addition of silver to1 palladium greatly increases the soIubility until a maximum is reached a t all temperatures at' 40% Ag beyond which it again falls rapidly. A t 138O an alloy containing 40% Ag dissolves more than four times as much hydrogen as pure palladium the solu- bility becoming zero a t 70% Ag.The relative increase of solu- bility in the case of an alloy containing 40% Ag increases with falling temperature until 270° but diminishes as the temperature falls further. Platinum in all proportions diminishes the solubility. The higher the temperature1 the less is the lowering of solubility produced by a given addition of platinum. A t constant' temperature the depres- sion diminishes more slowly than the platinum content. C. R. D.INORGANIC CHEMISTRY. ii. 245 Physical Constants of Chlorine. MAURICE PELLATON ( J . Chim. phys. 1915 13 426-461).-Measurements have been made of the vapour pressure of liquid chlorine of the orthobaric densi- ties of liquid and saturated vapour and of the critical constants.The chlorine used in the investigation was obt'ained by heating auric chloride. The vapour-p'nessure measurements extending from - 78.9O up to the critical temperature can be represented by the formula logp=A - B I T - C log T in which when p is expressed in atmo- splieres A =4*922232 log B = 2.9676491 and log C = - 1.8967405. The critical temperature is 144*0° the critical pressure 76.1 atm. and the critical density 0.573. The ordinary b. p. is -34.5O. The orthobaric densities are in satisfactory agreement with the law of the rectilinear diameter and the density of liquid chlorine may be represented by the empirical formula dl = a + b (144 - t ) + c 2/ 144 - t in which a = 0.687014 b = 0*0002379 and c = 0.0622109.The same type of formula also represents the density of the saturated vapour the values of the constants being a = 0.48219 b = 0.002451 and The heats of vaporisation of liquid chlorine a t various tempera- tures have been calculated from the vapour pressure data. The ratio of the critical density t o that calculated from the simple gas laws is 3.635 and the value of Trouton's constant is 20.67. These and other results indicatel that chlorine behaves as a normal substance. Measurements are also recorded of the dissociation pressure of auric chloride a t t'emperatures between 140° and 260O. The pres- sure increases from 4.5 mm. a t 140° to 931 mm. a t 260° and the variation with temperature can be expressed by the formula log p=&4 -BIT-Clog T in which A =51*6852 log R-3.841148 and log C = 1.117057.Oxidation of Hydrazine. VII. The R6le of Nitrous Acid in the Formation of Azoimide. A. W. BROWNE and 0. R. OVERMAN ( J . Amer. Chem. SOC. 1916 38 285-302 and Zeitsch. anorg. Chenz. 1516 94 217-239. Compare A 1905 ii 449; 1909 ii 233 658; 1911 ii 1084 1085).-A numbec of experiments on the oxidation of hydrazine and ammonia by various oxidising agents have been carried out. It is shown that no indication of the formation of appreciable quantities of nitrous acid or nitric acid could be obtained by treatment of ammonium sulphate in sulphuric acid solution with oxidising agents such as Hydrogen peroxide potassium chlorate potassium persulphate potassium permanganate hydrated ferric oxide pot'assium iodate mercuric oxide and mer- curic chloride under the conditions prevailing in the earlier experi- ments of Browne and Shetterley on the oxidation of hydrazine.Ammonium sulphate in a solution strongly acidified with sulphuric acid is but slightly affected by prolonged treatment with such oxidising agents as hydrogen peroxide potassium chlorate and potassium permanganate a t the boiling point. The addition of c =0*068526. H. M. D. 11'ii. 246 ABSTRACTS OF CHEMICAL PAPERS. ammonium sulphate to a reacting mixture of hydrazine sulphate sulphuric acid and hydrogen peroxide does not increase but rather decreases the yield of azoimide obtained. Potassium nitrite oxidises hydrazine sulphate in sulphuric acid with forma- tion under comparable conditions of larger yields of azoimide and of much smaller yields of ammonia than are obtained by the action of hydrogen peroxidel on hydrazine sulphate. I n view of the experi- mental results obtained and of various other considerations the theory offered by Sommer (A.1913 ii 952) in explanation of the formation of azoimide and of ammonia by oxidation of hydrazine by means of oxidising agents which contain no oxygen is in all probability to be1 regarded as untenable. J. F. S. Black Phosphorus. P. W. BRIDGMAN ( J . Arncr. Chem. SOL 1916 38 609-612. Compare A. 1914 ii 647).-The author has previously shown (Zoc. cit.) that white phosphorus when heated a t 200° a t a pressure of 12,000 kilos is converted into' black phos- phorus. The premnt paper deals with the formation of black phosphorus from red and violet phosphorus in the presence and absence of catalysts.When white1 phosphorus and red phosphorus with a trace of sodium are subjected t o a pressure of 4000 kilos a t room temperature and then heated at ZOOo at constant volume there is a rise of pressure of 500 kilos. A A t 200° the pressure was then raised t o 12,500 kilos for ttwenty minutes and then t o 130,000 kilos for forty-five minutes. On cooling and releasing the pressure it was found that thc white phosphorus was entirely converted into violet phosphorus but thatl the red phosphorus was unchanged. A piece of kiolet and a piece of red phosphorus in the presence of iodine were then subjected t o a pressure of 8000 kiloe a t 20° the tempe'ratnre raised to 200° a t constant volume and the pressure then raised to 12,500 kilos for five and a half hours. No black phosphorus was formed but the red phosphorus had been converted into violet phosphorus.All other attempts t o convert red phos- phorus into black phosphorus failed. An experiment was carried out on the rate of formation of black phosphorus from white phos- phorus by measuring the rate a t which the pressure changes. It is shown that a t 200° and 12,000 kilos there is a slow fall in pressure for about fifteen minutes which amounts t o 400 kilos and then a sudden drop of pressure of 4000 kilos after which even though the pressure was brought to its original value there was no further drop of pressure. This indicates that there is a period of prepara- tion before the black phosphorus is formed suddenly.The experi- ments establish the facts (i) that black phosphorus is stable com- pared with white phosphorus a t 200° a t pressures above 4UOO kilos; (ii) that violet phosphorus is stable colmpared with white phos- phorus a t 4000 kilos and somewhat below 2 0 0 O ; and (iii) that violet phoFphorus is stable compared with red phosphorus a t ZOOo betwelen the pressures of 8000 and 12,000 kilos. J. F. S. Action of Hydrogen Sulphide on Arsenic Acid. WILLIAM FOSTER (J. Amer. Chem. SOC. 1916 38 52-57).-The action of1NORaANIC CHEMISTRY. ii. 247 hydrogen sulphide on solutions of arsenic acid in the presence )of hydrochloric acid of various concentrations has been studied with the object of deciding between the discrepant results of Travers and Usher (T 1905 87 1370) and McCay (Amer.Chem. J. 1887 9 174). As the result of a large number of qualitative and quantitative experiments i t is shown that arsenic acid is never reduced directly t o arsenious acid and sulphur but that when a solution of arsenious acid is treated with hydrogen sulphide the compounds react to form monosulphoxyarsenic acid H,As03S. This substance is not very stable and in the presence of dilute acids breaks down gradually into arsenious acid and sulphur. I n the presence of concentrated acids the decomposition is much more rapid. Concentrated hydrochloric acid brings about the decom- position very rapidly even a t zero. A low concentration of hydro- gen sulphide also favours the decomposition of this compound. These facts account for the presence of arsenic trisulphide and free sulphur in precipitates obtained by treating solutions of arsenic acid with hydrogen sulphide.When solutions of arsenic acid are tres bed with a rapid stream of hydrogen sulphide no reduction takes place even if no mineral acid is present I n an experiment it was observed that arsenic acid saturated with hydrogen sulphide yielded pure arsenic pentasulphide after the solution had stood f o r ninety-one hours. It was also found that no1 reduction occurred in solutions of arsenic acid in the presence of hydrochloric acid ranging in concentration from 0.9% to 32% that is when the solu- tions were treated a t 15O with a rapid stream of hydrogen sulphidel. These results are in complete agreement with those of McCay but in most cases are1 a t variance with those of Travers and Usher.J. F. S. [Colloidal Arsenates.] EUGEN DEISS (KoZZoid. Zeitsch. 191 5 i16 16).-A claim for priority against Klemp and Gyulai (A 1915 ii 256) in respect of the preparation of manganous arsenate jellies. If a solution of potassium dihydrogen arsenate is used instead of trisodium arsenate transparent- jellies of manganous arsenate are obtained in the absence of both ammonium salts and acetic acid. H. M. D. Boric Acid Solutions in Preeence of Litmus. FR. FICHTER ( J . Chim. phys. 1915 13 399-401).-According t o an observation of Rose (Annalen 1852 84 216) if a solution of litmus reddened by the addition of acid is added to a concentrated solution of borax until the red colour is very faint the colour changes to blue when the solutJon is diluted.This has been attributed to! increased hydrolysis of the sodium borate but i t is shown that tlie effectl cannot be interpreted in this way and is to be explained in terms of the ionisation of the boric acid which is set free by the acetic acid. H. M. D. The Problem of the Diamond. Enm BAUR K. SICHIJNG and E. SCHENKER (Zeitsch. anorg. Chem. 1915 92 313-328).-Assum- 11*-3ii. 248 ABSTRACTS OF CHEMICAL PAPEKY. ing the value f o r the heat of transformation of diamond into graphite to be 180 cal. per gram-molecule at 1 7 O (Roth and Wallach A. 1913 ii 384) and calculating by means of the formula of Nernst and Lindemann the diamond is found to become less stable with increasing temperatlure. Assuming both phases to be incompressible a pressure of 6250 atmospheres a t O0 olr of 44,000 atmospheres a t 2000O would be necessary t o convert graphite into diamond.It appears however that the specific heats of the two modifica- tions become almost equal a t a red heat. Possibly the curves cross and above 1000° absolute the specific Mat of diamond is greater than that of graphite. The tsiple point under high pres- sures may be between 4000O and 6000° abs. Whatever assumptions may be made the formation of diamond in the blast furnace or in molten metal must lie far outside any possible range of stability. The natural occurrence of diamond is opposed to its formation as an intermediate metastable phase. When mixtures of iron 2nd magnesium dicates prepared by the thermit method are mixed with calcium carbide and heated elec- trically only graphite is obtained even when the temperature is lowered tIo 1100-1200O by the addition off a flux.Experiments under high pressures using an apparatus capable of reaching 2000O under 10,000 kg.Icm.2 by means of carbon resist- ance using mixtures of silica and carbon have also) failed t o give any form of carbon but graphite. Negative results ar0 also obtained with silicates and carbides in the same apparatus (compare Thrdfall T. 1908 93 1333). Preparation and Properties of Colloidal Carbon. PERCY CYRIL LESLEY THORNE (T. 1916 109 202-209).-Atternpts to prepare a colloidal carbon by the dehydration of sucrose by sulphuric acid gave a sol containing a small amount of carbon but its properties were obscured by the presence of complex decomposi- tion products.A stable sol was obtained by passing an electric current (OB5-4*0 amperes a t 200 volts) through dilute sodium hydroxide solution between carbon electrodes with the positive pole just touching the surface of the liquid. The sol showed a distinct Tyndall cone; in layers more than a few mm. thick it was black and contained particles visible with the ultramicroscope. It was very sensitive to electrolytes and analysis of the coagulum showed that it contained in addition t o an inorganic residue considerable amounts of oaygen (19.05%) and hydrogen (2.35%). Organic matter is also formed in the sol and its presence as also! that of a trace of alkali o r some electrolyte seems necessary to ensure the stability of the sol. The Solidiflcation of Silver-Arsenic Alloys.W. HEIKE and A. LEROUX (Zeitsch. anorg. Chem. 1915 92 119-126).