摘要:

ii. 108 ABSTRACTS OF CEEMICAL PAPERS Analytical Chemistry. Theory of Indicators Used in Acidimetry. RUD. WEGSCHEIDER (Zeitsch. physikal. Chem. 1915 90 641-680).-A theoretical paper in which a theory of indicators is developed on the assump- tion that undissociated compounds and their ions when these have the same constitution as the parent substance are similarly coloured and all colour changes are to be ascribed to constitutional changes. Formula are deduced which give the concentration of free acid or base a t stated hydrogen ion and indicator concentra- tion and also the concentration of the indicator which must be employed in order exactly to titrate such a solution. The author differentiates between ideal and non-ideal indicators. The ideal indicators are those f o r which the one form occurs only in the ionised condition and the other form in the non-ionised condition.I n the case of single coloured indicators the ideal indicators behave differently from the non-ideal indicators. Ideal indicators increase in sensitiveness with concentration whereas with non-ideal indicators a maximum of sensitiveness appears a t a definte con- centration. Non-ideal indicators generally are less sensitive than ideal indicators except that just a t the equivalent point the advantage of the ideal indicator over the non-ideal is very small. For the calculation of all data i t is necessary in the case of single colour indicators to have knowledge of the apparent dissociation constant of the colourless indicator and the real dissociation constant of the coloured form.For t,itration to the point of equivalence in alkaline solution coloured indicator acids are better than coloured indicator bases and in the same way in acid solution coloured indicator bases are better than coloured indicator acids. Indicators with two colours behave in different ways. The behaviour in all cases can be completely represented from the apparent dissociation constant. Ideal and non-ideal two-coloured indicators behave similarly. The equilibrium constants that is the dissociation constants df both forms and the reaction constant of the change from one form to the other of non-ideal indicators can only be determined by the usual chemical and optical methods when a spectral region exists in which only one form abmrbs light. J.F. S. Apparent Transformation of Indicators. F. LIEBERT (Chem. Weekblad 1915 12 1088-1091). Compare de Vries this vol. i 56).-The author cites a number of examples of colour change of indicators before titration is complete. A. J. W. Testing Distilled Water as Regards its Suitability for the Preparation of Salvarsan Solutions. J. TILLMANS and H. MILDNER ( Z e i t s c h . angelc. Chem. 1915 28 469-474).-The dis- tilled water used for preparing salvarsan solutions for injectionsANALYTICAL CHEMISTRY. ii. 109 should be free from large numbers of bacteria soluble constituents of glass and heavy metals. The presence of a large number of bacteria in the water is usually indicated by a high oxygen absorp- tion (from permanganate) and by the presence of ammonia and nitrous acid and estimations of these will afford evidence of the suitability of the water apart from an actual bacteriological analysis.One hundred C.C. of the water when boiled with AT/lOO- permanganate solution in the presence of dilute sulphuric acid sliould not reduce more than 0.2 C.C. of the permanganate solution; ammonia and nitrous acid should not be present. Provided that the distilled water is not contaminated by tap-water as is shown by the absence of chlorine nitric acid and calcium the presence of soluble constituents of glass is indicated by the appearance of a red coloration when the boiled water is treated with a few drops of rosolic acid solution. The presence of traces of iron in the water is not of importance; tin is not dissolved by distilled water but tests should be applied for the detectdon of lead copper nickel and zinc.w. P. s. Persistence of Hydrogen Peroxide in Milk. E. HINKS (Analyst 1915 40 482-489).-1t was found that hydrogen peroxide when added to milk was destroyed rapidly a t first that the rate of destruction diminished and that if the concentration of the hydrogen peroxide was high enough t o withstand the initial rapid destruction the residual peroxide remained constant in amount over long periods (up t o eighteen months). The age of the milk was the most important factor in regard to its behaviour towards hydrogen peroxide; fresh milk had the least effect whilst milk three days old and in which the catalytic activity had in- creased considerably was capable of destroying relatively large quantities of hydrogen peroxide within one hour.The rate a t which the hydrogen peroxide was decomposed increased with the temperature up to 3 7 O . I n the case of a sample of fresh milk in which the initial concentration of hydrogen peroxide was 0*2% about 33% of the peroxide was still present after the lapse of one year. It is pointed out that owing to the destruction of peroxydase by hydrogen peroxide it is necessary when testing for the presence of the latter to add some fresh milk as well as the reagent (benzidine pphenylenediamine etc.) in order to ensure the presence of peroxydase; the addition of fresh milk is also neces- sary in testing heated milk for the presence of hydrogen peroxide. The possibility of a milk having received an addition of hydrogen peroxide must be considered when these reactions are used for the detection of previous heating since a milk containing peroxide will react in certain circumstances in exactly the same way as a heated milk.w. P. s. Estimation of Bromine and Iodine in the Presence of Chlorides. L. W. WINKLER (Zeitsch. angezu. Chena. 1915 28 4 7 7 4 8 0 494496).-1n the case of bromides containing but small quantities of chlorides the bromine may be estimated byii. 110 A USTl{AC'I'S OF ClI EMICaL PAPERS acidifying the bromide solution with sulphuric acid and titrating the boiling mixture with permanganate solution the latter being added in small quantities at a time until a pink coloration remains on boiling the mixture for about one minute. If large quantities of chloride are present the bromide solution is titrated in a flask attached to a condenser the end-point of the titration being denoted when the drops of distillate no longer exhibit a yellow colour due to the presence of bromine.I n the case of sea-water a portion of the sample is placed in a flask acidil'led with sulphuric acid and distilled with the continual addition of small quantities of per- manganate solution. The distillate is collected in sulphur dioxide solution hydrogen peroxide solution or alkali hydroxide solution and the resulting hydrobromic acid or hypobromite is then esti- mated by the usual metliods. For the estimation of iodine in tlie presence of bromides and chlorides the sodium nitrite method is recommended. The sample is acidified and shaken with sodium nitrite solution in the presence of carbon tetrachloride ; after several of these treatments the separated carbon tetrachloride solu- tioris are t,reated with carbamidel t o decompolse traces of nitrite and then titrated with thiosulphate solution.Bromine may be estimated i f present in the sa,me portion of the sample. For this purpose the solution remaining after the separation od the carbon tetra- chloride is acidified with sulphuric acid distilled until dissolved carbon tetrachloride and nitrous acid have been expelled and then titrated with permanganate solution as described. w. P. s. New Method of Estimating Iodine in Organic Preparation 8. E. RUPP and F. LEHMANN ( A d . Pharm. 1915 253 443-451).- The method depends on the fact that chlorine and bromine in organic preparations are removed in the elementary state by heat- ing with sulphuric acid and potassium permanganate in the presence of a silver salt whilst iodine is retained in the form of silver iodate provided an excess of permanganate is always present.Twenty C.C. of concentrated sulphuric acid and 25 C.C. of iVjl0- silver nitrate are heated in a 500 C.C. Kjeldahl flask until the flask is filled with white fumes. The mixture is then cooled 2.5 grams of finely powdered potassium perma-nganate are added and a small glass tube containing the substance (0.25 -gram) is allowed t o slide into the mixture. I n those cases in which a vigorous evolution of gas does not ensue by shaking 5 C.C. of water are added immediately; in the contrary cases the addition of the water is postponed until the vigorous reaction has almost ceased.After the addition of the water the mixture is vigorously shaken for one t o two minutes and is then kept for fifteen minutes with frequent shaking. The flask is then closed with a filter-funnel and heated in a sloping position a t first gently until the liquid boils then strongly. By repeated rotation of the Rask any particles of substance or of manganese dioxide carried into the neck are washed back into the liquid. The heating is maintained until the manganese dioxide has been almost entirely decomposed and a deep blue solution has been obtained. This is thoroughly cooled,AXALYTICAL CH EAllb'i'H I'. ii. 111 treated with a freshly-prepared solution of 5 grams of crystallised ferrous sulphate in 100 C.C.of water and is vigorously shaken f o r rz few minutes until the oilver iodide has curdled and the super- natant liquid is quite clear. The contents of the flask are tlieii washed into a large beaker and the excess of silver is titrated with fT/ 10-thiocyanate. I n some cases less energetic treatment suffices to decompose the organic preparation. For example 0.5 gram of airol (bismuth gallate iodide) is boiled for two to three minutes with 20 C.C. of 25% nitric acid and 20 C.C. of A'/lO-silver nitrate the mixture is diluted with 50 C.C. of water and allowed to cool a little potassiuni permanganate is added t o oxidise any nitrous acid and then ferrous sulpliate until the red colour has disappeared and the excess of silver is titrated with iV/10-thiocyanate; not more than 12.1 C .C . Absorption of Oxygen in Alkaline Solutions and a New Absorbent for Oxygen. F. HENRICII (Ber. 1915 48 2006-2009). -When studying the autosidation of orcinol (A. 1915 i 564) the author noticed that the reaction proceeded much more quickly in the presence of potassium hydroxide than in the presence of sodium hydroxide. I n connexioii with other work involving the estimation of oxygen in gaseous mixtures the relative value of the two alkalis has been tested in the coinmon absorbents. It is found that sodium hyposulphite or pyrogallol solutions are more efficient when made up with potassium hydroxide than with the equivalent of sodium hydroxide. The very concentrated alkaline solutions of pyrogallol are some- times unsuitable and therefore the author has sought f o r another absorbent among the trihydroxybenzenes. An excellent solution far surpassing pyrogallol in activity and stability is made as follows 11 *4 grams of crude powdered hydroxyquinol triacetate prepared by the action of acetic anhydride on pbenzoquinone (Tliiele A.1898 i 469) is suspended in 20 C.C. of water shaken in a hydrogen atmosphere with a concentrated alkali hydroxide cont'aining 17.4 grams of KOII o r the equivalent (6 niols.) of NaOH and then the solution is diluted in the pipette with 130 C.C. of water. J. C. W. Titration of Thiosulphates in the Presence of Sulphides and the Estimation of Thiosulphates in the Presence of Sulphites Bisulphites and Sulphidep. SANDER (C7iem. Zeit. 1915 39 945-947. Compare A.1915 ii 161).-A method for the estimation of thiosulphate and sulphide when present in the same solution depends on their different behaviour towards mercuric chloride. When mercuric chloride is added t o sodium sulphide solution a black precipitate of mercuric sulphide a t first forms which on the furthes addition of mercuric Chloride changes to white mercuric thiochloride SHgCl + 2Na,S = 4NaCl + (2HgS,HgCi,) ; sodium thiosulphate reacts with mercuric chloride according to the equation f-"a,SL03 + SHgCI -t 2H,O = 2Na,S04 + 4HC11+ (2HgS,€1gC!l2). of the last (=20% of iodine) should be consumed. c. s.ii. 112 ABSTRACTS OF CHEMICBL PAPERS An aliquot portion of the solution containing the two salts is titrated with N / 10-iodine solution ; another portion of the solu- tion is then treated with an excess of mercuric chloride ammonium chloride is added and the mixture titrated with $/lo-sodium hydroxide solution using methyl-orange as indicator. The number of C.C.of alkali solution used divided by 2 gives the quantity of N / 10-iodine solution required for the thiosulphate and the differ- ence between the two titrations corresponds with the iodine re- quired for the sulphide. A method described by Bosshard and Grob (A 1913 ii 525) may be used for the estimation of thio- sulphate in the presence of sulphite. An alternative method consists in titrating the two salts with iodine solution; another portion of the sample is then treated with mercuric chloride and the acidity formed from the thiosulphate titrated with alkali solu- tion.The reaction between sulphites and mercuric chloride is shown by the equation Na,SO + HgC1 = NaC1+ HgC1-NaSO,. For the estimation of thiosulphate sulpide and sulphite in the presence of each other a definite volume of the solution containing these salts is added to an excess of N/lO-iodine solution previously acidified with 10 C.C. of N/10-hydrochloric acid and the excess of iodine is titrated with N/lO-thiosulphate solution; let A be the number of C.C. of iodine solution used. The same solution is then titrated with N / 10-sodium hydroxide solution using methyl-orange as indicator; after deducting the 10 C.C. of N/lO-hydrochloric acid added previously the result corresponds with the quantity of N / 10-iodine solution ( B ) required for the sulphite.Another equal portion of the original solution is now treated with an excess of mercuric chloride ammonium chloride is added and the acidity of the mixture is titrated with N / 10-sodium hydroxide solution (C) ; the ammonium chloride is added to prevent precipitation of mercuric oxide by the alkali. Then the amount of N/lO-iodine solution used by the thiosulphate is C/2 for the sulphite B and for the sulphide A -(B+C/2). A mixture consisting of 0.2471 gram of Na,S,O 0.1249 gram of Na2S0 and 0-1207 gram of Na,S was analysed by this method with the following results Na,S,O 0.2483 gram; Na2S0 0.1261 gram; Na,S 0*1201 gram. w. P. s. Estimation of Ammonia Nitrogen in Steer’s Urine. DONALD C. COCHRANE ( J . Biol. Chem. 1915 23 311-315).- Figures f o r nitrogen as free ammonia in the urine of cattle are untrustworthy because of the decomposition of ammonium car- bonate and special precautions must be adopted t o overcome this rapid decomposition ; chloroform and toluene fail t o prevent it.Sulphuric acid added to the urine of a steer in quantity sufficient t o fix the ammonia present as carbonate and t o slight excess retards decomposition t o such an extent as to allow time for analysis. W. D. H. A Source of Error in the Analysis of Coal which Contains Large Quantities of Alkaline Earth Carbonates. KNUBLAUCH (Zeitsch. angew. Chem. 1915 28 492-494).-Attention is directedANALYTICAL CHEMISTRY. ii. 113 to the fact that during combustion calcium and magnesium carbonates when present in a coal evolve carbon dioxide and that the latter is absorbed in the potash bulbs thus causing the result for carbon to be too high.When oxygen is estimated by difference an error is introduced of the ash of the coal is not treated with ammonium carbonate and again ignited gently before being weighed. Unless the necessary corrections are made f o r these errors the true calorific value of a coal cannot be calculated from the results of the elementary analysis of the sample). W. P. S. Estimation of Carbon Dioxide and a New Form oP Absorption Tower Adapted for the Titrimetric Method. E. TRUOG ( J . Znd. Eng. Chem. 1915 7 1045-1049).-The methods available f o r the estimation of carbon dioxide are reviewed. The gravimetric method by weighing absorption apparatus gives good results only when aspiration is slow; when large amounts of carbon dioxide are in question the method is troublesome.The titri- metric method of absorption in alkali hydroxide and double titrai tion has the disadvantage of uncertain end-points. The author recommends absorption in barium hydroxide solution in a special absorption tower consisting essentially of a suction flask into the neck of which a fairly wide glass tube about 2 feet long extending to within 118th-inch of the flask and two-thirds full of glass beads is fixed. The top of the tube is closed with a cork through which passes a 50 C.C. dropping funnel and a tube leading to the aspirator the funnel being closed with a soda-lime tube. In use the tower is first freed from carbon dioxide in the usual way the funnel is charged with standard baryta solution which is allowed to run over the beads in the glass tube thus producing efficient contact between the solution and the carbon dioxide which is aspirated fairly rapidly into the suction flask through its side aperture and so up the tower.Absorption being complete the baryta solution is washed into the suction flask and rapidly titrated. G. F. M. Apparatus for Measuring the Carbon Dioxide Evolved During Alcoholic Fermentation. L. LINDET ( A m . Falsv 1915 8 295).-The apparatus described consists of a glass cylinder such as is used for drying gase’s having a tubulure at the bottom; this tubulure carries a side tube which is bent upwards and then downwards a t a height of about 4 cm. below the top of the cylinder. The neck of the cylinder is closed wit’h a rubber stopper through which pass the delivery t u b from the fermentation flask and a short length of tube; the upper end of this tub6 passes through a oork which closes the neck of an invert’ed flask.The cylinder and the flasi are filIed with light petroleum. As the carbon dioxide collects in the upper part of the cylinder an equivalent volume of “petrol” is discharged through the side tube and is collected in a graduated cylinder; its volume is equal t o that of the evolved carbon dioxide. The light petroleum in the inverted flask serves to keep the level of the light petroleum in the cylinder constant. VOL. CX. ii. 5 w. P. s.ii 114 ABSTRACTS OF CHEMICAL PAPERS. Practical Methods for the Determination of Radium. 11. The Emanation Method S.C. LIND (J. I d . Eng. Chem. 1915 7 1024-1029. Compare A. 1915 ii 486).-A detailed description is given of a number of methods of cliemical treatmerit deaigned with the object of preparing emanation from radium ores and reaiduea obtained in the commercial production of radium for measurement in the electroscope previously described. The eman- ation may be removed either from a solut.ion o r from a fusion. I n the former case excess of barium and a rather high concentra- tion of nitric acid must be maintained in order t o prevent as far as possible the formation of radium sulphate from which the emanation is only expeiled with great difficulty. The boiling off is conducted in a special apparatus consisting essentially of a flask connected with a gas burette charged with hot sodium hydro'xide solution and leading from its upper end into the electroscope chamber.When the radio-active substance is insoluble in water or acids fusioln with alkali casbonatel is resorted to and in many cases the e'manation may be expelled from the fused product by dissolving it in nitric acid in the flask of the above-mentioned apparatus. G. F. M. Estimation of Potassium in Potassium Salts by the Perohlorate Method. G. HAGER and J. KERN (Landzu. Versuchs- Stat. 1915 87 365-380).-Investigation of this method (com- pare A. 1914 ii 817) showed that the solubility of potassium per- chlorate in alcohol increases as the strength of the alcohol decreasee. The presenm of perchloric acid and of barium sodium and mag- nesium perchlorates decreases the solubility of the potassium salt.Alcohol of a t least 96% by vol. and containing up t o 1% of per- chloric acid should be used for washing the potassium perchlorate when dealing with a fairly pure potassium salt. A concentrated alcoholic solution of perchloric acid should be used in the prepar% tion of the alcoholic solution of this acid employed for washing the potassium perchlorate. The method yields low results when applied t o the estimation of potassium in samples containing much sulphate owing t o the fact that potassium salts are occluded in the barium sulphate during the necessary preliminary removal of sulphates ; other methods for the estimation should be used for such samples [cornparel Thin and Cumming T. 1915 105 361; Davis ibid. 16791. TN. P. s. Perchlorate and Cobaltinitrite Methods for the Estimation of Potassium.T. D. JARRELL (J. Assoc. Oficial Agric. Chenz. 1915 1 29-32; from J. SOC. Chcm. Ind. 1915 34 1170).-The author has applied these methods to the estimation of potassium in potassium chloride and in fertilisers and finds that neither method is satisfactory in its present form. J. c. w. Elect ro-analysis of Silver Without Platinum Electrodes. J. G U Z B ~ N and J. ALEMANY (Annl. Fis. Quim. 1915 13 343-350). -An account of results obtained in the electro-deposition of silverANALYTICAL CHEMISTRY ii. 115 on a nickel-plated copper cathode. passive iron or graphite. The anode consisted either of A. J. W. Estimation of Silver i n Organic Preparations. J. HERZOG (Arch. Phurm. 1915 253 441-442).-Lehmann’s method (A.1915 ii 650) is recommended. Two grams of potassium per- manganate may in general be regarded as a suitable amount of the oxidising agent but the optimum quantity for each individual preparation must be determined by experience. c. s. Volumetric Estimation of Cadmium and Zinc. HENHIK ENELL (Zeitsch. anal. Chem. 1915 54 537-546).-When cadmium sulphide is shaken for some time with an excess of iodine reaction takes place according to the equation CdS + I = CdI + S. The excess of iodine is then titrated with thiosulphate solution and the quantity of cadmium calculated from the amount of iodine con- sumed. This method yields approximately correct results but i t tends to be untrustworthy and is not recommended. A better method depends on the reaction between cadmium sulpliide and silver nitrate CdS + 2AgN0 = Ag,S + Cd( NO,),.The cadmium sulphide obtained in the usual way is collected on a filter and washed with a warm 2% ammonium sulphate solution (to each 250 C.C. of which are added twenty drops of 10% sulphuric acid) until the wash-water no longer gives a reaction with silver nitrate. The filter and precipitate are then transferred t o a stoppered cylinder and shaken with 50 C.C. of water and 20 C.C. or more of N/lO-silver nitrate solution. Five C.C. of 25% nitric acid are now added the mixture is again shaken for one minute filtered and the excess of silver is titrated in an aliquot portion of the filtrate. A similar method may be used for the estimation of zinc. To obtain the zinc sulphide in a condition in which it may be readily filtered and washed the zinc salt solution is rendered slightly ammoniacal 2 C.C.of 25./ acetic acid are added the solution treated with hydrogen sulphide then heated on a water-bath for fifteen minutes and 1 gram of ammonium sulphate is added. The precipitate is washed with a warm 2% ammonium nitrate solution which has been rendered slightly ammoniacal and then acidified with acetic acid. The method yields from 99.5 t o 100.1% of the Colorimetric Method for the Determination of Copper and Iron in Pig Lead Lead Oxides and Lead Carbonate. BERNARD S. WHITE ( J . Znd. Eng. Chem. 1915 7 1035-1036).-From 10-30 grams of material are dissolved in hot nitric acid (1 l ) 32 C.C. of sulphuric acid (1 :1) are added and the precipitate washed by decantation and then on filter-paper.(In the case of red lead hydrogen peroxide is added after the nitric acid to decom- pow the lead peroxide). To the filtrate a slight excess of ammonium hydroxide is added and the iron egtirnated eolorimetrio ally in the precipihte by dissolving it in hydrochloric acid and adding a few drops of nitric acid and ammonium thiocyanate soln- zinc present. w. P. s. 5 - 2ii. 116 ABSTRACTS OF CHEMICAL PAPEHS. tion. The copper is estimated in the filtrate by adding to the faintly acidified solution six drops of 1 10 potassium ferrocyanide solution filtering dissolving the precipitate in ammonium hydroxide rendered faintly acid with hydrochloric acid and com- paring the tint with a standard made by adding the requisite amount of copper sulphate solution to 10 C.C.of ammonium chloride 2 drops of hydrochloric acid and 90 C.C. of water. Zinc if present in large amount should be removed by precipita- tion wit’h sodium ammonium phosphate previous t o the copper estimation. G. F. M. Rapid Volumetric Procedures for Estimating Combined Alumina and Basic Alumina or Free Acid in Aluminium Salts. WILFRED 177. SCOTT (J. I d . Eizg. Chem. 1915 7 1059-1061).-The basia alumina or free acid in aluminium salts or technical liquors is estimated by Craig’s potassium fluoride method (A. 1911 ii 335) with minor modifications such as the addition of 10 C.C. N/2-sulphuric acid Do the hot aluminium solu- tion before adding the fluoride and titsating back with N/2- potassium hydroxide. Combined alumina is estimated by titration in boiling solution with N / 2-sodium hydroxide with phenol- phthalein as indicator until a pink colour persistent for at least a minute in the hot solution is obtained.A co,rrection must be introduced for ferric and ferrous iron which are nearly always present in technical liquors since they are likewise dissociated and titrated with the aluminium in the above process. Ferric iron is estimated by titra€ion with stannous chloride before and total iron after oxidation with permanganate and the percentage of FeO x 0.47 + Fe20 x 0.64 is deducted from the aluminium titration. The results obtained show good agreement with gravimetric mti- mations. G. F. M. Detection of Iron in Filter Paper which bas been Treated with Hydrofluorrc Acid. A. GAWALOWSKI (Zeitsch.anal. Chem. 1915 54 547-549).-The traces of iron in filter-paper which has been treated with hydrofluoric acid are usually present in the form of a ferrous-cellulose compound. The iron may be detected by the thiocyanate reaction after the paper has been acidified with dilute hydrochloric acid or sulphuric acid. I n this case the red coloration appears only after the paper moistened with the acid and reagent has been exposed to the air for a short time so that the ferrous iron is oxidised. If dilute nitric acid is used in the te’st the coloration appears more quickly but change& gradually t o yellow. w. P. s. Estimation of Osychloride and of Free Hydrochloric Acid jn Solutions of Ferric Ohloride. R. FEIST (A~ch. Phctrm. 1915 253 451-456).-Romyn’s method (A.1915 ii 489) does not give any information as t o the ratio of the iron t o the chlorine and therefore does not show whether in addition t o the acid pro- duced by hydrolysis any exce9s of hydrochloric acid is present.ANALYTICAL CBEMISTRY ii. 117 The author therefore recommends in addition the estimation of the iron and of the total chlorine by Volhard’s method. C. S. Formic Acid as a Reagent in Essential Oil Analysis. WM. H. SIMMONS (Analyst 1915 40 491-494).-Terpineol is decomposed aimwt completely by f ormylation ; geraniol and linalool are both converted into an appreciable quantity of ester whilst santalol is only decomposed slightly. Citronellol menthol and the borneol in rosemary oil may be estimated approximately by formylation. The process consists in heating for one hour a mix- ture of 1 vol.of the oil and 2 vols. of 100% formic acid on a water- bath under a reflux apparatus washing the esterified oil with saturated sodium chloride solution until free from soluble acid neutralking St and estimating the quantity of potassium hydroxide required for itg saponification. w. P. s. Estimation of Reducing Sugars. A Volumetric Method for Estimating Guprous Oxide without Removal from Fehling’s Solution. F. M. SCALES (J. Biol. Chenb. 1915 23 81-87).-The cuprous oxide without filtration is converted into cuprous chloride and then transferred to a known quantity of dilute iodine solution; the iodine which is not reduced is then titrated with sodium thiosulphate. The method gives as accurate results as the gravimetric method and takes much less time.The method may also be used for the estimatioii of copper. W. D. H. Use of Dry Yeast in the Estimation of Sugar in Urine. A. BOLLAND and A. KRAUSZ (Chem. Zeit. l915,39,947-948).-Dried pressed yeast is preferable to ordinary yeast in the fermentation test for sugars in urine; i t may be kept for many months and does not undergo autofermentation within the period of time required for the test. About 0.5 gram of the dried yeast is mixed with the urine to be tested and the mixture is filled into an Einhorn’s fermentation tube ; any sugar present is fermented completely in fifteen to twenty hours a t the ordinary temperature. The presence of acetone in the urine does not affect the activity of the yeast. w. P. s. - Microchemical Chitin Reaction. V.VOUK (Ber. Deut. bot. Ges. 1915 33 413-415).-The object is heated for twenty to thirty minut,es in a beaker with concentrated boiling potassium hydroxide solution. The conversion into chitosan is then complete and the reddish-violet coloration can be obtained in the usual manner. N. H. J. M. [Estimation of] Beneoyl Peroxide. L. VANINO and F. HERZER (Arch. Pharm. 1915 253 426-440).-Thel paper gives an account of the melthods of prelparation the properties and the technical medicinal and physiological applications of benzoyl peroxide already recorded by various investigators and contains nothing new except a methad of estimation. The peroxide 0.2-0.3 gram aDdii. 118 ABSTRACTS OF CHEMICAL PAPERS. 10-15 C.C. of alcohol are heated on the water-bath an excess of W / 2-potassium iodide is added and the mixture faintly acidified.After being heated on the water-bath for four minutes the mixture is allowed t o cool and is titrated after thirty minutes with thio- sulphab solvtion. The results are accurate. c. s. Formaldehyde-Fat-Quotient of Milk. G. A. STUTTERHEIM (Pharm. TVeekblad 1915 52 1729-1731).-From the results of a great number of analyses the author draws the conclusion that in good milk the f ormaldehyde-fat-quotient should not exceed 2.40. A. J. W. Fat Analysis. I. Soluble and Insoluble Fatty Acids. F. H. SMITH (Chem. News 1915 112 319-320).-The saponifica- tion number insoluble and soluble fatty acids and the mean mole- cular weight of the insoluble fatty acids may be1 estimated in one portion of a sample of fat (for example butter-fat) as follows Five grams of the1 fat are saponified by boiling with a definite quantity of alcoholic potassium hydroxide solution and the excess of alkali is then titrated; the saponification number is calculated from the result.The neutral solution is evaporated to remove alcohol the residue dissolved in water and ths insoluble fatty acids are liberated by the addition of a slight excess of W/5-hydro- chloric acid; the! mixture is then cooled in ice-wate'r the liquid portion filtered and the insoluble fatty acids washed dried and weighed. The filtrate is titrated with standard alkali solution and the result after allowance f o r the excess of N/5-hydrochloric acid added is expressed in terms of butyric acid or as mg.of potassium hydroxide per gram of fat. The insoluble fatty acids are dissolved in alcohol and the solution titrated to obtain the mean molecular weighti of these acids. w. P. s. Estimation of Water and Fats in Feeding Stuffs. K. SCHERINGA (Phnrm. Weekblad 1915 52 1732-1733).-A descrip- tion of a simple type of apparatus f o r estimating moisture and fat in such foods as cheese and cocoa. The extract from the sub- stance is placed in a thick-walled round-bottomed flask fitted with a twoihole rubber stopper and two tubes. One of the tubes is drawn out to a capillary and air is drawn through the flask by means of a water-pump sol as to create a partial vacuum and a continual circulation of air. The flask is heated in a water-bath. A. J. W. Molecular Weight Estimations of Vegetable Oile.H. J. BACKER (Chem. Waekblad 1915 12 1034-1040).-An account of thO determination of the density refractive index and the iodine and saponification values of certain vegetable oils. The molecular weights have been debermined by the cryoscopic method with benzene as solvent. They have also been calculabd from the sapofiification value ( V ) from the equation M = 168000/ V . A . J. W.ANALYTICAL CHEMiSTHT. ii. 119 Ring Test for Acetone in Urine. C. J . REICHARDT (Phnm. Zoif. 1915 60 765).-E’ive C.C. of urine are mixed in a test-tube with 2 grams of ammonium chloride and 5 drops of a freshly- prepared sodium nitroprusside solution and ammonia is poured on the surface of the mixture. I f the urine cont’ains more than 0.15 part of acetone per 1000 a violet-coloured zone appears within a few minutes a t the junction of the two liquids; with smaller quantities of acetone a red-coloured zone first appears and changes t o violet in about twenty minutes. If the urine’ is free from Ammonia and Amino-acids in Urine.W. C. DE GRAAFF (Pltarm. Weekblad 1915 52 1777-1781 ).-An account of estim- ations of ammonia in urine by Bonnema’s method (A 1915 ii 648) and a dismission on the presence of amino-acids in urine. acetone a coloured zone does not develop. w. P. s. A. J. W. Estimation of Amino-acids in the Urine. IVAR BANG (Riochem. Zeitsch. 1915 72 101-103).-1t is shown that urine can be decolorised in the presence of alcohol by animal charcoal which under these conditions does not remove any of the acids.It can then be employed for the estimation of the amino-acids (+ ammonia) by Sorensen’s formalin titration method. The urine before decolorisation is treated with barium chloride and barium hydroxide. S. B S. The Estimation of the Amino-acids of Feeding-stuff8 by the Van Slyke Method. 11. H. S. GRINDLEY and M. E. SLATER [with H. C. ECKSTEIN and J. C. Ross] ( J . Amer. Chem. SOC. 1915 37 2762-2769).-Ths lack of concordance between the previous results of the authors and those of Nollau (A. 1915 i 932) is ascribed t o differences in experimental details. The value of the Van Slyke method f o r the estimation of the chemical groups characteristic of the amino-acids of proteins is again asserted and i t is suggested that the high results obtained by this method for humin nitrogen are due in part t o the presence of soluble carbo- hydrates during the hydrolysis of thel proteins and to the presence of cellulose which may mechanically protect some of the protein from complete hydrolysis. The experimental results published in this paper indicate the existence of marked variations in the free and combined amino- acid content of the common feeding-stuffs whether referred to the total nitrogen present o r t o the weight of the feeding-stuff itself.These conclusions are based on experiments with blood meal tankage wheat barley oats white soja beans cottonseed meal and lucerne hay. D. F. T. Estimation of Urea in Urine by the Urease Method C,YRUS H. FISKE ( J . Bio2. Chem. 1915 23 455-458).-The urease method can be made more exact by taking precaut.ions to prevent any escape of ammonia through the acid which receives it.W. D. H.ii. 120 ABSTRACTS OF CHEMICAL PAPERS Estimation of Alizarin and Certain Other Dyestuffe. EDMUND KNECHT and EVA HIBBERT ( J . SOC. Dyers 1915 31 241-244).-For the estimation of alizarin anthrapurpurin or flavopurpurin a weighed quantity of 0.02 to 0.05 gram of the substance is dissolved in 50 C.C. of alcohol the solution is boiled in a flask into which a current of carbon dioxide is passed and 10 C.C. of 20% sodium potassium tartrate solution are added followed by a measured excess of titanous chloride solution. The mixture is again boiled and the excess of titanous chloride titrated with iron alum solution. All three of the substances show intense blue-green colorations with the excess of titanous chloride ; this colour disappears when the last trace of titanous salt has been oxidised by the iron alum.Four atoms of hydrogen are required for the reduction of each of the substances; in the case of alizarin this would correspond with the reduction of the substance to deoxyalizarin. The colouring matters gallocyanin and prune are also quantitatively reduced by titanous chloride two atoms of hydrogen being sequired; primuline is not affected by titanous chloride but primuline-red formed by diazotising it and combining Which Constituents of Sour Milk are Precipitated in the Alcohol Test? F. REISS and G. DIESSELHORST (BCied. Zewtr. 1915 44 565-567 ; from ilfoZk.-Zeit. 1915 742).-The precipitate obtained with 70% alcohol contains the whole of the nitrogen originally present in the milk. Calcium phosphate was found both in the precipitate and filtrate whilst magnesium phosphate to a great extent remains in solution although some was found in the precipitate. Two samples of milk were employed the acidity of which was 11.2 and 29.4 respectively. The Electrometric Estimation of the True Reaction of the Blood. Josk MA. DE CORRAL (Biochem. Zeitsch. 1915 72 1-25).-The author gives a general criticism of the technique of the various methods that have been employed. The results obtained by himself for the hydrion concentration do not differ appreciably from those found by other observers. DONALD D. VAN SLYKE MARIAM VINOGRAD-VILLCHUR and J. R. LOSEE ( J . Biol. Chem. 1915 23 377406).-After incubating serum and substrate the mixture is freed from protein by colloidal ferric hydroxide and the free aminsnitrogen is estimated in the concentrated filtrate by the micro-apparatas. The amount of digestive change is estimated by the yield of amino-acid. Every serum whether from pregnant or non-pregnant individuals showed protein digestion when incubated with placenta; the range in activity is wide and the tendency is .for pregnant sera to give a somewhat higher result. The differ- ences are too small however to make the test decisive even from the quantitative point of view. Carcinoma tissue is digested to about the same extent as placenta. with P-naphthol is easily reduced. w. P. s. N. H. J. M. S. B. S. The Abderhalden Reaction. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9161005108

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i. 113 Organic Chemistry. Preparation of Aluminium Ethoxide. FARBWERKE YORN. MEISTER LUCIUS & BRUNING (D.R.-P. 286596; from J . SOC. Chenz. Itid. 1915 34 1168).-Dry alcohol is t,reated with alumin- ium in the presence of a very small quantity of mercuric chloride (as a catalyst) and in the preseace or absence of alkyl haloids o r iodine. The mixture is then distilled under reduced premure when a dist'illate freel from mercury is obtained. J. C. W. Preparation of 7-Me thylbutinol and its Homologues. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 285770; from J . SOC. Chem. Ind. 1915 34 1167).-The alkali compounds of acetylene o r its homologues are treated with acetone o r its homo- logues in an inert medium. J. C. W. Simple and Mixed Alkyl Phosphates. W. A. DRUSHEL ( A mer.J . Sci. 1915 [iv] 40 643-648).-Trialkyl phosphates were prepared'by the action of phosphoryl chloride on the corresponding sodium alkyloxides in suspension in dry ether. Contrary t o state- ments in the literature they were all up to triisobutyl phosphate found t o be distdllable in a vacuum without decomposition. Al- though stable towards cold AT/ 10-hydrochloric acid they were readily hydrolysed by aqueous barium hydroxide and from the barium salts of the dialkyl hydrogen phosphates produced mixed trialkyl phosphates were obtained by the silver salt method. The hydrolysis of the mixed trialkyl phosphates by barium hydroxide proceeds in two directions simultaneously and not as stated by Lossen and Kohler (A. 1891 1013) by the removal of one of the alkyl groups which occurs twice to the exclusion of the group that occurs only once so that the praduct contains e3ter.s of the types HRR'PO and HR,PO,.Tables are given showing the effect of various alkyl groups on the velocity constants of the hydrolysis of simple and mixed trialkyl phosphates by hydrochloric acid a t looo. The following physical constants are given for the phosphoric esters Trimethyl b. p. 197O/760 mm. D22 1.200; triethyl b. p. 215O/ 760 mm. DZ2 1'056; tripropyl b. p. 131°/15 mm. D22 1.007; tri- isobutyl b. p. 152O/15 mm. D22 0.965; dimethylethyl b. p. 203O/ 760 mm. D22 1.161 ; dimethylpropyl b. p. 116O/15 mm. D22 1'180; methyldipropyl b. p. 129O/20 mm. D22 1.059; diethylpropyl b. p. 130°/20 mm. D22 1.077; eithyldipropyl b. p. 145O/20 mm. D22 1.025.G. F. M. The Mechaniem of the Action of Tribasic Sodium Pb osphate on the a-Monochlorohydrin of Glycerol. 0. BAILLY (Compt. rend. 1915 161 677-680).-A critical investigation of the interaction of trisodium phosphate and glycesol monochlorohydrin in which VOL. cx. i. fi. 114 ABSTRACTS OF CflEMICAL PAPERS. the author shows that the changes are not so simple as that stated by King and Pyman (T. 1914 105 1238) (1) Na3P0 + CH,Cl*CH(OH)*CR,*OH = NaCl + P0,Na2*CH,*CH(OH)*CH~*OH The two substances were mixed in equiinolecular proportions the mixt-ure being kept a t 18" and a t definite int<ervals determinations were made of the sodium chloride formed of the trisodium phos- phate destroyed and of the glycerophosphate formed. The results show that whilst the sodium chloride formed and the trisodium phosphate destroyed are in molecular agreement throughout the amount of sodium glycerophosphate formed is always much less than that required by equation (I) the difference being very marked for the first ten hours. The author considers that the formation of sodium glycerophosphate takes place according t o equations (2) and (3) (2) Na8P0 + CET,Cl*CH(OH)*CH,*OH = 0 /\ Na,HPO + NaCl + CH,*CH*CH,*OH 7\ (3) C€€,*GH*CH,*OH + Na,HPO = P0,Ns,*r,H2*CH(OH)*C€~~*O€€ since he has shown thatl the glycide and disodium hydrogen phos- phate do react slowly to give sodium glycerophosphate about 80% of the glycide being transformed into glycerophosphate in about eight days.W. G. Electrolysis of the Alkali Salts of Aliphatic Sulphocarboxylic Acids.FR. FICHTER and THEODOR LICHTENHAHN (Ber. 1915 48 1949-1963).-The anodic oxidation of sulphoacetic acid and its potassium and ammonium salts of potassium sulphopropionate and ammonium sulphopropionate dissolved in the free acid of potassium methanesulphonate and of methanedisulphonic acid and its salts has been investigated. I n the case of sulphoacetic acid and its salts the chief products are sulphurid acid and carbon dioxide but carbon monoxide ethylenie formaldehyde sulphur dioxide and methane- and ethane-disulphonic acids may be detected the latter as their baxium salts. The normal product analogous t o the electro-syn- thesis of ethylene is ethanedisulphonic acid thus 2S03H*CI12*C02H + 0 = C2H4(S03H)2 + 2C0 + H20. Just after the commencement of the electrolysis however the neutral solution becomes alkaline and later on it accumulates neutral sulphates conditions which are favourable' to the Hofer and Moe'st reaction (A.1902 i 736) in which hydroxyl ions convert the fission product. of electrolysis into an alcohol. That is the residues *CK,*SO,H not only coalesce t o form ethanedisulph- onic acid but they give methanolsulphonic acid OH*C"H,-SO,H. This of course is speedily oxidised to the aldehyde CHO*S03H which will give sulphuric acid and formaldehyde on hydrolysis (and therefore also sulphur dioxide and carbon monoxide) or be oxidised t o sulphoformic acid CO,H*SO,H and finally t o sulphuric acid andORGANlC CHEMlSTRY. i. 115 carbon dioxide. The production of ethylem and methanedisulph- onic acid is attributed to anothelr reaction of the *CH,*SO,H residue thus 4*CH,*SO,H = ZCH,(SO,H) + C,H,.Just as the production of butane from a propionate falls very much behind the electrosynthesis of ethane the chief gaseous product being ehhylene so the main result of the electrolysis of a sulphopropionate is the formation of sulphuric acid ethylene and carbon dioxide thus SO,H*CH,.CH,*CO,H + 0 = H2S04 + C,H4 + CO,. Here again secondary reactions take place and carbon monoxide formaldehyde sulphur dioxide and acetic acid may be detected among the products. The electrolysis of potassium methanesulphonate leads to the pro- duction ol' carbon dioxide the sulphate and a little persulphate and also formaldehydesulphonic acid which becomes obvious on boiling the solution.No carbon monoxide o r hydrocarbon is formed. The result is an oxidat.ion unaccompanied by synthetic processes thus CH,*SO,H + 4 0 = CO + H,S04 + H20 and CI13.S0,H + 2 0 = CHO*SO,H + H20. Similarly methanedisulphonic acid or its salts is merely oxidised to sulpliurio acid and carbon dioxide just as it is by 30% hydrogen peroxide. I n the course of thel experiments i t was observed that barium metlhanedisulphotnate crystallises not only in the well-known form of very thin rhombic tablets but in very characteristic centi- metre-long transparent needles arranged in concentric groups. This form is obtained by crystallisation from dilute solutions a t a low temperature in the presence of a trace of acid (for example a drop of 2N-HCl). The needles belong t o the same system as the tablets.F o r the details of the current densities employed and the methods for identifying and isolating the products the original should be consulted. J. C. W. Trichloro-tert.-butyl Acetate (Acetylchloretone). T. B. ALDRICH (J. Amer. Chem. SOC. 1915 37 2720-2723).-When P-trichloropropan-P-ol CCl,*CMe,*OH is heated with a mixture of acetic anhydriae and sodium acetate it is converted into the corre- sponding acetate CCI,-CMe,*OAc b. p. 145-146O/246 mm. Hydro- lysis is effected only slowly with water o r dilute acids but concen- trated nitric acid causes rapid hydrolysis. The acetab has anzes- thetic properties similar to those of the parent alcohol but its toxicity towards guinea-pigs is slightly less. Fatty Acid Esters of Ethylene Glycol. R.F. RUTTAN and J. R. ROEBUCK (Trans. Roy. SOC. Canada 1915 9 1-ll).-The authors have prepared a number of mono- and di-acid esters from ethylene glycol by direct esterification a t high temperatures and with con- stant stirring. About 30 grams of the acid were mixed with an amount of glycol more than sufficient to convert the whole of the acid into mono-ester and the mixture was heated a t 185-187O in an open flask being constantly stirred by a platinum stirrer. The mixturel after fusion was freed from glycol by washing with hot D. F. T. f Si. 116 ABSTnhCTS OF CHEMICAL PAPERS. water and from free acid by iieutralisation with calcium hydroxide. The mono- and di-acid esters were separated by crystallisation from hot alcohol the di-acid ester separating out first.Ethylene ~list~earate C,H (C18H3,0,) crystallises in pearly plates in. p. 7 5 O 1.4385 0.8581; 100 grams of alcohol dissolve 0.010 grain a t Oo 0.028 gram at 25O 0.037 gram a t 2B0 and 0.112 gram a t 403 (compare Wiirtz APitk. Chim. phys. 1859 [iii] 55 436). The moji ost enm t e C,H,(OH) (C1,H3,02) crystallises in pearly plates m. p. 58*5O n;;5 1.4310 Dbl) 0.8780; 100 grams of alcohol dissolve 0.64 gram a t Oo 1.31 grams a t 7 * 4 O 2.10 grams a t 16O 4.17 grams a t 25O 10.61 grams a t 29O. 3 t h ylc. tz e d i p ? ni i ta t e C,H (C ,,H3,02) cry st allises in pearly plates in. p. 68*7O 9 2 g 7 1.4378 D77.9 0.8594; 100 grams of alcohol dissolve 0.018 gram a t Oo 0.087 gram a t 25O 0.109 gram a t 29O 0.31 gram a t 38O. The moizopnlmitnte C,H4(OH)(Cl,H,,0,) crystallises in pearly plates in.p. 51*5O n::s 1.4411 D60.5 0.8786; 100 grams of alcohol dissolve 1-62 grams a t Oo 5.76 grams a t 7*4O 10.67 grams a t 16O 24.08 grams a t 25O. Ethylene dimargarate C2H,(C17H3302)2 crystallises in needles or waxy scales in. p. 65*5O 122 1.4392 D67.1 0.8605; 100 grams of alcohol dissolve 0.024 gram a t Oo 0.101 gram a t 25O. The m0120- ?norprcite C,H,(Ol€)(C,,€13,02) crystallises in thin plates m. p. 5O*Zc ng 1.4440; 100 grams of alcohol dissolve 1-72 grams a t Oo. The esters with oleic acid were not satisfactorily separated as their solidification points seemed very near each other and t h a t of oleic acid itself. Ethylene chlorohydrin when heated in a sealed tube for twenty hours a t 105-115° with equivalent quantities of either stearic or palmitic acid gave the corresponding chloroethyl ester the action ceasing when 18-20% of the acid remained uncombined.Chloroethyl stearate C2H,C1*CI8H3,O2 crystallises in waxy scales m. p. 48-5O D49.5 0.9049 1.4433 ; 100 grams of alcohol dissolve 0.20 gram a t Oo 0.28 gram a t 7'4O 1.29 grams a t 16O 2-10 grams a t 25O 3.62 grams a t 29O. Chloroethyl palmitate C,H4C1-Cl,H,,O2 crystallises in pearly plates m. p. 41*5O w g 5 1.445 D46*I 0.9097; 100 grams of alcohol dissolve 0-48 gram a t Oo 1.16 grams a t 7'4O 3.8 grams a t 16O 8.87 grams a t 2 5 O 15.31 grams at 29O. Chloroetliyl stearate when heated with the calculated quantity of silver palmitate a t 140° for three t o four hours or with potassium palmitat'e for a much longer time gives ethylene stearopalmitate C2H,(C,8H3502)(CIFH3102) m.p. 65O n 2 1.4391 D7O.5 0.8584; 100 grams of alcohol dissolve 0.011 gram a t Oo 0.035 gram a t 25O 0.049 gram a t 29O 0.213 gram a t 39O. W. G. Catalytic Bleaching of Palm Oil. SOSALE GARALAPURY SASTRY (T. 1915 107 1828-1831. Compare Eng. Pat. 17784 of 1913).- A series of experiments is described on the bleaching of palm oil by blowing air or oxygen through it both air and oil being a t 80-90° in the preslence of the salts and oxides of manganese cobalt nickel iron and lead. Manganese borate and particularly cobalt borate,ORGANIC CHEMISTRY. i. 11'7 are found to be very efficient catalysts f o r this purpose f o r 60-70 grams of a crude oil were completely bleached in the presence of 0.01% of the latter by a current of air flowing a t the rate of abouf 17 litres per hour for lhree and a-half hours.The1 bleaching was permanent and oils treated in this way retain their characteristic perfume and soap-making qualities. KNOLL k Co. (D.R.-P. 284762; from J . SOC. Chem. Ind. 1915 34 1166).- Cobalt cliolate [C,,H,50,J,Co is prepared by the interaction of an alkali cholate with a cobalt salt or by other common methods. It readily swells in water but dissolves sparingly in water and alcohol and not a t all It has disinfecting properties when taken internally but therapeutic doses do riot injure the mucous membrane of the stomach. J. C. W. Preparation of a [Cobalt] Salt of Cholic Acid. in ether benzene o r chloroform. J. C. 117. Magnesium Citrate in Aqueous Solution. FRANCINE SWART and C.BLOMBERG ( J . Pharm. Chim. 1915 [vii] 12 387-391).- The authors do not agree with the existence of a heptahydrate of magnesium citrate as described by L6ger (A. 1915 i 496). They explain the slow separation of magnesium citrate tridecahydrate from aqueous solution as due t o the ionisation of the citrate giving rise to two complex ions (compare A. 1915 ii 737) which slowly recombine t o form the molecule which then crystallises as the tridecahydrate. They reaffirm the existence of the basic mag- nesium citrate Mg,CT*OH previously described by Blomberg (Phcwni. Tl~eebblcrd. 1915 September) and explain its formation by means of these complex ions. Magnesium Citrate in Aqueous Solution. E. LI~GER (J. Phnrm. Chim. 1915 [vii] 12 391-394).-A reply t o Swart and Blomberg (preceding abstract).W. G. W. G. Bromoacetglxylose and P-Triacetylmet hylxylosid e. J. K DALE ( J . Amer. Chem. SOC. 1915 37 2745-2747).-By treating xylose with a saturated solution of hydrobromic acid in acetic anhydride a t the ordinary temperature bronzot8.iacetyZx?/Zos~ crystals m. p. 10Zo [a]:" +212.2O (in chloroform) can be produced. This substance in acetic acid solution reacts with silver acetate giving 6-tetra-acetylxylose (compare Hudson and Johnson follow- ing abstract) and when treated in inethyl alcohol with silver nitrate yields 6-triacetyl?nethylxy~os~de thin plate-like crystals m. p. 115O fa]:' -60'5* which is converted by cold dilute sodium hydroxide solution into B-methylxyloside (Fisclier A. 1895 i 439). D. F. T. The Isomeric Tetra-acetates of Xylose.The Acetates of Melibiose Trehalose and Sucrose. C. S. HUDSON and J. M. JOHNSON ( J . ,4?ncr. Chem. Soc. 1915 37 2748-2753).-Tetra- acetylxylose m. p. 128O (corr.) (Stone A. 1894 i 104; Bader A 1896 i 336) when heated in acetic anhydride containing a littlei. 118 ABSTRACTS OF CHEMICAL PAPERS. zinc clilorid-e undesgoes chemical change as is clear from the occur- rence of a marked increase in the optical activity of the solution and there can be separated from the solution an isomeride m. p. 59O (corr.) ; an unstable alcoholate of this substance was isolated as an intermediate product in the process of separation. The1 optical activity of the new compound is [a]go +88*9O in chloroform +80*4O in benzene and +95*S0 in acetic acid whereas for the original compound m.p. 1 2 8 O the values for solutions of approxi- mately the same concentration (approx. 10%) were [ a ] f -25-l0 - 2 2 * 3 O and - 7 . 3 O respectively in the same three solvents; the former compound is therefore termed a-tet,ra-acetylxyIose as a prob- able derivative of the known dextrorotatory a-xylose whilst the less fusible hvorotatory compound is termed P-tetra-acetylxylose from its presumed relationship with the hypothetical P-xylose. On hydro- lysis of the a-tetra-acetyl derivative with alcoholic potassium hydr- oxide at Oo only ordinary xylose was obtained but acetylation of xylose with a mixture of acetic anhydride and commercial pyridine (compare Behrend A. 1907 i 481) gave a mixture of the a- and B-f orms of the tetra-acetyl compound.The tetra-acetylxylose ob- tained by Ryan and Ebrill (A. 1908 i 716) by the action of silver acetate on chloroacetoxylose in acetic acid is shown t o be the P-isomeride and an improved method is given for the preparation of chloroacetoxylose consisting in boiling xylose with acetyl chloride and a trace of zinc chloride until the sugar is completely dissolved. An acetic acid solution of hydrogen bromide rapidly converted both the a- and the P-tetra-acetyl compounds into one and the same bromoacetoxylose (compare Dale preceding abstract) which was convertled by methyl alcohol and silver nitrate into P-triacetyl- methylxylosidk. Melibiose octa-acetate m. p. 177.5O (corr.) [a] + 102.5O and + 101*9O in chloroform and acetic acid respectively when heated a t looo in acetic anhydride containing a little zinc chloride undergoes a marked increase in optical activity presumably due t o the forma- tion of an isomeride but the latter could only be isolated as a syrup.The new and more active isomeride will be the a-form whilst the original compound is t o be represented as the 8-isomeride. Trehalose octa-acetate m. p. 96-98O [ulto + 1 6 2 . 3 O in chloro- form and sucrose octa-acetate m. p. 69O [a]:' +59*6O in chloro- form showed no alteration in optical activity when dissolved in acetic anhydride with a little zinc chloride thus indicating the non- existence of isomerides as would inde'ed be expected from the lack of muta-rotation and the non-aldehydic character of these suqars. D. F. T. A Second Crystalline Lzevulose Pen ta-acetate (a-Lzevulose Penta-acetate).C. S. HUDSON and D. H. RRAUNS ( J . Amer. Chem SOC. 1915 37 2736-2745).-By the action of zinc chloride in acetic anhyAride solut\ion on lzvulose tetra-acetate the authors have obtained a d-lzevulose penta-acetate m. p. 70° [a!." +34*75O (in chloroform) and therefore quite distinct from the isomeric penta- acetate m. p. logo [a]go -120*9* recently described by the authorsORGANIC CHEMISTRY. i. 119 (A 1915 i 502). This new penta-acetate shows the same stability as that earlier described towards zinc chloride and therefore the method applicable to the establishment of equilibrium between aldose acetates fails in this case of a ketose derivative. The penta- acetatei ni. p. 1 0 8 O is obtained when lzvulose tetra-acetate is treated in the cold with sulphuric acid and acetic anhydride so that the same cyclic system must be present in both the penta-acetates which are therefore designated by the terms a- and P- f o r the more fusible and the less fusible isomerides respectively.a-Lzvulose penta-acetate can also be obtained directly from lzvulose by the action of zinc chloride in acetic anhydride solution and by the action of pyridiiie in the same solvent but the process described above is the most satisfactory. The best method for the production of laevulose tetra-acetate is with an acetic anhydride solution of zinc chloride and hvulose a t Oo stopping the reaction as soon as the last substance has passed into solution. A 30% yield of tetra-acetate can thus be obtained. ~ - L ~ v u l o s e penta-acetate when treated with an acetic acid solu- tion of hydrogen bromide is converted into laevulose tetra-acetate probably by way of the corresponding bromoacetyl compound.The a-peiita-acetate is unaffected by similar treatment 60 that it is probably correct t o regard the t'etra-acetate as a P-compound. As the original crystalline lzvulose was a P-compound and as the a- and P-penta-acetates do not give an equilibrium mixture i t is probable that in the production of the former from lzevulose a 113 olecular rearrangement occurs in one of the less acetylated deriv- atives but no experimental indication was forthcoming as to the stage of t.he acetylation at which rearrangement occurs. The authors have also prepared from lzevulose tetra-acetate a crystalline tetra-acetylmethyl-hvuloside which is to be described later.D. F. T. Action of Cyanides of the Alkali and the Alkaline Earth Metals on Sugars. E. RUPP and A. HOLZLE (Arch. Pharm. 1915 253 404-415. Compare A. 1914 i 142).-The preparation of a-glucoheptoic anhydride from dextrose is effected more con- veniently by barium cyanide than by potassium cyanide. The latter causes the formation of dark-coloured by-products but when its hydrolytic dissociation is diminished by the use for example of potassiurn ziacocyanide ths reaction product is obtained and remains nearly colourless. Zinc cyanide o r mercuric cyanide has no action on dextrose in aqueous solution. a-Glucoheptoic anhydride has recently come into use as a diabetic sugar under the name hediosite. Basic barium glucoheptoate OH-CH,*[CH*OH]5*CO*0.Ba.0H colourless crystalline precipitate is obtained by heating hediosite and barium hydroxide (1 rnol.) in saturated aqueous barium hydroxide at' 75O.The basic salt being sparingly soluble can be utilised to isolate the product of the reaction between dextrose and an alkali cyanide the yield of hediosite by this method being 30-33%. The velocity of reaction of a 10% dextrose solution and potassium 11.i. 120 ABSTRACTS OF CHEMICAL PAPERS. cyanide (1 mol.) has been followed polarimetrically the results being controlled by estimations of the ammonia evolved. About one-half of the sugar has reacted within two hours and the reaction ceases after three days. The estimation of the cyanide undecom- posed shows that the coiisumption of the cyanide increases rapidly with the concentration of the solution; the amount of potassium cyanide decomposed in a 10% dextrose solution in a few days is about the same as that decomposed in a 0.1% solution after one month.The consumption of the cyanidel is enormously accelerated catalytically by alkalis; a solution of dextrose and potassium cyanide when faintly acidified with sulphuric acid suffers in the course of weeks no greater loss of cyanide than does the same solution within a few hours after the addition of two drops of dilute sodium hydroxide or a few drops of aqueous ammonia. Mannose and potassium o r barium cyanide react in aqueous solu- tion with the evolution of ammonia and the formation of barium mannosecarboxylate from which the corresponding lactone is 0btaine.d by acidification.Laevulose and potassium or barium cyanide react hydrogen cyanide followed after several hours by ammonia being evolved ; the product obtained by evaporating the solution over sulphuric acid in a vacuum is probably potassium laevulomcarboxylatel but the free acid could not be isolated. The behaviour of galact,ose is quite similar t o that of lzevulose. I n the case of lactose hydrogen cyanide is evolved followed after several days by ammonia. The solution contains a dark-coloured viscous mass which was not further examined ; estimations of the undecomposed cyanide' after the lapse of- days show that the biosel reacts smoothly with 1 mol. of the cyanidel the more rapidly the greater is the coacentration of the solution but subsequently a second molecule of the cyanide is very slowly decomposed.These results are interpreted as indi- cating the formation of potassium lactosecarboxylate which is then hydrolysed to potassium glucoheptoate and galactose the latter being subsequently converted slowly into potassium galactosecarb- ox ylate. The behaviour of maltose is very similar t o that of lactose except that a second molecule of the cyanide scarcely enters int'o reaction. c. s. Preparation of Melibiose. C. S. HUDSON and T. S. HARDING (t7. Amer. Chem. SOC. 1915 37 2734-2736).-By a modification of the method of Bau and Loiseau (A. 1904 i 225 475) the authors have been able t o prepare melibiose from raffinose with a yield of 175-200 grams of pure1 crystalline pro'duct from 500 grams of the triose.Pure raffir-oset (500 grams) obtained by the process of Hudson and Harding (A. 1914 i 1166) was t,aken in approximately 10% aqueous solution together with baker's yeast (10 grams) acetic acid (one or two drops) and malt sprouts (I gram) the latter serving as a nitrogenous food; after thirty-six to forty-eight hours a t the ~ r d i n a r y temperature the optical activity had fallen t o approxi-ORGANIC CHEMISTRY. i. 121 mately that calculated for the resulting melibiose the kevulose having undergone further fermentation to carbon dioxide and alcohol. The solution was then filtered cleared with basic lead acetate solution decolorised by carbon and after evaporation t o a syrup cause'd to crystallise by the addition of alcohol and a nucleus of melibiose.D. F. T. Complex Metallic Ammines. 11. Additive Compounds Formed from trans-DichlorodietbylenediaminecobAltic Chloride. THOMAS SLATER PRICE and SIDNEY ALBERT BRAZIER (T. 1915 107 17 13-1 740).-The f crrmation of the additive compound between trans-dichlorodiethylenediaminecobaltic chloride and thiodiacetic acid (A. 1915 i 942) has led to the investigation of other dibasic acids including not only those containing sulphur but also acids of the oxalic acid series and certain unsaturated dibasic acids. It was found that all dibasic acids do not give rise to additive com- pounds; with one o r two exceptions the compounds formed are of two types which may be formulated as [Cl,Co en,]AH,H,A and [Cl,Coen,]AH where H,A is a dibasic acid. Acids which give compounds of the first type are malonic chloromalonic bromo- malonic glutaric acetonedicarboxylic thiodiacetic sulphonyldi- acetic and maleic acids whilst the following acids give compounds of tlie second type uxalic methylmalonic ethylmalonic dimethyl- malonic diethylmalonic dichloromalonic dibromomalonic succinic dibromosuccinic t'artaric meso-tartaric adipic dithiodiacetic dithiodipropionic fumaric citraconic mesaconic and itaconic acids.Thiodipropionic acid gives a compound of the type [Cl,Co ea,]Cl,H,A. A detailed consideration of the results hitherto obtained by Werner in connexion with analogous compounds together with the above reaults. leads the authors to the conclusion that the additive .-.GI compounds should be formulated as A<H--[--.C1 Co enJAH t l e hydrogens of t'he acid being connected withLthe chloriles of the complex by subsidiary valencies.An explanation of the fact that only certain dibasic acids give additive compounds is given in the light of the results hitherto obtained by Boeseken (A. 1913 i 1147) and Irvine and Steel (A. 1915 ii 669) it being shown that in all probability the acids giving rise t o compounds of the first type have their hydroxyl groups in the &position with respect t o each other malonic acid for example having the configuration ~ O * C H z * ~ o * the hydroxyl groups are then in a favourable posi- OH OH' tion for their hydrogen atoms to combine with the chlorine atoms of the dichloro-compound. Of the acids giving compounds of the second type it is shown that all of thelm with the exception of tlie substituted malonic acids and citraconic acid probably have their hydroxyl groups in the anti-position with respect to each other that is not in a favourable position for their hydrogen atoms to combine with the chlorine atoms of the dichloro-compound.The fact that cert.ain substituted malonic acids together with citraconic f "i. 122 ABSTRACTS OF' CHEMICAL PAPELIS. acid do not give additive compounds although their hydroxyl groups are probably in the cis-position with respect to each other is explained on the assumption that the substitution of hydrogen by radicles with much larger molecular volumes as for example methyl ethyl and the halogens influences the relative positions in space of the hydroxyl groups in such a manner that they are not favourably situated for forming an additive1 compound.I n order t o prepare the various compounds cold concentrated solutions of trans-dichlorodiethylenediaminecobaltic chloride and the acid were mixed the proportions taken being one molecular equivalent of thel chloride t o rather more than two molecular equi- valents of the acid. If no precipitate was formed sufficient sodium carbonate t o form the sodium hydrogen salt of the acid was added when precipitation rapidly took place. When the acid forms an additive compound i t is immateria.1 whether it be present in the reaction mixture as the free acid or the sodium hydrogen salt. All the compounds thus obtained were micro-crystalline. The' fresh aqueous solutions do not contain ionic chlorine but on keeping they slowly change in colour probably with the formation of chloro- aquo-compounds. trans - Dichlorodietlzyle?zediaminecobaltic hydrogen oxalat e YC,04H,2H20 where Y = [Cl2Co en2] forms emerald-green striated and elongated plates. I n one case under conditions which have to be investigated further the trans-dichloro-chloride and ammonium hydrogen oxalate gave crystals of oxalt'c acid-trans-dichlorodi- 4 t hylenedinniiiz eco baltic hydrogen oxalate YC,04E,C,H,0,. From the hydrogen oxalate oxalatodiethylenediaminecobaltic chloride [C,04C0 .en2]C1,4H20 is readily obtained by boiling the solution and subsequent concentration. Mnlonic nci~-trans-~t'ch?orodi- e t hylen ediaminecobaltic hydrogen malonat e forms dark emerald-green blunt prisms ; when the dichloro-chloride and the malonic acid were in the proportions of 2 l by weight instead of 3 :4 as in preparing the above compound mnlonic acid- trans-dichlor~~ietl7tyle~~cdicsmin ecobaltic chloride YCl,CH,(CO,H) was obtained.trans-Dir hlorodie thylenedinmin ecobaltic hydroge tz diethylmaZonat e YC02=CEt;,*C0,H crystallises as emerald-green square plates mixed with a few needles; the corresponding hydrogen dirnet hylmaloriate YCO,*CMe,*CO,H gives nodular aggregates of dark emerald-green crystals. The hydrogen ethyl- mnlonate YCO,*CHEt*CO,H and the h?/drogen methylmalonate YCO2*CHMe*C0,H each form emerald-green blunt-ended prisms. trans-Dichlorodieth ylen edinmineco bal tic hydrogen dibromomalon- Ute YC02-CBr,-C0,H consists of apple-grelen blunt-ended pris- matic crystals; the aqueous solution loses carbon dioxide on the water-bath and on evaporation dibromoacetic acid-trans-dichlorodi- at hylenediaminecobal tic (lib ro monceta te YCiH0,Br,,CHBr2* CO,H is ohtained in the form of milky green irregular plates.Bromomalonic acid-trans-cFichlorodieth ylenediamin eco baltic hydro- .c/e n bromomalond t e YCO,*CHBr*CO,H CHBr (CO,H) crystallises in emerald-green plates; the corresponding chloromalonate YC,O,H,,CH,( CO,H),,2H,O,ORGANIC CHEMISTRY. i. 123 YCOa*CHC1*C!O,H,CHCl(C0,H) also gives emerald-green crystals. Each of these compounds when thoroughly washed with alcohol loses a molecule of the halogenomalonic acid giving respectively trans-dichlorocliethylenediaminecobaltic hydrogen. bromomnlonate YCO,*CHBr*CO,H and the corresponding trans-hydrogen.chloro- nialonate YC0,-CHCl*CO,H. trans-Dicklorodiethylenediamine- cohaltic J L ~ ~ P O Y E I L dichloronzalonate YCO,*CCl,*CO,H crystallises as a conglomerate of light emerald-green plates; the aqueous solu- tion loses carbon dioxide on the water-bath and on evaporation emerald-green crystals of dichloroncetic acid-trans-dichlorodi- ethylen edia 771 ii~eco baltic dichloroaceta te YC,H0,C12 CHCl,*CO,H are obtained. Under similar conditions the additive compound with chloromalonic acid gives emerald-green flat prisms of chloroacetic n c id-tr ans-d i c h 1 or odi e t JL y 1 e 17 eclin nz i n e co b a 1 tic c h 1 or oa c e t a t e YC,H,O,Cl,CH,Cl*CO,H although the p i r e compound is best obtained from chloroacetic acid and the trans-dicliloro-chloride.trans - Dich lorodie th yletzedicrminecob alt ic Jbydrogen succimte Y C0,*[CH2],.C0,H,H,0 cryst,allises in dark emerald-green blunt- ended prisms. The hydrogcia dihromosucciaate YCO,*[CHBr],*CO,H gives malachite-green crystals of indefinite shape. The Jhydrogen tartra t e YCO,* [ CH-OH J2*C0,H H,O and J~ydrogen meso tartrate YCO,*[CH-OH],*CO,H crystallise as a felted mass of emerald-green needles and as an emerald-green conglomerate of very small plates ( 1) respectively. gives dark emerald-green square plates as also does the JLydrogen dith iodinceta te YCO,*CH,*S,*CH,* CO,H,H,O. ThO Ji ydrogcn di- t h io dip4 o pi0 11 n t e Y C 0 C H 11 e S C H Me - C 0 H H ,O gives pa 1 e emerald-green crystals whilst the hydrogen fumarate YCO,*CH:CH*CO,H gives irregular plates of the same colour.The hydrogen citrcrconiite h ydrogeia mesaconnte and hydrogen ifacouate YC5H504 form respectivelv emerald-green crystals pale green plate^ and emerald- green needles. Glutaric ncid-trans-clic~~lorodieth?/lP?iedi~mi7aPco~attic hydrogen glutarate YC0,-[$2H,]3*C0,H,[CH,1,(CO~H)2 gives dark emerald- green elongated plates. The following are also additive compounds Jrydrcqeiz thiodiacetnte YC0,*CH2*S*CH,*C0,H,S(CR,*C0,H) emerald-green plates ; Jbydrogen siilphon?lldincetn't~ very sinall emerald-green plates ; hydrogen maleate einera Id-green needles. d k m in eco hnl t ic h yzroqe n t h i d i n ce tn t e [Br,Co en,]CO,*CH,*S*CH,*CO,H,S( C'R,-CO,H) forms pea-green crystals whilst t hiodipro pionic ncict-trans-dichloro- d ~ e t h ~ l e n e d i a m i n e c ~ ~ a l t i c chloride YCI,S(CHMe*CO,H) crystai- lises in dark grass-green plates.The following cis-isomerides were also obtained cis-dichlorodi- The JLXidrogen adipate YCO,*[CH,],*CO,K YCO,*CH,*SO,*CH,*CO,H,SO,( CH,*CO,H) YC,H,OI ,C,H,O Thiodince t2 c ncid-trans-dibroi,iodie th ?$en e- f * 2i. 124 ABSTRACTS OF CHEMICAL PAPERS. ethyle,zedian~iizeco~altic oxdate Y2C204 violet crystals ; cis-hydro- gen succinate YC0,*(CH,)2*C0,H violet short bluntrended prisms ; and cis-udipate Y2(C0,),(CH2) violet prisms with blunt ends. A pure substance was not isolated from acetonedicarboxylic acid but the results indicated the formation of an additive compound. A solution of the additive compound formed with thiodiacetic acid when treated with potassium iodide gave a vivid green precipi- tate consisting of a conglomerate of very small tabular crystals of t r a ns-d ic h 1 or odi e t h y 1 e n edia min e co b n I f ic iodide YI.T . S. P . A New Oxidation Method. 111. Action of Aldebydes on Primary Hydroxyamines. I<. HESS and CL. UIBRIG (Ber. 1915 48 1974-1985. Compare A 1914 i 199).