-The investigation of t h i s system by Friedrich and Leroux (A. 1906 ii 283) is incomplete owing t o the alloys having been prepared under atmospheric pressure. The alloys have now been prepared by fusion in sealed porcelain o r siloxide tubes (Heike A. 1913 ii C. H. D. G. F. M.INORGASIC CHEMISTRY. ii. 249 477). The electric furnace is so mounted that the tube may be inverted t o mix the metals. When the vapour pressure of the arsenic is high the tube is enclosed in an outer porcelain vessel packed with sand. The freezing-point curve shows a single eutectic point a t 540° and 25 atomic % of arsenic. Solid solutions are only formed from 0 t o 6 atomic %. Alloys between this composition and the eutectic undergo a transformation a t 595O whilst a second transformation a t 3 7 4 O is observed over almost the whole range of composition.The first is due t o a reaction between the solid and liquid phases forming a new solid solution with a limiting concentration of 10.5 atomic % and the second t o a eutectoid decomposition of the lather. Both changes may be suppressed by undercooling. The composition of the eutectoid is not indicated. Cold dilute sodium hydroxide is used f o r etching but the eutectoid structure is best developed by mesns of potassium cyanide and the same solution is used f o r alloys containing the twq solid solutions whilst under- cooled alloys are best etched with warm sodium sulphide. The freezing point of arsenic is found to be 814*5O+_0*5.C. H. D. The Ternary System CaO-Al,O,-MgO. G. A. RANKIN and H. E. MERWIN ( J . Amer. Chem. SOC. 1916 38 568-588).-con- centration melting-point curves have been obtained for the binary systems lime-magnesia magnesia-alumina and spinel-alumina. The melting point; of magnesia has been found to be 2800° and there is no indication of a second form existing. Alumina is found to exist in two forms Al,O (a) artificial corundum m. p. 2050° and A&03 ( P ) a new form produced by melting alumina and allow- ing i t t.o cool siowly. It has not been found possible to reconvert the &form into tke a-form after it has once been produced. B-Al,O is hexagonal often appearing in groups of overlapping triangular plates with perfect basal cleavage. The composition-melting point diagram of A1,03-Ca0-Mg0 has been determined.Boundary curves and fields of existence are plotted and spatial diagrams given in the paper. The ternary system is of a simple character since there are no ternary compounds stable in contact with the melt. The working out of the system therefore involved the equilibrium of the three components and the binary compounds 3Ca0,A1,03 5Ca0,3A 1,0 Ca0,A1203 3Ca0,5A1,04 Mg0,Al,03 in ternary solutions. The whole of the relationships found t o exist between th3 components an3 compounds in binary systems and in the ternary system are shown in a series of concentration-temperature diagrams. The optical and crystallographic properties of the com- poaents and pure compounds have been given in a previous paper (A 1915 ii SO) butt a few new detaiIs are included in the present paper f o r 5Ca0,3A1,o3 and Ca0,A1,03.Solid Solutione of Compounds of Calcium Strontium Barium and Lead with those of the Rare Earths and their Importance in Chemical Mineralogy. FERRUCCIO ZAMBONINI ( R e p h t pp. 185 1915).-The author has investigated by thermal J. F. S.ii. 250 ABSTRACTS OF CHEMICAL PAPERS. crystallographic and microscopic methods the formation of solid solutions between compounds of calcium strontium barium and lead and the corresponding compounds of met'als of the1 cerium and yttrium groups. The systems investigated and the results obtained are briefly as follows BaC12-CeC13 gives crystals of the type BaC12,2€€,0 containing up t o 2.19% of cerous chloride. Ca(NO,),-Y(NO,) forms crystals of the type Ca(N03),,4H,0 containing up t o 2.2% of hexahydrated yttrium nitrate.Sr(NO,),-Y(NO,) gives crystals of the type Sr(NO,h with not more than O.S6% of yttrium nitrate and crystals of the type Sr(N0,),,4H20 with 1-80/ of hexahydrated yttrium nitratel. PbS0,-Di,( SO,) and BaS0,-Di,( SO,) no miscibility. PbMoO,-C~,(h!fo0,) forms mixed crystals containing up to 77-78% of cerous molybdate. The systems PbM00,-La,(Mo0~)~ PbMoO,-Di,(MoO,) PbMo0,-Pr,(MoO,) PbMoO,-Nd,(MoO,) and PbW0,-Ce,(WO,) show complete miscibility. PbMo0,- Y,(MoO,)~ forms mixed crystals containing up to 13.6% of the yttrium salt and C'aMo0,-Ce,(MoO,) mixed crystals containing up to 59.1% of cerous molybdate. CaMo04-DiS(Mo04) mixed crystlals .codtaining 38.8% of the didymium ' salt.CaMo0,- La,(MoO,) mixed crystals containing up to 58% of the lanthanum salt. CaMo~O,-Y,(&IoO,) mixed crystals containing up t o 4.7% of the yttrium salt. CaMoO,-Y,(~~oO,),-Ce,(MoO,) mixed crystals containing 24.7% of the yttrium salt and 21% of thO cerium salt. SrMo04-Ce,(Mo04) mixed crystals containing 39.7% of the1 cerium salt. SrM00,-La,(Mo0,)~ mixed crystals with 37.5% of the lan- thanum salt. BaM00~-La,(Mo0~)~ mixed crystals with 13.1% of the barium salt. C"aW04-Ce2(W0,) mixeld crystals containing 10.3% of the cerous salt. Pb,(PO,),-CePO mixed crystals of the type Pb,(PO,) with 3% of cerous phosphate. Pb,(PO,),-CeVO mixed crystals with 3.0% of cerous vanadate. Ca,(PO,),-CeP0,- CaCl chloroapatite containing up t o 13"/; of cerous phosphate. Ca,(P0,),-DiP04-CaC12 chloroapatite with 3% and chlorospodiosite with 9% of didymium phosphate. Ca,(P0,)2-YP0,-CaC12 chloro- apatite with 6% of yttrium phosphate.The1 molybdates and tungstates of the rare earth metals have molecular volumes about three times as great as those of the corre- sponding compounds of lead and calcium. It is evident that the view which is generally accepted namely that isomorphous com- pounds capable of giving an extended series of solid solutions possess similar molecular volumes is erroneous. Confirmation of this con- clusion is afforded by a number of other instances; thus in the syst'ems Bas-CaS and BaO-CaO the larger molecular volume is respectively 52.7% and 55.0% higher than the smaller one. I n the case of nickel and cobalt the compounds of the metal with the higher atomic weight have the lower specific gravities whereas with praseodymium and neodymium the reverse is the case.Numerous crystallographic data are given f o r the mixed crystals obtaiiTed. Ths results given by the mixed molybdates and tung- states show that the magnitudes of the angles are not necessarilyINORGANIC CHEMISTRY. ii. 251 a function of their composition and need not lie between those of the pure compo'nents. Further the values of a c f o r the molybdates of yttrium lanthanum cerium praseodymium and neo- dymium reveal no relation between the value of c and the atomic weight of the 5et'al or the molecular volume of t3he salt (compare Jaeger A. 1914 i 797). The above result,s are discussed in relation to the chemical com- position of yttrofluorite hellandite eudialyte and eucolite the minerals of the melanocefib group knopite and cliurchite.T. H. P. Solubility of Gypsum in Sea-water. A. MANUELLI (Ann. Chinz. Applicata 1916 5 13-24).-Determinations have been made of the solubility of gypsum a t lS0 i n sea-water from the Adriatic and in various mixtures of it with distilled water. The results show that an approximately fixed proportion of calcium sulphate is dissolved by sea-water and its aqueous solutions containing from 1 2 t o 37 parts of saline residue per 1000; similar results were obtained with an artificial sea-water free from carbonates. I n both cases the proportions of dissolved calcium sulphatel calculated from the calcium oxide are greater than those calculated from the sulphur trioxide; the cause of this phenomenon has not been ascer- tained.Itl is evident t h a t the constancy in the relations between the proportions of differentl salts in sea-water is due not tot the attainment of a condition of saturatdon with respect to! certain salts but t o the enormous extent t o which river waters are diluted in the whole mass of sea-water. T. H. P. Density of Lead from Radioactive Minerals. THEODORE W. RICHARDS and CHARLES WADSWORTH ~ R D ( J . Amer. Chem. Soc. 1916 38 221-227).-The density of ordinary lead and of lead from radioactive minerals has been determined a t 19.94O by weigh- ing in a modified Ostwald-Sprengel pyknometer. It' is shown that ordinary lead of atomic weight 207.2 has a density of 11.337 whereas lead from Australian radioactive sources od atomic weight 206.3 has a density of 11.288.The materials in both cases were purified by fractional crystallisation of the nitrate and chloride and the subsequent treatment was identical in both cases. Con- tinued fractionation of the radioactive lead had no effect on the density. The diff ereace in density is particularly interesting because it is practically parallel with the ato'mic weight which indi- cates t h a t radioactive lead and ordinary lead have the same atomio volume the values being respectively 18.276 and 18.277. J. F. S. Separation of the Rare Earths giving the more Soluble Double Sulphates from Brazilian Monazite Sand. C. JAMES and A. J. GRANT ( J . A4m~~sr. Chem. Soc. 1916 38 41-47).-The material used in this investigation was the solution obtained after potassium sulphatle had been added to the mixed rare earth sulpliat'es in quantity insufficient t o precipitate completely thB whole of the cerium metals.The solution was precipitatled byii. 252 ABSTRACTS OF CHEMICAL PAPERS. oxalic acid and the oxalatm ignited t o oxides. The mixture con- tained considerable quantities of lanthanum cerium,. praseodymium and neodymium in addition t o samarium gadolinium and the yttrium earths. This mixture was first roughly fractionated as double magnesium nitrates in the following way The mixed nitrates with magnesium nitrate in solution were evaporated until about one-half the material had crystallised on cooling. The crystals were twice recrystallised and then placed on one side the mother liquor being fractionated until the spectrum of samarium or erbium became intense.When this stage was reached the mother liquor was precipitated by oxalic acid and the oxalates ignited t o oxides this operation having the effect of removing large amounts of iron and aluminium. I n this way three fractions were obtained ( a ) The least soluble portion consisting of white or green crystals composed of lanthanum cerium and praseodymium magnesium nitrates with traces-of the neodymium compound ; ( h ) more soluble deep amethyst crystals consisting mainly of neodymium magnesium nitrate with traces of thO doubls magnesium nitrabes of samarium praseodymium cerium and lanthanam ; ( c ) oxides from the mother liquor containing neodymium samarium europium gadolinium terbium dysprosium holmium yttrium erbium thulium,.ytter- bium and lutecium. The cerium was removed from the fraction (a) by boiling the solution with potassium bromate and powdered marble (James and Pratt A. 1911 ii 935). A number of experi- mental details and precautions are described in connexion with this process. After the removal of the cerium the solution was precipi- tated by oxalic acid the oxalate ignited t o oxides and these con- verted into double ammonium nitrates and fractionateld whereby lanthanum and praseodymium were obtained. Neodymium was obtained pure) by continuing the recrystallisation of ( b ) . Fraction (c) was converted into double magnesium nitrates and fractionally crystallised from 1 1 nitric acid and whenever the mother liquor failed t o crvstallise properly a considerable quantity of magnesium bismuth nitrate was added.This rapidly removed the1 remaining europium and gadolinium. As soon as the mother liquors were free from gadolinium they were precipitated with 'oxalic acid. Con- tinuing this fractionation for some tJme five fractions were obtained (i) crude neodymium magnesium nitrate (ii) samarium magnesium nitrate (iii) bismuth magnesium nitrate containing europium magnesium nitrate (iv) gadolinium magnesium nitrate containing terbium dysprosium holmium and small amounts of ytt'riurn and (v) oxalates mainly yttrium but containing dyspros- ium 'holmium. erbium thulium ytterbium lutecium and traces of terbium. Gadolinium was obtained pure from fraction (iv) by conversion into oxalate igniting t o oxide! and dissolving in bromic acid.The1 bromates were submitted t o a long series of fractional crystallisations when gadolinium was obtained a t the less sohihle end in a very pure condition. The fractions between gadolinium and dysprosium contained the terbium. Dysprosium and holmium were obtained from the bromate fractions more soluble than terbium and from the yttrium earth oxides (c). Both' materialsINORGANIC CHEMISTRY. ii. 253 were converted into bromates and crystallised from water when six fractions were obt'ained (a) least soluble dysprosium holmium and yttrium bromates containing traces of terbium ; ( P ) yttrium bromate containing some dysprosium and holmium ; (y) yttrium bromate containing very small amounts of dysprosium holmium and erbium; (6) yttrium bromate containing very small amounts of erbium; (E) yttrium and erbium bromates; (3) bromates of erbium thulium ytterbium lutecium and celtium.The least soluble portions of the bromates were mixed according t o their compositions with the corresponding fractions forming tlie inore soluble e r d of the terbium gadolinium series and fractionated. After prolonged fractionation the terbium separated in the least soluble fractions a;id the dysprosium was slowly removed from the holmium. The fractions (y) and (6) were mixed and worked up for yttrium by ihe four following methods (i) the basic nitrate method (ii) the nitrite method (iii) the chromate method and (iv) the cobalticyanide method. The basic nitrate and nitrite methods are the best for large quantities of material.The authors boiled a solution of nitrates of yttrium and erbium and added sodium hydroxide until crystals of basic nitrate began t o form. The liquid was then cooled and the rose-coloured crystals rich in erbium removed. The process was then repeated with the filtrate. The precipitates become paler in colour as the yttrium is concen- trated. The yttrium was further purified by boiling a dilute solution of the nitrate with sodium nitrite which gave a very pure product. J. F. S. Solution of the Cerium Group Oxides by Certain Acids. MT. S. CHASE ( J . Znd. E i ~ g . Chenz. 