-The behaviour of liydroxylated primary amines towards formaldehyde acetaldehyde and benzaldehydel has been investigated. When diacetonalkamine is treated with formaldehyde in the cold i t first condenses according to the scheme NH,*CMe2*CH,*CHMe*OH + CH,O f OH*CH,*NH*CMe2*C€12*CHMe8-OH. A t about 50° however the product is an anhydride of the latter compound namely methylerLediacetonal?camine [P-methylene- nmin~o-~-r~zeth~/lpetztan-b-ol] CH,:N*CMes*CH,*CHMe*OH which is a very pale yellow oil b.p. 45-47O/23 mm. 150-155°/720 mm. and forms a picrate C,,H,,O,N long stout spikes m. p. 138-139O. I n the earlier paper this was mistaken f o r the isomeric diaceton- methylamine XHMe*CM%*CH,*COMe but it cannot be that for it is formed too easily and is too easily hydrolysed. A t higher tem- peratures further reactions take place. Thus when diacetonalk- amine was heated with 40% formaldehyde a t 142-145O in a sealed tube and the product was extracted with ether and then fraction- ated the following were isolated the above methylenediacetonalk- amine then d i m e tondimet h ylamine Ip-dirnethylamino-p-met hyl- p n t a n - & o n e ] NMe,*CMe,*CH,*COMe b. p. 59-61°/23 mm. a limpid mobile' highly refractive oil with a strong narcotic odour (picrate m.p. 183O) and finally methyldiacetonalkamine NHMe-CM%*CH,*CHMe*OH b. p. 73-75O/ 20 mm. The chief product obtained by heating diacetonalkamine with 40% acetaldehyde acidified with hydrochloric acid at) 115-120° was ethylene~iacetonalkamine r?-eth.ylenea?nino-P-m ethylpentan - 6 - 011 C,H,,ON a colourless mobile oil b. p. 42-47O/12 mm. with a powerful narcotic odour ( p i c m t e stout needles m. p. about 147O). Similarly benzaldehyde yields bemylidenediacetonalkamine [P-benz- ylidcn ect mi72 o-&met hylpen tan-8-01] CHPh:N*CMe2*CH,*CHMe*OH a yellow oil b. p. 94-95O/0*1 mm. 139-140°/19 mm. with a faint basic odour ( p i c m t e long prismatic needles m. p. 170-171°). The base is quickly transformed into the hydrochloride pink m.p. 199O when covered with concentrated hydrochloric acid and it is readily hydrolysed even in water. The urethane of diacetonalkamine [&xwbethoxyamino-j3-methyl- pen tnn-&ol] CO2Et-NH*CMe2-CH,-CHMe*OH was prepared as aORGANIC CHEMISTRY. i. 125 viscous oil b. p. 14Z0/23 mm. by the agency of ethyl chloroformate. When this is heated with an excess of 40% formaldehyde a t 145-1 50° it forms 0-carb e thoxy met hylamino-/3-methylpentan-6-one C02Et*NMe*CM~-CH2*COMe b. . p. 123-125O/ 14 mm. which readily yields formaldehyde again in the presence of water. If the urethane is mixed with alcohol and formaldehyde and heated a t ZOOo however it yields the melthylene cornpou?zd (OH*CHMe*CH,*CMe,*NH)2CH2 which crystallises in the triclinic system and has ni.p. 132O b. p. 165-170°/25 mm. Aminoethyl alcohol was shaken with propyl chlorof orinate and sodium carbonate solution and converted into ~ - c n r b o p r o p o x ~ a m ~ n o - ethyl alcohol C0,Pr.NH*CH,*CH2*OH a viscous oil b. p. 150-151°/13 mm. When this is heated with 40% formaldehyde a t 145O it yields carb opropoxymet h ylaminoacetaldehycle CO2Pr*NMe*CH,*CHOY a highly refractive limpid pleasant-smelling oil b. p. 103-105°/ 13 mm. which reduces ammoniacal silver oxide and forms a hydr- azone. /3-Amino-a-phenyletliyl alcohol obtained by reducing benzalde- hyde cyanohydrin by sodium amalgam was also converted into the ure tA a n e [ fl-carb e t hox?ya rn in. o-a-phe nyle t h y l alcohol] OH* CHPh.CH,*NH*CO,Et pearly leaflets m. p. 8G0 by the agency of ethyl chloroformate.When this is heated with excess of formaldehydel a t 140-145O it yields phenyl car6ethox?/methylami?~omet~~~l I* ,,e t one COPh*CH,*NMe*CO,Et b. p. 181-183O/16 mm. Behaviour of Amino-acids towards Neutral Salts in Aqueous Solution. P. PFEIFFER [with J. ~ U R G L E R and FR. ~ ~ I T T K A ] (Ber. 1915 48 1938-1943. Compare A. 1915 i 868).-In connexion with physiological processes it is important to determine whether the corcplex ‘‘ neutral-salt compounds ” of the amino-acids and poly- peptides with salts of the alkali and alkaline earth metals can exist as such i n equilibrium with their components and complex ions in aqueous solutions. This has been tested by determining tlie solu- bilities of various amino-acids in salt solutions by observing the influence of salts on the rotation of d- and Z-alanine in aqueous solution and by measuring the depression of tlie freezing point of w a k s containing glycine and various salts.I n all cases in which “ neutral-salt compounds ” are known t o exist in the solid state the solubility of the amino-acid in the particular salt solution is much increased. The1 rotation of alanine is raised as much as six times by certain sdts just as it is by mineral acids. The depression of the freezing point of water caused by glycine+a salt is less than the sum of the depressions caused by the separate solutes. It seems therefore t h a t the complex molecules do exist in aqueous solution. J. C. W. Preparation of Compounds of Urethanes and Diurethanes with Metallic Bromides.GEHE & Co. (U,R.-P. 284734; from J. C . W.i. 126 ABSTRACTS O F CHEMICAL PAPERS. J . SOC. C h m . Ind. 1915 34 1166).-Urethanes (4 mols.) are heated with calcium or strontium bromide (I mol.) in a suitable solvent for several hours. The products especially the double compound of calcium bromide with ethyl carbamate CaBr2,4NH,*CO,Et are powerful liypnotics and are useful in the treatment of nocturnal epilepsy; they have no deleterious action on the heart o r respira- tion. J. C. W. Preparation of Carbamide Nitrate from Cyanamide. OESTER- REICHISCHER VEREIN FUR CHEM. UND METALL. PRODUICTION (D.R.-P. 285259; from J . SOC. Chem. Z7zd. 1915 34 1166).-Carbamide nitrate is precipitated almost quantitatively when concentrated solutions of cyanamide and nitric acid are mixed a t below 20° thus CN-NH + HNO + H,O = CO(NH,),,HNO,.J. CT. W. Reaction of Nitroprusside with Thiocarbamide. L~VIO CAMBI ( d t t i R. Accad. Lincei 1915 [v] 24 ii 434-441. Compare A. 1913 i 606; 1914 i 967).-The author has investigated the reddish- violet salt obtained by Hofmann (A. 1900 i 591) by the action of sodium nitroprusside on thiocarbamide and regarded by him as having the formula [Fe(CN),NO*S*C(NH)*NH,INa,. That this formula is erroneous is shown by the analytical results which give 1 7 and not 1 8 for the ratio Fe N ; in correspondence with this fact is the author’s observation that the synthesis of the compound is accompanied by the liberation of nitrogen. It is known also that in presence of a weak acid alkali nitrites transform thiocarbamide into thiocyanic acid with quantitative evolution of nitrogen (com- pare Werner T.1912 101 2180; Coade and Werner T. 1913 103 l22l) NH,*CS*NH -+NH,*CS*OH -f HNCS. The assump tion is theref ore made that the nit“roso-group of the nitroprussids reacts not with the sulphur atom but with the amino-groups of the thiocarbamide KaOII 3Na2Fe(CN),N0 + CS(NH,),-+ Na,[Fe”(CN),NO-NH*CO*SH] + Na3[Fe(CN),,H,0] + N2 the first of these products representing Hofmann’s reddish-violet salt. The formation of the aquo-salt (compare Hofmann Zoc. cit.) in considerable proportion has indeed been observed and the accuracy of this representation of the reaction is indicated by the following results. The interaction of sodium nitroprusside and thiocarbamide in methyl-alcoholic solution in presence of excess of sodium alkyloxide yields an orange-yellow salt which undoubt- edly contains one thiocarbamide residue t o two atoms of iron and has probably the formula Na,[Fe”(CN),. ..NO*NH*CO*S*Fe”(CN),] ; in aqueous solution this’ compound decomposes with formation of Hofmann’s salt. Treatment of the latter with sodium hydroxide in aqueous methyl-alcoholic solution yields a deliquescent brownish- orange-yellow salt of the composition Na,[Fe(CN),NO*N*CO*S] ; this undergoes irnniediate hydrolysis t o the original salt in aqueousORGANIC CHEMISTRY. i. 127 solution whilst when kept for a long time in a vacuum in presence of water it undergoes partial decomposition with liberation of nitrogen dioxide. By silver or mercuric salts in the hot Hofmann’s salt is rapidly decomposed with liberation of nitrogen dioxide in the proportion l N 0 1Fe ; under similar conditions the salt obtained from thiocarbamide in methyl-alcoholic solution liberates nitrogen dioxide in the proportion 0*5NO:lFe in accordance with the formula given above.Reduction of Hofmann’s red salt by means of sodium amalgam gives a yellow salt Na,[Fe//(CN),*NH,*NH*CO*SH] in which the presence of the hydrazine residue NH,*NH* is demonstrated by the behaviour towards mercuric salts or oxide silver salts or Fehling’s solution whicli cause rapid decomposition with liberation of nitrogen even in the cold; bromine water also liberates nitrogen but yields no nitroprusaide whereas under similar conditions the red salt gives nitroprusside but no gas.Hofmann’s formula was based solely on the reaction of the red salt with ferric chloride which gives a green coloration o r precipi- tate but the author has observed similar behaviour with ferro- cyanides containing nitroso-ke$ones these being also intensely coloured. The possibility of the formula Na,[Fe///(CN),NO*NH*CO*S~ for the red salt is discussed; this salt does not however exhibit the characters of ferricyanides whilst the ferrous formula is in accord with its behaviour towards alkalis. T. H. P. The Hydraeide of Cyanoacetic Acid Oximinocyanoacetic Acid and Nitrocganoacetic Acid. AUGUST DARAPSKP and DIETRICH HILLERS ( J . pr. Chem. 1916 [ii] 92 297-341).-Methyl cyano- acetate (1 mol.) when heated in alcoholic solution with hydrazine hydrate (2 mols.) was converted into cyanoacetylliydrazide the hydrocJdoricle (crystals m.p. 145O) of which when treated in aqueous solution with sodium nitrite under a layer of ether was converted into cyanoucetylazide CN*CH,*CO-N a pale yellow explosive oil of extremely pungent odour ; this substance reacted with aniline in ethereal solution giving cyanoacetanilide and with boiling alcohol yielding cyaiao?izeth~luretl~ane CN-CH,*NH-CO,Et silky needles or slender prisms m. p. 1 4 5 O . When heated with diluted hydrochloric acid the urethane compound underwent dis- ruption giving carbon dioxide alcohol ammonia and glycine aminoacetonitrile probably being formed as an unisolatable inter- mediate product. The last reaction is of little importance as a method of preparing glycine but an analogous series of reactions with the alkyl derivatives of ethyl cyanoacetate may prove useful for the preparation of other amino-acids. It is of interest that the above method for the preparation of glycine from chloroacetic acid through cyanoacetic acid gives a product in which the amino-group and the carboxyl groups are held by different valencies from those occupied by the same groups in the product prepared by the action of ammonia on chloroacetic acid.These two modes for the prepara- tion of glycine can therefore serve as the basis of a proof of t h oi. 128 ABSTRACTS OF CHEMICAL PAPERS. equivalence of the four bonds of the carbon atom by applying them to ordinary chloroacetic acid and t o chloroacetic acid prepared by the stages CH2Ci40,H -+ CN*CH,*CO,H -+ C0,H*CH,*C02H + CO,H*CHCl*CO,H + CH,Cl*CO,H and CH,C1*C02H + CO,H*CH,*CO,H + CO,H*CH@l*CO,H -+ CO,H*CH(CO,H)*CO,H + CO,H*CCl(CO,H)*CO,H -+ CH,Cl*CO,H.Methyl oximinocyanoacetate (Conrad and Schulze A. 1909 i 21 1) reacted with an equimolecular proportion of liydrazine hydrate in alcoholic solution giving the hydmzine salt CN*C (:NO*N,H,)*CO,Me a yellow crystalline solid decomp. near looo after sintering a t 7 8 O . When the reagents were heated together in alcoholic solution on a water-bath the product was the ltydrazine salt yellow needles decomp. a t 1 3 5 O of oximinocyanoacetylhydrazine lustrous brown leaflets m. p. 1 6 6 O (decomp.) the latter being liberated from the salt by careful treatment in the cold with thel theoretical amount of hydrochlonc acid ; silver salt brown ; lead salt brown ; hydro- chloride yellow crystals decomp.a t 204O. If the hydrazine salt is treated in aqueous solution with benzaldehyde benzaldazine and oxim itmcynn oace t y l be n z?llidenekydruzitae CN*C(:NOH)*CO*NH-N:CHPh yellow needles decomp. a t 1 4 8 O are obtained the latter compound being also produced by the action of benzaldehyde on oximinocyano- acetylhydrazine itself. The hydrazine salt reacts in an analogous manlier with an excess of acetone giving bisdimethylazimethylene and oximinocyanoacet ylisopropylidene hydrazine CN*C( :NOH)*CO*NH*N:CMe coinpact yellow prismatic crystals m. p. 2 0 5 O . When the hydr- azine salt of oximinocyanoacetylhydrazine is treated in concen- trated aqueous solution under a layer of ether with sodium nitrite and dilute hydrochloric acid oxirninoc.yanoacetylazide CN*C(:NOH)-CO*N an explosive yellow crystalline solid of low m.p. is obtained which reacts with sodium hydroxide solution and aniline respec- tively giving sodium azoimide and oximinocyanoacetanilide (Dim- soth and Dienstbach A. 1909 i 62) and with Soiling alcohol yielding oximin ocyanomet Jtylure thane CN-C( :NOH)*NH* CO,Et colourless granular crystals m. p. 96-97O. Hydrolysis of the last product with hydrochloric acid gives rise to carbon dioxide alcohol ammonia hydroxylamine and oxalic acid the latter substances probably resulting from the decomposition of an intermediate amino-oximino acetonitrile NH,* C ( NOH) *CN. Jf e t h yl ? I i t rocyanoa ce fat e CX*CH(NO?) *CD2Me colourless silky needles (with lH?O) m.p. 76O was obtained as its potnssium salt CN*C(:NO,K)*CO,Me lustrous leaflets m. p. 2 6 4 - 2 6 G O (decomp.) by oxidation of methyl oximinocyanoacetate with potassium per- nianganate in aqueous solution; the free ester was liberated by converting it into the silver salt and decomposing with hydrogen sulphide. When treated in warm methyl-alcoholic solution with an equimoleoular proportion of hydrazine hydrate this ester gave aORGANIC CHEMISTRY. i. 129 yellow crystalline hydrazine salt m. p. 1 6 8 O but with longer heating and a sesquimolecular quantity of hydrazine hydrate the product was the hydrazine salt CN*C(N02*N2H,)*CO*NH*NH2 silky needles m. p. near 200° (decomp.) after sintering near 140° of nitrocyanoacetylhydrazine ; this hydrazine salt when treated with benzaldehyde yielded benzaldazine and the free nitrocyanoacetyl- liydrazine.By treating the potassium salt of methyl nitrocyano- acetate with hydrazine hydrate the analogous PO tassium salt CN*C(NO,K)*CO*NH*NH' long prisms was obtained. Nitrocyano- acetybhydrazide CN*CH(NO,)*CO*NH*NH obtained by the action of dilute hydrociiloric acid on the above hydrazine o r potassium derivative forms colourless needles (with 1H,O) and can be recrystallised rapidly from warm water without alteration but on boiling with water it is converted into the yellow anhydrous com- pound a similar dehydration being also effected in the hydrated saIt by heating a t 110-120O. The nitro-group renders nitrocyano- acetylhydrazide decidedly acidic in character and it is probably to this cause that the noteworthy stability towards acids and alkalis i3 due; even when boiled with sodium hydroxide solution o r dilute sulphuric acid for hours no scission of hydrazine occurs and even heating f o r six hours a t 120-130° with hydrochloric acid in a sealed tube only causes a partial hydrolysis. When treated with excess of hydrazine hydrate the hydrated form of nitrocyanoacetyl- hydrazide gives the above-described colourless hydrazine salt but the anhydrous compound yields a yellowish-red isomeride decomp.a t 200° after Pinbring a t 185-195O which when its red aqueous solution is acidified regenerates the anhydrous form of the free compound whereas under similar conditions the colourless hydr- azine salt yields the hydrated compound.The ammoizizcm salt also was obtained in an almost colourless form and in an orange-yellow form both crystaking in needles. Indications werel also obtained of the existence of a coloured modification of the potassium salt. This existence of two isomeric series of salts is regarded as analogous to the case of the nitroketones and dinitroparafins (Hantzsch A. 1907 i 500 555 ; Hantzsch and Voigt A. 1912 i 151 ; ii 508). By shaking with benzaldehyde in aqueous solution containing a little hydrochloric acid nitrocyanoacetylhydrazine can be converted into the benzylidene derivative# CN*CH(NO,)*CO*NH*N:CHPh a microcrystalline powder which carbonism without melting and is very readily resolved by warm water into benzaldehyde and nitro- cyanoacetylhydrazide.Sodium nitrite in aqueous solution reacts with nitrocyanoacetylhydrazide giving the sodiunz salt (yellow needles) of the ?zitroc?/anocccet?/lazidp CN*CH(NO,)*CO*N an almost colourless crystalline hygroscopic mass (with 1H,O) of low 111. p. which was obtained by cautious treatment of the salt with dilute sulpliuric acid. pale yellow granular crystals and when boiled with alcohol pro- duced a brown tarry mass which probably contained some of the expected urethane as treatment with boiling hydrochloric acid gave rise t o the formation of carboq dioxide ammonia and hydrogen The azide gave an aniline salt C,H803N,,H9O,i. 130 ABSTRACTS OF CHEMICAL PAPERS. cyanide ; in boiling aqueous solution also nitrocyanoacetylazide decomposes vigorously the products being similar t o the final pro- ducts from the treatment with hydrochloric acid with the addition of carbon monoxide.The above results iiidicate that with the intro'duction of the cyanoacetyl- oximinocyanoacetyl- and nitrocyanoacetyl-radicles into liydrazine this compound undergoes a gradual and regular weaken- iiig in basic character. D. F. T. Preparations of Esters of Hydrazinemonocarboxylic Acid. E. MERCK (D.R.-P. 285800; from J. SOC. Chem. Zizd. 1915 34 11 67) .-Reaction is brought about between equimolecular propor- tioiis of hydrazine hydrate and an ester of carbonic acid. J. C. W. Relations between the Constitution and the Physical Pro- perties of Isomeric and of Homologous Hydroaromatic Compounds. K. VON AUWERS (Annalen 191 5 4 10 287-336. Compare following abstract).-The author has collected from all trustworthy sources the magnitudes of the b.p.'s densities refrac- tive indices and exaltations of the specific refractions and disper- sions of cyclohetxane cyclohexene cyclohexanol and cyclohexanone and as far as possible of their mono- di- tri- tetra- and penta- methyl derivatives; in a few cases values f o r the methylene deriv- atives of cyclohexene and its methyl hoinologues are recorded. The data have been sifted and tables compiled containing values some of which are quite trustworthy others are the most probable and yet others am somewhat uncertain. Relations are then traced between these values and the constitutions of the various com- pounds. The most important of these are the following I n the case of isomeric compounds (I) the b.p. of saturated alcohols and ketones falls when the methyl group is in proximity to the hydroxyl or carbonyl group; the b. p. of unsaturated hydrocarbons rises with approximation of the methyl group t o the double linking. (2) The density in all four classes of compound increases with the pscking of the methyl groups in the molecule and with their proximity to the double linking the liydroxyl group o r the car- bony1 group. (3) Similar relations hold although less pronouncedly f o r the refractive indices. (4) The molecular refraction of isomeric substances of all four classes is greater the farther are the side- .chains from on0 another and from the double linking o r the oxygen- ated group. (5) The molecular dispersion is normal in all saturated and in endocyclic unsaturated compounds.The preceding relations only hold f o r mono- and di-methyl deriv- atives; in the case of more highlv methylated compounds generalisa- tions cannot be made owing to lack of trustworthy data. With regard t'o homologous compounds (1) I n cyclohexanes and cyclohexenes the introduction of methyl regularly causes an increase in the b. p. but in cyclohexanols and cyclohexanones such is fre- quently not the case. (2) As a rule the density of the oxygenated derivatives decreases as the number of methyl groups increases.ORGANIC CHEMISTRY. i. 131 (3) No regularities can be tsaced for the refractive indices of homo- logous compounds since here the constitutive influences are alto- gether predominant. It is noteworthy however that with few exceptions the value of )?go for all homologues of cyclohexene is the same about 1.445.c. 5. Simple Hydroaromatic Hydrocarbons Alcohols and Ketones K. VON AUWERS R. HINTERSEBER and WILHELBI TREPPMANN (A nnalen 1915 410 257-287).-Tlie compounds described in the paper are f o r the most part not new but have been prepared in a state of great purity and the magnitudes of various physical pro- perties hcve been measured in order to correlate these with t.he constitutions ; the saturated hydrocarbons and ket'ones are believed to be quite pure but the authors do not guarantee that the alcohols and unsaturated hydrocarbons are free from possible stereo- isomerides. The alcohols are hygroscopic and the observation has been made that the density continuously increases when these are submitted t o prolinged dryiiig a t a gentle heat in a current of hydrogen.Phosphoric oxide is recommended for convertihg secondary carbinols into unsaturated hydrocarbons and potassium hydrogen sulphate f o r tertiary carbinols. Saturated hydrocarbons are best obt'ained from secondary carbinols through the bromides. cycZoHexane has b. p. 80-0-80~2"/749 mm. D:1'2 0-7869 na1*42910 W~ 1.431 19 ?zP 1.43668 and 7 z y 1.441 16 st 10.85O. cycZoHexene has b. p. 83-83-5"/760 mm. I):"'6 0.8143 YZ 1*44653,1z 1.44981 nB 1.45620 and ny 1.46194 at 15.1". Methylenecyclohexane has b. p. 100~5-102~3'/756 inm. DY 0.8055 n 1.44934 nu 1.45222 ?zp 1.45958 and n 1.46568 a t 15.5'. 1 3 Diniethylcyclohexane prepared by Crossley and Renouf's method (l'.1905 87 1497) has b. p. 118-130' D,2180*7701 7 z a 1.42157 ?zD 1-42398 i z B 1.42940 and ~ ~ ~ 1 . 4 3 3 9 4 at 32.0'. 1 8-Dimethyl- Al-cycZoliexene has D:3'7 0.83 15,7t 1 *45906 n 1.46 1 i 8 '125 1.46908 and iz. 1 4'7517 at 13.5'. 1 3-Dimethyl-A3-cycZoliexene has b. p. 121-126°/760 min. 13g2'6 0.7998 1~~1.44863 n 1.44533 I L 1.45215 and uy 1.46795 at 22.4". 1 3-Dimethy1-4~-cycZohexeiie has b. p. 126-127*/746 mni. 0.797 PZ 1*44086,1z 1.64361 7l.B 1*45020 and ?iY 1.45587 at 21*lG. 1 4-Dimethyl-hl-c?ycZohexene has b. p. 124-126'1751 niin. 0-7985 I L 1-44112 7~~1.42372 izB 1.45056 and ny1.45636 at 22.0'. Ethylidenecyclohexae has b. p. 1 36.0-136-4°/7G6 niiii. D:' 0.8239 7~~1.46094 n,1-46389 ?zJ 1.47139 and i i Y 1.47773 a t 17.6". 1 3 5-Trimethylcyclohaxene b p.139-141"/766 mm. D:" 0.7941 w a 1.44102 7zD 1*4437S 128 1.45057 and iz 1.45638 at 24.7' reacts with hydrogen chloride and with hydrogen bromide in cooled glacial acetic acid to form 1 3 5-tI.inzethyLcyclohexyl chloride b. p. 68-69"/20 mm. Uy5 0.9217 ~ ~ ~ 1 . 4 5 1 8 2 12 1.45455 I Z ~ 1.46035 and IT 1.46555 a t 15*Z0 and the bromide lo. p. 95 -98"/23 Dim. Dil'l 1.1749 na1-47951 n,1*48380 9zp 1.48971 and ny 1.49532 at 11.1" ; neither of these derivatives could be satisfactorily converted into 1 3 5-trimethyl- cyclohexane.i. 132 ABSTRACTS OF CHEMICAL PAPERS. 1 3-Dinzethy1-5-?~zethylenecylohexa?ze C,H,Me,:CH prepared by heating 1 3-dimethylcyclohexylidene-5-acetic acid a t about 220' in a slow current of carbon dioxide has b. p. 135-136'/744 mm.D:4.60 7918 n 1.44334 n 1.44628 np 1*45313',and ny 1,45917 at 14.6" and yields 1 3-dimethylcycZohexan-5-one by oxidation with faintly alkaline 2% potassium permanganate. cycZoHexano1 has m. p. 23' Di7" 0.9373 nu 1.45902 n 1.46055 ?zp 1-46685 and ny 1.47146 a t 37.0". 1-Methylcyclohexanol has m. p. np 1.46428 and ny 1.46908 at 24.65'. I-MethylcycZohexan-2-01 has b. p. 167*4-167*6" D:"" 0.9333 n 1.46352 nD 1.46585 np 1.47180 and ny 1.47665 a t 13.4'. 1-Methyl- cyclohexan-3-01 has b. p. 76-78'/14 mm. D2'3 0.9182 nu 1.45217 72 1.45444 np 1-46031 and ny 1.46502 a t 24.3'. 1-Methylcyclo- hexan-4-01 has b. p. 74.7-75.3'/12 mm Dy5 0.9183 nu 1.45366 n D 1.45594 np 1.46160 and ny 1.46651 a t 32.5'. 1 3-Dimethylcyclohexan-3-01 has b. p. 79-81'/21 mm. DF'9 0.9028 1~~1.45177 nD 1.45414 np 1.45984 and ny 1-46463 a t 22.9'.1 4-Dimethylcyclohexan-4-01 has b. p. 70-72'/19 mm. (Sabatier and Mailhe and also Wallach have obtained this substance in the solid state) D~90*9060 nu 1.45317 n 1.45534 np 1.46141 and ny 1,46622 at 23.9'. 1 3-Dimethylcyclohexan-5-01 has m. p. 36-38' (other preparations remained liquid) DF'4 0.8810 nu 1.44440 n 1.44700 np 1.45238 and ny 1.45727 at 38.4'. 1 3 5-Trimethylcyclohexan-5-01 has b. p. 82-83'/19 mm. D:6'300.8880 n 1,45108 n 1.45371 np 1.45991 and ny 1.46422 a t 16.3". cycloPentanone has b. p. 23*2-23-6'/10 mm D:"3 0.9513 n 1.43587 n 1 43817 np 1.44390 and ny 1.44867 a t 17*33. cyclo- Hexanone has b. p. 156*6-156*8" Dy'3 0.9503 nu 1.45024 rt 1.45261 nS 1.45859 and n 1.463'70 a t 15.3'. cycLoHeptanone has Dy'9 0.9495 n 1.45801 n 1.46027 n p 1.46646 and ny 1.47149 at 21.9'.1-Methylcyclohexan-2-one has b. p. 167'/740 mm. 0.9300 n 1-44827 n 1-45049 np 1.45653,and ny 1.46135 a t 14.6'. 1-Methyl- cycZohexan-3-one has b. p. 60-60*2'/15 mm. D:'l5 04139 nu 1.44092 IZ 1.44313 np 1.44914 and nv 1.45394 a t 25-15'. 1-Met,hylcyclo- hexan-4-one has b. p. 55*8-56*4'/10.5 mm. 0.9119 n 1.44092 ~ ~ ~ 1 . 4 4 3 2 2 np 1.44918 and ?zy 1.45413 a t 24.4'. 1 3-Dimethylcyclo- hexan-5-one has b. p. 180' D:*'7 0.8962 1~~1.44270 n 1.44492 24-25' b. p. 56.5'/10 mm Dt4'" 0.9251 %,1.45631 n D 1.45874 np 1.45101 and ny 1.45579 at 14.7'. c. s. Thermal Reactions of Aromatic Hydrocarbons in the Vapour Phase. W. F. RITTMAN 0. BYRON and G. EGLOFF (J. Ind. 13mg. Chem. 1915 7 1019-1024. Compare this vol.i l).-The decomposition of aromatic hydrocarbons when heated in the vapour phase proceeds in the direction cymene + xylem -+ toluene + benzene -+ naphthalene + anthracene + tarry matter carbon and gas and scarcely appreciably in thel reverse direction. Any one hydrocarbon therefore gives rise t o any or all of the products following it in the above scheme according to conditions and not t o any of those preceding it. The paper is fully illustrated withORGANIC CHEMISTRY. i. 133 tables ahowing the quantitative results of the cracking experi- ments. G. 3'. M. Some Aromatic Fluoro-derivatives and the Nitration of p-Fluorochlorobeneene. FRED. SWARTS (Rec. ti-av. chzm. 1915 35 131-153).-A quantitative study of the nitration of pfluoro- chlorobenzene a number of fluoro-compounds being prepared and used f o r the identification of the products of nitration.The p-fluorochlorobenzeiie used was prepared from p-fluoroaniline by Gatterman's reaction. It had m. p. -26'9O; b. p. 130*15O/757.3 inin. (corr.) ; DO 1.2573; D11.2 1.2355 ; 72 '' 1.49432 ; 7~:'~ 1.50957 ; 9~:''~ 1.52085 ; nY2 1.49890 (compare Wallach and Heusler A. 1888 362). 6-I"l~~o~o-3-~7~1oro-l-nitrob en.ze12 e is prepared by diazotising 4-fluoro-3-nitroaniline in solution in concentrated hydrochloric acid. It crystallises from light petroleum in colourless prisms m. p. 10*2O b. p. 138.5/29 mm and is readily decomposed by aqueous alkali hydroxides giving the Corresponding salts of 4-chloro-2-nitrophenol. With sodium methoxide a t 25O the fluorine atom is replaced by the group *OMe and with alcoholic ammonia 4-chloro-2-nitroaniline is obtained.Attempts t o prepare 5-fl~oro-2-chloro-l-nitrobenzene by the action of phosphorus pentachloride on 4-fluoro-2-nitrophenol were not suc- cessful but i t was finally obtained from the corresponding fluoro- nitroaniline. pFluoroacetanilide when nitrated with acetyl nitrate in acetic acid solution a t Oo yielded 4-flzioro-2-?zitroacetanilide pale yellow prisms m. p. 71*5O which on hydrolysis with dilute hydro- chloric acid gave 4-fZ1coro-2-nit~oaniZ~~ze~ orange-coloured prismatic crystals m. p. 92-45O. This aniline when submitted t o Gatterman's reaction gave 5-fZzioro-2-chloro-l-nitrobe?~zene prisms in. p. 37.25O ; b. p. 238'5O. It is much more resistant to the action of alkalis than its isomeride being unacted on in the cold but when heated with sodium methoxide in a sealed tube at l l O o for thirty hours both the chlorine and tlie fluorine atoms were removed and the substance resinified.p-Fluorochlorobenzene was nitrated by slowly adding it t o con- centrated nitric acid cooled to -loo the temperature not being allowed t o rise above -7O the product being finally poured on to ice. The unchanged fluorochlorobenzene was distilied off under re- duced pressure and a small amount of 2-chloro-5-nitrophenol formed was removed by washing with a solution of sodium carbonate. The final nitrated mixture had a solidification point 23*75O and was analysed first by decomposition of the 6-fluoro-3-chloro-1-nitrobenz- ene with sodium metlioxide a t 25O and secondly by preparing the solidification-point curve of mixtures of the pure isomerides.The two methods agree in showing that in the nitration the NO group enters the ortho-position to the chlorine t o the extent of 62.25% and into the ortho-position to the fluorine to the extent of 27.75%. W. G. m-Difluorobenzene and its Nitration. FRED. SWARTS (Bee. trav. chim. 1915 35 154-165).-m-Difluorobenzene is readilyi. 134 ABSTRACTS OF CHEMICAL PAPERS. obtained by the diazotisatioii of rn-fluoroaniline in liydrofluoric acid solution followed by distillation. It has b. p. 82.8-82*85°/ 757.3 mm. 82*2O/742 mm. (cori-.) ; D15.5 1.1651 ; 17fij.j 1.43601 ; 144871 ; It was nitrated by slowly adding it t o coiicentrated nitric acid a t -4-Oo the product being poured on t o ice after one hour.When purified the product had m. p. 9 ' 5 2 O ; DI34 1.4577; 122 1.50998 ; T Z ~ ' 1.53220 and was mainly 2 4-diflu-oro-1-nitrobenz- ene with a trace of some other compound. A determination of the depression of the freezing point of pure 2 4-difluoro-1-nitrobenzene by the addition of fluorodinitrobenzene showed that the original nitration product contained a t the most 0.434% of 1 3-difluoro-2- nitrobenzene. 2 4-Difluoro-1-nitrobenzene is decoinposed by sodium methoxide giving 5-flr~oro-2-nitronnisole rn. p. 48.B0 b. p. 272O together with some 4-nitroresorcinol ni. p. 73O. When reduced with iron in the presence of sulphuric acid thel difluoronitrobenzene yielded 2 4-difluoronniliile m. p. - 7*5O b. p. 169*5O/ 753 mm. giving 2 4-difluoro~cetcsnil~~~ 111.p. 120'9O. When nitra.bd in the warm o r a t looo by nitric acid (D 1-52) and sulphuric acid m-difluorobenzene yielded quantitatively 4 6-6;- flzcoro-1 3-dinitrobeizzene colourless prisIyLs m. p. 74O. With sodium methoxide a t the ordinary temperature i t yielded the dimethyl ether of 4 6-dinitrcresorcinol m. p. 155*4O and with alcoholic ammonia in excess a t the ordinary temperature 4 6-dinitro-m- plienylenediamine m. p. 296O. Using cnly 2 mols. of ammonia the product was 3-fluoro-4 6-dinitrocniZine 111. p. 186*6O together with a small amount of 4 6-diiiitro-m-phenetid~~~ ni. p. 169O. Preparation of [Chlorine] Substituted Products of Toluene. L. CASSELLA & Co. (Eng. Pat. 16317 (1914); from J. Sac. Chem. Ind. 1915 34 1203).-Dry chlorine is passed over dry toluene in presence of anhydrous iron chloride a t 12-15O the mixture being stirred.When the trichlorotoluene which is thus formed crystal- lises out the temperature is raised t o 35O gradually increasing to 50° and treatment with chlorine is continued until the necessary increase in weight has occurred. On fractional distillation a yield of 90% of the theory of tetrachlorotoluene is obtained. Only traces of tile rentachloro-compound are produced as indicated by the slight precipit\ation on diluting a sample with an equal volume of carbon disulphide. Further chlorination of tetrachlorotoluene at 100-130° in violet or ultraviolet light gives tetrachlorobenzylidene chloride. G. F. M. Reactions in Energetic Solvents. I. The Direct Replace- ment of Sulpho-groups by Chlorine.HANS MEYER (MoTzatsh. 1915 36 719-722).-1n 1860 Carius observed that methane- and ethane-sulphonyl chlorides when heated at 150-1G0° with phoa phorus pentachloride underwent change according to the equation R*SO,Cl+ PCl = RC1+ SOCI + POCI,. The author has now dis- covered that thionyl chloride is especially favourable to the scission of sulphur dioxide from sulphonyl chlorides and lie believes that thionyl chloride was largely instrumental in producing the results obtained by Carius. 1'45628. W. G.ORGANIC CHEMISTRY. i. 135 At 160-180O in the presence of thionyl chloride aromatic sulphonic acids as also their chlorides and anhydrides are converted into the corresponding chloro-compounds with liberation of sulphur dioxide.Thus p-chlorobenzenesulphoiiic acid quantitatively yielded pdichlorobenzene and sodium benzenesulphonate gave chloro- benzene. With derivatives of the anthraquinone group the neces- sary temperature is higher and a t 200-220° the a- and P-sulphonic acids derived from anthraquinone were converted into the corre- sponding chloroanthraquinones. I n the absence of thionyl chloride whether other solvents such as tetrachloroethane are present or not the decomposition of the sulphonyl chlorides is only partial and frequently more complex in nature. D. F. T. Reactions in Energetic Solvents. 11. The Direct Replace- ment of Nitro-groups by Chlorine and a New Method of Chlorination. HAXS MEYER (Momtsh. 1915 86 723-730. Compare preceding abstract);-Other substituents in aromatic com- pounds besides tlie sulphonyl group can be replaced by chlorine under the influence of thionyl chloride the present publication only giving reaults on the replacement of the nitro-group. 4-Chloro- 3-nitrobenzenesulphonic acid pchloronitrobenzene 2 5-dichloro- nitrobenzene and nitrobenzene when heated with thionyl chloride a t temperatures between 140° and 180° lost their nitro-groups almost quantitatively with formation of 1 2 4-trichlorobenzene pdichloro- benzene 1 2 4-trichlorobenzene and chlorobenzene respectively.With m-nitrobenzenesulphonic acid the yield of m-dichlosobenzene was not so good direct chlorination occurring simultaneously to some extent so that the product also included a substance m. .p. 1G5-175C containing a high percentage of chlorine.A similar result was obtained with o-nitroanisole which gave a tri- chlorophenol in addition to o-chloroanisole. 1 5-Dinitroanthraquinone a t 180-200° was converted into 1 5-dichloroanthraquinone but with naphthalene compounds chlorination occurred very readily naphthalene itself a t 170-180° reacting with thionyl chloride giving 1 4-dichloronaphthalene. The presence of certain groups facilitates direct chlorination even of the benzene nucleus ; azobenzene reacts with thionyl chloride a t 180--2OOc giving 2 Z/-dichloroazobenzene together with its 4 4I-isomeride. A t somewhat higher temperatures namely 230-250° the suc- cessive substitution of t h e hydrogen atoms of a methyl radicle attached t o an aromatic nucleus may be effected ; thus toluene gave benzylidene dichloride and benzotrichloride whilst a-methylanthra- quinone yielded the monochloro- and dichloro-methyl derivatives. By the use of suitable solvents however the methyl group in such substances as tolueaesulphonic acids may be protected so that the action of the thionyl chloride is restricted to the replacement of the sulphonic group by chlorine. Sulphonatian of Benzene.’ 11.GERHARD MOIIRMANK (Aizitaleiz 1915 410 373-385).