1916 8 239-240).-0xides of the cerium group are fairly readily dissolved by sulphuric hydro- chloric and nitric acids but not by acetic acid. The addition of hydrogen peroxide accelerates the solution of the oxides in the mineral acids even when the latter are diluted and only a small excess of acid is required.Hydrogen peroxide does not however Revision of the Atomic Weight of Neodymium. 11. GREGORY PAUL BAXTER WILLIAM HENRY WHITCOMB OLUS JESSE STEWART and HAROLD CANNING CHAPIN ( J . Amer. Chem. SOC. 1916 38 302-310. Compare A. 1911 ii 285).-Neodymium nitrate was purified by prolonged fractional crystallisation of the nitrate from concentratled nitric acid. The chloride was produced from this by conversion in oxalate ignition and solution in distilled hydro- chloric acid. The chloride was then analysed by comparison with silver. The mean value of the atomic weight of neodymium is thus found t o be 144.261. The average of this value and the value previously found by Baxter and Chapin (Zoc.cit.) is 144.268 so t h a t the rounded figure Nd = 144.27 (Ag = 107.88) would seem t o be the result of both sets of investigations Oxidation of Manganese Solutions in the Preeence of Air. VICTOR LENHER ( J . Arner. Chem. SOC. 1916 38 638-640).-A increase the solubility of the oxides in acetic acid. w. P. s. J. F. S.ii. 254 ABSTRACTS OF CHEMICAL PAPERS. number of tubes were partly filled with a 1% solution of manganous chloride and about 1 gram of calcite and one of the following substances were added lead bismuth tin arsenic antimony mercury ccjpper zinc nickel cobalt cadmium silver gold mercuric sulphide millerite pyrites chalcopyrite and zinc blende. The tubes were sealed and the time required for the production of hydrated qanganese dioxide by the air oxidation noted.I n a tube containing only the solution and calcite the first noticeable separa- tion took place after several weeks. Lead and bismuth accelerate the1 reaction producing the same effect in a few hours. All the other substances had no accelerating effect. I n fact in the case of antimony tin and arsenic there was a retarding action but this was due not t o a negative catalysis but to the reducing action of the salts of these metals which would be formed. The bearing of the above action on the production of pyrolusite beds in nature is considered. J. F. S. A Slag containing Manganese. RICHARD LORENZ (Zeitsch. nizorg. Ckem. 1915 92 35-36).-A slag from a manganese furnace of a brown colour was found to contain manganese in ultra-microscopic particles similar t o those1 of gold in ruby glass,.The particles have a golden lustre in the ultra-microscope. It is not certain whether the manganese owes its origin to reduction of one of its compounds in the molten slag or t o volatili- sation of the metal and entrance1 of the vapour into the slag. The former mode of origin corresponds with that of ruby glass and the latter with the origin of metal fogs. Experiments to produce a similar glass by melting manganese under a layer of glass have given negative results although manganese vapour condenses to drops on the sides of the crucible. Artificial Preparation Fusibility and other Properties of Silicates of the System 2FeO,SiO + 2CaO,SiO,.B. S~LIVANOV ( J . SOC. Chem. Ind. 1916 35 307; from Bev. SOC. Russe Mttall. 1915 11 328. Compare A. 1915 ii 837).-Mixtures of pure silica lime and iron peroxide containing 60% FeO were melted in an iron cruciblg in a crypt01 electric resistance furnace and cooling curves taken. The cooled product was in each case analysed and from the results obtained the equilibrium diagram was constructed. Fe,SiO melts a t about 1260O [?I and a maximum a t about 1 2 6 0 O [ 21 corresponds with the compound 2Fe,SiO,,SCa,SiO,. Between these two points a eutectic point a t 1160O corresponds with about 33% (molecular) Ca,SiO,. When the mixtures were heated in a current of hydrogen reduction began at the following temperatures corresponding with the annexed percentages of Fe,SiO, loo% 225O; 85% 210O; 65% 205-210O; SO% 170O; 40% 1 8 0 O ; and 3076 250O.Preparation of Pure Iron and Iron-Carbon Alloys. J. R. CAJN E. SCHRAMM and H. E. CLEAVES ( J . ZmZ. Eng. Chem. 1916 8 21 7-223).-The iron was prepared electrolytically and purified by fusion in magnesia crucibles; the magnesia used in making the C. H. D. G. F. M.INORGANIC CHEMISTRY. ii. 255 crucibles was prepared by converting magnesite into magnesium acetate and igniting the latter. The ingots obtaineid were sound and free from blow-holes. By fusing the pure iron with definite quantities of carbon in a magnesia crucible in a vacuum furnace a series of iron-carbon alloys were prepared containing 99.96% of the two elements. w. P. s. The Action of Sulphuric Acid on Alloy Steels. LESLIE AITCHISON (T.1916 109 28&-298).-Fine drillings of the steels passed through a sieve are covered with 10% sulphuric acid and allowed to remain for a fixed time. After filtration the solution is analysed and the proportions of the tlwo metals compared with those which would be1 found if the original ratio of the1 two metals in the steel had been preserved. The composition of the carbides in alloy steels is taken to be that determined by Arnold and Read (A. 1910 ii 1971; 1911 ii 1092; 1915 ii 567). Vanadiuni does not pass into solution until the steel contains 5.4% of the metal showing that up t o that point the whole of the vanadium is present in the1 carbide which is not attacked by sulphuric acid under the conditions of the experiment. Chromium is present.both in solid solution and also in the carbide and the latter is slightly attacked. Alloys containing large percentages of chromium however give up very little to the acid. Tungsten is entirely present as carbide up t o ll*5% and this is not attacked by acid. Nickel on the other hand is present only in solid solution until high percentages are reached whilst cobalt is contained only as carbide. Manganese is present both in solid solution and in the carbide the latter being partly attacked owing t o its fine state of division in the sorbitic pearlite. Double carbides are much less susceptible t o attack by acid than pure iron carbide. Crystals of Iron Phosphide from a Blast-furnace. L. J. SPENCER (Llfia. Nn.c/. 1916 17 340-343).-Small tin-white needles with brilliant metallic lustre and strongly magnetic were found sparingly in drusy cavities together with crystals of iron carbide and of metallic iron in a large mass of metal from a blast- furnace near Middlesbrough.The crystals belong to the sphenoidal-hemihedral class of the tetragonal system a c = 1 0.3469. Their composition is presumably Fe,P and the material is identical except in the absence of nickel with the meteoric rhabdite. L. J. S. The Formation of Isomorphous Mixed Crystals between Cobalt Oxide and Manganous Oxide and between Cobalt Oxide and Nickel Oxide. J. ARVID HEDVALL (Zeitsch. anorg. Ghem. 1915 92 381-384 *).-When cobalt oxide and manganous oxide are heabed together in a large excess of potassium chloride solid solutions are obtained which vary continuously in colour with the composition.It is uncertain whether the miscibility is con- tinuous o r not. Minute cubo-octahedra of nickelous oxide are obtained by C. H. D. * and Arkiv Kern. Min. Geol. 1916 6 No. 2 1-5.ii. 256 AESTRACTS OF CHEMICAL PAPERS. repeated heating of the amorphous oxide o r hydroxide to 1000° in an excess of potassium chloride. They are light yellorwish-green and have D 7-45. Mixtures of cobaltous and nickelous oxides yield homogeneous octahedra and cubo-octahedra. The colour and specific volume vary continuously indicating that complete miscibility probably occurs. C. H. D. The Reduction of Metallic Oxides with Hydrogen at High Pressures. EDGAR NEWBERY and JOHN NORMAN PRING (Proc. Roy. SOC. 1916 [A] 92 276-285).-The effect produced by heating various metallic oxides a t telmperatures above 2000O in contact with hydrogen a t a pressure of 150 atmospheres has been investi- gated in a specially designed apparatus consisting of a magnesia crucible heated by means of the current passing through a tungsten wire.The water vapour produced in the reaction was removed by metallic sodium. Under these conditions chromic oxide and manganese dioxide are reduced t o the corresponding metals. Prepared in this way the metals are probably purer than those obtained by any of the methods used hitherto. The m. p. was quite sharp in both cases the mean values corrected t o " black body" temperature being 123Oo*5O f o r manganese and 1615 f 1 5 O f o r chromium. Other oxides examined were1 only partly reduced vanadium pentoxide columbium pentoxide and titanium dioxide giving the correspond- ing monoxides uranium oxide U,O giving the dioxide UO and cerium dioxide CelO giving the sesquioixide Ce,O, Aluminium oxide magnesium oxide zirconium dioxide yttrium oxide and thorium dioxide were not reduced under the conditions of the experiment. R.M. D. Molybdenum Semipentoxide and its Salts. F. MAWROW and M. NIKOLOW (Zeitsch. anorg. Chem. 1915 92 135-144).-When the violet hypophosphomolybdenum compound (A. 1902 ii 25 144) is rubbed with ammonia the yellowish-brown precipitate may be washed and dried and is then sparingly soluble in watler with a neutral reaction. It dissolves in acids and may be reprecipi- tated by ammonia. I f washed with dilute ammonia and then with absolute alcohol the residue1 has the! composition NH,Mo,0,,3H20.On ignition in a current of carbon dioxide the oxide Mo205 is obtained. The sodium compound NaMo20,,3~,0 is obtained by treating the original violet compound with sodium hydroxide. It yields a dark violet substance NaMo?O on helating. The corresponding barium compound BaMo,O,,SH,O may also be obtained in the hydrated and ailhydrous form3. C. H. D. Oxidation and Reduction without the Addition of Acid. 11. The Reaction between Stannous Chloride and PotaBsium Dichromate. MARKS NEIDLE and JOSHUA C. WITT ( J . Anzer. Chenz. SOC. 1916 38 47-52. Compare A. 1915 ii 780).-The oxidatdonMINERALOGICAL CHEMISTRY. ii. 25’7 of stannous chloride by potassium dichromate in the absence of acid has been studied. It is shown that the stoicheiometric rela- tionships are the same as those obtaining in the presence of acid. When potassium dichromate is added in the theoretical quantity to a solution of stannous chloride in the absence of acid brownish- and greenish-blue gelatinous masses are formed which dissolvs and form a clear deep o’live-green solution when the whole of the dichromata has been added.These solutions appear red by trans- mitted light. The solutions were examined by dialysis and by extraction with alcohol and are shown t o consist of potassium and chromium chlorides together with colloidal solutions of hydrated stannic and chromic hydroxides. On dialysis a clear sol of the approximate composition 6Sn0,:1Cr,03 is obtained and this sol contains the whole of the tin and about one-half of the chromium used in the reaction. The course of the reaction is given by the equation 2K2Cr,0 + 6SnC1 + (63 + y)H,O 4KC1+ 6Sn0,,zH20 + Cr203,yH20 + 2CrC1 + 2HC1. J. F. S. Hetero-poly-acids containing Vanadium. IV. Compounds containing Vanadic and Tungstic Acids. WILHELM PRANDTL and HANS HECHT (Zeitsch. anorg. Chem. 1915 92 198-212. Compare A. 1915 ii 469).-A solution of tungstic acid in am- monia acidified with acetic acid a t first contains a paratungst,ats but passes in the course of a felw months into the hexatungstate (metatungstate) from which hydrochloric acid does not precipitate tungsten even on prolonged boiling. Solutions of alkaline vana- dates also yield hexavanadates with a sufficient quantity of acetic acid ; otherwise lower v a n a d a h are obtained. The following salts have been prepared by the action of acetic acid on solutions of mixed alkali tungstates and vanadates Na3V30,,18NaHW0,,36H,0 colourless crystals losing vanadium on recrystallisation ; Na4V,Ol7,6NaHWO4,32H,O and 35H,O yel- lowish-red ; K,V,0,7,6KHW04,7H,0 yellowish-red ; (~H4),~,0,,,4(NH,),H,~~3011,~H,0 and 8H,O o’range-red rhombohedra ; K4V60,,,4K,H,W,0,,,20H,0 and 18H,O ; Na4V,0,,,4Na,H,W30,,,38H20 and 40H,O ; Ba2V60,,,4BaH,W30,,,30H20 and 35H20 ; and also a series of known salts which are now formulated as M,’H2V,0,,,2M,/H3W,O,,,zH2O all of which form deep red octa- lied r a. C. H. D.