-The catalytic influence of sodium mercury D. F. T.i. 136 ABSTRACTS OF CHEMICAL PAPERS. and iron on the sulphonation of benzene has been described by Behrend and Mertelsmann (A. 1911 i 189). The author has examined the influence of members of the other groups of the periodic table namely aluminium lead arsenic selenium and manganese and also of cadmium and bismuth.Benzene vapour is passed into 97% sulphuric acid a t 235-245O containing the catalyst and the resulting m- and pbenzenedisulphonic acids (and in the case of lead the monosulphonic acid also) are converted through the sodium salts into the acid chlorides the crystals of which are separated mechanically. The results show that none of the substances approaches mercury in its catalytic effect. Manganese has scarcely any influence and cadmium has but little more. The other catalysts produce about the same effects with the exceptions of selenium which in the form of selenious acid causes carbonisation (although a t 160-170° i t has no sffect benzenelsulphonic acid only being produced) and of lead which in the form of lead sulphate brings about the forma- tion of 80.8% of the meta-disulphonic acid 9.7% of the para-acid N-Halogen Derivatives of the p-Halogen-substituted Benzene- sulphonamides.ROBERT REGINALD BAXTER and FREDERICK DANIEL CHATTAWAY (T. 1915 107 1814-1823).-The soluble sodium salts of various sulphonmonochloroamides have recently received con- siderable attention owing to their use in the treatment of infected wounds. Simple compounds of this nature were described some years ago (T. 1905 87 145) and a number of phalogen-substituted substances have now been prepared. The sulphondihalogenoamides are obtained by the action of the acids HOX on the amides and these give the sodium salts of the sulphonmonohalogenoamides when treated with sodium hydroxide. The sodium salts of the phalogenobenzenesulphonic acids which were required for the preparation of the sulphonyl chlorides were obtained by gradually adding the halogenobenzene to fuming sulphuric acid (10% SO,) a t below 60° and then pouring the cold solution into brine a t Oo.The salts were dried and separated from sodium chloride by solution in alcohol and then converted into the chlorides by grinding with phosphorus pentachloride. p-Chlorobenzenesulphondic?doroamide C,H,Cl*SO,*NCl crystal- lises in colourless rhombic prisms m. p. 83O and the dibromoamide in pale yellow six-sided rhombic prisms m. p. 102O (compare Kastle Keiser and Bradley A. 1896 i 555). Potassium pchloro- benzenesulphonchloroamide C,H,Cl*SO,K:NCl,H,O forms glisten- ing elongated prisms which lose water and then decompose violently a t about 160°; the sodium salt also crystallises with 1H,O and decomposes violently a t about 190°.p-Bromobenzenesulphondichloroamide (ibid.) gives potassium p-bromobe?zzerLesulphonchloroamide colourless needles with 1H,O which. explode a t 165O and the sodium salt 1H,O explosion p. 1 7 8 O . p-Bromo benze?aesulphondibromorrmide crystallises in pale yellow elongated rhombic prisms m. p. 132-133O (decomp.) and yields and 9.5% of the monosulphonic acid. c. s.ORGANIC CHEMISTRY. i. 137 the salts of pbromobenzenesulphonbromoamide ; potassium lR,O explosion p. 193O; sodium 1H,O expl. p. 211O. p-lodobeuzenesulphondic Jdoroamide crystallises in elongated rhombic prisms m. p. 147O and gives the salts of lpiodobeiizene sulFlionchloroamide; potassium 1H,O expl.p. 150O; sodium 1H,O expl. p. 185O. p-C Ji lorob enzeii esulpkonmet hylamide C,H,Cl*SO,*NHMe f orins shining whise plates m. p. 59O and yields the chloroa?iiicZe CGH,C1*SO,*NbkC1 six-sided rhombic prisms m. p. 66O and the bromonmide pale yellow rhombic prisms m. p. 99O. p-Chloro- b e w e nes dphonb en zylumide C,H,Cl-SO,*NH*CH,Ph crystallises in white needles m. p. 108-109° and forms the chloroamide rhombic prisms in. p. 1 2 4 O and bromoamide m. p. 1 1 2 O . The sulphonyl chlorides were also' condensed with various anilines and a large number of sulphovanilides and their corresponding chloroamides are described. C,H4C1* SO,*NPhCl forms six-sided rhombic prisms m. p. looo ; p-bromobe~zze~aeszcZphon- phe iL?/lchloroamide crystallises in elongated rhombic prisms m.p. 104O and the p-iodo-compound in colourless rhombs m. p. 139-140O. The p-chlorobenzenesulphonyl derivatives of substituted anilines are as follows -m-chloroanilide transparent rhombs m. p. 1 0 6 O ; -m-cJdoropJtenyZchloroamide C,H4C1*S0,~NCl*C,H,C1 rhombic prisms m. p. 90°; -p-chloronnilide needles m. p. 148O; -p-chloro- phenylchloroamide prisms m. p. 1 2 7 O ; -2 4-dichloroanilid~~ plates m. p. 108O; -2 4-dz'chloroph enylchloroamide prisms m. p. looo; p-bromounilide prisms m. p. 163O; -p-bromo- plenylchloroamide prisms m. p. 1 2 7 O ; -2 4-dihromoanilidr prisms in. p. 116O ; -2 4-dibromophe?zylchloroanzide prisms m. p. l l O o (decomp.); -p-iodoanilide prisms m. p. 173O; -p-iodo- pJ~eiz?/lchloroamide very unstable m. p. 70° (decomp.) ; -0-nitro- nnilide pale yellow prisms m.p. 114O (deoomp.) ; -0-nitrophenyl- cliloroarnide prisms m. p. 148O (decomp.) ; -m-nitroanilkZe pale yellow needles m. p. 124O ; -m-nitrophenylchloroamida almost colourless prisms m. p. 131O (decomp.) ; -p-nitroanilide yellow needles m. p. 159O (decomp.) ; -p-nitrophenylchloroamide prisms m. p. 1 4 3 O (decomp.); -0-toluidide colourless needles m. p. 1 1 1 O ; -o-tolylcl~loroa?nide prisms m. p. 1 2 7 O (decomp.) ; -p-toluididP prisms m. p. 8 8 O ; -p-tolylckloroamide prisms m. p. l l O o (decomp.) ; -p-tolylbromonmide pale yellow prisms m. p. 91O. The p-brornobenzenesulplion?/l derivatives are as follows -p-chloro- n?dide C,H,Br*SO,*NH*C,H,Cl prisms m. p. 138O ; -p-chloro- phenylchloronmide prisms m. p. 1 4 2 O ; -2 $-dichloroanilide prisms m.p. 134O ; -2 4-dichloro~hen~~Zchloronmine prisms m. p. 97O ; -p-,romoanilide prisms m. p. 141O ; -p-bromoph enylchloroamicTf> prisms m. p. 141O; -2 :4-dibromoanilide prisms m. p. 147O; -2 4-dibromophenylchloroamide prisms m. p. 1 1 7 O ; -p-iodonnilidp prisms m. p. 160° (decomp.) ; -p-iodophcn ylchloroamide very un- stable decomp. below 100° ; -o-nitron??ili& yellow needles m. p. 130O; -o-nitrophenylchloroam~de) prisms m p 160° (decomp.) ; p-C h loro b e nzencstilpJLonphen ylch lo roa mide,i. 138 ABSTRACTS OF CHEMICAL PAPERS. -m-nitroaidide yellow needles m. p. 140° ; -m-nitrophenylchloro- nmide long yellow prisms m. p. 140° (decomp.) ; -p-nitroanilide needles m. p. 183O ; -p-nitrophenylchloroamide prisms m. p. 1 6 4 O ; -0-toluidide prisms m.p. 119O ; -0-tolylchloroamide prisms m. p. 129O (decomp.) ; -p-toluididc prisms m. p. 99O ; -p-tolylchloroamide prisms m. p. 131O. The ypiodobenze?aes2ilphollyl derivatives are as follows -p-bromo- nnilide rliombic plates m. p. 1 7 4 O ; -p-bromopherLylchloroamide C,H,I*SO,*NCl*C,H,Br prisms m. p. 137O (decomp.) ; -p-iodo- clnzlzde glisbening plates m. p. 1 6 7 O (decomp.) ; -p-iodophenylchloro- nmide very unstable m. p. 142O (decomp.) ; -0-nitronizilide very pale yellow plates in. p. 137O ; -0-nitrophenylchloronmide very pale yellow prisms M. p. 167O ; -m-nitronnilide long yellow prisms m. p. 157O ; -m-?iit.1.opiiPnylc?~Zoroamide prisms m. p. 164O; -p-nitro- o d i d e glistening plates m. p. 154O; -o-toluidide long plates m. p. 161O ; -0-tolylchloroamide prisms m.p. 1 loo; -p-toluidide prisms in. p. 135O; -p-tolylchloroamide prisms m. p. 137O (decomp.). J. C. W. Nitrophenanthrenep. ADOLFO M E L ~ (diznl. E'is. Q i h L . 19 15 13 381-389).-A preliminary note describing the influence of the experimental conditions on the nitration of phenanthrene. A. J. W. A New Transformation of Acenaphthylene and Synthesis of Diacenaphthylidene a New Yellow Hydrocarbon. J. DOLIBSKI and K. DZIEWO~SKI (Ber. 1915 48 1917-1931).-The polymerisation of acenaphthylene under the influence of light and heat demonstrated the extreme lability of the substance (compare A. 1912 i 844; 1913 i 847; 1914 i 825). This is still further exemplified when the hydrocarbon is treated with traces of mineral acids for two' other so,lvmerides result.One of them is believed I d c==c-- to be diacenaphthylidene C,o€16<bH ~Ho>C!loH6 whilst the ' other is a complex subc,tance a t least Lpentameride. A solution of acenaphthylene in glacial acetic acid (50 grams to 120 grams) was mixed with 0.5 C.C. of concentrated hydrochloric acid and then warmed for an hour or two on the water-bath. The clear liquid gradually deposited a pale yellow heavy precipitate (40 grams) which was separated into the component polymerides by means of beazene the complex one being freely soluble. A better yield of the dimeride was obtained by treating the picrate of acenaphthylene with hydrochloric acid. 7 7-Diacenaphthylidene (diitapkthylenebuteii~~ C2iH16 was ob- tained in golde'n-yellow glistlening leaflets or tablets m.p. 2 7 7 O (corr.) which gave a greenish-blue solution in concentrated sulph- uric acid. Very dilute solutions in the aromatic hydrocarbons (for example a 0.00125% solution in benzene) exhibited a very intense violet-blue fluorescence which disappeared in bright sunlight owing to oxidation of the hydrocarbon. The dipicrate was obtained inORGANIC CHEMISTRY. i. 139 dark red needles m. p. 216-217O. The constitution of the hydro- carbon was ascertained by oxidation with sodium dichromate and acetic acid to naphthalic anhydride and by reduction with red phosphorus and hydriodic acid t o 7 7-diacenaphthyl (loc. c i t . ) . Bromine was not absorbed directly by the hydrocarbon but acted substitutively. On warming the' substance with a solution of bromine in carbon disulphide.it was transformed into 8 8-dibromo- diuceiwph t h ylide 11 e ?lo ' >(: C<yl ' ciliated orange-yellow C 11 13r c tl I h ' needles decomp. 203O which was oxidised to naphthalic anhydride. I n the cold however substitution in the naphthalene residues took place the product being aaf-dibroniodiaceiznphthylidene C,4H,,Br ciliated yellow needles m. p. 310° (decomp.) which was oxidised to a-bronionaphthalic anhydride. A fine suspension of the hydrocarbon in acetis acid was also treated with nitric acid (D 1.5) when aaf-di?zitrodiace?2nphthylide,ze C,,H,,O,N was obtained in dark red glistening needles which decomposed without melting a t above 360° and were oxidised t o a-nitronaphthalic anhydride. I n the polymerisation of acenaphthylene itself the chief product (70-80% yield) was the complex polymeride.This differs from the polyacenaphthyleiie obtained by thermo-polymerisation (loc. c i t . ) in m. p. and in being reiadily soluble in acetone and easily oxidised to naphthalic anhydride and it is theref ore designated allo-poly- ncenanhthwlene. It w2s obtained as an amorDhous. vellow sub- 1 d stance m. p. 185-190° approximating to the fkmula bG0H40. J. C. W. Some New Organic Compounds of Vanadium. A. T. MERTES and HERMAN FLECK ( J . Ind. E r ~ g . Chem. 1915 7 1037-1038).-When treated in the cold variously in carbon tetra- chloride o r benzene solution vanadium tetrachloride formed in- soluble additive compounds with certain organic bases. The following were isolated in an analytically pure condition With aniline a black powder of the composition 4NH,Ph,VC14 ; with dimethylaniline a green tar having the formula 4NMe,Ph,VC14 ; with phenylhydrazine a violet substance of constitution similar to the above ; with toluidine ammonia niethylamine and diphenyl- amine products were obtained approximating to the formulze 3CGH,Me*NH,,VCl4 4NH3,VC1,,4H,0 GNH,Me,VCl,,H,O and 3NHP1i,,2VCl4 respectively. A solution of vanadium tetrachloride in benzene deposited on keeping a purple compound with evolu- tion of hydrogen chloride.It varied in composition according to the length of time the solution was kept. Anthracene also formed a similar substitution product. Vanadium was estimated in the above compounds in the filtrate obtained from a lime fusion after precipitation of the chlorine with silver nitrate by precipitating as lead vanadate dissolving this in nitric acid and evaporat'ing with sulphuric acid to remove the lead reducing with sulphur dioxide and titrating the hot solution freed from excess of sulphurous acid with A7/ 20-permanganate.G . F. M.i. 140 ABSTRACTS OF CHEMICAL PAPERS. Monotropic Polymorphic Anilides. FREDERICK DANIEL CHATTAWAY and WILLIAM JAMES LAMBERT (T. 1915 107 1766--1773).-A close study of the behaviour of anilides when crystallising suggests that all anilides are capable of forming three very distinct types of crystals namely very slender hair-like crys- tals slender needles o r prisms and stout compact crystals. A large number of anilides can be made t o crystallise in two of these forms and some have been obtained in all three varieties.For example whea pbromoacetanilide and 2 4-dibromoacetanilide are allowed t o crystallise from hot alcoholic solutions they separate in long needles which slowly give place to the stable compact form. The rate of transformation varies with the solvent and the anilide used and increases rapidly with the temperature. Between Oo and the m. p. the compact form is stable and the solids therefore show no transition point within these limits. The view is held however that the transition point is much below the ordinary temperature but is unrecognisable because of the slow rate of the change. The point could be determined by measuring the solubilities of the two forms over a considerable range of temperature but this is a matter of extreme difficulty owing t o the rapidity of transform- ation in the warm solutions.Within the limits which have been f ouiid practicable the solubility curves for the two modifications ar0 parallel and therefore the two anilides are provisionally classed as monotropic. The development of the crystals is illustrated by photographs and the paEer also records careful determinations of the solu- bilities of p-chloro- 2 4-dicliloro- p-bromo- 2 4-dibromo- 4-chloro- 2-bromo- and 2-cliloro-4-bromo-acetanilides in alcohol a t from 5O t o 45O. J. C. W. Phenyl Esters of Oxalic Acid ROGER ADAMS and H. GILMAN ( J . Amer. Ch.ent. SOC. 1915 37 2716-2720).-Aryl oxalates can be prepared in almost quantitative yield by adding oxalyl chloride ( 5 grams) t o ice-cold pyridine (25 c.c.) crushing well the resuIting additive compound and gradually adding the phenol (2 mols.) dissolved in a few C.C.of pyridine. The mixture is kept a t Oo for two hours and is then poured into a mixture of concentrated hydrochloric acid and ice when the ester is precipitated. In addition t o the normal oxalates derived from pcresol a- and 8-naphthols and guaiacol the following esters were prepared o-Nitrophen~~Z oxalate C,O,(C,H,*NO,) yellow needles m. p. 185O ; o-nldehydopli euyl oxnlate C,O,(CGH,*CHO) plates m. p. 153-154O ; vnniZZ?yl oxnlate C20,[C,H3(0Me)*CHO] crystals ni. p. 203-204O ; p-ncet?/l-a-92nphth?/I oxalnte C20,(C,,H,Ac)2 leafy crystals m. p. 197O ; o-carbornethox,~pTten;yl oxalate C204(C,H,*C02Me) needles m. p. 158O. Quinol gave rise t o an ozalate C,O,(C,H,*OH) m.p. 2 1 2 O but if the reaction was allowed t o occur without cooling a mixture was obtained from which after treatment with acetic acid needles m. p. 226O could be isolated probably of the acetate of di-ph ydroxyp henyl ether C,,H,,04. D. F. T.ORGIANlC CBEMISTRY. i. 141 Preparation of 6-Nitro-3-aminophenol and its Methyl Ether. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 285638 ; from J . SOC. Chem. Ind. 1915 34 1135) .-When 4-nitro-1-acetyl- aminobenzene-3-sulplioiiic acid (nitroacetylsulphanilic acid) is heated at a high temperature under pressure with methyl-alcoholic alkali the acetyl group is saponified and the sulplionic acid group is replaced by liydroxyl o r methoxyl. m-Phenetidine and Some of its Derivativee. FRBDBRIC REVERDIN and J.LOKIETEK (BUZZ. Soc. chim. 1915 [iv] 17 406-409. Compare A. 1915 i 878).-~n-Phenetidine has been prepared by a new method and from it a number of derivatives have been obtained. Acetyl-m-aminophenol when heated for two hours in alcoholic solution with sodium hydroxide and ethyl bromide is readily ethylated giving ace to-m-phenetidide OEt*C,H,*NH*COMe greyish- white platsea m. p. 96-97O. Ethyl sulphab can also be used for the ethylation. This acetyl derivative is readily hydrolysed by heating on a water-bath with 35% hydrochloric acid giving the free base yielding a hydrochloride colousless leaflets and a picrate yellow needles m. p. 158O. The following acyl derivatives have been prepared by the usual metho,ds Formyl-m-ph eizetidide OEt*C,H,*NH*COH m.p. 52O ; benzo-m-phenetidide OEt*C,H,*"H*COPh long white needles m. p. 103O ; tolueTte-p-sulpho-m-phenetidide OEt~C,H,*NH*SO,~C,H,Me yellowish-white leaflets m. p. 157O ; o-nitro t oluene-p-sulpho-m-phenet idide OE t~C,H,~NH*SO,~C,H~Me*NO needles m. p. 8 8 O and 2' 4/-dzmtro-3-ethosy&phenylart~iiie OEt*C,H,*NH*C,H,(NO,) orangeyellow crystals m. p. 151O. m-Phenetidine has been diazotised and coupled with fl-naphthol giving a compound C,,H,,O,N red needles m. p. 107O y.ielding a sodium salt insoluble in cold water. Coupled with salicylic acid the diazo-salt gives a compound which dyes wool bright yellow; coupled with resorcinol a compound reddish-brown ; coupled with naphthionic acid an orange-red conzpzcizd ; and coupled with 1 4-naphtholsulphonic acid a red compozciid.Aromatic Telluretine Compounds. 111. (Conclusion). KARL LEDERER (Ber. 1915 48 1944-1949. Compare A. 1913 i 615 724 1182).-Some diary1 tellurides have been condensed with more halogeno-acids and esters and some triaryltelluronium picrates have been prepared. A mixture of diphenyl telluride and ethyl iodoacetate deposited when expoBed to light for a few days garnet-red crystals of diphenyl- telluronium iodide (from the free iodine) followed later by ethyl diph e n y 1 t ell ur e tin e iodide [iod odi ph e n y 1 t el l u r k c e t at el TePh,I* CH CO,E t m. p. l l O o (decomp.). A solution of diphenyl telluride in a-bromopropionic acid was warmed a t 60° for some time and then diluted with ether when J. C. W. W. G .i. 142 ABSTRACTS OF CHEMICAL PAPERS.dip?& e n y 1 t ellure tin e [a-b row odiiph eny l t elluri- propionic acid] TePh,Br-CHMe*C02H was precipitated as a white powder m. p. about 9S0. Similarly a-bromobutysic acid gave dz'ph4rLyl-a-butyryltelluTetine bromide [a-bronzodiphenyltelluri- trutyric acid] TePh2Br*CHEt*C02H m. p. 84-85O whilst ethyl a-bromobutyrate yielded the( corresponding ethyl ester an amorphous substance m. p. 142-143O and ethyl a-bromoiso- bu t$y r a t e formed b ro mide [a-bromodiphenyl t elluriiso~bu tyra t e] TePh2Br*CMe2* CO,Et m. p. about 1 3 0 O . A solution of di-ptolyl telluride in methyl bromoacetate gradually deposited the compound (C,H7)2TeBr-CH2*C02Me,CH2Br.C0,Me m. p. 6S0 from which the free methyl di-p-tolyltellztretine bromicle [ bromodi-ptolyZteZZu~~~cetute] was obtained by repeated crystallisa- tion from chloroform and ether in aggregates of small prisms m.p. 92-93O. The corresponding ethyl ester had in. p. 102-103°. Di-o-tolylmethyltelluronaum chloride (C,H,)2TelLleC1 was ob- tained by boiling the corresponding iodide with silver chloride and water. It crystallised from water in four-sided plates with 2H20 m. p. 93O and again at 14B0 and from chloroform with Triphenyltelluronium hydroxide TePh,*OH was obtained by boiling the iodide with silver oxide and water as an alkaline resin which formed a p'crate broad yellow needles m. p. 1 6 0 O . Tri-p-tolyltelluronium hydroxide a resin m. p. about l l O o also formed a picrate long prisms m. p. 194-195O whilst the resinous tri-octolybtellwroniecm hydroxide yielded a picrate long yellow prisms m.p. 1 8 2 O a chloride stout coiumns m. p. l'i5-176O and a bromide m. p. 197-198O. Z romide e t h y Z d i ph e n ?/l-a-is o b u t y r y 1 t el 1 ur e t in e iCHC13 1~1. p. 155-156'. J. C. W. Some New Oxidation Derivatives of Cholesterol. ST. ~IINOVICI and (MME.) TH. ZENOVICI-EREMIE (Bzill. Sci. Acad. Roumaine 1915 4 194-205. Compare Minovici and Vlahuta A. 1912 i 697).-The authors have oxidised cholesterol with hydrogen peroxide under varying conditions and have obtained five different compounds to which they have been unable to assign any definite constitution. When 10 grams of cholesterol were dissolved in 200 C.C. of glacial acetic acid on a water-bath and a mixture of 50 grams of hydrogen peroxide in 100 C.C. of sulphuric acid (20%) slowly added and the mixture slowly boiled for two hours a clear oily liquid was obtained which when separated and washed with water solidified t o white floccula.These when crystallised from acetone and water gave a compozcnd C2,H,,O4 acicular needles m. p. 1 6 0 O ; [a] + 41.47O. Submitted t o Salkowski's reaction for cholesterol the compound gave a colourless chloroform solution the acid being coloured orangeyellow. I n the Liebermann- Burchard reaction no play of colours was obtained but only a deep violet-red coloration. The compound did not give Lifschutz's reaction for oxycholesterol. The substance contains no hydroxyl phenolic o r ketonic group and is not an ozonide o r a peroxide.ORGANIC CHEhZISTRY. i. 143 It is very probably a lactone and contailis an acetyl group.It does not unite with bromine. When warmed with hydrobromic acid i t yields a compozcnd ClnHzsBr m. p. 130° and with hydrochloric acid a compound C,,H,,Cl m. p. 150O. The mother liquors from the compound C,,H,,O gave an oily substance which resinified on contact with air and after purification the compo?cnd was obtained as a yellow powder. The substance is slightly acid in character and is soluble in alkalis and gives a silver salt. It is probably a resin acid having the composition C,H,,O,. If in the original oxidation of the cholesterol an excess of hydrogen peroxide was used an amorphous compound was obtained which was not characterised. I f the original proportion of hydrogen peroxide was used but added in larger portions a t a time a compound was obtained in white lamellar crystals m.p. 200O. By slowly adding 20% sulphuric acid alone to a solution of cholesterol in gently boiling acetic acid on cooling a crystalline compound m. p. l l O o - l l l o was obtained. It was not cholesteryl acetate since it was not decomposed by boiling with alcohol or water. It differed from cholestanyl acetate in that with phosphorus pentachloride it gave a crystalline chloro-compound ni. p. 95-97O and with bromine in carbon disulphide a crystalline bromo- derivative m. p. 116-118°. W. G. Sitosterol and Stigmasterol. A. HEIDUSCHKA and H. W. GLOTH (Arch. Pharm. 1915 253 415-426).-After a brief sum- mary of the work of Burian Windaus Ritter Pickard and Yates and Jaeger on these two sterols the following new derivatives are described. Sitosteryl salicylnte C,7H,,0-CO*C,H,*OH has m.p. 147O and separates from ether and alcohol in colourless gelatinous flocks which ultimately become crystalline. Sitosteryl phenyl- cnrbamate C,,H,,O,N forms crystals m. p. 174O. By direct treat- ment with an excess of bromine sitosterol yields decabromosito- sterol C2,H%0Brl0 a brown powder m. p. about 185O and octabromositost erol C27H380BrS a yellow powder in. p. about 120° the former of which is almost insoluble in alcohol. Just as Windaus converted cholesterol by oxidising its dibromide with acidified permanganate and debrominating the product by zinc and acetic acid into cholestenone so has sitosterol been now con- verted into sitosteaone C27H440 crystals m. p. 82O which forms a semicarbazone crystals m.p. 254O (decomp.) sintering a t 243O. Stigmasterol forms a palmitate C,,H,90*CO*C,,H, silky crystals m. p. 99O stearate crystals m. p. lolo oleate colourless crystals m. p. 44O salicylate colourless needles in. p. 175O and cinnamate colourless crystals m. p. 155O. By the oxidation of stigmasterol tetrabromide and debromination of the product a crystalline substance m. p. 140° was obtained which did not exhibit the properties of a ketone. c . s. The Substituted Benzoylbenzoic Acids. ALICE HOFMANN (Moizatsh. 1915 36 805-824).-The author brings forwardi. 144 ABSTRACTS OF CHEMICAL PAPERS. further experimental proof of the fact that the presence of halogeii substituents in phthalic anhydride facilitates the Condensation of the latter with benzene derivatives.When 3 6-dichlorophthalic anhydride is heated with dicliloro- benzene and a little aluminium chloride a t 200° some hydrogen chloride is eliminated and there is also produced 3 6 2’ 5-tetrci- cldorobenzoylberzzoic acid needles m. p. 205-207O which on heating a t 140° with sulpliuric acid is converted into 1 4 5 8- tetrachloroanthraquinone (compare Schilling A. 1913 i 493). During this condensation the acid undergoes slight concurrent decomposition into dichlorobenzene and 3 6-dichlorophthalic acid the latter being observed as a sublimate of the anhydride. The tetrachlorobenzoylbenzoic acid was converted by thionyl chloride into the acid chloride which on treatment with methyl alcohol yielded the methyl ester needles m. p. 145-148O a second modifi- cation of this ester m.p. 1 7 2 O being obtained by the interaction of the acid and the alcohol in the presence of a little sulphuric acid ; the former modification (termed the pseudo-form) could be converted into the latter (the “normal” form) by boiling with methyl alcohol and a little sulphuric acid. Tetrachlorophthalic anhydride and chlorobenzene reacted at 140° in the presence of a little aluminium chloride producing pentachlorobenzoylbenzoic acid m. p. 165O which resembled the above tetrachloro- analogue in giving a non-crystalline “ pseudo ” methyl ester when the acid chloride was treated with the alcohol and an amorphous (‘normal” ester when esterified directly by methyl alcohol in the presence of sulphuric acid. When heated a t 140° with sulphuric acid pentachlorobenzoylbenzoic acid yielded peiitachloroanthraquinone. The condensation of tetrachlorophthalic anhydride and dichloro- benzene in the presence of aluminium chloride a t 220° gave hexa- chloro b enzoylb enzoic acid colourless crystals m.p. 238-239O which like the preceding acids could be converted through the chloride m. p. 181-184O into a ‘(pseudo” methyl ester m. p. 180-182° and by the usual process of esterification into an amorphous normal ” methyl ester. It also underwent intra- molecular condensation when heated with sulphuric acid yielding hexachloroanthraquinone pale yellow needles m. p. 298O. I n the usual manner tetrachlorophthalic anhydride and nitro- benzene condensed together giving tetrachloronitro b enzoyl b enzoic acid colourless crystals m.p. 242-245O the acid chloride (colour- less crystals) of which was converted by methyl alcohol into an amorphous methyl ester. By the addition of bromine to a heated mixture of phthalic acid and fuming sulphuric acid there was obtained tetrabromophthalic acid yellow crystals m. p. 268O which underwent condensation with benz_ene in the presence of aluminium chloride giving tetra- brornoben2oylbenzoic acid m. p. 230-232O; the methyl ester platelets m. p. 1O8-11lo when heated with sulphuric acid in the usual way apparently gives rise to a bromoanthraquinonesulphonic acid the tetrabromoanthraquinone presumably being less resistantORGANIC CHEMIS‘I’RY. i. 145 than 1 2 3 4-tetrachloroanthraquinone towards sulphuric acid ; the free acid however when carefully treated with sulphuric acid may be made to yield tetrabromoanthraquinone orange-red needles m.p. 200-202° (in a closed tube). With bromobenzene tetrabromophthalic anhydride undergoes condensation producing pentabromobenzoylbenzoic acid m. p. 228-230° which yields an oily “normal ” methyl ester and an amorphous ‘‘ pseudo” modification m. p. 178-183O and can also be made t o undergo further condensation to pentabromo- anthraquinone m. p. 230-240° the yield however being poor. Tetrabromophthalic anhydride and dibromobenzene interacted under the usual conditions producing hexabromobenzoylbenzoic acid m. p. 218-219O from which was obtained by heating with sulphuric acid a small quantity of hexa~bromoanthraquinone Ths condensation of tetrabromophthalic anhydride and dichloro- benzene gave tetrabromobenzoyldichloro benzoic acid m.p. 240- 245O. In a similar manner tetraiodophthalic anhydride and benzene gave tetraiodo b enaoylb enzoic acid microscopic yellow crystals m. p. 230-231O (sodium salt silver leaflets) from which it was found impossible to produce the corresponding tetraioclo- anthraquinone. D. F. T. Preparation of Sulphomethylbenzophenone - o - carboxylio [Sulphomethyl-o-benzoylbenzoic] Acids and Substitution Pro- ducts. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 285700; from J . SOC. Chem. Ind. 1915 34 1135).-The chlorides of benzoic acid or its substitution products are condensed with m-xylene the new substances are sulphonated and the resulting as-dimethylbenzophenonesulphonic acids having the sulphonic group in the xylene residue are oxidised.The o-carboxylic acids which are thus obtained may be condensed to anthraquinone deriv- atives by means of concentrated sulphuric acid. Preparation of Derivatives of 2-Hydroxy-3-naphthamide. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 284997; from J . SOC. Chem. Ind. 1915 34 1136).-The hydroxynaphthylamides of 2-hydroxy-3-naphthoic acid are obtained by condensing amino- naphthols with the haloids or with the acid itself in the presence of dehydrating agents. Whereas the anilide is only soluble in lime water and even so only t o a slight extent the new amides dissolve readily in warm dilute sodium carbonate. They are freely absorbed from such solutions by unmordanted cotton which then acquires very intense clear fast shades with diazo-solutions.J. C. W. 111. p. 280-285’. J. C. W. Preparation of Hydroxytriarylmethanecarboxylic Acids. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 286433; from J . SOC. Chem. Z d . 1915 34 1135).-A mixture of an aromatic o-hydroxycarboxylic acid (2 mols.) and an aromatic aldehyde (1 mol.) is treated with zinc chloride and phosphoryl chloride reaction being completed by warming a t 70°. The phosphoryl VOL. CX. i. Yi. 146 ABSTRACTS OF CHEMICAL PAPERS. chloride is recovered by distillation under reduced pressure. o-Chlorobenzaldehyde and o-creosotic acid yield chlorodihydroxy- climethyltriphenylmethanedicarboxylic acid. J. C. W. Phenylfumario Acid. G. KARL *~LMSTROM (Ber. 1915 48 2009-2010) .-A substance has been obtained in another connexioii which must be regarded as phenylfumaric acid but as it did not agree with Barisch's description (A.1880 43) the acid has been prepared by boiling phenylmaleic anhydride (Alexander A. 1890 1136) with 2N-sodium hydroxide. PA enylfumaric acid C,,H,O separates from benzene as a felted mass of needles m. p. 128-129O and from water in which i t is very soluble with 2H,O. It quickly reduces permanganate and is easily Converted into phenylmaleic anhydride by melting. J. C. W. Preparation of Compounds of Phenolphthalein and Alkali Carbonates. A. VON SZTANKAY and C. GEYER (D. R.-P. 286030; from J . SOC. Chem. Znd. 1915 34 1167).-Cmcentrated solutions of the alkali carbonates are treated with phenolphthalein either in solution or as a freshly prepared suspension in water a t the ordinary temperature.Compounds of the type 2C,,H,,0,,6Na2C0 are formed. They are strongly alkaline are stable only in aqueous solution and the therapeutic doses are much smaller than is the case with the known alkali salts of phenolphthalein. J. C. W. The Synthesis of Certain Substituted Syringic Acids. MARSTON TAYLOR BOGERT and EDWARD PLAUT (J. Anzer. Cheni. SOC. 1915 37 2723-2733).-A record of the earlier part of an investigation of derivatives of . syringic acid (4-hydroxy-3 5- dimethoxybenzoic acid). Methyl bromogallate trimethyl ether prepared by the action of bromine on methyl gallate trimethyl ether in acetic anhydride solu- tion was obtained for the first time in the solid state prisms m. p. 90° (corr.) b. p. 202O/16 mm. (compare Hamburg A.1899 i 364). Syringic acid was converted by the Fischer-Speier reaction into the methyl ester (Graebe and Martz A. 1903 i 262; Bogert and Isliam A. 1914 i 532) ethyl ester crystals m. p. 55'8O (corr.) and isoaniyl ester needles m. p. 1 0 1 O (corr.). On acetylatioii a t the ordinary temperature by acetic anhydride the methyl ester was converted into its acetyl derivative OAc*C,H2(0Me),*C02Me crystals ni. p. 129O (corr.) whilst bromination in cold acetic anhydride gave methyl 2-bsomosyriiigaf c OH*C6HBr(OMe),*CO,1e crystals m. p. 89O (corr.) which was also obtained by partial tiemethylation of methyl bromogallate trimethyl ether by heating with hydrobromic acid. Syringic acid in cold acetic acid solution is converted by nitric acid into 4 5-dinitropyrogaIlol-1 3-dimetliyl e t h e r pale yellow crystals m.p. 154O (corr.) the change being analogous to that undergone by trimethylgallie acid but in solution in acetic anhydride a t - 5 O methyl syringate undergoes nitration t o m ~ f I q ( ! 2-nitros?/s~npte OH*C,H(OMe),(NO,)*CO,Me paleORQANIC CHEMISTRY. i. 147 yellow crystals m. p. 68.3O (corr.) which can also be obtained by heating methyl nitrogallate trimethyl ether with hydrobromic acid. Ethyl 2-nitrosyi.inyccte almost colourless silky needles m. p. 7 4 O (corr.) was prepared in an analogous manner to the methyl ester. Tlie latter substance was reduced by tin and hydrochloric acid to i t i f thyl %amin osyringnt P OH*C,H (OMe)2(NH2)*C0,Me colour- less crystals in. p. l l O o (corr.) which gradually darkens in the air ; li,!~c?l.ociilr,ric~e needles m.p. 192O (corr.) ; diacetyl derivative large crystals m. p. 139'9O (corr.). By diazotisation in diluted sulphuric acid solution and subsequently heating a t looo the methyl ester was converted into 2 4-dz%yd~*ozy-3 5-~~iiietl~c),r.yhett r- oic ncid C,H(OH),(OMe),*CO,H pale yellow crystals m. p. 165O (tlecoinp.) ; dincetyl derivative crystals decomp. at 162O. I n a preliminary experiment in which the product from the thermal decomposition of the dihydroxyclimethoxy-acid was recrystallisetl from alcohol and subsequently treated with methyl sulphate and sodium hydroxide solution there was obtained a siibstcciicP glassy needles m. p. 89O (corr.) possibly apioiiol tetramethyl ether. D. F. T. Derivatives of Methylvanillin and a New Condensation Product.B. L. VANZETTI (Atti R. Accad. Limei 1915 [v] 24 ii 467-470. Compare Korner and Vanzetti A. 1912 i 352; Fritsch A. 1904 i 94).-Veratrylic acid [3 4 3' 4/-tetramethoxy- benzilic acid] cannot readily be obtained by transposition or oxida- tion of the corresponding ketonic compounds according to the schemes *CH(OH)*CO* + >C(OH)*CO,H and *CO*CO* -+ >C(OH)*CO,H although in other cases these changes are almost quantitative. Thus whilst benzoin is transformed directly into beiizilic acid by means of a current of air in presence of alkali iii the hot veratroin merely undergoes quantitative oxidation to veratril under these conditions. Veratrylic acid may be obtained moderately pure (m. p. about 68O) but by no means in quantita- tive yield by the prolonged action of alcoholic potassium hydroxide on verakril in the hot.Another starting point for preparing veratrylic acid is veratro- phenone (3 4 3/ 4/-tetramethoxybenzophenone) m. p. 144*5O which may be obtained by converting veratric acid into' veratroyl chloride m. p. 70-71° and treating the latter with veratrole (1 mol.) in presence of aluminium chloride. The further stages are represented by the scheme The various compounds obtained in this way which is not very coiivenieiit for preparing the acid are t o be described elsewhere. Fusion of veratril with potassium hydroxide also gives poor yields of veratrylic acid although high yields of benzilic and anisylic acids and somewhat lower ones of piperonylic acid are obtainable in this way.'The yield of veratrylic acid varies considerably with 9 2i. 148 ABSTRACTS OF CHEMICAL PAPERS. the temperature of the fusion and in some cases more complicated transformations occur the mass becoming dark coloured and resinous. Treatment of the resin with various solvents yields an orange-yellow compound m. p. 1 9 8 O and crystallisation of this from acetic acid gives shining brownish-red needles which a t 110- 1 20° are converted into the orange-yellow compound. With cold concentrated sulphuric acid the latter gives a greenish-blue colora- tion which changes in a few minutes to a red coloration; sub- sequent dilution either spontaneous or otherwise produces a reddish turbidity owing to precipitation of the compound in the form of powder. Except that the proportion of hydrogen is rather low the composition of this compound approximates closely to that of veratril.The transformation which the veratril undergoes i n the formation of this compound appears t o be analogous to the thermal decomposition of benzilic acid which is now under investigation. T. H. P. Preparation of Tetrachlorobenzalde byde and New Colouring Matters therefrom. 1,. CASSELLA & Co. (Eng. Pat. 1915 13970; from J. SOC. Chem. Ind. 1915 34 1243).-Tetrachloro- benzaldehyde is obtained as a white powder which crystallises from ether in colourless needles m. p. 97-98O by dissolving tetra- chlorobenzylidene chloride in six parts of concentrated sulphuric acid a t 90° and pouring into iced water. The above solution in sulphuric acid or tetrachlorobenzaldehyde itself condenses with o-hydroxycarboxylic acids such as o-cresotic acid to give leuco- compounds which on oxidation with sodium nitrite in sulphuric acid nitric acid nitro-compounds or fuming sulphuric acid yield valuable new dyes of the triphenylmethane series.These dyes surpass in intensity and fastness other known dyes of a similar character and are distinguished by their bright greenish-blue shade. G. F. M. Semicarbaeones. V. Semicarbazom s of Benzaldehy de and Some of its Substitution Products. JAMES ALEXANDER RUSSELL HENDERSON and ISIDOR MORRIS HEILBRON (T. 1915 107 1740- 1752. Compare T. 1912 101 1482; 1913 103 377 1504; 1914 105 2892).-The absorption spectra and the power t o form salts with dry hydrogen chloride of various semicarbazones have been investigated.Semicarbazones with hydroxy- or methoxy-groups in the nucleus are found t o absorb two molecular proportions of hydrogen chloride giving yellow to red salts. If the nucleus contains a strongly nega- tive substituent such as chlorine or nitroxyl the semicarbazone only absorbs one proportion of the gas forming a practically colourless salt. The acetylation or benzoylation of salicylaldehyde has no influence on the additive capacity of the semicarbazone but the pnitrobenzoyl derivative gives a semicarbazone which only absorbs 1 mol. of hydrogen chloride. No definite result could be obtained in the case of pdimethylaminobenzaldehydesemicarbazone which absorbed nearly 4HC1 and ptolualdehydesemicarbazone which combined with nearly 2HC1.ORG A N I C C HEM ISTR Y .149 Some semicarbazones were observed to form labile more coloured modifications which are probably the isomerides of the stable products finally obtained after repeated crystallisations. The absorption spectra were examined in solutions in alcohol alcoholic sodium ethoxide and concentrated sulphuric acid. With the exception of the p-dimethylamino- and p-nitro-compounds the semicarbazones show a band in N 1 10000-alcoholic solution a t about 1 / X 3500. The addition of sodium ethoxide t o the solutions of the Iiydroxy- but not methoxy-compounds displaces the band towards the red. Semicarbazones containing hydroxyl or methoxyl in the ortho-position show a band in concentrated sulphuric acid at about l/X2600 which is not exhibited by the others.p-Tolualdehydesemicarbazone gave a yellow Irydrochloride C,H ,ON,,l&HCl which rapidly decomposed in the air. Salicylaldehydesemicarbazone gave an unstable yellow &hydro- chloride and a straw-yellow fairly stable sulphate C,H,O,N,,H,SO decomp. 150O. o-Methoxybenzaldehydesemicarbaxone colourless needles m. p. 215O (decomp.) formed a dark orange fairly stable dihydrochtom'de. p-Hydroxybenzaldehydesemicarbazone when first formed contained a yellow admixture probably the labile iso- meride and it yielded an unstable yellow dihydrochloride and a yellow sulphate. pMethoxybenzaldeliydesemicarbazone was ob- tained in a labile form small transparent yellow prisms m. p. 168O very soluble in acetone and the usual colourless form ni. p. 2 0 9 O (decomp.). It gave an unstable orange-yellow CFihydro- chloride and a mustard-yellow stable sulylzate decomp.152O. Vanillinsemicarb'azone formed a very unstable orange-yellow dihydrochloride. Veratraldehydesemicarbazone yielded an un- stable orange di?bydrochloride decomp. 1 30°. Piperonalsemicarb- azolze dihydrochloride deep orange-red lost hydrogen chloride in the air. 2 - Hydroxy - m - methoxybenzaldehydesemicarbazotze CgH1103N3 colourless needles m. p. 225O (decomp.) gave an un- stable yellow &hydrochloride m. p. 1 5 8 O (decomp.). 2 3-Di- m e t hoxy b en za Zde h ydesemicar b n zo ne white needles m . p. 2 3 1 O (decomp.) yielded a dirty yellow dihydrocldoride. The chlorobenzaldehydesemicarbazones gave the following un- stable hy&oc?dorides ortko cream coloured decomp.203O * metu colourless decomp. 198O; para pale yellow decomp. 182;. The nitrobenzaldehydesemicarbazones yielded the following hydro- chlorides ortho cream coloured unstable decomp. 2 1 2 O ; I T M ~ C I cream coloured unstable decomp. 2 2 2 O ; p r a pink stable n o t decomposed a t 275O. o-Acetoxybe?zznldehydesenLicarbazone C,0H1103N3 a colourless granular powder m. p. 167O gave an unstable dark yellow &hydro- chloride. o - Benzoyloxyb e~zzaldei~ydesenzicar~azo~~e colourless needles rri. p. 195-196O (decornp.) formed a creani coloured unstable dihydrochloride. 2 - p - Nifroben~zoyloxybet~znldehyde CI4HgO,N was obtained by the action of the acyl chloride on salicylaldehyde in pyridine solution in the form of pale yellow leaflets m. p. 1 2 8 O which yielded the semicarbnzone NO,* CbH,*CO*O*C,H,*C'H N*NH*CO *NH2,i.150 ABSTRACTS OF CHEMICAL PAPERS. pale yellow needles in. p. 2 1 8 O (decomp.) ; hydrochloride colour- less and unstable. pDimethylaminobenzaldehydeseinicarbazone showed the same absorption band in alcohol as the p-hydroxy-compound did in alcoholic sodium ethoxide. When first formed i t was dark red but the recrystallised substance was white and the I/ ydrochlom'de 3-4HC1 was very unstable and greenish-blue. J. C. W. Constitution of the Salts of Phenol-aldehydes. 11. H. PAULY ( B e y . 1915 48 2010-2018. Compare A. 1915 i 689). -A continuation of the controversy with Hantzsch (A. 1915 i 55 1 1062). Hantzsch adheres t o his quinonoid isomerism theories to explain the coloured salts of phenol-aldehydes but Pauly main- tains that all the problems connected with the manifold activities of the carbonyl group are best explained by valence-electron formulation.The following salts are described The sodium salts of salicyl- aldehyde CiH,O,Na,C,H,O,,~H,O (Ettling 1840) and C,H,O,,C,H,O,Na (Hantzscli 1906) both of which are pure white; the sodizcm salt of isovanillin C",H,O3Na sulphur-yellow needles ; and tlie sodiu I ) / salt of bromoisovanillin C,H,O,BrNa a bright yellow crystalline precipitate. Hronioisoilnnillzii or probably 2-bromo-5-hydroxy-4- methoxybenzaldeliyde tlie product of the actioii of bromine d i s solved in acetic acid 011 isovanillin forms snow-white needles m. p. 208'. J. C. I%'. Isomerism of the Oximes. VII. 5-Bromovanillinoxime 5-Nitrovanillinoxime and 6-Nitropiperonaloxime.OSCAR LISLE BRADY and FREDERICK PERCY DCNN (T. 1915 107 1858-1862). -It has been found that certain negative substituents in the benzene ring seem t o favour the existence of two isomeric oximes. The effect of introducing such groups into1 vanillinoxime has there- fore been examined 'for tliis contains groups namely methoxyl and hydroxyl which inhibit the formation of a second isomeride. 5-Broino- and 5-nitro-vanillinoximes could only be obtained in the nn ti-form however which shows that the negative groups do not count,erbalance the effect exercised by the other groups. Unlike vanillinoxime piperonaloxime can readily be obtained in the syir- form m d therefore it was expected thatq tlie 6-nitro-derivative would also exist in the two forms.Strange t o say i t does not form a hydrochloride so the two distinct inodifications could not be cliaracterised. 5-Rrornoz'(/!)L17i,io,7.i/r/ P C,H80,NBr was obt'ained from the pro- duct of the direct bromination of vanillin in colourless needles 111. p. 179O. The position of the' bromine atom was proved by converting the oxime ultimately into 5-bromo-4-hydroxy-3- melthoxybeilzoic acid (Robertson T. 1908 93 792). The oxinie was first converted by boiling acetic anhydride into 5-brorno-4- ucetorry-3-?n e t h oxyb en Z O I I it rile C,,H,O,NBr colourless crystals in. p. llO-lllo and this was hydrolysed by boiling with diluteORGANIC CHEMISTRY. i. 151 sodium hydroxide f o r a few minutes to 5-byorno-4-hydroxy-3- ?t~efhoxybeizaoiait~ile needles m.p. 144O (sodium salt shining plates) and then on continuing the boiling t o t110 above acid. The oxime formed a diacetate C12H120,NBr a microcrystalline powder m. p. 1 2 2 O and a hydrochloride m. p. 175O (decomp.) from both of which the original oxime could be recovered. 5-Nitrovanillinoxiine as obtained from the aldehyde by means of hydroxylamine had m. p. 2 1 6 O (Vogl A. 1899 i 698 gave 111. p. 200-201°) and formed a red sodium salt. It was con- verted into a dincetate C,2H130,N2 a yellow crystalline powder in. p. 1 1 2 O and a nzoi~oacetate orange needles with 1H,O m. 11. 1 4 7 O the latter being obtained most conveniently by the action of acetyl chloride1 dissolved in pyridine. It also yielded a hydro- chloride iii. p. 2 0 4 O (decomp.) but all these derivatives gave the original oxiiiie when suitably treated.6-Nitropiperonaloxime was converted into the ncetnte C,,H,O,N yellow iiePYdles m. p. 1 4 2 O . J. C. W. Chlorination Experiments with Antimony Pentachloride KARL STEINER (Momtsh. 1915 36 825-829. Compare Eckert and Stleiner A. 1915 i 564 565).-An extension of tlhe earlier investigation. When -heated with antimony pentachloride benzopheiione gave Iiexachlmobenzene &s the main product together with a little ~7~rchlo?.obeiicopheno,7e CO(C,Cl,) colourless needles m. p. 318O and perchlorobenzoic acid. Benzil gave rise t o hexachlorobenzene with a little perchlorobenzoic acid. 1 2-Naphthaquinone yielded tetrachlorophthalic acid and perchloronaphthaquinone. Under similar treatment benzoic acid and benzoyl chloride yielded hexachlorobenzene together with a mixture of chlorinated beiizoic acid9 whilst phthalic acid gave a mixture of the same iia.turet.With benzoylbenzoic acid the chief products were per- chlorobenzoylbenzoic acid and 1 2 3 5 6 7 8-heptachloroanthra- quinoiie accompanied by small quantities of tetrachlorophthalic acid and hexachlorobenzene. By using a suitable solvent such as tetracliloroethane tlie action of the antimony pentachloride can be moderated and with a 10% solution of antliraquinone in this liquid the chief product is 1 4 5 8-tetrachloroanthraquinone. D. F. T. Indones. 11. Synthesis of 3-Phenvl-2-methylindone. R. DE FAZI ( A t t i R. Accad. Lincei 1915 [v] 24 ii 343-348. Com- pare A. 1915 i 1063).-Similarly t o 3-phenyl-2-ethylindone 3-phenyl-2-methylindone (compare Rupe Steiger and Fiedler A.1914 i 281) may be obtained by the action of cold concentrated sulphuric acid on ethyl 8-hydroxy-BB-diphenyl-a-methylpropionate (Rupe Steiger and Fisdler Zoc. c i t . ) :i 1.52 ABSTRACTS OF CHEMICAL PAPERS. The oxime of 3-phenyl-2-methylindone C16Hi30N forms shining yellowish-green prisms m. p. 199-200° and in the cold gives a blood-red coloration with concentrated sulphuric acid and a ruby- red coloration with concentrated nitric acid ; the semicarbazone forms orange-red indented leaflets m. p. 219-220° (Rup Steiger and Fiedler Zoc. cit. gave m. p. 200-201°) and gives intense blue and cherry-red colorations in the cold with concentrated sulphuric and nitric acids respect'ively ; the semioxamzone C,,Hl5O2N3 forms tufts of intensely yellow shining needles m.p. 203-205° and gives blue and cherry-red colorations in the cold with concentrated sulphuric and nitric acids respectively. The semicarbazone of 3-phenyl-2-ethylindone (compare A 1915 i 1064) Cl,H,,ON forms tufts of shining orange-yellow needles m. p. 198-199O and gives cherry-red and intense blue colora- tions in the cold with concentrated nitric and sulphuric acids respectively. T. H. P. Quinhydr-nes. WILHELN HIW:MUKD ( J . p i - . CIzcm. 19 15. [ii] 92 342-370. Compare A. 1909 i 109; 1911 i 654).-After a discussion ,Of the various constitutions proposed f o r t<he quin- hydrones the author decides in favour of the suggestion of Willstatter and Piccard (A 1908 i 475) who apply to these compounds a formula of the type the undulating lines indicating partial valencies.This view of the structure is considered to be in good accord with the tendency of the quinone constituent of some '' mixed " quinhydrones (that is quinhydrones in which the quinone and the phenol are1 not derived from the same parent hydrocarbon) t o remove hydroxylic hydrogen atoms from the accompanying phenol and so to effect oxidation t o the t'rue quinhydrone corresponding with the phenol. The following quinhydrone compounds are described the general method cf preparation being to mix a light petroleum solution of the quinone with an ethereal solution of the phenol and to allow the mixture t o crystallise. From thymoquinone and quinol the coni- pound 2~l,Hl,02,3C6H,0 red needles decomp.137O ; from thymoquinone and resorcinol an unstable red compound decomp. 43-45O the proportion of resorcinol being between unimolecular and sesquimolecular; from thymoquinone and catechol a red oily compound 2C,,H,,02 3c&H,O,. pXyloquinone with quinol and catechoil respectively gave red needles m. p. 153-156O and red msnoclinic crystals m. p. 87O; each of the molecular composition CsH80,,2C6H,02. m-Xyloquinone in a similar manner with quinol and catechol gave isomeric compounds of the same composition very deep red leaflets m. p. 12O-12lo and long red needles m. p. 44-45O respectively. Likewise o-xyloquinone with quinol and catechol gave similar compou?zds deep red needles with a green lustre m. p. 118O and red needles m. p. 60-62O respectively. Resorcinol formed no quinhydrone compounds with the xyloquinones.C,H,*O H 0 PU,~H,-O I€ *O*C,H Chlorobenzoquinone and quinol gave a c o v ~ p o ~ n d 2C,H,02a3C,H,( OH),,ORGANIC CHEMISTRY i. 153 bronze-coloured crystals m. p. 123-124O (compare Ling and Baker T. 1893 63 1314; Schmidlin A. 1911 i 727). ni- Dichloro- trichloro- and tetrachloro-benzoquinone when mixed with quinol oxidised this substance to ordinary benzoquinone- quinol quinhydrone. Benzoquinone with gentisic acid P-resor- cyclic acid and protocatechuic acid gave rise respectively to very deep red needles of no definite m. p. red prisms of no definite m. p. and deep red crystals m. p. 179-180° the products being isomerides of the composition C6H,0,,2C,H604. Benzoquinone with orcinol gave deep red prisms of a compound C6H40,,C,H802 hydrated orcinol also giving red crystals of a compound With gallic acid and ethyl gallate benzoquinone was converted into ordinary quinhydrone.The results show that although there is no simple law ruling the composition of the quinhydrones a considerable regularity exists in the influence exerted by various substituent groups. For the analysis of the above products the author made use of the titanium trichloride method (Knecht and Hibbert A. 1911 ii 76). C6H,O,,C7H,O,,H,O. D. F. T. The Action of the Three Isomeric Aminophenols on a-Naphthaquinone. EMIL GROSSMANN ( J . pr. Chem. 1915 [ii] 92 370-390).-The general method of procedure was to allow the naphthaquinone (2 mols.) to react with the aminophenol (1 mol.) in h o t alcoholic solution the resulting compound being formed by the condensation of one molecule of each the second molecule of naphthaquinone serving as the necessary oxidising agent.The condensation of paminophenol and naphthaquinone gave 2-p-hydroxyanilino-a-naphthaguinone C,,H,O,*NH*C,H,*OH red needles m. p. 225O which was reducible to a colourless compound. The formation of the condensation product was examined from a quantitative point of view and the mechanism was demonstrated to be as described above the second molecule of naphthaquinone being reduced to the corresponding quinol. The product gave cherry-red solutions in concentrated acids and blue solutions in alkalis ; it possessed only feeble acidic properties and the prepara- tion of the corresponding phenoxides miscarried with the possible exception of the potassium derivative in the attempt to produce which an unstable blue amorphous powder was obtained. Methyl- ation with methyl sulphate also failed t o give a satisfactory result the product consisting of a mixture of red needles and deep violet capillary needles.The methyl ether of 2-phydroxy- anilino-a-naphthaquinone C,,H50,*NH*C6H,*OMe was therefore prepared in the usual manner from naphthaquinone and p-anisidine in alcoholic solution containing a little acetic acid the product forming fiery red needles m. p. 158O; the corresponding e t h y l ether C,,H,0,*NH*c?6H4;OEt obtained from naphthaquinone and y- phenetidine consisted of deep red needles m. p. 264O; acetyl derivative C,,H,O,*NAc*C,H,~OEt a deep raspberry-red micro- crystalline powder m.p. 1 7 5 O . When treated in the cold with 9*i. 154( ABSTRACTS OF CHEMICAL PAPERS. acetic anhydride and concentrated sulphuric acid phydroxyanilino- a-naphthaquinone was converted into a diacetyl derivative CIoH50,*NAc*C6H4*OAc red prismatic needles m. p. 170° and with benzoyl chloride and pyridine i t gave a benzoyl derivative C,,H,O,*NH C,H4*OBz deep orange-red needles m. p. 210°. 2-m-l~ydroxya~aili~ao-a-~i a pli t h a gu ino 12 e was prepared in an analogous manner to its para-isomeride and was found t o form deep violet needles m. p. 242O soluble in potassium hydroxide t o an azure-blue solution and in sulphuric or hydrochloric acid to a cherry-red solution ; beizzoyl derivative deep red prismatic needles m. p. 208O. The methyl and ethyl ethers were obtained by effecting the condensation of naphthaquinone with nz-anisidine and ni- phenetidine the compounds forming long red needles m.p. 1 7 2 O and deep red needles m. p. 195O respectively. 2-o-Hydroxyanilino-a-napht?~n~i~inone prepared from naphtha- quicone and o-aminophenol is an almost black substance with very little tendency to crystallisation ; i t was obtained in brown flocks m. p. 175O and as a chocolate-brown microcrystalline powder m. p. 205O. The corresponding nzetlbyl and ethyl ethers obtained by effecting a similar condensation between naphthaquinone and o-anisidine and o-phenetidine formed deep red needles m. p. 146O and fiery red needles m. p. 152O respectively. Preparation of Chloroanthraquinones. AKTIEN GESELLSCIIAFT FCJR ANILIN-FABRIKATION (Eng.Pat. 1915 5182; from J . SOC. Chenz. Znd. 1915 34 1203).-Hydroxyl groups in anthraquinone derivatives are replaced by chlorine without affecting the ketonic groups or the hydrogen atoms of the nucleus by the action of the chlorine compounds of phosphorus. Thus for example 1- hydroxyanthraquinone when treated in nitrobenzene solution a t 150° with phosphorus pentachloride and boiled for three hours under a reflux gives after removing the nitrobenzene by steam tiistillation 1-chloroanthraquinone which is recrystallised from glacial acetic acid. Preparation of Anthraquinone Derivative8 [Mercaptans]. CHEMISCHE FABRIK GRIESHEIM-ELEKTRON (Eng. Pat. 8254 June 1915; from J . SOC. Chem. Znd. 1915 34 1136).-a-Hydroxy- or a-amino-derivatives of anthraquinone are heated with an alkaline sulphide with o r without added sulphur a t 140-150° when the hydrogen atom in the ortho-position with regard to the hydroxyl 0s amino-group is replaced by the thiol group.The products are valuable dyes or intermediate substances. Preparation of Dianthraquinone Oxides. AKTIEN GESELLSCHAFT FUR ANILIN-FABRIKATION (Eng. Pat. 24347 ; 1914 Dec. ; from J . SOC. Chem. Zna?. 1915 34 1135).-l-Nitroanthraquinone or its substituted products yield 1 1'-dianthraquinone oxide or its deriv- atives when heated with an acid-fixing substance such as an alkali carbonate' in a n indifferent solvent o€ t h e aromatic series. D. F. T. G. F. M. J. (2. W. J. C. W.ORGANIC CHEMISTRY. i. 155 Preparation of New Phenanthraquinone Dyes. E. R. WATSOP and K.C. MUKHERJEE (Eng. Pat 9311 June 1915; from J . Soc. C'henz. Incl. 1915 34 1136).-Bromo- or bromonitro-derivatives of phenanthraquinone are condensed with amines of the benzene or naphthalene series giving dyes which colour chrome-mordanted or unmordanted wool fast dark blue violet or greenish-blue shades. The fastness t o light is improved by sulphonation. Example bromo-2-nitrophenanthraquinone (100 parts) is boiled with aniline (1000) and copper powder (25) f o r two hours when the hot liquid is filtered into an excess of dilute hydrochloric acid the 2-nitroanilino- phenanthraquinone being precipitated. isoPulegolphosphonic Acid. FRAYCIS H. DODGE ( J . A n i c r . Chew. ~SOC. 1915 37 2756-2761).-A re-investigation of the compound originally termed citronellal-phosphoric acid and now designated isopulegolphosphonic acid which the author obtained earlier (A.7 1891 286) from citronella1 and phosphoric oxide in the presence of a little water.The substance is a monobasic acid m. p. 181-182O which crystallises in large monoclinic plates (a b c = 1-9828 1 1.9745 P=57*83O) ; potussizim salt C,,H,,P04K,3H,0 large plates ; socliiim salt plates; mngnesiiim salt plates; c d c i u t ~ i salt; silccr salt,. When cautiously heated the sodium salt decom- poses with formation of isopulegol. In spite of its monobasic character the acid is regarded as a phosphinic acid of the structure PRO(OH) the constitution of the radicle R being uncertain. The formation of this acid shows no promise of providing a reaction for the detection of citronella1 in essential oils.D. F. T. J. C. W. Constituents of Oil of Caesia. FRANCIS 1). DODGE and ALFRED E. SHERNDAL (J. Znd. Blzg. Chem. 1915 7 1055-1056).-The oil of Citinamonmm cassia contains at least 0.5% soluble in dilute alkali from which by acidification and steam distillation about 25% of its weight of salicylaldehyde was isolated. The' rest of the alkali soluble portion consisted of coumarin (60%) cinnamic acid (8-10%) and small amounts of benzoic and salicylic acids and an unidentified liquid volatilel acid. W. ADRIANI (Rec. trcrv. chim. 1915 37 180-210. Compare Fosse A. 1914 i 859).-An examination of the behaviour of xanthydrol towards substituted carbaniides and towards aromatic amines and their derivatives substituted in the nucleus or in the amino-group.Monosubstituted carbarnides give monoxanthyl derivatives with xanthydrol in alcoholic solution in the presence of acetic acid. The author has prepared xantl~ylmethylcarbanzide Cl5HI4O2N2 m. 11. about 230° phenylxanthylcarbamide m. p. 225O (compare Fosse loc. c i t . ) o-tolylxanthylcarbamide C,,H,,O,N m. p. 2 2 8 O p-tolyl- s.anthylcarb amide and /3-?mpht hylzant hylcnr bamide C,,~,,O,N,. Of the disubstituted carbamides the symmetrical derivatives do not form xanthyl compounds whilst the unsymmetric derivatives give monoxanthyl compounds such as diph eq7 y l m n thylcarbamidp G. F. M. Action of Xantbydrol with some Amides and Amines. p 2i. 156 ABSTRACTS OF CHEMICAL PAPERS. C,H,02N2 m. p. 179-180° and xanthyl-as-dimethylcarbamide C,,H,,0,N2 m.p. 225O have been prepared. s-Diphenylcarbamide and s-dimethylcarbamide were recovered unchanged. With aniline in the presence of a small amount of acetic acid in alcoholic solution xanthydrol gave dixant hytaniline C,,H,,O,N together with a small amount of xanthyla&ne ClSH150N m. p. 185'5-187O. The latter compound was also obtained by the action of xanthydrol on aniline hydrochloride under the usual conditions or by the action of xanthydrol on aniline in the presence of a large excess of acetic acid. The three toluidines gave dixanthyl derivatives. Thus dixanthyl- o-totuidine C133H2502N dixanthyl-m-toluidine and dixanthyl-p- t oluidine were prepared. Of the xylidines examined m-4-xylidine gave a dixmthyl C,,H,,O,N whilst m-2-xylidine only gave a ?nonoxanthyZ derivative m.p. 170.5O. The three nitroanilines all gave monoxanthyl derivatives rant hyl-o-nitroandine C,,H,,O,N xant hyl-m+,itroaniline and zanthyl-p-nitroadine being prepared. Neither 2 4-dinitroaniline nor picramide gave any xanthyl derivative. Of the anilines substituted in the amino-group methylaniline gave dixanthylme t hylaniline C33H2502N and dimethylaniline gave xanthyldimethylanilinel (compare Fosse loc. cit.). Diphenylamine yielded xanthyldiphenylamine CZ5Hl9ON and acetanilide gave a small amoant of xanthylaniline. From the naphthylamines there were obtained respectively di- xan th yl-a-napht hylamine C,Hz5O2N and dixanthyl-p-napht hyl- (I min e . As an example of aubstances in which the nitrogen is linked to a strongly negative group benzamide and methylnitroarnine were chosen.The former gave xunthylbenzamide C,,H,,O,N m. p. 218O and the latter gave xnnthylmethylnitroamine Cl,H,,0,N2 m. p. 1 1 7 ' 5 O . The behaviour of these compounds towards hydrochloric acid was then examined to see if xanthyl chloride was liberated as indicated .by an intense yellow coloration. Of the substances described above all gave a yellow coloration except xanthylaniline xanthylxylidine derived from m-2-xylidine xanthyldimethylanigne xanthyldiphenyl- amine and dixanthyl-a-naphthylamine. Dixanthylaniline gave the yellow coloration indicative of the formation of xanthyl chloride but a t the same time a precipitate of xanthylaniline m. p. 185*5-187O was obtained. These results indicate that in xanthylaniline xanthyldimethyl- aniline and xanthyldiphenylamine the xanthyl group and in di- xanthylaniline and dixanthylmethylaniline one of the xanthyl groups is attached to1 the benzene! ring and the other to the amino- nitrogen.I n the case of the monosubstituted carbamides and the asymmetric disubstituted carbamides the xanthyl group has entered the second amide group thus NHMe-CO*NH*C,,H,O and NM%*CO*NH*C,,H,O. I n the case of the derivatives from the three toluidines and m4-xylidine one of the xanthyl groups is attached t o the nitrogen atom and the other to the benzene ring.ORUANIC CHEMISTRY. i. 157 The evidence in the case of the three xanthylnitroanilines is not clear but the xanthyl group is possibly attached to the benzene ring. The two xanthyl groups in dixanthyl-a-naphthylamine are attached to carbon whilst in the l3-isomeride a t least one of the xanthyl groups is attached to nitrogen.I n xanthylbenzamide the xanthyl radicle is attached to nitrogen and this is probably true of xanthylmethylnitroamine since it gives the reaction for true nitroamines. Theise colour reactions with hydrochloric acid are confirmed by the green fluorescence test with sulphuric acid. The above-men- tioned exceptions do not give the green fluorescence characteristic of xanthydrol whilst all the others do. The author considers that the general constitution of these xanthydrol derivatives is better represented by formula I than by formula 11 bringing them into agreement with the accepted formula for xanthyl chloride. W. G. Process for Hydrogenating Unsaturated Substances.C. I!. BOEHRINGER & SOHNE (Eng. Pats. 1914 21583 and 21948; froin J . SOC. Chem. Znd. 1915 34 1225).-The unsaturated substance in aqueous or alcoholic solution or suspension is treated with hydrogen in presence of a suboxide of nickel copper iron or cobalt as catalyst. Details of the hydrogenation of quinine hydrochloride morphine cinnamylcocaine cinnamic acid and aminoacetonitrile are given. G. F. M. Preparation of a Derivative of Thebaine. $1. FREUND arid E. SPEYER (D.R.-P. 286431; from J . SOC. Chem. Ind. 1915 34 1168).-A new base C,,H,,O,N decomp. above 275O is obtained by treating thebaine in acid solution with hydrogen peroxide or potassium dichromate. J. C. W. Action of Grignard’s Reagent on Tertiary Pyrroles. K. HESS (Ber. 1915 48 1969-1974. Compare A.1914 i 725).-A reply to Oddo (A. 1914 i 1142). Hess and Wissing obtained some 2-acyl-1-methylpyrroles by treating 1-methylpyrrole with mag- nesium ethyl bromide and then with acyl chlorides. They assumed that magnesium 1-methyl-2-pyrryl bromide was first formed with t’he evolution of ethane. Odd0 pointed out that 1-methylpyrrole does not react with the Grignard reagent and assumed that Hess’s base contained free pyrrole. The author now states that his base was pure but that it certainly does notl give ethane unless water is present. It must combine with the magnesium ethyl bromide however otherwise this would react with the acyl chloride to give a carbinol which it does not. Moreovelr the additive compound which i t forms is unaffected by an acyl chloride until water is added when the 2-acyl-1 methylpyrrole and ethane are produced.i. 158 ABSTRACTS OF CEEMICAL PAPERS An arrangement is described by which it is possible to determine whether ethane is liberated even when such reactions are carried out in a hygroscopic liquid like ether and if so t o estimate it.J. C. W. Action of Derivatives of the Propane Series on Pgrrole. 11. KURT HESS and HEINRICH FINK (Ber. 1915 48 1986-2005. Compare A. 1913 i 1378).-The preparation of pyrroles substi- tuted by derivatives of propane opens up the possibility of synthesising certain bases of the pyrrolidine series such as hygrine cuskhygrine and tropine. A number of compounds of this nature have therefore been prepared. An ethereal solution of epichlorohydrin was treated with potassio- pyrrole when two products were obtained namely a-1-pgrryl- propylene by-oxide C',H,N*CK,*C fl-C'11 a limpid mobile oil \/' 0 with mustard-oil odour b.p. 93-94O/11 mm. and a dimeride of this a viscous odourless oil b. p. 195-200°/16 mm. The mechan- ism of the reaction is the same as in the action of epichlorohydrin on sodiomalonic esters and such compounds (Traube and Lehmann A 1899 i 417; 1901 i 501). The potassiopyrrole is first attached to the oxide ring and then potassium chloride is eliminated; thus C4H4NK + CH2-CH*CH2C1 = C,H,N*CET,*CH(C7K)*C~T2CI -+ \/ 0 C,H,N*CH2*CH-CH + KCI. \/ 0 This course would account for the production of the dimeride and is supported by the fact that monochlorohydrin and potassiopyrrole yield propylene oxide pyrrole and potassium chloride.Dichloroisopropyl acetate (acetyldichlorohydrin) also reacted with potassiopyrrolel to' form the above oxide and its dimeride. I n this caxe the hydrin se'enis to1 decompose into epichlosohydrin and acetyl chloride for the product also contains a new diucetylpyrrole C,H,O,N which remains behind as the potassium salt when the other substances are extracted with ether. The compound forms rectangular prisms m. p. 55* b. p. 105O/16 mm. The above a-1-pyrrylpropylene By-oxide was used in a number of reactions. Thus with an ethereal solutdon of magnesium ethyl bromide it reacted without any evolution of ethane to give y-bromo-a-l-~yrryZpro~?z-~-oT C,H,N*CH,*CH(OH)*CH,Br as a colourlees syrup h. p. 137-139°/14 mm. whilst in boiling benzene i t gave in addition a new pj/rryl alcohol probably C,H,N*CH,* CH (OH) CH,E t as a limpid oil with a faint odour b.p. 115-117°/14 mm. The bromohydrin was converted into the acetate y-bronzo-a-l-pyrryli~- propgZ acetate C4H4N*CR,=CH(OAc)*CR2Br by the1 action of magnesium ethyl bromide followed by acetyl chloride and byORGANIC CHEMISTRY. i. 159 similar meaiis into the p-tiifrobenzoate C,,H,,O,N,Br m. p. 79-80°. The acebate is an unstable aromatic syrup which gives a number of products when left with sodium methoxide of whicli only the chief has been isolated. This is probably y-nzethosy-a-l- pyrrylprolm n-B-ol C,H,N*CH,* CH (OH)*CH,* OMe which has h. p. 143O/12 mm. The propylene oxide readily combines with water when heated at looo in an atmosphere of nitrogen in a sealed tube t o forni a - l - ~ y r .~ y l p r o ~ ~ i e - ~ y - c l i o T as a limpid viscous oil b. p. 167-168O/ 15 mm. with a bitter taste. It also' absorbs hydrogen chloride in cold ethereal solution yielding y-c7Lloro-a-l-pyr~yl~ro~n-8-ol C,H,N*CH,*CH(OH)*CH,Cl b. p. 109-110°/ 12 mm. 122'5O/ 19 mm. This was methylated by means of methyl iodide and silver oxide the reaction requiring special care and y-chloro-8-methoxy- a-l-pjrrylpropise C,H,N*CH,-CH(OMe)*CH,Cl was obtained as a mobile fragrant oil b. p. 103~5-105°/20 mm. Attempts were inade to eliminate hydrogen chloride from this and potassiopyrrole was found t o be effective. This pives a mixture of Dvrrole. a bi- 2 . I cyclic co mpo mid probably of t1ie"f ormula 2>CH*OBIe c H y c H cH%H*N*CH a mobile oil with an intense not &pleasant odour b.p. 73-'74O/ 20 mm. and ~ - m e t h o ~ y - a y - d i - l - p y r r y l ~ r o ~ ~ ? ~ e (C,H,N*CH,),CH*OMe a very stable viscous oil b. p. 149*5-150*5°/20 mm. Methyl- alcoholic potassium hydroxide also effects the removal of hydrogen chloride giving the above bicyclic compound and also 8-nzethoxy- a-l-pyrrylpropun-y-ol C,H,N*CH2*CH (0 Me) CH,*OH b. p. 105-108°/26 mm. Dichlorohydrin was also methylated by carefully treating a solu- tion of it in methyl iodide with silver oxidel. The dichloroiso- propyl methyl ether CH(CH,C1)2*OMe thus obtained is a mobile highly refractive very volatile oil with a refreshing odour b. p. 47'5O/20 mm. 159-159.5O/740 mm. which reacts with potassio- pyrrole in benzene solution t o give the above1 bicyclic compound CH:C-CH C,H,,ON and an isomeride probably I >NH CH.OI\Ie of the formula (annexed) which is an unstable oil b.p. 104~5-106°/11 mm. s-Dichloroacetone wa5 boiled with acetic acid and excess of anhydrous potassium acetate and thus converted into chloroacetylnzethyl acetute CH,Cl*CO*CH,*OAc b. p. 112-114°/16 mm. JOHN GUNNING MOORE DUNLOP (tlic late) (T. 1915 107 1712-1713).-aa-Dimethylglutarimide has been relduced by means of sodium and boiling amyl alco.ho1 t o 3 3-cFirnefltylp~peridiize a strongly alkaline base with b. p. 1 3 7 O which forms a deliquescent JAydrochloride a fiydriodide m. p. 200° an aurichloride needles m. p. 182O and a benzoyl derivative needles m. p. 68-69O b. p. 204O/15 mm. It was desired t6 con- vert the base into 3 3-dimethyl-1 l-trimethylenepiperidinium CH C-CH,/ J.C. W. 3-genz-Dimethylpi~eridine.i. 160 ABSTRACTS OF CHEMICAL PAPERS. iodide in connexion with another research (compare T. 1912 101 1748) but this could not be realised. Preparation of a Carbonate of Sodium 2-Phenylquinoline- 4-carboxylate. CEIEMISCHE FABRIK AUF ACTIEN (VORM. E. SCHERING) (D.R.-P. 285499; from J . SOC. Chem. Ind. 1915 34 1167).-A compound C1,H,,O2NNa + C,,H,,O,N + H,CO which has more therapeutic value than 2-phenylquinoline-4-carboxylic acid or its sodium salt i6 obtained by the interaction of this acid and sodium carbonate or sodium hydrogen carbonate of the sodium salt and carbon dioxide or of 2-phenylquinoline-4-carboxylates and sodium hydrogen carbonate. J. C. W. Derivatives of o-Aminophenol and a-Amino-P-naphthol.E. VON MEYER ( J . I". Chem. 1915 [ii] 92 255-271).-An investiga- tion of the benzoxazolone compounds obtainable from o-amino- phenols and a-amino-P-naphthol by the action of carbonyl chloride. [With HUGO SAHLAND.]-~ 2-Dihydrobenzoxazolone (carbonyl- J. C. W. o-aminophenol) C,H,<-O->CO NH can be produced in better yield than that previously obtained (Schmitt and Hentschel ibid. 1888 [ii] 37 27) by allowing the action of the carbonyl chloride and o-aminophenol to occur in pyridine solution. With care o-hydroxyphenylcarbamic acid OII*C,H,*NH*CO,H m. p. 95O can be isolated as an intermediate product which a t looo passes into the oxazolone compound ; the silver salt undergoes a similar dehydr- ation a t l l O o .By treatment with phenylcarbimide and in alkaline solution with ethyl chloroformate dihydrobenzoxazolone is respec- tively converted into ethyl 1 2-dihydrobenzoxazolone-2-car6oxyZate *<U,H 4>N*Cil,Et. leaflets m. p. 78O and the corresponding nnilide O<!