ISSN:0368-1769    

DOI:10.1039/CA9161005244

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 25'7 Review of the Processes of Chemical Transformation in Potash Deposits. M. R~SZA (Zeitsch. anorg. Chem. 1915 92 297-300).-A summary of the results obt'ained in previous papers (A 1914 ii 376; 1915 ii 355 356 473).-A purely thermal decomposition of carnitllite into KC1 and MgC1,,4H20 can onlyii. 258 ABSTRACTS OF CHEMICAL PAPERS. occur rarely as the circulation of solution has the effect of pre- venting de,l;ydration. The1 decomposition is actually hydrothermal. C. H. D. Proustite from Cobalt Ontario. ARTHUR L. PARSONS (Miiz. Z a g . 1916 17 309-313).-Analysis by H. V. Ellsworth of the small crystals which were however imperfectly separated from impurities gave Ag. As. S. Sb. Fe. trace of Ni). Tnsol. Total. corresponding with proustite (Ag,AsS,) 94-62 ; pyrargyrite (Ag,SbS,) 3'77% ; smaltit'e 0.04% ; pyrit'es 0.05% ; arsenic 1.27%.A crystallographic description of the material is given a c = 1 :0*8015 and a new crystal-form recorded. co (+ 64.12 15.90 19.28 0.08 0.25 0.12 0.38 100.13 L. J. S. Crystallography and Dehydration of Torbernite. W. F. HALLIMOND (Min. Mug. 1916 17 326-339).-Torbernite is tetra- gonal with u c = 1 2.974. Refractive1 index 1.591. When the crystals lose water owing either tor rise in temperature t o less than looo o r t o being placed in a desiccator there is a change t o meta- torbernite-a crystalline f orm with definite optical characters. This alteration is dependent n o t only on the temperature but also on the partial pressure of aqueous vapour in the surrounding space.Torbernite was kept over sulphuric acid of various strengths (corre- sponding with definite vapour pressures) and a t various tempera- tures and afterwards examined t o ascert\ain if the change t o met'a- torbernite had taken place; the points when plotted fall on one or other side of the transition curve of torbernite The mineral is stable within very narrow limits. L. J. S. Natrolite from Kinbane Go. Antrim. F. N. ASHCROFT (Min. Mug. 1916 17 305-308).-A description is give11 of the1 occur- rence of fine specimens of delicate scicular crystals of natrolite in basalt near Kinbane (White Head) on the north coast of County Antrim. Associateld minerals are calcite! and analcite. Analysis gave the fo'llowing results in close agreement with the formula Na,O AI,O 3 SiO 2 H,O A1203 SiO,.(+trace Fe20,). CaO. Na,O. K,O. H,O. Total. 47.22 27.21 nil 15-86 0.06 9.70 100.05 L. J. S. Chabazite from County Antrim. G. F. HERBERT SMITH ; with topographical notes by F. N. ASHCROFT and chemical analyses by G . T. PRIOR (Min. Mag. 1916 17 274-304).-A detailed descrip- tion is given of the occurrence and crysttallographic characters of chabazite and the associated minerals (calcite analcite natrolite and mesolite) found in the flows of basaltic lava a t various locali- ties in County Antrim. 'The crystals (a c = 1 :1*0860) are of theMINERALOGICAL CHEMISTRY. ii. 259 gmelinite (hexagonal) o r phacolite (rhombohedral) habit and are usually t'winned on the c(ll1) or ~(100) planes o r on both. Refrac- tive indices for sodium light w = 1.490 E = 1.480.Analyses 1-111 are of crystals of the pielinits habit from White Head a t the entrance of Belfast Lough IV of crystals of the phacolite habit from Craigahulliai near Portrush and V of pliacolite from Killy- flugh iiear Ballymena SiO A1,0,. CaO. SrO. K,O. Na,O. H,O. Total. Sp gr. I. 46.64 20.04 7.00 0.22 0.63 3.81 21.84 100.18 2-09 II. 46.75 19-79 8.25 0.23 0.33 2.17 22.09 99.61 2.07 III. 47.81 19.73 5.01 0.02 0.31 6.13 21.56 100.57 2.06 IV. 48.61 18.06 8.19 0-60 2.13 0.33 21.68 99.60 2.09 V. 48.82 18-53 8.81 0.26 1.20 0.37 22.09 100.08 2.09 The formuh deduced from these analyses are respectively I. 124 (CaA1,Si,0,2,6H,0) + 7( Na,Al,Si,O 2,6H,0) + H20. $ 9 99 + liSiO,+ 9H,O. 9 9 + 3Si0 + 6H,O. 11. 15 + 4 111. 9 + 10 V.16 $ 9 + 2 $ 9 + 9Si0 + 15H,O. IV. 15 9 9 + 3(K2A1,~~40,2,6H,0) +8SiO + 12H,O. The amounts of silica and water in excess over that required for the usually accepted formula of chabazite namely (Ca,K2,Na2)A1,Xi,0,2,6H20 may be preaent in solid solutio,n as recently suggested by Foote and Bradley (A. 1911 ii 122; 1912 ii 568) in the case of nephelite and analcite. This formula may be written in the form ( Ca,Na,,K,)A1,Si,0,,2H2Si03,4H,0 ; here the first portion represents the lime-f elspar (CaA12Si,0,) and nephelite (Na,A1,Si20,) molecules and these may be replaceable by the alkali-felspar molecule (Na,K)AlSi,O,. Gmelinite and phacolite are both identical with the species chabazite diBering only in crystal habit and the difference in the amount of soda and potash shown in the above analyses is probably wit.hout significance.Gay Gulch and Skookum Meteorites Yukon Canada. R. A. A. JOHNSTON (Museum Bull. No. 15 [Geol. Ser. No. 261; Geol. Survey C C C ~ Z C I ~ 1915 1-31).-These masses of meteoric iron were found in the gold-bearing gravels of Pliocene age in two of the gulches tributary to the Bonanza Creek in the Klondike dis- trict the second of them a t a depth of 65 feet below the surface. One weighing 483 grams was found in 1901 in Gay gulch (partial analysis I by H. A. Leverin) and the other weighing 15-88 kilo- grams was found in 1905 in Skookum gulch (anal. 11). They are both nickel-rich irons showing a similarity in structure (coarse octahedral with chatoyant reflections on the etched surfaces nodules of troilite etc.) and they probably belong t o the same meteoritic shower dating back to the Tertiary period.Fe. Ni. Co. Cr. C. P. S. Xi. Total. Sp. gr. L. J. S. - 7.566 11. 80.65 18.20 0.91 0.002 0.015 0.194 0-002 0.003 99-976 7.561 - - - - I. 83.85 15.03 - - L. J. S.ii. 260 ABSTRACTS OF CHEMICAL PAPERS. Summation of Chemical Analyses of Rocks. H. II. ROBINSON (Amer. J . Sci. 1916 [iv] 41 257-275).-Although the sum of the results obtained in the complete analysis of a rock should be loo% such is rarely the case. Inspection of the 3391 analyses recorded by Washington (Bzlll. U.S. Geol. Survey Nos. 14 and 28 1903 1904) shows t h a t the sum is more frequently above 100 than below; in 1253 cases the sum varied frotm 9904 t o 99*99% and in 1846 it lay between I00 and 100.99%. The author discusses the! question in general skowing t h a t the errors are usually due t o want of skill on the part of t.he analyst and not particularly t o the untrust- worthiness of the methods employed. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005257

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 260 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Action of Neutral Salts on Indicators. I. M. KOLTHOFP (Clzem. IVeekbZad 1916 13 284-297).-Experiments on the effect produced by neutral salts on the colour of indicators show that the phenomenon is dependent on change in the concentration both of the hydrogen ions and the hydroxyl ions. Succinic Acid as a Standard. C. A. PETERS and V. SAUCHELLI (Amer. J. Sci. 1916 [iv] 41 244-248).-Results obtained by standardising ammonia solution against hydrochloric acid agreed closely with those found by the use of succinic acid electro- titrametrically as described by van Suchtden and Itano (A. 1914 ii 775) but no trustworthy values could be obtained by the action of succinic acid on ammonia using cochineal as indicator as described by Phelps and Hubbard (A.1907 ii 297). Use of Copper Oxide for Fractional Combustion of Hydrogen and Carbon Monoxide in Gas Mixtures G. A. BURRELL and G. G . OBERFELL (?7. I d . Emg. Chem. 1916 8 228-231).-The copper oxide method devised by Jager (compare A. 1909 ii 698) for the fractional combustion of hydrogen and carbon monoxide yields trustworthy results. A temperature of the copper oxide of between 275O and 300° is adapted for burning hydrogen and carbon monoxide in a wide variety of gas mixtures. A. J. W. W. P. S. w. P. s. Electrolytic Estimation of Iodine Present in Organic Matter. ROBERT B. KRAUSS ( J . Biol. Chenz. 1916 24 321-325. Compare A. 1915 ii 791).-The results obbained by the1 palladous iodide coZorinietric method may be checked by first de'positing the palladium on a weighed platinum cathode and then the iodine on a silver-plated anode.The method is far less sensitive than the colorimetric estimation. H. W. B.ANALYTICAL CHEMISTRY. ii. 261 Decomposition of Tetrathionates in Alkaline Solution as a Source of Error in Certain Iodine Titratione. ROBERT 31. CHAPIN (J. d r n e r . Chem. SOL 1916 38 625-626).-\h%en sodium tetratliionate produced in iodine titrations is allowed tot remain in the presence of alkalis or alkaline salts it is partly converted into sodium thiosulphate and sodium sulphite thus introducing the possibility of an error in the estimations. The effect of allowing sodium hydroxide sodium carbona tle ammonia and sodium hydro- gen carbonate t o act on sodium tetrathionate solutions for fifteen minutes a t 3G0 has been determined by titration with iodine.It is shown that with the exception of sodium hydrogen carbonate th9 conversion has taken place to a considerable extent. It there- fore follows that acid solutions containing tetrathionates if later to be titrated with iodine or subjected to any treatment involving the assumption that the tetrathionats present has remained un- affected should never be1 neutralised by any substance of distinctly alkaline properties. I n the case of arsenic estimations it seems safer to abandon the use o f sodium thiosulphate and t o substitute a dilute1 solution (0.5%) of sodium sulphite. J. F. S. Differential Iodometry. L. Estimation of Periodates Iodates Bromates and Chlorates in the Presence of each other.0. L. BARNEBEY (J. Amer. Ghern. SOC. 1916 38 330-341).-The conditions under which the above-mentioned substances can bet esti- mated in the presence of one another have been studied experiment- ally. It is shown that by careful regulation of the temperature concentration of the agents and especially of the acidity and the time of reaction all these substances can be estimated iodometrically either alone or in the presence of one another. When periodates are treated with potassium iodide in a saturated solution of boric acid containing sufficient borax t o diminish slightly the1 acidity a reduction occurs to iodate with the liberation of iodine. Iodates are acted on by O-lN-potassium iodide in 0*25A'-acetic acid solution liberating iodine. I n 0~2A~-hydrochloric acid solution containing 0.1N-potassium iodide bromates are completely decomposed liber- ating iodine.I n 6N-hydrochloric acid solution of 0.1-0.2N- potassium iodide chlorates are- completely decomposed liberating iodine and in this case after rendering the solution alkaline and then acidifying the iodine may be titrated by thiosulphate solu- tion. By combining the above reactions the whole of these sub- stances can be estimated in the presence of one another and in the presence of perchlorates which do not react readily with potassium iodide in acid solution. A number of test analyses are given in the paper which show that the method is trustworthy. J. F. S. Reagents for Use in Gas Analysis. 11. Chromous Chloride. R. P. ANDERSON and J. RIFFE ( J . Ind.Eng. Ghem. 1916 8 24-26. Compare A. 1915 ii 647).-Chromous chloride has been proposed for the absorption of oxygen but the authors find that it is not a very trustworthy reagent,. If prepared by treatingii. 262 ABSTRACTS OF CHEMICAL PAPERS. chromous acetate with hydrochloric acid the solution is not stable hydrogen being evolved gradually. By reducing violet chromic cliloride with hydrogen and filtering the solution through glass- wool (to re'movei insoluble substance8 possibly metallic chromium) a stable solution of the reagent is obtained but this does not absorb oxygen completely. w. P. s. Reagent for Use in Gas Analyais. 111. The Specific Absorp- tion of Alkaline Pyrogallol in Various Pipettes. R. P. ANDERSON ( J . Ind. Eng. Chem. 1916 8 131-133. Compare1 A.1915 ii 647).-Experiments with t'lie Orsat pipette and modifications of the same described by Hankus Nowicki and Dennis (A. 1913 ii 424) showed that as regards time consumed in manipulation and the specific absorption obtained the Orsat pipette is superior to any of the others when modified pyrogallol reagent (Zoc. cit.) is used for the absorption. The reagent is not however well suited for use in pipettes which have been designed f o r the1 absorption of oxygen without shaking (see f olloisving abstract). w. P. s. Pipettes Specially Adapted for Use with Alkaline Pyrogallol. R. P. ANDERSON ( J . I72d. Eng. Chern. 1916 8 133-135).-Two8 modifications of the Orsat pipette are described. I n one a perfor- ated porcelain cone supports the glass tubes and any precipitate which may form cannot collect and clog the lower ends of the' tubes.The other form is similar to a Hempel double pipettle but the cylindrical portion is smaller than usual and is filled with glass tubes the construction of the lower part of the1 cylinder being such that the tubes are held in position and db notl become clogged with precipitate. The reagent used in the pipettes contains 21.2 grams of pyrogallol and 66.6 grams of potassium hydroxide1 per 100 C.C. The specific absorption (compare A. 1915 ii 647) of this reagent f o r one minute contact is about 36 when treated in the above pipettes a t 20° with gas samples 100 C.C. in volume and con- taining 20.9% of oxygen. w. P. s. Reagents for Use in Gas Analysis. IT. Phosphorus in Solution. R. P. ANDERSON and W.BIEDERMAN ( J . I d . Eng. Chem. 1916 8 135-136).-The solution of phosphorus in castor oil proposed by Centnerszwer (A. 1910 ii 541) is not suitable for the estimation of oxygen the absorption of the gas being incomplete a t the ordinary temperature. Even assuming that compleb absorption can be attained by heating the reagent there appears t o be no reason why the latter should be preferred t o alkaline pyrogallol properly prepared (compare A. 1915 ii 647). w. P. s. Methods for the Analysis of Lime-Sulphur Solutions. ROBERT M. CHAPIN (,7. Znd. R'ng. Chem. 1916 8 151-156).- Methods are described f o r estimating the concentration of total (sulphide) base total jsulphide) acid and excess of acid o r base. The sulphide base numb,er is represented by the C.C.of NIIO-acidAKALY TICAL CHEMISTRY. ii. 263 solution required t o neutralise 10 C.C. of the sample using methyl- orange or Congo-red as indicator; in the case of lime-sulphur solutions which have already been used for dipping sheep sodium nitroprusside may be used as an external indicator. The reaction number depends on the fact that sodium tetratliionate reacts with lime-sulphur solution t o yield a solution which can be titrated in the usual way tlie result giving the acidity or alkalinity of the sample; the reaction proceeds normally only in a dilute ammonia- cal solution. The sulphide acid number is tlie differences between the base and reaction numbers o r i t may be estimated iodometri- cally in the solutdon resulting from the estimation of the reaction number; alternatively it may be found by titrating an ammoniacal solution of the sample with tetrathionatel solution nickel sulphate Rapid Control Method for the Estimation of Sulphur in Pyrites Cinder.H. C. MOORE ( J . I n d . Eng. Chenz. 1916 8 26-28).-The sodium peroxide fusion method is recommended. About 1.5 gram of the finely powdered sample is fused in a wrought-iron or nickel crucible with 7 grams of sodium peroxide the cooled mass is dissolvesd in water and slightly acidified with hydrochloric acid. About 0.5 gram of aluminium powder is now added and when the ferric salts have been reduced the solution is heated t o boiling cooled diluted t o 500 c.c. and filtered. Two hundred C.C. of the filtrate are diluted t o 450 c.c. 1 C.C. of concen- trated hydrochloric acid is added and the1 sulphuric acid is precipi- tated by treating tlie cold solution with barium chloride solution.After one hour the barium sulphate is collected washed with cold water ignited and weighed. The presence of considerable quantities of barium sulphate and silica in the cinder does not have an appreciable1 influence on the results obtained. Estimation of Sulphur in Spent Oxide. E. V. ESPENTIAIIN ( J . SOC. Chcnz. Ind. 1916 35 292-293).-Sulphur in the spent oxide of the gas works may be accurately estimated by heating 0.4-0.7 gram of the finely powdered and washed material with 4 grams of reduced iron in a hard-glass crucible whereby i t is com- pletely converted after seven t o ten minutes a t a dull red heat into ferrous sulphide. After cooling in an atmosphere of carbon dioxide it is decomposed in a conical flask with concentrated hydro- chloric acid and the evolved hydrogen sulpliide is passed into N/IO-iodine and titrated in the usual way.The carbon disulphide extract of the spent oxide gives the sulphur and tar whence by difference the t a r content is obtained. The estimation of total sulphur including that combined as sulphates and thiocyanates is carried out by heating the powdered but unwashed oxidel with iron as above these salts being thereby likewise converted into ferrous sulpliide which is estimated by decomposing with hydro- chloric acid as above described. G. F. M. Estimation of Sulphur Dioxide and Sulpbur Trioxide in Flue Gaees. R. J . NESTELL and E ANDERSON ( J . I d . E q .Chew,. 1916 8 258-260).-R definite volunie of the flue gas (say being used as the indicator. w. P. s. W. P. S.ii. 264 ABSTRACTS OF CHEMICAL PAPERS. 2000 c.c.) is aspirated through the following series of absorption vessels A U-tube containing a small quantity of water a double filter-paper held between the large ends of two funnels and a flask olntlaining iV/ 10-sodium carbonate solution and hydrogen peroxile; a glass t u b 3 feet long conducts the gases from the flue to the apparatus. After the tube has been withdrawn from the flue 1000 C.C. of air are drawn through the apparatus. The sulphur trioxide is retained in the form of sulphuric acid in the glass tube the U-tube containing water and by the filter-paper. The latter together with the rinsings of the tube and the solution in the U-tube is placed in a flask and titrated with standard alkali solutioln to obtain the quantity of sulphur trioxide present.The sulphur dioxide passes entirely into the sodium carbonate solution where it is absorbed and at the same time oxidised by the hydrogen peroxide ; titration of the excess of sodium carbonate gives the amount of the sulphur dioxide in the ffue gas. w. P. s. A New Method for the Iodometric Estimation of Thiocyanic Acid and Hydrogen Sulphide. F. P. TREADWELL and C. MAYR (Zeitsch. anorg. Chem. 1915 92 127-134).-The iodometric method for the estimation of thiocyanates by Thiel (A. 1902 ii 706) is tedious and there is danger of loss of iodine in the evolu- tion of carboa dioxide. I f nascent bromine1 is used inst\ead of iodine f o r the oxidation t'he titration may be carried out quite rapidly.The solution is diluted until about iVj5 or N / 6 and 5 o r 10 C.C. are introduced into a litre flask provided with a tap funnel and 50 C.C. of N/5-potassium brofmate and 10-15 C.C. of a 10% solution of potassium bromide are added. The flask is then evacuated with a filter pump and sufficient concentrated hydrochloric acid is allowed to enter without admitting air until the1 volume1 of liquid is increased by one-third. After shaking the flask is allowed t o remain for fifteen minutes when a solution of 2 o r 3 grams of potassium iodide is added without admitting air. After again shaking the separated iodine is titrated with N / 10-sodium thio- sulphate and starch. Thiocyanates and chlorides o r bromides may be estimated together by proceeding as above and also1 by titrating thiocyanate and haloid together by Volhard's method.The estimation of hydrogen sulphide by means of bromide and bromate is more exact than that by means of iodine the reactions being H,S + 4H,O + 8Br = 8HBr + H,SO and H,S + I = 2HI + S. When concentrated hydrochloric acid is added the1 solution at first becomes turbid from precipitation of sulphur but this is oxidised in fifteen to twenty minutes and the liquid becomes clear. I n very dilute solutions thirty minutes may bet required. When sulphides and thiocyanates are both present the sulphide sulphur is first estimat'ed by the ordinary iodometric method and then the total sulphur by the bromide-bromate method. Analyses are given to show the accuracy of the methods.C. H. D.ANALYTICAL CHEMISTRY. ii. 265 Quantitative Micro-elementary Analysis of Organic Sub- stances. J. V. DUBSKY (Chem. Zeit. 1916 40 201-203. Compare A. 1914 ii 485).-Certain modifications are introduced into the methods described previously by the author (Zoc. cit.). The supply of carbon dioxide in the estimation of nitrogen by the micro-Dumas method is obtained from a small tube containing sodium hydrogen carbonatel; the closed end of this tube is surrounded by wire gauze which is heated by a burner and the delivery t u b is provided with a wash-bulb containing a few drops of wat’er. I n the estima- tion of carbon and hydrogen there is no need to use a diffusion- stopper in the combustioln tube after the platinum boat containing the substance.Capillaries filled with calcium chloride and soda- lim0 respectively are used for the absorption of the water and carbon dioxide. w. P. s. Kjeldahl Method for Estimating Nitrogen. I. K. PHELPS and H. W. DAUDT (Proc. Amer. SOC. Biol. Chem. 1915; J . Biol. Chem. 1916 24 xxxv.).-The quantity of nitrogen in members of the following classes of cyclic compounds namely pyrrole pyrrol- idine pyridine piperidine quinoline isoquinoline purine glyox- aline quinoxaline and quinazolone can be estimated accurately by the Kjeldahl method provided the digestion is carried on f o r two and a-half hours with a boiling mixture of 25 C.C. of concentrated sulphuric acid 10 grams of potassium sulphate and 0.7 gram of mercuric oxide to 0.3 gram of the nitrogenous substancel.H. W. B. Comparison of Methods for the Estimation of Soil Pbos- phorus. W. 0. ROBINSON (J. I n d . Eng. Chem. 1916 8 148-151).