&%>N*CO*NHPh short needles m. p. 125O; a benzojyl derivative# O<-e 4>NBz crystlals m. p. 165O and a nitro-deriv- . -co- C H co- ative CO<~~>C,H;NO yellow needles rn. p. 242O were also prepared. Interaction with aniline produced a substance probably the and C,H4<O_>C:NP h insoluble in alkalis. Under similar conditions t o the preceding a-amino-P-naphthol was converted into 1 2dihydronaphthoxazolone (carbonylamino- naphthol) C,,H,<-O->CO prisms m. p. 206O which when heated with concentrated hydrochloric acid a t 150° undergoes fission into the origina.1 aminonaphthol and carbon dioxide.Treat'ment in alcohollic solution with methyl and ethyl iodide in the presence of potassium hydroxide produced respectively 2-met hyl-1 2-dihydro- naphthoxazolone C,,H,< >GO very pale red needles m. p. 184O and its 2-e thyl-analogue C,,H,<Y(~>CO needles M. p. NH NH NMe 0-ORGANIC CHEMISTRY. i. 161 141O. Acetylation and benzoylation yielded respectively 2-acetyl- 1 2-dih,yc%ro1zaphtlz~oxazolo?ze C,,H6<-O->Cd NAc pale red needles in. p. 121° and the corresponding 2-benzoyl compound colourless needles m. p. 256'. Treatment with aniline a t 250° effected fission of the heterocyclic ring with formation of P-hydroxy-a-naphthyz- taminoformanilide OH-C,,H,-NH*CO-NHPh needles m p.229' I n cold acetic acid solution chlorine converted the naphthoxazolone compound into a-chloro-1 2-dihydronaph thoxazolone c,oap<y>co uiifused atl 310° whereas in chloroform solution the product was an isomeric /3-chloro-compound pale yellow crystals of high m. p. ; longer treatment with chlorine in hot acetic acid solution gave rise t o dichloro-P-naphthaquinone. By heating with phosphorus penta- chloride and treating a hot acetic acid solution with chlorine a very pale reid dichloro-l 2-dihydronaphth oxcIzoloize KH C,,H,CI,<-()->C(' of high m. p. and a tetrachloroacetyl-l 2-dih~ydrona~hthoxnzolo~te a yellow crystalline solid m. p. 75O possibly of the structure ?Qb&->N-CO*CCI C HC1 were respectively obtained. Similarly by bromination in acetic acid solution a bromo-1 2-dihydronaphth- oxazolone C,,H,Br<-,>CO yellow neledles decomp.a t 250° NH and a dibromo-derivative C,,H,Br,<?E>CO yellow needles m. p. above 300° were obtained. Nitration in acetic acid solution by nitric acid or nitrous fumes in the latter case using a hot solution . yielded a nitro-1 2-dihycEronaphthoxazolone NO2*C1,Hs<-,>~ NH '0 needles decomp. near 270° m. p. above 300° whereas the action of sodium nitrite on a cold acetic acid solution gave 2-nitroso- 1 2-dihyd~onaphthoxazolone O<($~~>X*NO a yellowish-brown solid decomp. a t 170° m. p. 194O. [With PAUL RAS SFELD.]-M&~Y~ 4-amino-3-hydro~xybenzoate7 (" a-orthoform '7 is converted by formic acid into a formyl deriv- ative CHO*NH*C6H,(OH)*C0,Me colourless tetragonal leaflets m.p. 225O which a t 240' loses water with formation of methyl benzoxazole-5-carboxylate CO,Me*C,H,<~>CH yellow needles m. p. 99O. I n a similar manner the isomeric methyl 3-amino- 4-hydroxybnzoaf%e (" P-orthof orm ") is coavertible successively into itts formyl derivative silky neledles m. p. 222O and methyl benz- oxazole-4-carboxylate small needles m. p. 107O. The two methyl aminohydroxybenzoates can also be1 converted into their acetyl derivatives NHAc*C,H,(OH)*C'O,Me needles m. p. 18B0 and m. p. 204O respectively which can be dehydrated by zinc chloride a t looo and by acetic anhydride at 140-150° respectively givingi. 162 ABSTRACTS OF CHEMICAL PAPEHS. iit e t h y l 1-me thy1 b e1~zoxazole-5-carbozyla t e C0,Me*C6H,<~>CMa slender needles m.p. 103-104° and the isomeric methyl 1-methyl- be~iaoxazole-4-carbo~ylate silky needles m. p. 66O. Methyl 4-amino-3-liydroxybenzoate forms with ethyl oxalate ail trddztzve compound C22H,,0,,N needles m. p. 1 1 2 O which when tieated with excess of the ethyl oxalate is converted into methyl o,,,trT~ldi-(4-nn1 in o-3-h ydroxy b eir zoa t e ) C,O,[N H C,H (0 H) C O,Me] rods m. p. 298-300°; ammonium salt yellow powder; diacetyl derivative stellar groups of needles m. p. 171O; dibemoyl deriv- ative needles m. p. 231O. Methyl 3-amino-4-hydroxybenzoate gave 110 addit.ive compound with ethyl oxalate but on heating a mixture of the two substances met h y 1 o xaZyldi-( 3-amino-4-hydro xy b e nzoa t e) needles m.p. 312-313O was obtained which was also produced from a solution of the oxalat'e of the aminoester on prolonged boiling. When fused with phthalic anhydride methyl 4-amino-3-hydroxy- benzoate reacts giving a condensation product of the possible con- stitution (an- /\CO,Me nexed formula) I prisms. m. p. \/ 229O The same ester in dilute sodium hydroxide solution when treated with a toluene solution of carbonyl chloride gave leaflets m. p. 228O of 111 e thy1 1 2-dikydro b enzoxazolon e-5-curb oxyla t e co~"l".~'-o>cco-)c<~~:;;J 1 I-NH C6H4 \/ Y tlie alternative enolic constitution CO,M~*C,H,<;) >C*O H also being possible ; the compound gives a methyl derivative needles m. p. 16S0 and an acetyl derivative leaflets m. p. 170O. The interaction of me'thyl 3-amino-4-hydroxybenzoate and car- bony1 chloride has already been investigated (Einhorn and Ruppert A.1903 i 257). The action of carbon disulphide on this ester in alcoholic solution a t 160-170° gives methyl thio-1 2-dihydro- YH b enzo xaz ole-4-car b ox y la t e C0,Me 'C H3<~o->CS needles m. p. 228O which from its ability to dissolve in alkalis may have the tautomeric constitutio'n CO,Mo*C,I€,<~>C*S H. With the isomeric 4-amino-3-hydroxy-ester interaction with carbon disulphide occurs less smoothly. With nitrous acid methyl 4-amino-3-hydroxybeiizoate and its 3-ainino-4-liydroxy-isomeride are converted into dimonnhydrides N CO,Me*C,H,<O>N yellow solids decomp a t 70° and 1 1 7 O respec- tively with feeble explosion. Both products couple with phenols giving dyea D.F. T.ORGANIC CHEMISTRY. i. 16:j Preparation of Ether-like Derivatives of Barbituric Acid. CHEMISCHE WERKE VORM. H. BYK (D.R.-P. 285636; from J . Soc. C'hem. Znd. 1915 34 1167).-Alkylalkyloxyalkyl- or dialkyloxy- alkylmalonic acids or their derivatives are condensed with carbamide in the usual way giving products which are less toxic than diethyl- barbituric acid. Examples Ethyl malonate sodium ethoxide P-iododiethyl ether and carbamide yield ~ i - ~ - e t J i o s y e t J ~ y l i t i a l o i ~ ~ ~ ccrrbamide and ethyl malonate sodium ethoxide 8-iododiethyl ether ethyl iodide and carbamide yield ethyl-6-ethoxyeth ylmaloiiylca~b- uttiide and in turn from these' 5 5-cLi(B-ethozyeth?/l)bcirhitziric acid and 5-P thyl-5-P-e t Jz ox ye t 11 yl b a ~ b i t u ric a cid are formed.J. C. W. The Condensation of Aldehyde Diacetates and of Phenyl- hydrazones with 2-Thiohydantoin. BEN H. NICOLET ( J . ,41?ier. C'lzem. Soc. 1915 37 2753-2756).-It is already known that aromatic aldehydes cam be condensed with hydantoin 2-thiohydan- toin and substituted derivatives of the latter by boiling together with acetic acid and sodium acetate (Wheeler and Hoffmann A. 1911 i 498; Wheeler and Brautlecht A. 1911 i 500; Wheeler Nicolet and Johnson A. 1911 i 1031). The value of the condensa- tion lies in the possibility of reducing the products to benzyl- liydantoins which are readily hydrollysed to phenylalanines. The author now siiowe that the aldehyde in this condensation may be replaced by its diacetate or phenylhydrazone; the use of the latter derivative especially enables condensation products to be formed in cases where the corresponding aldehyde would be too volatile.Under the usual conditions of the condensation benzylidene diacetate and 2-thiohydantoin gave rise t o 2-thio-4-benzylidene- liydantoin and benzaldehydephenylhydrazone yielded the same pro- duct. With acetaldehydephenylhydrazone and 2-thiohydantoin the product was 2-thio-4-etIi ylidetzehydatztoiii YH.CO)C:CHMe a CS*NH yellowisli-brown crystalline powder m. p. rather indefinite a t 253O. D. F. T. 2 4 6-Triaminopyridine. HANS MEYER and ERICH RITTER VON BECK (J!onatsh. 1915 36 731-749. Compare Meyer and others A. 1912 i 514; 1913 i 530; 1914 i 438 439).-In an attempt to obtain 2 4 6-triaminopyridine citrazinic acid (2 6-dihydroxy- pyridine-4-carboxylic acid) was converted by the action of phos- phoryl chloride a t ZOOo into 2 6-dichloropyridine-4-carboxylic acid of which the1 nzPthyl ester C,H2NC1,-C0,Me needles m. p.8 2 O on treatment with hydrazine hydrate a t water-bath temper- ature readily gavel 2-c1iloi.0-6-hycEmzii~o~yri~i?~ e-4-carboxylh~ydrazide NH,*NH*C,H,NCl*CO*NH-NH needles m. p. 226O with redden- ing but the product obtained by working in alcoholic solution was 2 6-dicJztoropyridz'ize-4-cnr boxylhydrazide C,H,NC12*CO*NH*NH2 needles m. p. 1 8 4 O . This substance when treated in very dilute hydrochloric acid solution with sodium nitrite gave 2 6-dichloro-i. 164 ABSTRACTS OF CHEMICAL PAPERS ~ r i d i i z ~ - c a r b o x ~ l a z i d e C5H,NC12*CO*N3 a pungent feebly ex- plosive powder m.p. 89O which yielded ethyl 2 6-dichloro-4-pyridyl- carbamate C,H2NCl,*NH*C0,Et needles m. p. 132O when boiled with alcohol ; hydrolysis of this substance with aqueous alcoholic pot'assium hydroxide solution caused almost quantitative formation of 2 6-didhZoro-4-aminopyridine C,H,NCl,*NH colourless needles 111. p. 1 7 6 O . 2 6-Dichloropyridine-4-carboxylic acid was also heated a t 210° with a concentrated solution of ammonia and a little copper bronze when 2 6-diaminopyridine-4-carboxylic acid C,H2N(NH,),*C0,H was obtained as a .sparingly soluble powder the methyl e s h very pale yellow needles m. p. 1 7 3 O (&hydrochloride greenish-yellow needles m. p. 208O with decomp. ; dibenzoyl derivative needles m.p. 312O) of which slowly reacted with concenkrated ammonia solution at the1 ordinary temperaturel giving 2 E-diaminopyridine- 4-carboxyZamide C5H,N(NH2),*CO*NH2 leaflets m. p. 256O (decomp.) The methyl elster of the diaminopyridinecarboxylic acid failed t o react witlh hydrazine hydrate in boiling alcoholic solution but in the absence olf the alcohol the two1 substances interacted readily giving the hydrazide C,H,N(NH,),*CO*NH*NH colourless needles m. p. 260° (decomp.) in an open tnbe. It was not found possible to convert the hydrazide into the corresponding azoimide derivative probably ojn account of nitrous acid simultaneously affecting the amino-groups and endeavours to apply the corre- sponding dibnzoyldiamino-derivative to the reaction with nitrous acid were foiled by the1 failure to osbtain this substance from the action of methyl dibenzoyldiaminopyridinecarboxylate on hydrazine hydrate the product being the1 diaminopyridinecarboxyl- hydrazide itself.I n the absence of copper bronze the reaction pro- duct obtained from 2 6-dichloropyridine~4-carboxylic acid and corn- centrated ammonia solution a t 200° was 2-chloro-6-aminopyridine- 4-carboxylic acid needles of high m. p. (decomp.). The aim of the inveatigation wm successfully achieved by heating 2 6-dichloro-4-aminopyridine with ptoluenesulphonamide together with sodium carbsonate and a little copper bronze a t 180-190° and hydrolysing the1 resulting 4-amino-2 6-cFi-p-toZuenesulpho~yl- diaminopym'dine NH2*C5H2N(NH*S0,*C~H,Me)2 lustrous needles decsmp. above 360° with concentrated sulphuric acid when 2 4 6-triamino;ayridine C5H2N(NH,) was obtained as colourless needles m.p. 185O ; tIhe platinichloride reddish-yellow needles readily decomposes with liberation of platinum. F. KEHRMANN (Ber. 191 5 48 1931-1933).-The view that the green methylphenazonium periodide is a half-quinonoid compound is confirmed by its form- ation from the half-quinonoid iodide by the addition of iodine in alcoholic solution thus C,,H,,N,I,C,,H,,N,I + I + EtOH = (I,,H,,N,I,,EtOH (compare A. 1914 i 331). Oxidation of Uric Acid in Alkaline Solution. IiI. ROBERT BEHREND and RUDOLF ZIEGER (AnnaZe?z 1915 410 337-373. Compare Behrend A. 1904 i 950; Behrend and Schultz A D. F. T. [Methylphenazonium Iodides.] J. C. W.ORGANIC CHEMISTRY. i. 165 1909 i 272).-In tracing the course of the oxidation of uric acid in alkaline solution.Behrend (Zoc. cit.) assumes the intermediate ',N EVL;(OH~CO-T H. This must 'NH*C(OtI)*N H-CO formation of a substance CO be incorrect because Biltz's uric acid glycol (A. 1912 i 589) with which the preceding substance should be identical does not yield allantoin and uroxanic acid by hydrolysis but is converted into ammonia and syrupy products even by alkali carbonates in the cold. The suggation is now made that in its oxidation in alkaline solution uric acid is ruptured in the 1:6 position and an inter- NH*F(OH)*CO,H is produced. Attempts to synthesiss this substance from alloxanic acid and carbamide were unsuccessful. When an aqueous solution of alloxan tetrahydrate and a large excess of carbamide are heated to incipient boiling with 36% hydro- chloric acid carbamide alloxanate C4H40,N2,CO(NH2) is ob- tained together with a little alloxantin.The former crystallises from water in four-sided almost rectangular prisms decomp. 155-156O and is converted into carbamide nitrate by concentrated nitric acid and into normal or acid calcium alloxanate by calcium salts. Carbamidel alloxanate can also be obtained by warming uric acid glycol with 35% hydrochloric acid a t not more than 50°. When alloxan tetrahydrate is dissolved in warm water and the cooled solution after renoval of any alloxantin by filtration is treated with carbamide a substance C5HA06N4 colourless crystals decomp. 1 1 7 O or 133-134O is obtained which appears to be a saltc like compound of carbamide and alloxan monohydrate. It yields carbamide nitrate by treatment with nitric acid and is converted by 'heating alone or with glacial acetic acid into uric acid glycol; when boiled with acetic anhydride it yields an anhydride C5H606N4 microscopic nedles decomp.185-186O. Potassium ulloxan C4H,0,N2K pale red needles decomp. about 23Ci0 is obtained by dissolving alloxan tetrahydrate in warm water and treating the cooled filtered solution with 50% potassium hydr- oxide a t Oo. Methods are described f o r utilising this salt for the preparation of potassium alloxanate carbamide alloxanate and alloxanic acid. Methyl alloxanate C,H,O,N prisms decomp. 175-176O can only be obtained by warming alloxanic acid with thionyl chloride a t 40-50° and heating the resulting solid chloride with methyl alcohol.The aqueous solution of the ester reacts strongly acid towards litmus and decomposes hydrogen carbonates mediate substance Co<NH.C(OB)NH*CONR,' but is easily hydrolysed by 10% potassium hydroxide. c. s. Constitution and Colour. IV. Colour of Azo-compounds and their Salts. F. KEHRMANN (Ber. 1915 48 1933-1931. Compare A. 1908 i 699 993; 1913 i 1320).-Since azo-compounds contain two nitrogen atoms each of which may become the point of attachment of an acid by exerting it8 two additional valencies,i 166 ABSTRACTS OF CllEMlCAL PAI’ERS. they should give rise to two series of salts. This point has been tested by dissolving some azo-compounds in sulphuric acid of various strengths. Azobenzerie gives a very deep golden-yellow solution in con- ceiitrated sulphuric acid but a deep red in acid containing 25% SO which however soon becomes paler owing t o sulphonation.p-Aminoazobenzene gives a red solution in acid containing 25% SO a golden-yellow in the ordinary conceutrated acid and a bluish- red in ail acid of a certain dilution. Chrysoidin gives a golden- yellow solution in the concentrated acids and a bluish-red in diluted :wid. In the case of azobenzem i t is suggested that the two coloars are due to the mono-acid and the di-acid salts. The other cases are explained o n the assumption that salt formation a t the cliromo- pliolrei causes a deepening of colour whereas a t the amino-group i t iwially causes a lessening. J. C. W. A Decomposition of Cei fain o-Nitromandelic Acids.GERTRUDE MAUD ROBINSON and ROBERT ROBINSON (T. 1915 107 1753-1762).-Tn a previous communication (T. 1914 105 1466) i t was i2oted that 6-nitro-3 4-methylenedioxymandelic acid gave rise to a dark brown product when boiled with nitrobenzene. The nature of tbe decomposition has now been revealed in the first instance by a study of the action of heat on 6-nitro-3 4-dimethoxy- mandelic acid and i t is found that the chief products are azo- benzenedicarboxylic acids. The oxygen of the nitro-group oxidises the hydroxy-acid chain and the complete reaction may be repre- muted thus G -S i f r o -3 ; 4 -dime t Ib o x y tn a tad e I i c a c id NO,* CGH,( OMe),-CH(0H) *CO,H was prepared by the hydrogen cyanide synthesis from 6-nitrovertr- aldehyde in pale yellow needles m.p. 169-172O (decomp.). When this was heated in nitrobenzene a vigorous action took place and 4 ; 5 41 5/-tetrcrmethoxyrrxobeltze~ae-2 21-dicarboxylic acid was deposit,ed in crystals resembling haematite in colour and lustre. On triturating this with nitric acid (D 1-45) it yielded 2 2’-dinitro- 4 5 4’ 5’-tetramethoxyazobenzene [NO,*C,H,(OMe),],N which crystallised from nitrobenzene in brilliant red needles m. p. 315O (deconip.). An orange-coloured modification of the same compound identical in m. p. was obtained by the nitnration of azoveratrole by cold nitric acid (D 1.42) in acetic acid. Both forms dissolved in sulpliuric acid with intense blue colours but they were1 recovered in their original forms on dilution which precludes the idea of cis-trans-isomerism.Both f orm8 were also reduced by stannous chloride t o 4 5-diaminovaratrole which was isolated as 2 3-di- metlioxyphenanthraphenazine m. p. 259-261° by treatment with phenantliraquinone (compare Moureu 1896). [CO,H*C,H?(OMe),l,N,,ORaANlC ClIEMlS'l'HY. i. 16" Azoveratrole was obt.ained by a modification of Kauffmann and Kugel's method (A 1911 i 930) in glistening orange prisms m. p. 182O and not 1 6 3 O . When this was suspended in acetic acid and treated with fuming nitric acid it yielded apparently N 2 2'-tri- niti.0-4 5 4f 5f-tetranietholryhyclrcczobensene N0,*C,H,(OMe)2-NH*N(N0,).C,H,(OMe)2*N02 yellow needles m. p. 228O which was also1 converted into 2:3-di- methoxyplienanthraplienazine as above. The decomposition of 6-nitro-3 4-methylenedioxymandelic acid by heating in nitrobenzene solution differed somewhat from the above reaction in that nitrogen was also evolved.The chocolate- coloured product contained about 25% of other products besides the 4 5 4' 5/-dirnet?~ylerzetetrctozyazobenzer~e-2 2'-dicarboxylic acid LCH:02:C,H,(C02H)]2N2 but only this could be isolated. This was achieved through the soditim salt yellow leaflets and the acid was obtained in opaque masses of brick-red crystals m. p. 270° (decomp.). 'On nitration the carboxyl groups were replaced by nitroxyl giving 2 2'-dinitro-4 5 41 5f-dimet?~yletietetrooxynzrr- 71 Pnzene CI4HSOsN4 in crimson needles in. p. 305O (decomp.) which was reduced and then condensed with phenanthraquinone as above with the formation of 2 3 - r n e t h y l e n e d i o x y p l ~ e l z c t n t ~ ~ r a ~ ? ~ e r ~ ~ ( 6-Nitrohomopiperokyf chloride CH2:O2:CGH2(NO,)*CH2C1 was obtained by saturating an acetic acid solution of homopiperonyl alcohol with hydrogen chloride and then gradually adding nitric acid.It formed pale pink leaflets m. p. 86O and irritated the skin. When heated with nitrobenzene it changed into the above' 4 5 4' 5f-dimethylenetetraoxyazobenzene-2 2/-dicarboxylic acid whilst cold methyl-alcoholic potassium hydroxide converted it into 2 2'-di11itro-4 5 4' 5/-dimethylenetetraoxystdlbene brownish-red needles not molten a t 350O. The above a.zobenzene1 derivatives axe characterised by giving intense blue solutions in concentrated sulphuric acid even with the merest traces. J. C.W. [CH2:02:C,H2(NO,)12C,H2 The Preparation of Aliphatic Aminohydraeines. AUGUST DARAPSKY and HANS SPANNAGEL ( J . pr. Chem. 1915 [ii] 92 272-296).-A record of the results of a series of unsuccessful endeavours to prepare aliphatic aminohydrazines of the type NH2*CR*CR'*NH*NH2. The product of the interaction of dia~etylmo~noxime and hydr- azine varies with the solvent. I n aqueous solution a mixture of the former with hydrazine sulphate yielded the ketazine OHON CMe*CMe:N*N :CMe-CMe:N*OH (compare Forster and Day T. 1912 101 2240); dibenzoyl deriv- ative orange-red scales m. p. 215O. I n alcoholic solution using hydrazine hydrate t.he product is diacetylhydrazoxime m. p. 13S0 which has also been recently described (Eoc. cit.). OH*N:CMe*CMe:N*NH Thisi. 168 ABSTRACTS OF CEEMICAL PAPERS is unstable in aqueous solution readily undergoing conversion into the ket'azinel and hydrazine but is more stable in alcoholic solution and in this solvent reacts with aromatic aldehydes giving normal condensation products ; thus with salicylaldehyde o-hydroxybenzyl- idenediacetylhydrazoxime OH*N:CMe*CMe:N*N:CH*C6H4*OH yellolw needles m.p. 168O was obtained. An attempt t o confirm the structnre of this substance by an independent formation from diacetylmonoxime and o-hydroxybenzylidenehydrazine failed on account of the mfusal of these compounds to interact. Diacetyl- liydrazoxime gave a beizzoyl derivative ye'llow needles m. p. 201° and reacted with phenylthiocarbimide giving a thiosemicarbazone OH*N:CMe*CMe:N*NH*CS*NHPh flesh-red needles m.p. 201O. If a mixture of diacetylmonoxime and hydrazine hydrate in the absence of a solvent is boiled for several hours the oximino-group is replaced by the hydrazone group with the foxmation of diacetyl- diliydrazone NH,*N:CMe*CMe:N*NH m. p. 157O (dib enzylidenc derivative yellow needles m. p. 120° ; di-o-hydroxybeizzylidenc derivative yellow needles m. p. 245O) which in alcoholic solution in the presence of dilute hydrochloric acid undergoes change into dimethylaxiethane CMe<&i> N (compare Curtius and Thun A. 1891 1356). On account of t.he instability of diacetylhydrazoximel reduction t o the desired aminohydrazine could not be effechd and attention was therefore turned to the reduction of the more stable ketazine but without achieving the isolation of any reduction product.Benzilhydrazoxime (compare Forster and Day loc. cit.) was then submitted to reduction with so'dium amalgam in alcoholic solution but the product was meso-diphenylethylenediamine NH,*CHPh*CHPh*NH (Japp and Moir T. 1900 77 644). I n an attempt t o prepare benziIhydrazoxime by the action of hydroxylamine hydrochloride on benzilhydrazone a yellow substmce m. p. above 280° not show- ing the properties of an oxime was obtained. Aminoacetophcnone hydrochloride when treated in cold aqueous solution with hydrazine hydrate yielded diphenyldihydrocpyrazine the hydrazine hydrate merely acting as an alkali (compare Gabriel A. 1908 i 464) whilst with the heated reagents in the absencs of a solvent aminoacetophenoneaaine NH,*CH,*CPh:N*N:CPh*CH,*NH2 colourless needles m.p. 157O was obt'ained. When a solution of aminoacetophenone hydrochloride and hydrazine hydrochloride was neutralised with sodium hydroxide the effect on the first substance was merely that of an alkali the product being anhydrobisphen- acylamine (compare Gabriel loc. cit.). P-Bromopropylamine hydrobromide reacted with hydrazine hydrate in aqueous solution giving a basic viscous oil the com- position of which was represented approximately by the formula C3H,N ; tlhis gave an oily b enzoyl derivative. 8-Hydroxy- up-dlphenylethylamine was converted by phosphorus pentachloride into stilbene dichloride but the desired chlorodiphenylethylamine,ORGANIC CHEMISTRY. i. 169 NH,*CHPh*CHPhCl was prcduced by shaking a suspension of the hydrochloride of the hydroxydiphenylethylamine in acetyl chloride with phosphoxus pentachloride being obtained as an oil ; hydro- chloride m.p. 233O (decomp.) ; phtinichloride deep yellow needles m. p. 204O; nitrate tablets m. p. 185O; benzoyl derivative m. p. 195O. Chlorodiphenylethylamine in alcoholic solution is converted by hydrazine hydrate o r also by potassium hydroxide into di- >NTT colourless needles m. p. 83O ph enylet h yleneimine which does not reduce potassium permanganate and is reconverted even in ethereal solution by hydrogen chloxide into chlorodiphenyl- ethylamine hydrochloride. Benzo-€-chloron.liz?/lnmide when heated with excess of anhydrous Iiydrazine gave an oily product which when treated in aqueous solution with benzaldehyde instead of yielding the expected benzoylbenzylidenehydrazinoamylamine NHBz*[CH,],*NH*N:CHPh gave benzoylbenzylidenehydrazine NHBz*N:CHPh the chemical change having involved scission of the benzoyl radicle as benzoyl- liydrazine with concurrent conversion of the chloroamylamine into piperidine.D. F. T. $! H Ph c HPh Traneition Points of the Polymorphic Phthalylhydrazides. FREDERICK DANIEL CHATTAWAY and WILLIAM JAMES LAMBERT (T. 1915 107 1773-1 781) .-Phthalylphenylhydrazide and phthalyl- 13 henylnietliylhydrazide C,B,<CO>R*N co N P h and C,H,<::>N*N RlePh (T. 1911 99 2256 2261) are well-marked and readily obtainable examples of enantiomerides. The transition points f o r the two pairs have therefore been determined. This has been don0 in the first place by measuring the solubilities then in the cam of the second pair by observing the growth of the crystals of one form a t the expense of the other in acetone and finally by a dilatometric method.I n the case of phthalylphenylhydrazide the curve8 f o r the solubility in alcohol indicate a transition point a t about lUu; in chloroform a little above 9.4O; in ethyl acetate 9.2O; and in acetone 9.8O. The two forms are so much more soluble in the last three solvents and the transformation takes place so much faster that the transition points are more easily ascertained. The mean is about 9*5O. I n the case of phthalylphenylmethylhydrazide the solubility determination in alcohol indicates a transition point a t about 55O (by extrapolation) the second method gives 55-55*5O and the dilatometric method 55-55.2O.I n his theoretical deductions concerning the reversible trans- formation of polymorphic forms van't Hoff (1897-1898) showed that the ratio of the solubilities of the two forms must be constant for all solvents which only dissolve so little that the laws of dilute solutions are applicable. This conclusion has now been confirmedi. 170 ABSTRACTS OF CHEMICAL PAPERS. experimentally for the first time by the determination of the solu- bilities of these pairs of hydrazides. Aromatic-aliphatic Diaeoamino Compounds [ Arglazodicyano- diamides]. R. VON WALTHER and W. GRIESHANMER (J. pr. Chem. 1915 [ii] 92 209-255).-It has been discovered that not only does guanidine couple with simple diazonium salts producing stable compounds (investigation unpublished) but that' substances allied to guanidine namely dicyanodiamide cyanamide and dicyanodi- aniidine although less basic behave analogously towards diazo- compounds.Dicyanodiamide couples with an aromatic diazoxide in alkaline solution the solution when acidified depositing the diazoamino- compound. The first yield is polor but more can be obtained by making the filtrate alkaline and again acidifying; i t is suggested that tliis further formation of the diazoamino-compound may be due t o the dicyanodiamide in the alkaline solution existing in part as a disodium salt which a10110 is active towards the diazo-com- pound. The hydrogen atom of the *N,*NH* group in these diazo- amino-compounds is replaceable by metals and also by radicles but froin the fact that hydrolysis of the methyl derivative of p-toluene- azodicyanodiamide yields rnetliyltoluidine with a little pcresol i t is evident that in this case a t leastl alkylation does not entirely follow a single course.Benzeneazodicyanodiamide and its analogues are generally not very reactive. On hydrolysis in feebly acidic aqueous or alcoholic solution or suspension the former compound yields dicyanodiamide and tarry products without aniline thus indicating a structure C"*NH*C( :NH)*NH*N,Ph as opposed t o CN*NH*C ( NH) ON NHPh. 'hi strongly acidic solution or suspension the' products of hydrolysis are plienylguanylcarbamide and free nitrogen. The identity of the phenylguanylcarbamide was demonstrated by an independent syn- thesis by the hydrolysis of s-cyanophenylguanidine (Wheeler A.1903 i 751). I n explanation of tlie difference in behaviour of ~~enzeneazodicyanodianlide towards hydrolysis in feebly and strongly acidic solutions it is suggested t h a t in tlie former case the substance possesses its usual ( Z I I ti-configuration thus CS*NH*C(:N€l)*NH*N J. C. W. RPh + cN+wq:m)-sri + v2 + c!,~K,-T)TI whereas the stronger acid causes a conversion througIi the hydro- chloride into a syi)-configuratsioii CN*NH*C,:wR)*N t r y th sub- PhN" et ance 011 hydrolysis readily eliiiiiiiates nitrogen yielding phenyl- guanylcarbamide NH,*CO*NH*C( :NH)*NHPli. The isolation of an unstable hydrochloride leiids support to this idea but in 110 case have geometrical st.ereoisomerides been isolated. As is to be ex- pected the tendency to the addition of hydrogen chloride is less in the more acidic compounds of this class.In the description of theseORGANIC CHEMISTRY. i. 131 compounds the grouping NH:N*NH is termed triazen the first and third nitrogen atoms being designated by a and y (Wolff and Lindenhayn A. 1904 i 197). Beraeneazodicyanodiarnide (a-phen yltriaze ii-y-cyana niirioiniitLo- iiiethathe) CN*NH*C(:NH)*NH*N,Ph was prepared by mixing cold aqueous solutions of benzenediazonium chloride and dicyanodiamide and treating the diluted solution successively with solutions of sodium hydroxide and hydrochloric acid ; the product crystallises in prisms decomp. with slight explosion a t 123O. It! is decom- posed with mild explosion on contact with sulphuric acid. Boiling water causes decomposition into dicyanodiamide together with tarry matter in which a little phenol is present whilst hydrochloric acid of 15% concentration gives rise t o phenylguanylcarbamide.The following salts were prepa.red Sodium yellow needles ; ammoniurri prisms ; pyridine yellow ; siZuer explosive yellow powder; lead yellow ; cobalt bluish-red ; ferric yellow ; ferrous brown. By treating the sodium salt with an alco'holic solution of methyl iodide CN*NH*C( :NH)*N,*NMePh yellow needles decomp. a t 167-168O was obtained whilst with benzyl chloride and pnitrobenzyl chloride in a similar manner y-pheti yl- y-b e n z yl triazen-a-cyana rnidoirnin o met hati e CN-NH-C( :NH) *N,*NPli*CH,Pli I ieedles decomp. a t 165-1 66O and y-pl~eil.!jZ-y-p-)hitro7) eti syl triazetr -a- c.yaiw,~iit,oiniitivi7~et~ic[ti~ CN*NH*C(:NH)*N2*NPh*CH,.C,H4*N02 colourless needles decomp.at. 1 6 2 O were respectively obtained. p-ToZrcenenzodic!/anocFianzide (a-p-to7~~lt~iazei~-y-cyai1n??iii~o~niii~metfmne) CN-NH.C(:NH)-NH*N,-C,H,Me obtained by diazotising ptoluidine and proceeding as In the previous case forms yellow rhornbs decomp. a t 1 3 3 O ; sodium salt yellow needles; yotassiirw salt. The action of methyl sulpliate on the free compound in the presence of sodium hydroxide solution caused the format"ion of y-p- to7y7-y- I I I P th yl triaze?i-a-c!yana nt in o int in0 ?n et haw CN-NH*C( :NH)*N,*NMe*C,H,Me yellow needles decomp. a t 155-158O which on hydrolysis with dilute acid gave methyl-ptoluidine dicyanodiamide and a little p-cresol the formation of the latter proba,bly being due to t$eY presence of an isomeride.An alcoholic solution of benzyl chloride converted the sodium salt into y-p-tolyl-y-b eiiz.yltriazei~-a-cyaiianii~~~~- irnifto m e t 7m 12 e CN*NH*C (:NH) *N,*N( CH,Ph)* C6H4Me colourless needles decomp. a t 1 6 3 O whilst p-nitrobenzyl chloride under similar conditions produced y-p-toZ,Vl-y-p-nit rob e ? ~ z?/Ztl.iaze?~-a-c?/anamino- i mirhom e t han e CN0NH.C ( NH) ",ON( C,H,Me) *CH,*CGH4*N0 yellow needles deconip. at 1 5 8 O . An attempt to effect a rearrange- ment of ptolueneazodisyanodis.nide1 into the corresponding amino- azo-compound by warming with ptoluidine and aniline hydro- chloride evidently caused fission of the molecule the isolated pro- duct being aminoazo-ptoluene. o-Tolu en eazodicya n odia ??I ide (a-o- t oly 1 t riaz eqi - y-cyu I I a H I iriointin (1- methlane) CN*NH*C(:NH)*NH*N,*CsH4Me obtained in a similar nianner forms yellow needles decoinp.a.t 1 1 4 O ; sodizrnr salt yellow -ph e?) yl- y-m e t h y ltriaz en-a-cya 71 an2 in o iinino nz e t h a w ,i. 172 ABSTRACTS OF CHEMICAL PAPERS needles. y - o - Tolyl- y - methyltrimen - a - cyanaminoiminomethane CN*NH*C( :NH) N2*NMe*C6H4Me yellow leaflets decomp. a t 1 5 2 O and y-o-tolyl-y-b enzyltriazen-a-cyanaminoiminomethane CN*NH*C( :NH)*N,*N(C,H,Me)*CH,Ph pale yellow needles decomp. a t 160° were obtained similarly t o their para-isomerides. m-Tolueneazodicyan odiamide (a-m-t olyl triaz en- y-cyanaminoim ino- methane) yellow needles decomp. a t 1 1 5 O (potassium salt less soluble than the sodium salt) prepared in the usual manner was converted into y-m-tolyl-y-methyltriazen-a-cyu?i~minoiminonzetJ~a~~e yellow needles decomp. a t 1 4 8 O and y-m-tolyl-y-h enzyltriazen-a-cyan- ccminoirni7z.ometha7z e pale yellow needles and prisms decomp.at 1 5 3 O . ( a - p - c hlor o ph englt riu z o t i - y-cyanaminoiminomethane) CN-NH*C(:NH)*NH*N2-C6H,Cl yellow 1-liombs decomp. a t 140-160° (pJricFine salt yellow) was further converted into y-p-c hloroph eny l- y-me t h yl t riaz en-a-cyanamin oimiii o- niethnne CN*NH*C( :NH) *N2*NMe*C6H4c?l yellow needles decomp. a t 160° and into y-p-chlorophenyl-y-benzyltriazen-a-cyai2anziiioinii?io- methane CN-NH*C(:NH)*N,*N(C,H,Cl)*CH,Ph colourless needles m. p.. 170-175O. As with the benzeneazo-compound no very definite results were obtainable in reduction experiments with the pchlorobenzeneazo-compound and very little aminodicyanodiamide was pxoduced if any; a compound (or compounds) separated from the reduction product gave a p ' c m t e m.p. 190° and a pale yellow benzylidene derivative decornp. a t 1 7 0 O . ( a - p - bromopJ~enyltriuze,i- y-c yammimiminome t hane) CN*NH*C( :NH)*NH*N,*C,H,Br rhombs decomp. a t 160° (sodium salt; q,widine salt yellow) pre- pared in the general manner was convertible into y-p-bromophenyl- y-me t h y l triaaen-a-cyanaminoiminomethane CN0NH.C ( NH) *N,*NMe* C,H4Br yellow needles deoomp. a t 1 8 5 O and y-p-~~~~~~~~~~~~~~y-benzyltri- azen-a-cyanaminoiminome t hane CN =NH*C ( NH) *N,*N (C,H,Br) *CH2P h colourless needles decomp. a t 1 8 6 O . o-Curb oxyb enzeneazodicyanodiamide (a - o - curb o x y p k e i i y l tTiuze t i - y-cyanaminoiminomethane) CN*NH*C ( NH) *NH*N,*C,H,*CO,H prepared from diazotised anthranilic acid in the general manner is a yellow crystalline solid decomp.near 98O which is decomposed by boiling water intol salicylic acid dicyanodiamide and nitrogen ; sodium salt C,,H,,O,N,,Na ; silver salt C,,H,,O,N,,Ag an amorphous yellow solid. Attempts t o prepare a methyl o r benzyl derivative by way of the sodium salt were unsuccessful. I n an endeavour to convert benzeneazodicyanodiamide and its derivatives into the ethyl ester of the corresponding carboxylic acids by treatment with alcoholic hydrogen chloride i t was dis- covered t h a t nitrogen was eliminated with formation of an aryl- guanylcarbamide. There were thus prepared p-Chlorophenyl- gw.znyZcarbamide C,H,Cl*NH*C(:NH)*NH*CO.NH colourless rhomlx m.p. 1 2 5 O ; hydrochloride prisms m. p. 172-173O; platini- p-C hloro b en z enea zodicyanodia mide p-BromobenzeneazodicyamdiamideORGAKIC CHEMISTRY. i. 173 chloride yellow prisms; picrate m. p. 195O; silver salt colourless; t i ce t yl derivative C,H,Cl*NAc*C( :NH) *NH*CO *NH prisms m. p. 150-1 5 lo. Phe ?zylgziai~ylcarbnmide NHPh*C( :NH) -NH*CO*NH colourless hexagonal prisms m. p. 62-63O ; hydrochloride prisms 111. p. 174-175O; picrate m. p. 181-182O. p-Tolylgzianylcarbamidr C,H4Mel*NH*C(:NH)*NH*CU*NH2 rectangular leaflets m. p. 143O ; hydrochloride prisms m. p. 167-168O. o-Tolylgziu,zyTcarbamide octahedra m. p. 136O; hydrocldoride needles m. p. 73-74O.m-Toll/lguanylcarbamide hexagonal leaflets m. p. 97-98O ; hydro- chlorade prisms m. p. 183-184O. p-Bromophenylgzicrnylcarb- amide C,;H4Br-NH-C(;NH)-NH*CO*NH2 prisms m. p. 152O ; hydrochlorade leaflets m. p. near 170O. o-Carbozyyhenylyuanyl- cnrbamide CO,H*C,H,*NH-C( :NH)*NH*CO*NH prisms o r needles decomp. a t 275-280°; silver salt C9HH,03N,Ag,. An endeavour to extend the investigation of the effect of alcoholic hydrogen chloride to the methyl derivatives of the above compounds was prevented by the complexity of the reaction with these substances. I n the course of experiments attempting the synthesis of phenyl- guanylcarbamide by an independent method substances m. p. 155O 130° and above 280° were obtained from the interaction of silver cyanocarbamide and aniline hydrochloride under varying condi- tions.The interaction of phenylguanidine nitrate and potassium cyana,te under varying conditions yielded phenylgwznzdine car- bonate prisms m. p. 138O (decornp.) and a sparingly soluble sub- stance m. p. above 290° but failed to give the desired phenyl- guanylcarbamide which wa6 however successfully produced by heating cyanophenylguanidine CN-NH*C(:NH)*NHPh with dilute hydrochloric acid. diet h?llthiolphenylbi2Lret SMe*C( :NPh)*NH*CO*NH colourlelss needles m. p. 156O was obtained by a similar hydrolysis of s-cyanomethylthiolphenylisocarbamide SMe*C(:NPh)=NH.CN. The formation of phenylguanylcarbamide from benzeneazodi- cyanodiamide suggests that cyanophenylguanidine is an intermediate product and this substance can actually be isolated under suitable conditions.If benzeneazodicyanodiamide in ethereal suspension is treated with hydrogen chloride an unstable red substance is obtained which from its decomposition by warm water into cyano- phenylguanidine hydrogen chloride and nihrogen is in all prob- ability the hydrochloride of the syn-f orm of benzeneazodicyano- diamide. By a similar procedure all the benzeneazodicyanoldiamide derivatives described above with the exception of the o-carboxy- derivative which did n o t form a hydrochloride were made t o yield the corresponding cyano-arylguanidines. There were thus obtained s-cyano-p-tolylguanidine CN*NH=C( :NH)*NH*C,H,Me rectangular leaflets m. p. 207-208° ; s-cyano-m-tolylguanadane rectangular leaflets m. p. 193-194O ; s-cyano-p-chlorophenylguanidine CN*NH*C( :NH)*NH*C,H,Cl rectangular leaflets m.p. 197-198O ; s-cyano-p-bromophenylgzLcrrz- idine CN*NH*C(:NH)*NH.C,H,Rr rectangular leaflets m. p. nicyanodiamidine resembles dicyanodiamide in its ability t o 196-1 97'.i. 174 ABSTRACTS OF CHEMICAL. PAPERS. couple with diazo-compounds in alkaline solution the product obtained with an alkaline diazobenzene solution being b enzeneazo- rlicyanodirrnlidir,e (a - yhenyltriazen - y - carbnmidoiininoine fhnne) NH,*CO*NH*C( :NH)*NH-N,Ph yellow needles decomp. at. 176-177O which possesses feeble basic and still more feeble acidic properties; T/,yd~ochZoride yellow prisms decomp. near 92O ; picrate needles decomp. a t 70°. When treated with alcoholic hydrogen chloride solution this product behaves differently from its dicyano- diamidel analogue giving no cyanophenylcarbamide but only di- cyanodiamidinel and tarry matter.The coupling of cyanoamide in alkaline solution with a benzene diazo-oxide gives benzeneazocyanoamide which has already been described (Wolff and Lindenhayn Zoc. c i t . ) . The Refractive Indices of Solutions of Certain Proteine. IX. Edestin. CARL L. A. SCRWDT (J. Biol. Chem. 1915 23 487-493).