- The fusion methods (with sodium carbonate magnesium nitrate etc.) Washington’s method (decomposition with hydrofluoric and nitric acids) and Fisher’s method (two evaporations with aqua regia with an intervening ignition) of treating soils for the estimation of phosphorus all give trustworthy results. Vanadium (always present in soils) interferes with the estimation but its influence may bs eliminated by the procedure described by Cain and Tucker (A. 1913 ii 875); tungsten and titanium do not interfere. The insoluble precipitate sometimes obtained when the phosphomolyb- ,date precipitate is dissolved in ammonia is probably due t o the presence of iron aluminium titanium etc.which have not been removed by proper washing. w. P. s. New Method for Citrate-insoluble Phosphoric Acid. CHAS. H. HUNT ( J . Ind. Eng. Chew. 1916 8 251-253).-In the pro- posed method the sample is dissolved as for the estimation of total phosphoric acid and the solution is diluted to a definite volume. An aliquot portion of the solution is then treated with an excess of ammonia thO precipitate formed is collected washed dissolved in nitric acid and the phosphoric acid is estimated in this solution. The ratio between the citrate-insoluble P,O and the P,O precipi- tated by ammonia is approximately as 1 1.5; if therefore theii. 266 ABSTRACTS OF CHEMICAL PAPERS. amoant of P,O precipitated by ammonia is divide'd by 1.5 the quantity of citrate-insoluble P,O is found.The results obtained by the method agree well with those obtained by the usual (official) process. w. P. s. Estimation of Phosphoric Acid Soluble in Citric Acid in Basic Slag by the Iron Citrate Method. M. POPP (Chem. Zed. 1916 40 257-260. Compare A. 1912 ii 992; 1913 ii 336 876; 1914 ii 576).-Although ferric chloride varies considerably in com- position (samples examined by the author containing from 58.8% t o 99.6% of actual ferric chloride) the1 iron-citrate solution used to prevent the interference of silica always contains a quantity of iron sufficient for this purpose even when the solution is prepared from ferric chloride of poor quality. The hydrogen peroxide solu- tion used in the estimation maintains its strength for a considerable time if 0.005% of acetanilide is added; the presence of 0.5% of alcohol also preserves the strength of the solution.The quantity of hydrogen peroxide solution added should be from 1 t o 3 c.c.; larger quantities cause the results obtained to be too low. This is not the case when dealing with pure phosphate solutions mixed with manganese and calcium salts but the error always occurs with basic slag and is evidently due to some constituent of the latter P. CARLES (J. Phnmz. Chim. 1916 [vii] 13 219-221).-Arsenic is liable to be present in certain samples of sodium sulphah and the author suggests a modification of Marsh's test f o r detecting its presence. The issuing gas from the1 hydrogen generator is passed on t o a paper moistened with a solution of mercuric chloride and after the purity of the hydrogen has been ascertained about 25 grams of t h s salt under examination are placed in the hydrogen generating apparatus.The formation of a yellow o r brown stain on the paper indicates the presence of arsenic the depth of the colour giving an approximate measure of the amount present. A New Method for the Detection and Qualitative Separation of Arsenic Antimony and Tin. FRIEDRICH L. HAHN (Zeitsch. unorg. Chem. 1915 92 168-170).-0n account of the difficulty of the usual method of separation of t'hese metals the following modification is proposed The mixtnrs of sulphides and sulphur obtaineld in the usual way by the addition of acid to the solution in yellow ammonium sulphide is extracted with a cold 5% solution of sodium sulphide.The metallic sulphides dissolve readily whilst the sulphur remains as a powdery residue(. Aftler filtration the filtrate is made! alkaline with sodium hydroxide about twice as much of a 10% solution being added as was used of sodium sulphide. Hydrogen peroxide is then added and the s?lution is he'ated to boiling. The evoriition of oxygen shows that sufficient has been added. Should antimony be present i t soon separates as glistening (possibly silica). w. P. s. Officinal Sodium Sulphate. W. G.ANALYTICAL CHEMISTRY. ii. 267 crystals of Na2H,Sb,0 which cling to the glass where rubbed. To complete the precipitation one-fourth of the volume of alcohol is added. After filtration the alcohol is expelled by boiling and ammonium nitrateis added as a solid o r as a concentrated solution.Stannic acid is precipitated the separation being complete when the ammonia has been boiled off. Arsenic is precipitated from the filtrate as ammonium magnesium arsenate. The arsenic and antimony precipitates are very characteristic; the tin may be con- firmed by dissolving in hydrochloric acid and adding mercuric chloride in the usual way. One mg. of arsenic antimony and 2 mg. of tin may be detected in 1 gram of copper o r lead. Should i t be known ihat mercury is absent the hydrogen sulpliide precipitate may be treated directly with sodium sulphide solution more sodium hydroxide and hydrogen peroxide being then neces- sary to oxidise the sulphur t o sulphate much heat being developed.C. H. D. Simultaneoue Estimation of Carbon and Halogen by the Chromic Acid Method. PHILIP WILFRED ROBERTSON (T. 1916 109 215-221).-Carbon and halogen may be simultaneously estimated in organic compounds by the chromic acid oxidation method previously described (T. 1915 107 902). The substance is gently heated with a mixture of chromic and sulphuric acids and the evolved gases are carried along by a slow stream od oxygen through a heated silica tube containing platinised asbestos a U-tube containing glass-wool moistened with sulphuric and chromic acids to retain oxides of sulphur and a second heated silica tube (in the case of chloro+compounds) to decompose chromyl chloride into two absorption tubes the first containing 10 C.C. of 1.3N-sodium hydroxide and 2 C.C.of 2N-sodium sulphite and the second 10 C.C. of sodium hydroxide. The operation is complete in about one and a-half hours and the mixed contents of the absorption tubes are then treated with 5 C.C. of hot barium nitrate solution and after filtration the alkali in the filtrate is titrated with iV/3-nitric acid with phenolphthalein as indicator. The difference between this titration and the blank gives the carbon dioxide and halogen and the latter is then separately estimated in the) same1 solution by adding an excess of silver nitrate and nitric acid and titrating back with ammonium thiocyanate. Estimation of Carbon in the Organic Non-sugar Constituent of Saturation (Sugar) Scums. VL. STAX~K (Zeitsch. Zuckerind. Bolzm. 1916 40 201-206).-The carbon is estimated by oxida- tion with chromic acid-sulphuric acid solution.From 1 to 2 grams of the material are placed in a small flask provided with a glass sto'pper which carries a tapped funnel and a condenser. Ten C.C. of 0.5% alkali hydroxide solution are added and then 5 grams of crystallised phosphoric acid; the mixture is boiled gently t o expel carbon dioxide cooled 5 grains of chromic acid are added and the upper end of the condenser is connected with a combustion tube containing copper oxide and two pieces of silver gauze; this tube is G. F. M.ii. 268 ABSTRACTS OF CHEMICAL PAPJMS. heated in a suitable furnace. Concentrated sulphuric acid is now admitted t o the flask from the tapped funnel and the mixture is boiled; the condenser prevents steam from passing into the combustion tube.The gases leaving the latter are passed through a tube containing chromic acid then dried and thO carbon dioxide is absorbed in a soda-lime tube. A current of air free from carbon dioxide is passed through the apparatus when the oxidation has been completed. The sugar content of the sample is estimated in a separate portion and the quantity of carbon dioxide due to sugar is deducted from the total amount of carbon dioxide found. w. P. s. Rapid Method for the Estimation of Carbon Dioxide. W. H. WAGGAMAN ( J . Ind. Eng. Chem. 1916 8 41).-The carbonate is decomposed in a conical flask the upper parb of which is sur- rounded by a cooling coil. The delivery tube of the flask is con- necbd with a short inclined condenser and the other end of the latter is connected with the following series of absorption vessels A U-tube containing silver sulphate solution (to retain hydrochloric acid) a sulphuric acid bulb potash bulbs a calcium chloride tube a sulphuric acid bulb and a tubs containing barium hydroxide solution.The latter indicates any loss of carbon dioxide due to too rapid passage of the gas through the absorption bulbs and also shows when the potash bulb has become exhausted. A current of air is drawn through the apparatus the air being passed previ- ously through pot'assium hydroxide solution contained in a flask ; this flask also carries an Ostwald regulator by means of which the supply of gas to the burner under the decomposition flask is regulated. The apparatus may be used for the estimation of Estimation of the Carbon Dioxide Tension in the Alveolar Air.W. McK. MARRIOTT (Proc. Amer. SOC. Biol. Chem. 1915 xviii.; J. Biol. Chem. 1916 24).-The carbon dioxide tension in the sample of air is estimated by bubbling the air through a 0.01 N-solution of sodium hydrogen carbonate containing phenol- sulphonephthalein as an indicator. The reaction of the solution and the corresponding colour obtained are functions of the carbon dioxide tension. The colour is compared with that of standard solutiolns of mixed phosphates containing the indicator made up in such a way Ghat the bension of carbon dioxide in mm. may be directly read off. Changes in the barometric pressure and slight changes in temperature are without effect on the accuracy of the method. The results agree closely with those afforded by Haldane's method.H. W. B. carbon diocxide in soils organic substances etc. JV. P. s. Method of Gas Analysis. 0. A. KRONE (J. Ind. Eng. Chem. 1916 8 231-237).-A detailed description is given of a method and apparatus for the analysis of gas mixtures containing carbon dioxide illurninants oxygen carbon monoxide methane ethane hydrogen and nitrogea. F o r concentrations of oxygen not exceed-ANALYTICAL CHEMISTRY. ii. 269 ing 5% phosphorus is used to separate this gas; f o r higher con- centrations and when carbon dioxide and carbon monoxide are not present the use of copper in the presence of ammoniacal ammonium chloride solution is recommended for the purpose. w. P. s. Rapid Method of Estimating Alkali in Potable Water.M. WAGENAAR (Pharnz. IVeekblad 1916 53 232-238).-A modi- fied form of the barium hydroxide method f o r estimating the alkali metals in water. A. J. W. A Colorimetric Method Used by the Romans to Characterise Sofc Waters. A. TRILLAT (Compt. rend. 1916 162 486-48S).- The method of the Greeks and Romans (compare Hippocrates “ Trait6 des Airs des Eaux et des Lieu,” Chap. 36) for detecting the presence of alkalis in natural wst’ers by the decoloration of red wine can be made t o give an approximate measure of the hardness of different waters. The degree of hardness is indicated by the number of drops of red wine required to produce a colora- tion in the water as compared against a standard water. W. G. Rapid Method for the Analysis of Limestone for Agri- cultural Purposes.A. S. BEHRMAN (J. I d . Eng. Chem. 1916 8 42-43).-0ne gram of tjhe powdered limestone is mixed with 50 C.C. of N/Z-hydrochloric acid and a few drops of 3% hydrogen peroxide solution and heated a t 86O for thirty minutes. The mixture is then cooled 5 grams of ammonium chloride and some macerated filter-paper are added followed by 25 C.C. of N/2-am- monia solution. After fifteen minutes the precipitate etc. is collected on a filtler washed with 10% ammonium nitrate solution ignited and weighed; the weight gives the quantity of insoluble substances ferric hydroxide and aluminium hydroxide present. The filtrate is titrated with N/2-hydrochloric acid using methyl- orange as indicatosr. The total carbonates are found by subtract- ing the weight of the precipitate from 100 and the amount of hydrochloric acid required for the decomposition is a measure of the carbon dioxide in the carbonates; the actual quantities of calcium and magnesium carbonates in the sample may be calcu- lated from these data. The results obtained by the method are only approximately correct the error being about 2% or 3%.w* P. s. Micro-colorimetric Estimation of Calcium and of Inorganic Phosphates in the Blood Serum. JOHN HOWLAND F. H. HAESSLER and W. McK. MARRIOTT (Proc. Amer. SOC. Biol. Clzem. 1915 xviii.-xix. ; J . Biol. Chem. 1916 24).-The methods described are based on the fact that the red colour of a solution of ferric thiocyanate is discharged by certain substances among which are oxalates and phosphates. Calcium is precipitated as oxalate dissolved in acid added to a standard solution of ferric thiocyanate and made up to a definite VOT,.CX. ii. 12ii. 270 ABSTRACTS OF CHEMICAL PAPERS volume. The colour of the resulting solution is compared with that of a solution containing known amounts of calcium oxalate and ferric thiocyanate. The phosphates are precipitated as mag- nesium ammonium phosphate ; the precipitate is then dissolved in acid added to ferric thiocyanate solution and colour comparisons made as above. The calcium content of the serum in children is not diminished in cases of rickets except when accompanied by tetany. Para- thyroidectomy in dogs is followed by a progressive diminution in the calcium content' of the serum. H. W. B. Estimation of Calcium in Blood. JOHN 0. HALVERSON and OLAF BERGEIM (Proc. Amer.SOC. Biol. Chem. 1915 xxii.; J . Biol. Chem. 1916 24).-Ten C.C. of blood are deproteinised by means of picric acid and tlie calcium in the filtrate precipitated as oxalate. The precipit'ate is washed by centrifugal action and the oxalate titrated with O'OlN-permanganate solution. Magnesium is estimated in tlie filtrate by precipitation as mag- nesium ammonium phosphate the ammonia content of which is estimated aftter distillation colorirnetrically or by direct titration. H. W. B. Solubilities of the Sulphates of Barium Strontium Calcium and Lead in Ammonium Acetate Solutions at 2 5 O and a Criticism of the Present Methods for the Separation of these Substances by means of Ammonium Acetate Solutions. J. W. MARDEN (J. -4mer. Chem. Soc.1916 38 310-317).-The solu- bility of the above-named sulphates in ammonium acetate has been determined a t 2 5 O f o r several concentrations of ammonium acetate. A measured volume of the saturated solution was treated with a little sulphuric acid and evaporated to dryness gently ignited and weighed. The results show that tlie more concentrated the ammon- ium acetate solution the better will b0 the separation of lead sulphate from the other sulphabes. It is t o bet noted however that the solubilities even of barium and strontium sulphates are con- siderable in ammonium acetate as compared with those in water. A criticism of the various methods of separation of the four metals is given and a new method suggested. This consists in evaporating the solution to 20 c.c.adding 3 C.C. of 2N-sulphuric acid and an equal volume of ethyl alcohol. The mixtare is left f o r five minutes and filtered. The ptecipitate is washed five times with 5 C.C. of boiling SN-ammonium acetate containing 1% of ammonium sul- phate. The filtrate is evaporated t o a syrupy consistency 1 C.C. od concentrated sulphuric acid is added the mixture dried on the water-bath and ignited. After cooling 5-10 C.C. of N-sodium hydroxide are added,and the mixture rubbed with a rod filtered and the filtrate acidified with acetic acid. The addition of potass- ium chromat!e t o thO filtrate gives a yellow precipitate if lead is present. The barium and strontium sulphates are converted into carbonates by boiling with 4N-sodium carbonate and tested in the usual manner.J. F. S.ANALYTICAL CHEMISTRY. ii. 271 Detection of Cadmium. ROBERTO SALVADORI (Ann. Chzm. Applicata 1916 5 25-26).-Ammoniacal ammonium perchlorate solution (compare A. 1910 ii 1002) may be used advantageously in place of potassium cyanide f o r the detection of cadmium. To the nitric acid solution of copper cadmium and bismuth sulphides excess of ammonia solution is added the bismuth hydroxide being removed by filtration. Addition t o the blue filtrate of ammoniacal ammonium perchlorate solution results in the precipitation of cadmiumtetrammine perchlorate which dissolves in the hot but is reprecipitated on cooling. When a 20% solution of ammonium perchlorate solution in anmonia solution of D 0.9 is used 1 part of cadmium salt per 3000 of solution is readily detectable; in cases where less sensitiveness is sufficient the concentration of the re'ageat may be lowered to 15%.When the cadmium is mixed with the five-fold proportion of copper the reaction is delayed but not prevented. T. H. P. Rapid Method for the Analysis of Red Lead and Orange Mineral. JOHN A. SCHAEFFER ( J . Ind. Eng. Chem. 1916 8 237-238).-0ne gram of the sample is stirred with 15 C.C. of nitric acid (D 1.2) until all red colour has disappeared; 10 C.C. of dilute hydrogen peroxide solution (1 part of 3% hydrogen peroxide solution to 3.5 parts of water) are then added and when the lead dioxide has nearly dissolved complete solution is effected by the addition of a small quantity of hot water. The solution is now diluted to about 250 C.C. and titrated with standard permanganate solution having an iron value of 0.005.A control titration is made with the same quantities of nitric acid hydrogen peroxide and water and the difference between the two titrations multiplied by 3.058 gives the percentage quantity of red lead in the sample. The difference multiplied by 1.067 gives the percentage of lead dioxide. A convenient chart is given showing the quantities of red lead and lead dioxide corresponding with the volume of per- manganate used in the titrations. w. P. s. Standardisation of the Mercurials. DONALD E. STRICKLAND (1. Znd. E?2g. Chem. 1916 8 253-257).-The Hempel iodine titra- tion method yields trustworthy results for the estimation of mercury in calomel m d mercurous iodide pills and tablets; Rupp's form- aldehyde-iodine Eethod may be used f o r the estimation of mercuric chloride mercuric iodide and of mercury in ammoniated mercury ointment. The thiocyanatel method is suitable for the analysis of mercurial ointment mercuric nitrate ointment and red mercuric oxide ointment.The presence 'of lactose does not influence the estimation of mercuric iodide by Rupp's method (compare also A. 1911 ii 824). w. P. s. Electrolytic Estimation of Mercury in Mercury Oleates. B. L. MURRAY ( J . I71d. Eng. Chem. 1916 8 257).-About 1 gram of the mercury oleate is weighed into a mercury cathode cup and 20 C.C. sf 10% hydrochloric acid and 15 C.C. of toluene are added.ii. 272 ABSTRACTS OF CHEMICAL PAPEKS. The anode is placed in position and rotated a t about 800 revolu- tions per minute while the mixture is electrolysed f o r thirty minutes using a current of 3 amperes and 8 volts.As the electro- lysis proceeds the coatents of the cup become heated nearly to the boiling point of some of the constants; i t is essential that the heat should be sufficient to melt the mercury oleate but if the mixture boils too vigorously the cup should be cooled by a bath of cold water. When the mercury is all deposited the contents of the cup are washed out by siphonation with water and the metallic mercury is washed with alcohol dried with ether and weighed. w. P. s. Electrolytic Estimation of Mercury in Mercury Salicylates. B. L. MURRAY ( J . Znd. Eng. Chem. 1916 8 258).-About 0.3gram of the substance is placed in a mwcury cathode cup and dissolved in 10 C.C.of sodium sulphide solution (D 1-18>. Twenty C.C. of 1076 potassium hydroxide solution are then added and the mixture is electrolysed with a current of 1 ampere and 7 volts the anode being rotated a t 500 revolutions per minute. About thirty minutes are required for the deposition of the mercury. The electrolyte is then decanted the mercury washed with water alcohol and ether and weighed. w. P. s. Volumetric Estimation of Cerium by Means of Potassium Permanganate. VICTOR LENHER and C. C. MELOCHE ( J . Amer. Chem. SOC. 1916 38 66-70).-Cerous compounds are oxidised t o ceric compounds by potassium permanganate according to the equation 6Ce(NO,) + ZKMnO + 4H,O = 4Ce(N0J4 + ZCe(OH)+ + 2KNO + 2Mn0,. The ceric salt produced hydrolyses readily with the production of free acid and this tends t o make the reaction reversible; hence a base must be added t o neutralise this acid.A number of experiments are described in which various bases are used t o neutralise the acid. The titration may be carried out in either hot or cold solution but i t should be genelralIy finished hot and the permanency of the end-point tested by boiling the solution for a minute. Among the substances investigated were zinc oxide caIcium carbonate magnesium oxide! borax sodium hydrogen car- bonate sodium carbonate sodium hydroxide barium hydroxide and potassium hydroxide. Of theset zinc oxide and magnesium oxide a m by far the most satisfactory. Good results may be obtained with bcrax and sodium hydrogen carbonate whilst sodium carbonate yields fair but not entirely satisfactory results.The otrher substances do not give satisfactory results. Sodium acetate sodium silicate sodium phosphate sodium tungstate and sodium arsenate are entirely unsatisfactory. The method may be used for the estimation of tervalent cerium in the presence of quadrivalent cerium. J. F. S. Simple Bath Used for the Solution of Samples in an Oxygen-free Atmoephere. 0. L. BARNEBEY (J. Amer. Chenz. SOC. 1916 38 374-375).-The bath described was designed for theANALYTICAL CHEMISTRY. ii. 273 solution of minerals in which ferrous iron was to be estimated. It consists of an 8-inch porcelain dish in which are placed some glass beads and a 51' circular desiccator plate with supports. On the plat0 a triangle of heavy glass rod is placed and this serves t o support the dish in which the solution is t o take place.The whole is coavered with a 6N funnel which has had its stem cut off. A solution of 1 2-phosphoric acid is poured into the dish in such an amount that i t just reaches the inside dish. The whole is heated on a sand-bath and the st'eam generated expels the air and heats the dish and its contents. The contents of the dish can be stirred by means of a platinum or glass rod through the open end of the funnel. J. F. S. Analysis of Chromium Oxide. ALLAN J. FIELD (J. Ind. Eng. Chem. 1916 8 238-239).