-The solutions of edestin follow the law n - n1 = nc ; where i? is the observed index of the solution nl of the solvent c the percentage of protein and n a constant expressing a change in the refractive index due t o the addition of 1% of the protein. I n the case of edestin a=0*00174 +_0.00006. This remains constant even although the solvent produces hydrolysis.W. D. H. The Nature of Enzyme Action. IV. The Action of In- eoluble Enzymes. W. &I. BAYLISS (J. Physiol. 1915 50 85-94).- Urease Iipase emulsin invertase lactase papain peroxydase and catalase are active in media from which they can be filtered off by ordinary paper whilst the filtrates are inactive. Pepsin and trypsin are much inore active in suspensions than are the filtrates; these enzymes are capable of a small degree of colloidal solution i n such solutions. Enzymic activity is thus manifested a t the interface of contact between the solid enzyme phase and the liquid substrate phase. The catalysts concerned are not in true solution. The ‘Effect of Sodium Chloride on the Action of Invertase. H. A. FALES and J. M. NELSON ( J . Amer. Chern. SOC. 1915 37 2769-2786).-The concentration of hydrogen ion remains constant during the inversion of sucrose by invertase.The addition of sodium in the action may exert a twofold effect it caiises an increase in the coiicentration of the hydrogen ion if the concentra- tion of the hydrochloric acid present is greater than 0*0001 molar; and also effects a decrease in the activity of the invertase if com- parison is made between solutions of the same concentration with regard t o hydrogen ion. The latter effect varies according t o the concentration of the hydrogen ion and of the sodium chloride being least a t the optimum of the invertase action. The adjustment of the concentration of the hydrogen ion by the addition of mixtures of acids and salts (“buffers ”) as sometimes practised may intro- duce appreciable error unless it is restricted t o the neighbourhoocl of the optimum zone where the salt effect is a minimum. The addition of sodium chloride t o solutions of hydrochloric acid D. F. T. W. D. H.ORGbh’IC CHEMISTRY i. 175 cauaes an increase in the concentration of the hydrogen ion as measured by the E.M.F. method and by the hydrolysis of sucrose solutions. I n the region of enzyme activity i t is therefore necessary to measure the concentration of the hydrogen ion and i t is not permissible to calculate it from the concentration of the acid used. D. F. T. The Rstention of Activity by Urease and by Oxydase after Exposure to the Temperature of Liquid Air. JOSEPH Smum HEPBURN and CHARLES BLIZARD BAZZONI ( J . Franklin Ztist. 1915 180 603-605).-After exposure to the temperature of liquid air for 100 hours a solution of urease was found to have suffered but slight loss in its power of hydrolysing carbamide. The observed activity was 96.3% of that of the fresh solution. During the same period the activity of a solution which was kept a t ZOO in presence of 0.2% of tricresol was found to have fallen to 44.4%. Qualitative experiments show also that oxydase retains its power of reacting with Witte’s peptone after subjection to the temperature of liquid air for 33 hours. Preparation of 2-Chloro-4-dimetbylaminobenzene-l-arsinic Acid. C. F. BOEHRINGER S SOHNE (D.R.-P. 286546 ; from J . SOC. (:hem. Znd. 1915 34 1165).-m-Chlorodimethylaniline is treated with arsenic trichloride and the 2-chloro-4-dimethylaminobenzene- 1-arsenoxide so obtained is oxidised by means of hydrogen peroxide mercuric oxide or potassium permanganate. Compared with the non-halogenated compound 2-chloro-4-dimethylaminobenzene-2- arsinic acid is less toxic but has a greater therapeutic activity. J. C. W. H. M. D. Preparation of 4 4’- Dihydroxy-3 3’-diaminoarsenobenzene. fm ~TABLTSSEMENTS POULENC FR&RES (Eng. Pat. 1914 21421 ; from J . r C o ~ . Ch~nr. Incl 1915 34 1225).-3-Nitro-4-liydroxy- phenyl-1-arsinic acid is reduced by zinc and acetic acid a t 25-35’) and then in hydrochloric acid solution a t 50-60° in presence of a small quantity of sulphurous acid and is thereby converted into 3 3’-diamino-4 4/-dihydroxyarsenobenzene. The sulphurous acid appears to prevent the reduction being carried past the forinatioii of the arseno-compound. G. F. M. Preparation of a Bismethylhydrazinotetra-aminoarseno benzene. C. F. BOEHRINCER & SOHNE (D.R.-P. 285573; from J . Roc. C‘heni Z t i d . 1915 34 1165).-When 3 5-dinitro-4-methyl- nitroaminobenzene-1-arsinic acid is reduced by means of stannous chloride at 50° i t yields the hydrazine derizIafi?*e [ N H N Me C&,( NH&] ,As2 which has a pronounced trypanocidal action. J. c. w.

ISSN:0368-1769    

DOI:10.1039/CA9161000113

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 121 General and Physical Chemistry. The Oxy-hydrogen Flame Spectrum of Iron. SIR NORMAN LOCKYER and H. E. GOODSON (Proc. Roy. SOC. 1916 [A] 92 260-265).-ln continuation of previous work (ibid. 1911 [A] $6 78) further observations have been made on the oxy-hydrogen flame spectrum of iron. Sixty-four lines have been identified between h 3856.52 and ~5615.88 and of these fifteen have not beten previously recorded. These lines are divided into three groups according t o the relative strengths in comparison with the lines in an iron arc spectrum. The lines have also beten compared with the lines in the electric furnace spectrum and with the solar and stellar lines of iron. H. M. D. Kinetics of the Multirotation of Gelatin Sols. WOLFGANG OSTWALD (Kolloid Zeitsch. 1915 17 113-119).-From observa- tJons made by Trunkel (A.1910 i 648) on the' change in the optical rotatory power of gelatin sols with time i t is shown that the observed rotation [a,] changes with the time t according t o the equation [a,] = k . P O 6 . The coefficient k is a linear function of the concentration c and of the temperature 8 as represented by the equations k= 0*687(10Oc + 186) and k =9*17(38 - 0). The range covered by the experimental observations from which these f ormulz are derived is indicated by the following limiting values c -0.25 t o 0.76% 8 = 15O t o 25O and The kinetic investigation of other properties of gelatin sols has not yet befen sufficiently investigated t o say whether similar relations obtain in the case of the viscosity surface tension and other properties.H. M. D. - 1 1 2 O to -245O. The Existence of a Compound of Polonium and Hydrogen. ROBERT W. LAWSON (Monatsh. 1915 36 845-852).-1n the course of a determination of the range of the a-particles emitted by polonium in an atmosphere of hydrogen i t was found that the ionisation current a t a given distance from the source of says gradually increases with time. I n explanation of this effect it is suggested that a volatile compound is formed by the combination of polonium and hydrogen. This compound is rapidly decomposed by ionised oxygea. The analogy of polonium to the elements of the sulphur group is quite consistent with the theory put forward. H. M. D. Distribution of Solvents between Solutes. IV. Electrical Conductivity of Mixtures of Acids.A. G. DOROSCHEVSKI and V. I. FRTDMAN ( J . Buss. Phys. Chem. SOC. 1915 47 1615-1626. Compare A. 1914 ii 610).-The observed conductivities of mixed solutions of hydrochlo,ric and nitric acids are in agreement with the values calculated on the assumption of isohydry a t equivalent VOL. CX. ii. 6ii. 122 ABSTRACTS OF CHEMICAL PAPERS. concentrations the water in these solutions being theref ore distri- buted between the solutes in proportion t o their chemical masses; Wakeman's calculations of the conductivities of mixtures of acetic acid with various other acids (A. 1895 ii 68) are shown t o be erroneous t o some extent. Calculation of Barmwater's results (A. 1904 ii 10) shows that mixed aliphatic acids in dilute solution obey the1 above law and the8same is shown by the authors' measure- ments t o be t'he case with mixtures of acetic propionic and butyric acids in comparatively high concentrations (5-10%).T. H. P. A Study of Double Salts in Standard Cells. G. F. LIPSCOMB and G. A. HULETT (J. Physical Chem. 1916 20 75-82).-With a view to the application of double salts of zinc in the construction of. cells suitable as standards of electromotive force the authors have inveetigated the equilibrium relationships in the tesnary systems potassium sulphate zinc sulphate water and potassium chloride zinc chloride water a t 25O. Cells of the type Zn amalgam I S I I Hg,SO I Hg in which S repre- sents a solution saturated with respect to (1) the double salt K,S04,ZnS0,,6H,0 (2) the double salt and K,S04 and (3) the double salt and ZnS0,,7H20 were examined with the result that the third cell only was found t o give constant results. Its E.M.F.is 1.41976 a t 25O and the temperature-coefficient is -0.00133. The cell Cd amalgamISI IHg,Cl,[Hg in which S represents a saturate'd solution of the double salt 2KC1,CrC12,6H20 was also found t o give accurately reproducible and constant results. Its E.M.F. a t 25O is 0.70505 and thel temperature-coefficient + 0*00015. The corresponding zinc cell has an E.M.F.=1.01857 at 25O but hydrolysis appears bo take place slowly. H. M. D. Electromotive ForceB. WILDER 11). BANCROFT ( J . Physical Chem. 1916 20 64-74).-A plea for consistency in the derivation of the formulze for the E.M.F. of concentration cells of different types. It is shown that the formula f o r the reaction isotherm E=RT/nF .log 7cZp,/8p2 may be applied in the derivation of the E.M.F.'s of all such cells. H. M. D. The Periodic Passivity of Iron. A. SMITS and C A. LOBRY DE BRUYN (Proc. K . ,4 kad. TTTetensch. Amsterdam 1916 18 807-811). -Previous observations have shown that passive iron is rendered active under thel influence of chlorine bromine and iodine ions which act' as catalysts. The passive condition may be produced by ano'dic polarisation in suitable circumstances and according t o Smits this is due t o the disturbance of the equilibrium between the active and passive forms in the surface layers of the metal in consequence of the dissolution of the active (ferrous) modification. Halogen ions and anodic polarisation thus tend t o produce opposite effects and when an iron anode1 immersed in a solution of ferrous sulphate t o which chlorine ions have been added in suitable con- centration is subjected t o the influence of a current it is found that well-developed periodic phenomena are observed.The requisiteGENERAL AND PHYSICAL CHEMISTRY. ii. 123 concentration of the chlorine ions depends on the current density and the relative lengths of the active and passive periods can be varied by suitable adjustment of these factors. The oscillations in the electrode potential amount t o 1.74 volts and in the particular experiment which the authors describe the lengths of the two periods were each approximately equal t o six seconds. Transport Numbers in Non-aqueous Solutions. A. N. SACHANOV and A.M. GRINBAUM (J. 8us.s. Yhys. Chem. SOC. 1915 47 1769-!789).-The authors have measured a t the ordinary temperature (about 18O) the transport numbers for silver nitrate in aniline (dielectric constant 6.85) and mixtures of aniline with pyridine containing (1) 80 vol. % of the former (8*0) and (2) 50 vol. % (9.7). The results obtained together with those of Schlundt (A. 1902 ii 492) for solutions of silver nitrate in pyr- idine (12.56) and in acetonitrile (35.8) and those of Hittorf for solutions in water (81.0) give a complets view of the variation of the transport numbers for this salt with the concentration and with the dielectric constant of the solvent (compare Sachanov and Prsheborovski A. 1915 ii 729 ; Sachanov and Rabinovitsch A 1915 ii 730). I n the aniline-pyridine mixtures and also in pyridine and aceto.nitrile the transport number for silver diminishes as the conoen- tration increases. For one and the same concentration the trans- port number diminishes with diminution of the dielectric constant of the solvent. I n aniline on the other hand the transport number increases as the concentration increases from P = 5 to V = 1. These results are explained on the assumption of the formation of complex anions Ag(NO,),' and complex cations (AgNO,)'. Magneto-chemistry Applications to Analytical Chemistry. A. QUARTAROLI (Gazzetta 1915 45 ii 406423).-Even in moder- ately concentrated solutions ordinary salts such as thms of bhe alkali and alkaline-earth metals aluminium ammonium etc. which are diamagnetic exhibit in general susceptibilities differing little from that of water.Further the difference in susceptibility between concentrated solutions of magnetic salts and water is some hundreds of times as great as that between concentrated solutions of diamag- netic salts and water. In order to be able to utilise magneto- chemical data in quantitative analysis the author employs a method based on the fact that water is diamagnetic and that there exists for each magnetic salt a concentration a t which its aqueous solution is magnetically inactive. For the measurement of the% cosncentra- tions the use of Quincke's manometer is tedious and the authar employs an apparatus based on the fact that a current of air- bubbles escaping from a capillary tube dipping below the surface of a magnetic solution situate between the poles of an electro- magnet is retarded when the magnet is excited; on the other hand no retardation or acceleration occurs with a liquid which is inactive or more accurately has a susceptibility equal to that of air.The apparatus which is readily fitted up is depicted and the method H. M. D. T. H. P. 6-2ii. 124 ABSTRACTS OF CHEMICAL PAPERS. of using i t described. The accuracy attainable is shown by the fact that a distinction is readily made between manganous chloride solutioiis containing 2.59 grams (inactive) and 2.57 grams of man- ganese per litre; still greater accuracy would result from the use of a magnetic field of more than 25,000 gauss which was about the value employed by the author. These critical concentrations have befen determined f o r a number of ferric ferrous manganous cobalt nickel and copper salts.The influence of the anion is negligible excepting in the case of the sulphates and unless they are present in very large excess the ordinary diamagnetic salts or mineral acids produce o illy s n d alterations in the inactive concentration of the magnetic salt. I n determining the concentration of a salt of a magnetic metal in solution the latter is either diluted with water or concentrated by evaporation o r addition of a stronger solution of the salt until it becomes magnetically inactive. From the known degree of the dilution o r concentration necessary the initial concentration may be calculated. Where other metals are also present the method may often be used in conjunction with ordinary analytical methods.Its use in this way is described f o r the estimation of (1) chromium iron o r manganese in presence of aluminium; (2) iron and chromium together ; (3) iron manganese aluminium and phos- phate; (4) chromium and manganese; (5) nickel and cobalt. T. H. P. The Physical Properties of' Metals a s Functione of Each Other. A. H. STUART ( J . Inst. Metnb 1915 14 168-177).-When the atomic heats of those metals which obey the law of Dulong aiid Petit are tabulated the values are found t o lie between 5.93 and 6.67. Deviations not exceeding 2% of the observed specific heat may be attributed to experimental error and when the deviations from the law which exceed this are plotted against the atomic weights the points are found t o lie on two smooth curves corresponding with positive and negative errors respectively. These curves of deviation are closely represented by the formula zyl*o2=0-285 and ~ y ~ .~ * = 2 * 2 . A relation of the following form is also found Atomic weight= 1.41 x densitv -+ product of coefficient of elasticity and coefficient of linear expansion. C. H. D. Apparatus for Determining Melting-points at Temperatures above 270". P. RASSFELD ( J . pr. Chem. 1916 [ii] 92 467-468). -The apparatus consists ewentially of an inverted T-tube the horizontal limb of which passes through opposite sides of a small metal .(tin) bath. The thermornelt?er and capillary tube are adjusted in the vertical limb so that the1 substance can be seen by looking through the horizontal tube' against' a light. Such a bath can be quickly heated but is not influenced by draughts and therefore has a d v a n t a p over the Maquenne block or Thiele's copper block.J. C. W.GENERAL AND PHYSICAL CHEMISTRY. ii. 125 The Measurement of Very Low Temperatures. XXVI. The Vapour Pressures of Oxygen and Nitrogen According to the Pressure Measurements by von Siemens and the Temperature Determinations by Kamerlingh Onnee. G. HOLST (Proc. K. AEad. IVetensch. Amsterdam 1916 18 829-839).-A recalibra- tion of the platinum resistance thermometer which was used by von Siemens (A. 1913 ii 1023) in the determination of the tempera- ture in measurements of the vapour pressures of liquid oxygen and nitrogen has revealed small errors in the thermometer reatlillps The results obtained arel employed to correct tlie vapour-pressure tables given by von Siemens.JOHN L. HAUGHTON and D. HANSON ( J . Inst. Metnls 1915 14 145-153). -A glass or silica bulb containing air is inserted in the furnace and connected with a capillary tube containing mercury. A U-tube encloses a mercury switch by means of which a small currentj actuating a relay which controls the heating current is regulated. Variations of atmospheric pressure are compensated f o r by a second bulb of similar size on the other side of the U-tube cooled by ice. The principal difficulty of such a control arises from the lag of the a i r vessel behind the1 temperature of the furnace. To overcome this difficulty the bulb is made of annular form the specimen to be kept a t constant temperature being placed in the inner space so t h a t the lag reduces the fluctuations of temperature.A t 403O the fluctuations do not exceed lo. For higher temperatures the bulb should be of silica. C. H. D. EDMUND 0. VON LIPPMANN (Chenz. Zeit. 1915 39 985-986. Compare ibid. 1912 36 385 629 1201; this vol. ii 84).-A reply t o H. Schelenz; this writer does not7 seem to be aware of previous publications by the author. H. M. D. A Thermostat for Moderate and High Temperatures History of Specific Gravity. w. P. s. Binary Mixtures. I. The Densities and Viscosities of Mixtures containing Phenol. ARTHUR BRAWLEY (T. 19 1 6 109 IO-45).-Tn oxder to ascertain the factors which influence the viscosity of liquid mixtures and the possibility of determining the composition of any compound which may be formed measurements have been made of the densities and viscosities of mixtures of phenol with bases of varying strength over a wide range of tem- perature.For comparative purposes the viscosity-composition curves given by phenol in admixture with benzene chlorobenzene and nitrobenzene which may be regarded as indifferent substances were also determined. These curves show a very marked curvature and 81-0 convex towards the axis of composition. This behaviour is probably connected with the gradual breaking down of the associated phenol molecules. The curves for the' mixtures with aniline ptoluidine and quino- line show a maximum which becomes less clearly marked as tlie temperature is increased. That the character of these curves is determined by the acidic nature of phenol is shown clearly byii.126 ABSTRACTS OF CHEMICAL PAPERS. comparison of the curves with that f o r mixtures of phenetole and aniline). This is convelx towards the axis of composition. The position of the maximum varies with the temperature and further- more for all the mixtures examined i t is found that! the composi- tion of the mixture for which the deviation from the requirements of the mixture rule has a maximum value depends on the tempera- ture. When curves are drawn t o show the relation between the composition of the maximum deviation mixture and the tempera- ture i t is found that these are all convex towards the axis of com- position. A further characteristic is that they lie entirely on one side of the ordinate which corresponds wit.h equimolecular propor- tions of the components and if produced in the direction of higher temperatures they appear to approach this ordinate asymptotically.Jt is supposed that these peculiarities are thel result of unequal thermal dissociation of the molecular complexes of phenol and of the compound famed rise of t'emperature being favourable to the dominating influence of the1 compound. Mixtures of phenol with pyridine give sinuous curves which show a positive maximum a t higher temperatures only. The curves for the mixtures with dimethylaniline diphenylaminei and diphenylmethylaniine show no maximum and this is in agreement with the weaker basic nature of these substances the effect of compound formatiosn being t o a large extent counterbalanced by the effect of the dissociation of the molecular complexes of phenol.The curves for mixtures of phenol and acetone are convex towards the axis of composition and although evidence has been adduced in favour of the formation of a compound in this case i t would seem t h a t the influence1 of the dissociation of the complex phenol inolecules is predominant in detelrmining the nature of the1 curves. The density-composition curves deviate in most cases only slightly from the mixture rule line. Considerable deviations are found however in tho case of the pyridine mixture the maximum devia- tion occurring a t 59-60% of phenol whatever the temperature. Still greater deviations are shown by the quinoline mixtures the density curves for which show a maximum. The maximum devia- tion from the mixture rule line occurs a t 4704 of phenol and this cornposition remains unchanged when the temperature is altered. From a comparison of the viscosity and density curves it is evident that increase in delnsity is not the dominant factor in determining increase in viscosity. H.M. D. The Temperature-coefaciente of tb e Free Molecular Surface Energy of Liquids from - 80' to 1650'. XIII. The Surface Energy of Position-isomeric Benzene Derivativee. F. M. JAEGER and JUL. KAHN (Proc. K. Aka<d. Wetensch. Amsterdam 1916 18 595-616. Compare A. 1915 ii 747 748).-The results of the investigation of the surface tension of some thirty-six position isomerides are givea in the following summary which shows the temperature-coefficienta of the molecula,r surf acel energy and the equations for the change of density with temperature.Where t'heGENERAL AND PHYSICAL CHEMISTRY. ii. 127 temperature-coefficient changes appreciably with the temperature the limiting values are given the first value having reference tlo the lowest range of temperature o-Dinitrobenzene 1-95 D = 1.3349 - 0*001215(t - 100) + 0*05325(t - 100)2; m-dinitrobenzene 2-05 - 1-71 D = 1.3557 - 0*00106(t - 100) - O*O5l(t- 100)2; pdinitrobenzene 1.35 ; m-fluoronitrobenzene 1.82 D = 1.3484 -0-001202t + 0.0688t2; y - fluoronitrobenzene 2.09 D = 1.3509 - 0.0010275t - 0'067862; o - chloronitrobenzene D = 1.3866 - 0.001014t - 0-064t2; in - chlosonitrobenzene 2.19 D = 1.3788 - 0.00086t - O*O5llZt2; p-chloronitrobenzene 1.88 D = 1.3285 - 0.00117(t - 60) + 0.0688(6 - 60)2; pdichlorobenzene 1.83 D = 1.2531 -0*001064(t - 50) - 0*0664(t - 50)2 ; 1 Z-dichloro-4-nitrobenzene 1.96 D = 1.5464 - 0.001238t + 0.064t2; 1 3-dichloro-4-nitrobenzene 2-16 D = 1-5241 - 0.001028t - 0.0664t2; 1 4-dichloro-2-nitrobenzene 2.01 D = 1.5194 - 0*0C1012t - 0.0G8t2; o-bromonitrobenzene 2.19 D = 1.6642 - 0-001228(6 - 50) - 0*0632(t - 50)2; m-bromonitrobenzene 2-04 D = 1.6625 - 0.001 166( t - 50) - 0.0672( t - 50)2 ; pbromonitrobenzene 1.87; o-iodonitrobenzene 1.98 D = 1.9541 - 0*001422(t - 50); m-iodonitrobenzene 2-16 D = 1.9816 - 0*001342(t - 25) -0*0656(t - 25)2; pnitrotoluene 1-77 - 2-30 D =1.1239 - 0.000764(t -50) - O*O5lE(t - ; o-nitrophenol 1-35 - 3.20 D = 1.2832 - 0*000974(t - 50) - 0*0688(t - 50)2; m - nitrophenol 0.50 - 3.1 D= 1.2797 - 0*@00716(t - 100) - 0.0516(t - pnitrophenol 1-81 D= 1.2874 - 0-0@0855(! - 100) ; p-nitroanisole 1.49 - 2.80 D = 1.2246 - 0*0@093(t - 50) - 0.0624(t - 50)2; 0-cresol 1-92 D=1*0693- 0*0@0966t + 0*05104t2; pcresol 1.80 D = 1.0526 - 0.000888t + O*O%t2; o-chloroaniline 1.97 - 1.1 D = 1.2388 - 0-001047t + O*O5lt2; p-chloroaniline 1.98 - 1.24 D = 1.2337 - 0.000903t ; m-nitroaniline 1.74 D = 1.2269 - 0*00087(t - 100) ; p-nitroaniline 1.3; 3-nitro-o- toluidine 1.27 - 1.9 D = 1.1900 - 0*0008815(t - 100) ; 5-nitro-o-tolu- idine 4.2 ; 3-nitro-ptoluidine 3.08 D = 1.1821 - 0.000882( t - 100) ; sylvestrene 2-28 - 3.9 TI = 0.8779 - 0.0007t - 0.068t2; terebene 2-16 D = 0.8932 - 0.000846t.The results obtained show that the molecular surface energies of position isomerides a t one and the same temperature are not in general equal although this would seem to be suggested by certain earlier obsa vations.The energy-temperature curves of halogen- or nitro-substituted aromatic compounds are frequently very similar but great differences $re found in the behaviour of the isomeric nitro-phenols. The corresponding anisoles show much smaller differ- ences and i t is supposed that the anomalous behavious of the nitrophenols relatively t o one another is connected with structural differences other than those corresponding with ordinary position isomerism. Thew differences to which attention has been frequently directed are thus clearly reflected in the energy-temperature curves. Within the group of the halogen-substituted nitrobenzene deriv- a€ives as in the halogen derivatives of benzene the molecular surface energy a t a given temperature increases with increasing atomic weight of the halogen.2.16 H. M. D.ii. 128 ABSTRACTS OF CHEMICAL PAPERS. The Temperature-coefficients of the Free Molecular Surface Energy of Liquids from -80” to 1650”. XIV. Measure- ments of a Series of Aromatic and Heterocyclic Substances. F. M. JAEGER and JVL. KAHN (Proc. I{. Akad. TVetensch. Amster- dam 1916 18 617-635).-The results obtained for the twenty- eight compounds examined are summarised as in the preceding abstract 1 2 4 - chlorodinitrobenzene 2-23 D = 1.5267 - 0*001158(t - 50) + 0*067(6 - pdibromobenzene 2.15 D = 1.8649 - 0*0016475(t - 80) - 0*06625(t - 80)2; 1.65 - 2-80 D = 1.8606 - 0.0015t - O*O616tZ; o-bromotoluene 2.09 D = 1.4470 - 0.00119t ; phenol 1.36 - 1.94 D = 1-1097 -0.001208t + 0.05144tZ; 2 4 - dinitrophenol 1.90 D = 1-4507 - 0*000962( f - 100) - 0*0662(t - 2 4 6-trichlorophenol 1.57 - 3.02 D = 1.5236 - 0*001382(t - 50) -0*05168(t - 50)z; pnitrophenetole 2.0 D = 1.1656 - 0*00096(t - 50) ; 2-nitroresorcinol; veratrole 3.47 - 1.66 D = 1.1051 - 0.000958 -0.062462 ; 4 5-dinitroveratrole 2.32 - 5.5 D = 1.3374 - Om001035(t - 120) - 0*0675(6 - 120)2; ethyl cinna- mate 2.41 D = 1.0687 -0.0009346 + 0.0656t2; anisaldehyde 2-06 D = 1.1421 - 0.000894t + 0*0624t2; benzophenone 2.27 D = 1.1064 - 0*00077(t - 25) - 0.064(t - 25)2 ; 3 4 3’ 4’-tetrachlorobenzophenone ; 2 4 2’ 4’-tetrachlorobenzophenone dichloride 1-21 - 2.32 I> = 1.4570 - 0*0009425(t - 140) ; me8thylaniline 1.90 D = 1.0146 - 0.001004t + 0*O648t2; pnitromethylaniline 1.3 - 3.3 D = 1.2049 - 0*0008125(t - 150); nitrosomethylsniline 1.63 - 2.27 D = 1.1430 - 0.000868t ; diisobutylaniline 3-43 - 2.73 D = 0.9319 - 0.000924t + 0.05176t2 ; diphenylamine 2.31 D = 1.0628 - 0.000892(6 - 50) + O.O5ll2(t - 50)2; dibenzylamine 2.53 D = 1-045 - 0-00082t ; azoxy- benzene 1-53 - 4.98 D = 1.1764 - 0.000782t ; a-dihydrocampholenic acid ; ethyl a-dihydrocampholenate 2.46 D =0*9445 - 0.0008t; fur. furaldehyde 2.70 D= 1.1851 - 0.001176t + 0.0696ts; thiophen 1-90 D = 1.0873 - 0.0012246 + 0*Os96t2; piperidine 1-98 D = 0.8821 - 0~00092 t.These data are discussed with reference t.o the influence of substi- tution on the molecular surface energy a t constant temperature.As a general rule it would seem that this energy increases when the hydrogen atom is replaced by the halogens the nitro-group and by hydrocarbon radicles. ALAN LEIGHTON ( J . Physical Chew. 1916 20 32-50).-Previous experi- ments on the adsorption of sodium hydroxide by cellulose have led to contradictosy conclusions and the present series was designed to throw further light on the nature of the mercerising process. The experiments were made with a “ normal ” cellulose prepared by heating be& grade absorbent cotton f o r eighteen hours a t looo in a solution containing 20 grams of sodium hydroxide per litre. After this treatment the cotton was washed with water then with dilute hydrochloric acid and again with water until neutral. It was then washed with alcohol and ether and died a t 115O.The “normal ” cellulose was submitted t o the action of sodium hydroxide solutions of varying concentration f o r three hours. By iodobenzene H. M. D. The Adsorption of Sodium Hydroxide bv Cellulose.GENERAL AND PHYSICAL CHEMISTRY. ii. 129 centrifuging the mercerised cotton f o r an hour a t about 4000 revo- lutions per minute i t was found possible t o remove almost com- pletely the adhering liquid. The cotton and the residual solution were then analgsed. The results obtained show that the quantity of sodium hydroxide taken up by 1 gram of cellulose is a continuous function of the concentration of the solution. There is no evidence whatever t o justify the assumption t h a t a definite chemical compound is formed. The actual quantity of sodium hydroxide adso,rbed per gram of cotton increases from 0.1 gram in a solution containing 25 grams per litre t o 0 92 gram in a solution containing 475 grams per litre.The quantity of adsorbed water remains constant until the adsorbed sodium hydroxide reaches about 0.34 gram per gram of cotton but f o r larger quantities of the hydroxide the amount of adsorbed water gradually decreases from 4.0 grains t o 0.82 gram. The former value corresponds with solutions which contain less than about 100 grams of sodium hydroxide) per litre and the latter with a solution containing 475 grams per litre. H. M. D. The Preparation of Collodion Membranes of Different Permeability. WILLIAM BROWN (Biochem. J. 191 5 9 591-61’7).- Collodion thimbles of regularly increasing degree of permeability may be prepared by soaking air-dried thimbles in alcohol-water mixtares of increasing alcohol content. The diffusive capacity of any substance through collodion may be specified in terms of the alcohol strength required t o produce the membrane which just prevents its passage.This may be termed the “alcohol index ” of the substance. W. D. H. The Laws of Solution. HENRY Ih CHATELIER (Conzpt mnd. A reply t o Colson (compare this 1916 162 29-32).-Polemical. vol. ii 15). W. G. The Irrational Character of the Formulae of Solubility and Heats of Wetting. ALBERT COLSON (Conzpt. nmd. 1916 162 222-224).-A reply to Lea Chatelier (preceding abstract). W. G . I Hydrates in Solution. GERTRUD KORNFELD (Iklonatsh. 19 15,36 865-897).-’I’he properties of aqueous solutions of pyridine seem to show t h a t combination takes place between the two substances but the question is by no means settled.I n the further investigation of the behaviour of these substances towards one another freezing- point measurements have been made for a number of solutions obtained by the addition of measured quantities of pyridine and water to the same solvent. The freezing-point data show that no measurable combination occurs in aniline but that this takes place to a small extent in urethane and formamide and to a relatively large extent in ethylene dibromide. The compound thus indicated has the formula 2C,H,N,H20. Frcm the freezing-point curve for pure aqueous solutions of 6*ii. 130 ABSTRACTS OF CHEMICAL PAPERS. pyridine according to which the molecular weight of the pyridine gradually increases from 82 in a 1% solution t o 148 in a 17% solution the conclusion is drawn that the compound 6C,H,N,H20 is present in the more concentrated solutions. The behaviour of copper sulphate ferric chloride sodium sulphate and calcium chioride in formamide solutions and the effect of the addition of water have also been examined by freezing- point measurements.These are also considered t o furnish evidence in support of the view that salt hydrates are formed. H. M. D. Growth of Crystal Polyhedra in their Fusions. R. NACKEN (Jahrb. &fan. 1915 ii 133-164).-Experiments were made on the rate of growth of single crystals of salol (m. p. 41.7O) and benzo- phenone (m. p. 47.7') in small tubes filled with the fused material and kept at the melting-point temperature in a water-bath. The crystal was supported on a copper sod which was maintained a t a slightly lower temperature the heat of crystallisation being thereby conducted away.Within certain limifx the rate of crystallisation is proportional to this t'emperature difference but with under-cooling it is increased and the curves show a maximum. L. J. S. Metallic Crystal Twinning by Direct Mechanical Strain. C. A. EDWARDS ( J . Inst. Metals 1915 14 116-144. Compare TimofBev A. 1912 ii 1054).-That twinning may be produced directly in metals by mechanical strain without subsequent anneal- ing is proved by elxperiments with tin twinning being practically absent when the temperature during straining is looo whilst numerous twins are produced a t low temperatures even when the metal is strained in liquid air.Zinc behaves in a similar manner. Evidence is also given for the view that twinning re'sults in an increase of hardness (A 1915 ii 565). C. H. D. The Theory of Emulsification. T ~ I L D E R D. BANCROFT ( J . Physical Chem. 1916 20 1-31. Compare A. 1915 ii 530).