-Fusion with sodium peroxide is recom- mended t h s resulting chromate being then estimated iodometrically. The author finds that the! fusion may be carried out in a platinum crucible without appreciable damage to the latter if the' crucible containing about 0.5 gram of chromium oxide and 3 grams of sodium peroxide is placed in a larger porcelain crucible which is heated so that the mixture just melts.The heating should be continued for twenty minutes the mass then dissolved in water the solution boiled for twenty minutes filtered t o remove any ferric hydroxide neutralised with hydrochloric acid and diluted to 250 C.C. One hundred C.C. of this solution are now treated with 10 C.C. of concentrated hydrochloric acid 3 grams of potassium iodide are added and the liberated iodine is titrated with thio- sulphate solution. I n the absence of sulphates the chromium may be estimated gravimetrically as barium chromate. The oxide is fused with sodium peroxide as described the mass dissolved the solution neutralised with acetic acid 0.5 C.C.of glacial acetic acid is added the solution diluted to 400 c.c. and treated while boiling with dilute barium acetatel solution added drop by drop. The barium chromate is collected washed with dilute alcohol dried and weighed. w. P. s. Use of Hydrofluoric Acid in the Separation of some Heavy Metals from Tin Antimony Tungsten and Molybdenum by Means of the Electric Current. LEROY W. MCKAY and N. HOWELL FURMAN ( J . Amer. Chem. SOC. 1916 38 640-652).- Details are given of methods f o r the' electrolytic estimation of a number of metals in thO preser.ce of other metals. The electrolyses are all effected in a mixture of nitric acid and hydrofluoric acid. The analyses which have! been carried out include the separation of silver from tin and antimony mercury from tin and antimony copper from molybdenum copper from tungsten and molybdenum lead from tungsten lead from molybdenum lead from tungsten and molybdenum mercury from tungsten mercury from molyb- denum mercury from tin antimony tungsten and molybdenum and silver from tin antimony tungsten and molybdenum.The results in all cases are very good but in some of the cases theii. 274 ABSTRACTS OF CHEMICAL PAPERS. highest de'gree of accuracy is only obtained when a correction is applied for the amount of plattinurn contained in the deposit. This is not a large quantity and rarely exceeds 0.5 mg. J. F. S. Electrometric Titration of Vanadium. GEORGE LESLIE KELLEY and JAMES BRYANT CONANT ( J .Amer. Chem. Soc. 1916 38 341-351).-A method is described by which vanadium may be estimated by titration with a ferrous salt using the sudden change in E.M.F. as indicator of the end of the reaction. A quantity of a vanadate is placed in a beaker dissolved in 175 C.C. of water and 25 C.C. of sulphuric acid (D 1.4) are added. A platinum elec- trode rotavi stirrer and the connecting tube of a calomel elec- trode are inserted in the solu.tion. The1 electrodes are connected with a potentiometer dry cell and suspension galvanometer in the usual way. Stiandard ferrous sulphate is then run in from a burette; the galvanometer needle commences to move off the scale but is brought back by an adjustable resistance in the circuit This goes on until about three-fourths of the equivalent amount of ferrous sulphate has been added then the needle remains a t rest until the end-point is reached when it gives a sudden movement.If in the titration an excess of ferrous sulphate has been added this can be titrated back by potassium dichromate solution until the needle is just brought back t o its position of rest. The best condi- tions for these titrations are low temperature (loo) high acid concentration and low concentration of chromic and ferric salts. A comparison of the results obtained by this method is made with the results obtained by four of the standard methods. The results are found to be in close agreement. The oxidation of vanadium to the quinquevalent condition by nitric acid has been found unsatisfactory f o r quantitative purposes.The oxidation by potass- ium permanganab has been found entirely unsatisfactory f o r this method in the absence of chromium. The same remark applies t o ammonium persu1phat)e. J. F. S. Behaviour of Antimony Deposits towards Hypochlorite. W. VAUBEL and A. KNOCKE (Chem. Zeit. 1916 40 209-210).- The ordinary hypochlorite test for distlinguishing between antimony and arsenic deposits o r mirrors yields trustworthy results only when the hypochlorite solution used is freshly prepared. Old hypo- chlorite solution always contains some chlorite and this dissolves antimony deposits such as are obtained in the Marsh apparatus. The antimony deposits or mirrors vary in composition; grey deposits are not soluble in hypochlorite solution containing chlorite but the black deposits are quite soluble.Black deposits on a porcelain surface become insoluble after some days' exposure to air. w. P. s. Electrolytic Estimation of Bismuth in Bismuth /3-Naphthol. B. L. MURRAY ( J . Ind. Ertg. Chem. 1916 8 257-258).-A quan- tity of 0.3 gram of the sample is ignited in a porcelain crucible until all organic matter bas been oxidised. Tlie residue) consistingANALYTICAL CEEMISTRY. ii. 275 of bismuth oxide with a small amount of metallic bismuth is dissolved by heating with a mixture of 4 C.C. of nitric acid (D 1.4) and 5 C.C. of water and the solution rinsed with water into a mercury cathode cup the volume of the solution being made up t o 20 C.C. The solution is now electrolyse'd with a current of 4.5 amperes and 6 volts the anode being rotated a t 1000 revolutions per minute; the time required is about forty-five minutes.When all black masses have disappelared the anode is stopped and the cathode washed without interrupting the current then dried with ether and alcohol and weighed. The increase in weight of the mercury cathode is due t o the bismuth which has been depositeld on and amalgamated with the mercury. w. P. s. Colorimetric Estimation of Acetylene. E. R. WEAVER ( J . A nzer. C'hem. SOC. 1916 38 352-361).-A colorimetric method f o r the estimation of small amounts of acetylene is described. The method consists in conducting the gas under examination through an ainmoniacal solution of cuprous chloride containing gelatin alcohol and liydroxylamine hydrochloride and colmparing the colour of the red colloidal solution so obtained with a suitable st'andard which may be either a solution of a red dye or a piece of ruby glass.The most efficient absorbing solution is made by dissolving 0.25 gram of gelatin in hot watler diluting t o 500 c.c. and adding 500 C.C. of 95% alcohol and 1-25 grams of hydroxylamine hydrochloride. To 20 C.C. of this solution 10 C.C. of concentrated ammonia and a small amount of cuprous chloride are added. After the absorption of the acetylene the solution is diluted t o 100 C.C. and compared in a colorimeter with the standard. The standard used by the authors consisted of 0.21 mg. of chromoanilbrown-R 0.04 mg. carmoisine-B 2.5 grams of gum arabic and 100 C.C. of water. A more convenient although less accurate standard is a fixed depth of a solution of azolitmin.If 10 C.C. of a solution of azolitmin containing 1 part of the dye in 2500 parts of water are used as standard the amount of acetylene in 100 C.C. of the colloidal solution may be calculated from the equation x = 0 . 1 3 ~ + 0.03 where x is the number of milligrams of acetylene and y is the reciprocal of the number of C.C. of colloidal solution required t o match the standard. The method is very sensitive. Amounts of acetylene as small as 0.03 mg. may be detected and amounts up t o 2.0 rng. estimated with an accuracy of 0.05 mg. Hydrogen sulphide and large amounts of oxygen and carbon dioxide interfere with the reaction but these may be removed by passing the gas through a hot alkaline solution of pyrogallol. J. F. S. Estimation of Cholesterol in Blood.W. R. BLOOR (J. BioZ. Chem. 1916 24 227-231).-Three C.C. of whole blood plasma or serum are run in a STOW stream of drops into1 about 75 C.C. of a 3 1 mixture of redistilled alcohol and ether in a 100 C.C. flask which is well agitated during the process. After boiling the contents of the flask are cooled brought t o the mark with alcohol-ether mixed and filtered. Ten C.C. of the alcohol-ether extract areii. 276 ABSTRACTS OF CHEMICAL PAPERS. measured into a small beaker and evaporated just t o dryness on a water-bath. Any heating after dryness is reached produces a brown colour which renders the subsequent estimation difficult or impossible. The cholesterol is now extracted from the dry residue by boiling out three or four times with successive small portions (3-4 c.c.) of chloroform and decanting into a 10 C.C.glass-stoppered graduated cylinder. The combined extracts after cooling are made up to 5 c.c. 2 C.C. of acetic anhydride and 0.1 C.C. of concen- trated sulphuric acid are added and the solution after mixing placed in the dark for fifteen minutes. The colour is then com- pared in a Duboscq colorirneter with that of a solution similarly prepared from 5 C.C. of a standard cholesterol solution in chloroform containing 0.5 mg. of cholesterol. ThO results obtained are always about 20% higher' than thorn afforded by the Autenrieth-Funk method but are believed t o be the more accurate owing to the better extraction of the cholesterol and the avoidance of the long digestion with strong alkali a t a high temperature involved in the older method.H. W. B. Analysis of Morphine Hydrochloride Standardised Morphine Hydrochloride Solution and Morphine Syrup. $1. FRANCOIS and E. LUCE (J. Phusm. Chim. 1916 [vii] 13 145-155).-1n addition to the usual tests and methods prescribed f o r the analysis of morphine hydrochloride the1 authors recommend that the hydro- chloric acid be also estimatesd by titration with silver nitrate solu- tion using potassium chromate as indicator; the result of this estimation gives the molecular weight 'of the base and c o m e quently will indicate' whether any base other than morphine is present. I n the case of morphine hydrochloride solution the quantity of the salt present is estimated by evaporating a definite volume of the solution and weighing the residue; here again the estimation of the hydrochloric acid is advantageous. Morphine may be separated from morphine1 syrup by mixing 50 grams of the sample with 50 grams of water 20 grams of sodium sulphate and 0.5 gram of asbestos and then adding 50 C.C. of N/lO-iodine solution. After thirty minutes the asbestos and the adhering morphine periodide are collelcted on a cotton-wool filter thO periodide is then treated with sulphurous acid the solution obtained is rendered ammoniacal and extracted with amyl alcohol. The amyl alcohol extract is now shaken with dilute hydrochloric acid the aqueous solution sepa- rated evaporated and the residue subjected to the usual tests f o r the identification of morphine. The quantity of morphine present in the syrup is estimated by treating 10 C.C. of the sample with 1 C.C. of 10% iodic acid solution adding 1 C.C. of ammonia after the lapse of five minutes and comparing the coloration p r o d u d after a further forty-five minutea with that given by a known amount of morphine under similar conditions. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005260

出版商:RSC    

年代:1916

数据来源: RSC