-A gelneral discussion of phenomena which are supposed to afford evidence in support of the view that gases and vapours are selec- tively adsorbed by all solids and liquids. This adsorption is said t o be a source of error in the determination of the molecular weights of substances in solution by air-bubbling methods. The change of the surface tension of mercury with time cannot however be satisfactorily explained in terms of the gas adsorption a t the mercury surf ace.H. M. D. The Emulsifying Action of Soap. A Contribution to the Theory of ktergent Action. S. A. SHORTER and S ELLINGWORTH (Proc. Roy. SOC. 1916 [A] 92 231-%7).-Recent work on emulsi- fication has shown that saponification plays no part in the emulsi- fication of oils by alkali and that the lowering of the interfacial tension and the emulsification depend on the presence of free fatty acid in the oil. I n furthelr investigation of the nature of detergent action measurements have been made by a stalagmometric method,GENERAL AND PHYSICAL CHEMISTRY. ii. 131 of the influence of potassium hydroxide and of potassium oleate in presence of excess of alkali and of oleic acid on the surface tension of water against pure benzene and benzene containing small quan- tities of oleic acid (acidified benzene). II n and 11 are the drop numbers of pure water against pure and acidified beiizene respectively N and N the corresponding values f o r a soap solution then it may be assumed that thel effect of the undecomposed soap is t o change the acidified benzene drop number from n t o AT?z,/n that is t o say in the ratio,iY/n.The effect of the alkali is then represented by a change in the drop number from Niz,/n t o AT,. The ratio of these numbers N,r/Nna affords a measure of the surface activity of the alkali. The actual magnitude of the surface activity will of course be measured by the logarithm of this ratio and hence the ratio of the surface activity of the alkali t o that of the soap will be given by log (N,n/Nn,)/logN/n.I n terms of the above ratios i t is found that towards acidified benzene the surface activity of the alkali produced by hydrolysis is much smaller than that of the undecomposed soap; further that the surface activity of the free alkali in a soap solution is less than that of the same quantity of alkali in pure water and that the addition of alkali to a soap solution increases the surface activity of the soap. The last-mentioned effect is much too large t o be explained by the suppression of hydrolysis. I n explanation of the phenomenon it is suggest-ed that the alkali exerts a coagulating influence on the soap t.he result of which is an increase in the average1 size of the semi-colloidal particles and hence an increase in the “ surface1 activity” of the soap.I n refmence t o the nature of this coagulating influence i t is pointed out that other electrolytes such as potassium and sodium chlorides also increase the “surface activity” of the soap but the effect of salts is much smaller than that of alkali. H. M. D. The Influence of Capillary-active Substances on t h e Stability of an Arsenic Trisulphide Sol. C. F. VAN UUIN (KoZZoid Zeitsch. 1915 17 123-130. Comparel Kruyt and van Duin A. 1914 ii 182).-In continuation of previous experiments on the influence of organic substances on the coagulation of colloidal arsenious sulphide by electrolytes observations have been made with pure isobutyl alcohol. The adsorption of the alcohol from aqueous solution by charcoal was also examined the changes in concentra- tion being determined stalagmometrically .By comparison of the results with those previously obtained for phenol and isoamyl alcohol i t is found that the influence of the three substancee on the coagu- lating concentration of electrolytes runs parallel with the absorb- ability of the three substances by animal charcoal. Further expelriments in which adsorption measurements were made on the one hand with chemically pure substances and on the other with commercial samples have shown that impurities have no appreciable influence on the adsorption of isobutyl alcohol whereas the adsorption curves f o r phenol and isoamyl alcohol vary markedly with the degree of purity of the substances. This varia- 6”-2ii. 132 ABSTRACTS OF CHEMICAL PAPERS tion is suggested as.the basis of a method for the examination of the purity of phenol and isoamyl alcohol. The method employed in the preparation of pure isobutyl alcohol depends on the formation of an isobutyl ether of trinitrophenyl- methylnitroamine when ordinary isobutyl alcohol (b. p. 105-1 loo) is allowed to react with tetsanitrophenylmethylaniine on the water- bath. The excess of isobutyl alcohol and the isobutyl nitrite formed are distilled off and the ether repeatedly crystallised from ethyl alcohol until colourless. M. p. 95O. The ether is then decomposed by ammonia whereby isobutyl alcohol is set free. The solution is acidified with sulphuric acid filtered and the filtrate subjected to distillation in steam. This is followed by treatment with potassium carbonate and metallic calcium. The pure substance has b.p. 108-108*2° a t 771 mm. H. M. D. Forms of Distribution of Metallic Silver. R. ED. LIESEGANG (Ko7Zoid Zeitsch. 1915 17 141-145).-As the result of earlier experiments cii the interaction between substances which diffuse towards one another in a gelatinous medium the view has been expressed t h a t the growth of precipitates is limit,ed to one side of the initial precipitation film. This is shown not to be the case in the interaction of silver nitrate and quinol. Other experiments on the reaction of silver nitrate with ferrous sulphate and with ferrous chlcride by diffusion in a gelatin medium show t h a t the structure and mode of distribution of the resulting silver depend on the concentration of the ferrous salt solution.H. 31. n. The Adsorption Capacity of Living Yeast PAUL ROHLAND and FRANZ HEYDER (Ko7Zoid Z:eitscli. 1915 17 139-141).-com- para tive observations on the adsorption of various dyes by colloidal eilimtes animal charcoal and yeast show thatl there is a certain parallelism in the behaviour of these adsorbents. Invariant Uaivariant and Bivariant Equilibria. 111. F. A. H. SCHREINEMAKERS (Proc. I<. ,4 find. TVctP?isch. A m s t d r r m 1916 18 820-4328. Compare -4. 1915 ii 619).-A discussion of the types of equilibrium in quaternary systems. The Equilibrium Liquid-vapour of the System Argon- Nitrogen. G. HOLST and L. HAMBURGER (Proc. K. Akad. W’eteizsch. ,1msterdam 1916 18 872-894).-Measurements have been made in order t o obtain the relations between the pressure tempera.ture and composition in the condensation of mixtures of nitrogen and argon.From the experimental data diagrams have been constructed show- ing the connexion between the composition of the co-existing phases and the temperature a t different pressures and between the pressure and the composition a t constant temperature. The ratio rf of the components in the liquid phase is connected with the corresponding ratio r f o r the vapour phase by the equation Iogr’=a+ b log r where a and h are constants. Since T and r’ do not differ very H. M. D. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 133 much it is t o be expected t h a t argon and nitrogen will not be easily separated by any process of fractional condensation or distilla- tion.F o r gaseous mixtures the change in 2x1 with varying pressure can be represented with an error of less than 0*1% by the equation y u = RI’(1 + U/ r ) in which B is a constant which depends on the composition of the mixture. New measurements of the vapour pressures of liquid oxygen nitrogen and argon are recorded and a redetermination of the temperature and pressure a t the triple point f o r argon has given T=83.8l0 (abs.) and p=521.4 mm. A method for the estimation of the cornposition of mixtures of argon and nitrogen is described which depends on the absorption of the nitrogen when subjected t o the action of the glow discharge through potassium vapour. The results obtained by this method are in agreement with those derived from density measurements provided that the kalue recently obtained by Schultze (A.1915 ii 833) f o r the density of pure argon is used in the calculations. H. M. D. Critical End-points in Ternary Systeme. 111. A. SMITS (Proc. K. .4 kcid. TT’etet7sch. AmstPrdccnz 1916 18 793-807).-A theoretical paper dealing with special cases of equilibrium in t er 11 a r y systems. H. M. D. The Propagation of Flame in Mixtures of Hydrcgen and Air. The ‘‘ Uniform Movement.” WILLIAM ARTHUR HAWARD and TATSURO OTAGAWA (T. 1916 109 83-89).-The phenomena which precede1 the development of the explosion wave in mixtures of hydrogen and air resemble closely those which have been observed for mixtures of methane and air. When a mixture is ignited a t the open end of a horizontal tube closed a t the other end a ‘‘ uniform movement ” of the flame is set up which has been examined with reference to its dependence on the composition of the gas mixture and the diameter of the tube.According t o Mallard and Le Chatelier maximum speed is obtained with a mixture containing 40% of hydrogen b u t the authors’ results show that the maximum extends over the range 38-45% of hydrogen. For mixtures containing up to 35% of hydrogen the speeds i n a 11.5 mni. tube are greater than in a 9 mm. tube whilst in a 25 mm. tube the speeds for mixtures con- taining up t o 54% of hydrogen are considerably greater than those obtained in tubes of 9 and 11.5 mm. diameter. On the other hand the velocities of the uniform movement in mixtures containing ii1oi.e than 54% of hydrogen are almost identical in the three tubes.According t o these results i t would seem that the cooling effect produced by the walls of the tubes becornes inappreciable when the thermal conductivity of the gaseous mixture is high. In this connexion i t is t o be noted that the thermal conductivity of hydrogen is about six times as large as t h a t of air. H. M. D.ii. 134 ABSTRACTS OF CHEMICAL PAPERS. Influence of Pressure on the Combustion of Explosive Gas- Air Mixtures. E. TERRES and F. PLENZ (Chem. Zentr. 1915 ii 1278-1279 ; from J . Gasbeleucht. 1914 57 990-995 1001-1007 1016-1019. Compare ibid. 1914 57 893).-The influence of pressure on the explosive limits of mixtures of hydrogen carbon monoxide and methane with air and on the processes of combus- tion has been investigated by estimations of the products of the reactions.Increase' of the initial pressure restricts the region of explosion particularly with the mixtures containing carbon mon- oxide; the upper limit of explosion of methane furnishes however an exceptioa t'o this rule. The explosion limit is by no means a sharply defined region diminishing concentration leading gradually from the region of explosion through one of decreasing partial combustions to mixtures which do not ignite. With hydrogen and methane such partial combustions are lacking a t the upper limit of explosion. The explosive limits are defined as the concentrations of combustible gas a t which the heat developed in unit time exactly covers the loss so the combustion either just does or just does not proceed through the mixture. With rise of temperature these limits are extended.As regards the ignition i t is found that no essential difference exists between ignition by heating and ignition by a spark; the1 locality of the ignition does however exert a marked influence on the value of the partial combustions. The Velocity of Ionic Reactions. GERTRUD K ORNFEtD (JIonntsh. 1915 36 941-943).-0n the assumption that the neutralisation of weak bases by weak acids might require a measurable time f o r completion conductivity measurements have' been made according t o the method described by Benedicks (A. 1910 ii 280) t o deter- mine the! time required for the neutralisation of N/lO-solutions of phenol and pyridine. These &OW that the process is complete in less than 11250th of a second.H. M. D. T. H. P. Studies in Catalysis. 111. Preliminary Measurements of the Infra-red Absorption Spectra of Hydrogen Chloride Potassi urn Chloride and Methyl Acetate in Aqueous Solution. RAPHAEL HEBER CALLOW WILLIAM CUDMORE MCCULLAGH LEWIS and GERALD NnDDER (T. 1916 109 55-67. Compare T. 1914 105 2330; 1915 107 233).-In order to test the assumption that homogeneous catalysis is due to infra-red radiation emitted in quanta by the catclyst and absorbed by the reacting substances comparative measurements have been made of the wave-lengths of the bands in the infra-red absorption spectra of water and of aqueous solutions of hydrogen chloride potassium chloride and methyl acetate over the range 1 p-2.1 ,,u. The spectra of the solutions of these three substances are very similar in that in all cases the bands occur a t 1.12p 1 .5 5 ~ ~ and 2.1 p (approximately) and thus correspond with the bands of the solvent (1*Op 1-50 p and 2.0 p) with a slight displacement in every case in the directicn of greater wave-length. The acid and salt solutions differ however in other respects for the absorption ofGENENAL AND PHYSICAL CHEMLSTKY. ii. 135 hydrogen chloride solutions increases with the concentration whereas solutions of potassium chloride show diminished absorption with increasing salt concentration. It is suggested that the observed relations are t o be attributed to the formation of additive compounds between the solute and the solvent. The greater absorption of hydrogen chloride as compared with potassium chloride solutions is said t o be in agreement with the radiation theory of catalysis in that a positive catalyst is one which increases the radiation density at certain wave-lengths in the infra-red region and i t is known that an absorption band increases the radiation density below the band and diminishes i t above the band.H. M. D. Studies in Catalysis. IV. Stoicheiornetric and Catalytic Effects due to the Progressive Displacement of One Reactant by Another in the “Acid ” Hydrolysis of Methyl Acetate. ROBERT OWEN GRIFFITH and WILLIAM CUDMORE MCCULLAGH LEWIS (T. 1916 109 67-83. Compare preceding abstract).-Earlier experiments on the rate of hydrolysis of methyl acetate in presence of an acid catalyst have shown that the velocity-coefficient k calcu- lated from the equation k = 1 / t . log a / (a - x) increases very appre- ciably with tlie concentration of the ester. New measuremenb have been made with varying concentrations of methyl acetate and with hydrochloric acid and trichloroacetic acid as catalysts which confirm this result Since the reaction is really bimolecular and reversible the velocity is represented by the equation in which b is the initial concentration of the ester w that of the water and k1 and k are the coefficients of the opposed reactions. The data show that k also increases with the concentration of the ester. The increase in k and ill cannot be accounted f o r by correct- ing the velocity-coefficients f o r the change which takes place in the degree of ionisation of the acid with increasing ester concentration. On tlie assumption that the reactive substance is an additive compound of ester and water the observed increase in the velocity- coefficients with increasing ester concentration can be explained in terms of the greater dissociating power of water in comparison with that of methyl acetate. I n this sense the water exerts a negative catalytic effect in that it tends to reduce the quantity of the reactive complex. Incidentally measurements were made of t.he equilibrium con- stant I< = rester] [water]/ [methyl alcohol] [acetic acid]. In hydro- chloric acid solutions not exceeding IN the’ mean value of I< is 4.6. dx/dt = k,(b - X ) ( W - X) - &x2 H. M. D. History of Sympathetic Inks. L. VAN~NO (Arch. Phamt. 1916 253 505-511).-Instances are given of the use of sympathetic inks as far back as 230 B.C. c. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005121

出版商:RSC    

年代:1916

数据来源: RSC

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ii. 136 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Preparation of Iodine Monochloride. Josh J. CERDEIRAS (Anal. Fis. Quim. 1915 13 460-462).-Iodine monochloride is best prepared by passing dry chlorine over excess of iodine. It forms a red liquid b. p. 102'. Oxidation of Hydrogen Sulphide by Means of Ozone in Steam at 120". U. BRESCIANI (Ann. China. Applicata 1915 4 343-346).-Under these conditions the oxidation of hydrogen sulphide t o sulphuric acid is not complete even when the ozonised air is in very large excess. Sulphites Thiosulphates and Polythionates. 111. Action of Mercuric Chloride on Sulphuroue Acid Sulphites Thio- sulphates and Polythionates. A. SANDER (Zeitsch nizgezo. Chew 1916 29 11-12 16).-In previons work on this subject (A. 1915 ii 161 629) the author has assumed that the statement of Feld (A.1911 ii 289 769) is correct namely that the' action of mer- curic chloride on thiosulphates and polythionates is an oxidising one) as expressed for example by the equation Na,S30 + 2HgC1 + 2H,O = N3,S04 + Hg,Cl,* 2HC1+ H,SO,+ S. This is apparently supported by the1 fact that the1 precipitate obtained is white. Further investigation however supports the older statements of Herschel Rose and Kessler (1819-1849) that the white precipitate obtained is the compound Hg3S,Cl formed by the interaction of mercuric sulphide and the excess of mercuric chloride the reactions taking place according to the equations 2Na,S,03 + SHgCl + 2H,O = Hg3S,Cl + 4NaCl+ 2H,S04 ; 2K,S30 + 3HgC1 + 4H,O = Hg3S,Cl + 4KC1+ 4H,S04 ; 2K,S40 + SHgCl + 4H20 = Hg3S,C1 + 4KC1+4H,S04+2S.The samel amount of acid is liberated as according t o Feld's equations so that previous estimations depend- ing on acidimetry are correct. The validity of the last equations was proved by weighing the quantity of precipitate obtained in various experiments the precipi- tate consisting of the compound Hg,S,Cl mixed in the case of the t'etrathionate with sulphur. The estimation of a mixture of trithionate and tetrathionate can be best carried out as follows The solution is oxidised with hydrogen peroxide in the presence of a known excess of sodium hydroxide the reactions being Na,S,O + 4H,O + 4NaOH = 3Na2S0 + 6H,O ; Na2S40p + 7H,02 + 6NaOH = 4Na2S0 + 10H,O. The unused alkali is then titrated. Another sample of the solution is heated with mercuric chloride (Zoc.c i t . ) and the acid liberated is estimated. From these two1 results i t is easy t o calculate the amounts of tri- and tetra-thionate present. G. CES'ZRO (Chem. Zeiztr. 1915 ii 874; from Bull. SOC. franc. Mintrd. 1915 38 38-74).-The A. J. W. T. H. P. T. S. P. Constitution of Thio-salts.INORGANIC CHEMISTRY. ii. 137 author discusses the structural formulz of thio-salts R:I1S3,rnR1IS where RIII repre’sents As Sb Bi Fe etc. and RII Cu2 Pb Hg etc.; m is termed the basicity of the thio-salt and varies from 4 t o 12. The various types of thio-salts are considered in relation t o natural minerals especially argentiferous pyrites pyrrhotite and berthierite. The natural thio-salts are divided into the following types poly-salts in which m is less than 1 ; meta-salts with m = 1 ; salts intermediate to meta- and pyro-salts m lying between 1 and 2 ; pyro-salts with rn = 2 ; salts intermediab t o pyro- and ortho-salts m being between 2 and 3 ; ostho-salts with m=3; argentiferous pyrites which represent molecular mixtures of a poly-salt having m={ with an ortho-salt; basic thio-salts with m between 3 and 4 ; and perbasic thio-salts with rn between 5 and 12.T. H. P. Baeyer’s Tension Theory and the Structure of the Diamond ERNST MOHR (Chem. Zentr. 1915 ii 1065; from Sitzungsber. d. Heidelberger Bknd. Tl’iss. Mathern. naturwiss. Kl. [Abt. A] 1915 7 18 pp.).-The author’s considerations are based on Saclise’s theory according t o which two different tension-free forms of cyclo- hexane are conceivable with the atoms of the ring not in one plane.Sachse’s models are not a t variance with observation if i t is assumed that impacts with other molecules are sufficient t o give to the cyclohexane ring all the possible forms in t u r n ; the number of isomerides with cyclohexane and its substitution products are then with tension-free arrangement of the carbon atoms the same as if the atoms of the ring were situated permanently in one and the same plane. The case of tension-free ring-combinations in which several carbon atoms of one cyclohexane ring belong also t o another ring is explained. Superposition of a number of such combinations leads to large carbon atom systelms of simple regular st’ructure all the carbon valencies in the interior being satisfied without tension; only a t the surface of the system do valencies protrude unsatisfield into space.I n one form of this model the six atoms of each cyclohexane ring stand exactly above the six ring- atoms of the next lower layer (“geradex Bau”); in a second possible form the rings are so arranged that the centre of each lies immediately above a ring carbon atom of the adjacent layer (“ schiefer Bau ”). The latter carbon atom system is identical with the space-lattice of the diamond derived by Bragg from the reflection of X-rays by crystals (Proc. Roy. SOC. 1913 [,4] $9 277). The constitution of graphite may be regarded as correspond- ing either with the direct superposition of the cyclohexane rings or with a space-lattim in which the structure is alternately direct and oblique.T. H. P. The Electrolysis of an Aqueous Solution of Potassium Orthosulphoantimonite [Potassium Thioantimonite] and the Constitution of this Compound. J. A. MULLER ( B d . Soc. chim. 1916 [iv] 19 3-8).-1n the experiments the cathode was of antimony and the anode’ of platinum. I n the first series both electrodes were in the solution of the thioantimonite whilst in theii. 138 ABSTRACTS OF CHEMICAL PAPERS. second aeries only the cathode was in this solution the anode being in a 17% solution of sodium hydroxide the two solutions being seperated by a porous diaphragm which was impregnated with the solution of the thioantimonite. I n the first series of experiments a precipitate of antimony was obtained a t the cathode together wit.h a fee,ble evolution of gas whilst a t the anode a precipitate of antimony sulphide containing a little free sulphur and some potassium sulphide was obtained.The results of the second series of experiments show that during the electrolysis there do not pass from the cathode cell to the anode cell any negative ions contain- ing potassium but there does pass in this direction a certain weight of a grouping corresponding with the formula SbS,. The author considers that these results indicate that the original com- pound is really the combination of the radical SbS with three atoms of potassium and not the combination of three negative groups KS with an atom of antimony. W. G. Approximate Determinations of the Boiling Points of some Alkali Haloids. L. H. BORGSTROM (Jahrb. *&fin.1915 ii Ref. 298 ; from Tidskriften. Teknikern 1915 24).-'I'he following values are the means of several determinations which varied 10-2oo LiCl ...... 1360" NaCl ...... 1490" KCl ...... 1500" NaBr ...... 1455 KBr ...... 1435 NaI ...... 1350 KI ......... 1420 L. J. S. The Constitution of Brasses Containiog Small- Percentages of Tin. 0. F. HUDSON and R. M. JONES ( J . Irzst. Metals 1915 14 98-1 15).-That portion of the ternary system copper-zinc-tin has been examined which includes alloys containing from 50% t o 70% of copper and from 0% t o 5% of tin. An equilibrium diagram for this region has been determined. There are no distinct differences between the y constituent of the brasses and the 6 constituent of the bronzes and the two substances appear t o pass continuously into one another.The constituent which appears light blue under the microscope may thus be termed y when in contact with P I or 6 when in contact with a. C. H. D. The Copper-Rich Kalchoids. SAniuEL L. HOYT and PAUL H. M. P. BRINTON ( J . Inst. Metals 1915 14 178-188. Compare A. 1914 ii 366 ; Hudson and Jones preceding abstract).-The position of the eutectoid h e in the copper-zinc-tin alloys has been further determined and the syst7em is shown t o be truly ternary. Both therma.1 curves and microscopical examination are employed. C. H. D. The Micro-chemistry of Corrosion. IV. Gun Metal. CEcIr H. DESCH and HENRY HYMAN ( J . Inst. Metnls 1915 14 189-198. Compare A. 1914 ii 367 655; 1915 ii 689),-The corrosion ofINORGANIC CHEMISTRY. ii. 139 copper-tin alloys containing zinc has been examined by the method previously described.The total corrosion is much less than that of the brasses under similar conditions and the course varies in a marked degree with the applied E.M.F. When the current. is small only the a-phase is athacked but with larger currents the eutectoid is also corroded. The protective action of the layer of basic tin salts is strongly marked. The a-constituent develops a distinct crystalline structure during corrosion. I n quenched alloys contain- ing a and fl there is very little difference between the two con- stituents in their rate of corrosion. C. H. D. Polyiodides. 111. The System CuI-I,. R. KREMANN and V. BORJANOVICS (Monatsh. 1915 36 923-927. Compare A. 1913 ii 15).-Cooling curves for mixtures of cuprous iodide and io.dine previously heated for several hours a t teniperatures varying from 180° t o 240° have shown no evidence of the formation of any compound.The only change indicated by these curves corresponds with the freezing point of iodine a t 1 1 4 O . This result has been confirmed by measurements of the vapour pressure of the iodine in equilibrium with the above mixtures a t 2 6 O . The values obtained were identical with the vapour pressure of pure iodine. H. M. D. Aluminium.-Aluminates. ERNST MA~ETIX (,Voaz. Sc? . 1 9 15 [v) 5 225-232).-Aluminium hydroxide produced by the hydrolysis of aluminates is quite different in properties from that produced by the precipitation of solutions of aluminium salts with ammonium hydroxide. It is of a sandy nature non-hygroscopic and when dry has a composition corresponding with the formula A1,o3,3H,0.On heating i t commences t o lose water a t about 1 6 0 O ; a t 225O it contains 2M,O and at 235O lH,O but it is only completely dehy- drated in the neighbourhood of 1000°; the loss of water during heating does not take place a t a uniform rate. The partly dehy- drated hydroxide takes up water again on exposure t o the air t o the extent of half that which has been lost but this water is readily removed in a desiccator or on heating a t looo. The author endeavours t o explain these results by means of constitutional f ormulz. The hydroxide obtained by precipitation with ammonium hydr- oxide when d-ried a t 80° has a composition approaching that of A1,0,,2H,O.The loss of water on heating takes place fairly uniformly and i t is impossible t o say that a t any particular temperature a definite hydrated oxide exists. When mixtures of alumina and barium carbonate no matter in what proportions are heated a t temperatures not exceeding 1500° the aluminate' Al,O,,BaO is always formed. A t the temperature of the electric arc trzbarium aluminate A1,0,,3BaO is obtained from a mixture of alumina and barium carbonate in the molecular p(ro- portions of 1 3. It is soluble in water and the solution gives with calcium chloride a precipitate of the formula (A1,03,3CaO)5,3CaC12. Solutions in water of the product obtained by heating mixtures ofii. 140 ABSTRACTS OF CHEMICAT4 PAPERS. alumina and barium carbonate a t temperatures up t o 1500O are not stable and slowly deposit aluminates which are less and less rich in barium. From a solution made from alumina and barium carbonate in the molecular proportions of 1 1 on concentration a barium alziminccte 10A1,0,,1lBa0,55H,O can be obtained as needles ; by precipitation with alcohol an nlicininate (doubtful whether pure) 5A1,03,4Ba0,4H,0 is obtained.Uiccrlciurn al?imiirnt? A1,0,,2CaO is obtained by heating a mix- ture of alumina and calcium carbonate in the molecular proportion of 1 2 a t 1500O. By appropriate variation of the composition of the mixture used the aluminates Al,O,,CaO A1,03,3Ca0. 2A1,03,3Ca0. 5A!,O,,GCaO and 10A120,,11Ca0 have been ob- tained but not properly investigated. Their solubility in water is very small. Double aluminates of the alkali metals and alkaline earth metals can be obtctined by heating mixtures of alumina alkaline earth carbonates and sulphates o r chlorides of the alkali metals. Prom mixtures of alumina barium sulphatel or calcium sulphate and carbon s~~lpl~ido-nl~~rni~~cctes are obtained of which the following have been isolated A1,03.2BaS ; 2A120,,3BaS.A mixture of silica alumina and calcium carbonate in th+ molecular proportion of 2 l 2 when heated t o 1400O gives the silico-aluminate 2Si0,,A1,03,2Ca0 which is insoluble in water. Under similar conditions using the molecular proportion 2 1 1 the silico-nlzc?niizate 2Si0,,A1,03,Ca0 is obtained. The Conservation in the Cold of Solutions of Sodium Aluminate. G. A. Ls ROY (Co?npt. wizcZ. 1916 162 74-7.5).- Concentrated solutions of sodium aluminate which slowly decom- pose when allowed to remain a t the ordinary temperature can be kept unaltered for an indefinite time a t -lo to - 2 O in an ice.chest. W. G. Constitution of Ultramarine. HISINRICH PUCHNER (Kolloid Zeitsch. 1915 17 119-123).-1n the course of experiments on the effect of sodium chloride solutions on various types of soil it has been found that when calcareous sand containing humus and gypsum obtained from the1 neighbourhood of Miiiiich is subjected t o the action of sodium chloride solution in such a way t h a t the solution is drawn up through the soil by capillary action the aqueous extracts from the middles portion of the soil yield a residue which on ignition exhibits the dark blue colour characteristic of ultramarine.Analyses of such residues show that the1 development of the blue colour is connected with the proportion of sulphate in the residue. The general behaviour of the residues seems t o show conclusively that the blue colour is really due t o the formation of ultramarine. I f the sodium chloride is replaced by potassium chloride the1 effect is not obtained. The observations are discuss'ed in reference to whether ultra- marine is a definite chemical compound or whether the blue colour is connected with adsorption phenomena but no definite conclusion is drawn. H. M. D. T. S. P.INORGANIC CHEMISTRY. ii. 141 Anhydrous Sulphates. VIII. Manganous Sulphate with Lithium Sodium and Potassium Sulphates. G. CALCAGNI and 1). MAROTTA (Gaszptta 1915 45 ii 368-376.Compare A. 1914 ii 52 205).-The fusion diagrams of the systems MnS0,-Li,SO MnS0,-nay so and MnS0,-K2S0 have been investigated. The first yields no compound between its constituents but the others give 3MnS04,Na2S0 MnS0,,3Na2S04 and 2&!tnSO,,I<,SO,. The Influence of Oxygen on Some Properties of Pure Iron. WESLEY AUSTIN (J. Iron Steel I ~ s f . 1915 92 157-163).-Alloys of iron apd oxygen are prepared by melting together iron and ferric oxide in a small arc furnace lined with magnesia. The product does not in any case contain more than 0.288% of oxygen. The A3 point is lowered by oxygen but the A2 point is un- changed. Pearlite is absent. Microscopical examination shows that the oxide is mechanically mixed appearing in globules. The alloys may be worked above 900° or between 750° and 850° but are brittle between those temperatures.The alloys are very resistant to atmospheric corrosion but are more readily attacked by a i d s than mild steel. ' Blue-brittleness ' occurs as high as TOOo C. H. D Sulphur in Malleable Cast Iron. R. H. SMITH ( J . Iron Steel Inst. 1915 92 141-156).-Sulphur is not removed from white iron in tlie ordinary annealing process whether the surrounding mixture be reducing oxidising or neutral. When oxidation takes place the sulphur tends t o diffuse into the unoxidised portions of the iron. Sulphur does not produce an injurious effect until its quantity exceeds 0.15%. The Occurrence and Influence of Nitrogen in Iron and Steel. N. TSCHISCHEVSKI (J. Iron Step1 Inst. 1915 92 47-105).-For the estimation of nitrogen in iron o r st'eel the metal is dissolved in hydrochloric acid the solution made alkaline with lime and the ammonia in the distillate estimated by means of Nessler's reagent or by titration with N/lOO-sulphuric acid.The addition of zinc which is sometimes recommended is t o be avoided. None of the nitrogen of tlie metal passes off as nitrogen oxides. A tin tube should be used f o r the distillation on account of the alkalinity of Iron in powder or filings reacts with dry ammonia a t 200° the maximum sate of absorption being a t 450° the compound formed being Fe,N. Carbon is practically without influence on the absorp- tion of nitrogen. Manganese reacts with ammonia a t 600-700° with considerable development of heat forming the compound Mn3N2 and finally MnN.Manganese also reacts with dry nitrogen but more slowly. Manganese nitride is soluble in molten iron. Silicon nitrides also dissolves in iron and as this compound is very stable i t remains in the residue when the steel is dissolved in acid f o r the purpose of analysis and so introduces an error into the C. H. D. glass.ii. 142 ABSTRACTS OF CHEMICAL PAPERS. estimation of nitrogen. Aluminium nitride passes into solid solution in iron. The cementation of iron by ammonia leads t o the formation of a brittle layer of nitride whilst the interior of the metal contains crystals of the same substance. Nitrogen hardens steel and decreases its ductility. Phosphorus in Iron and Steel. W. H. HATFIELD ( J . ITOIZ Steel Znst. 1915 92 122-140. Compare Stead A.1915 ii 778). -White irons containing about 2.9% of carbon are little changed in properties by the presence of phosphorus in quantities up to 0.20%. Above 0.25% free phosphide makes its appearance. When such iron is etched by means of Stead's copper reagent the varia- tions of deposition which are obtained may be due t o the irregular distribution of other elements besides phosphorus. C. H. D. C. H. D. The Carburiaation of Iron a t Low Temperatures. T. H. BYROM ( J . Iron Steel Inst. 1915 92 106-121).-MiId steel exposed for several years t o the action of blast-furnace gases a t about 50O0 becomes convezted almost completely into carbides analysis indicating a mixture of Fe,C and Fe,C. Electrolytic iron strips are readily carburised by carbon monoxide a t 550-600°.A layer of iron sulphide is also formed on the specimens exposed t o blast-furnace gas. I n the interior of the metal the carbide is formed at the boundaries of the crystal grains. The Influence of Heat Treatment on the Specific Resistance and Chemical Constitution of Carbon Steels. EDWARD D. CAMPBELL ( J . Iron Steel Inst. 1915 92 164-180).-The specific resistance of carbon steels increases with the temperature from which they are quenched. This is in accordance with the view t h a t the dissolved carbides dissociate with rising temperature ( J . Iron Steel Inst. 1899 ii 223). A steel containing 0.35% of carbon quenched from different temperatures shows a close parallel- ism bet'ween the specific resistance and the colour produced by the solution of the1 same specimens in cold nitric acid.When steels are regarded as solid solutions sufficient attention is not usually given t o the solute. The study of aqueous solutions is not regarded as that of the influences of various solutes on the properties of water but t'he properties of steel are commonly treated as modifica- tions of those of iron by the presence' of dissolved molecules. The term '' ionoids " is used t o denote the products of dissociation of the solutes in metallic solid solutions. The effect of the ionoids is to increase the specific resistance of the solvent metal. C. H. D. 0. LEHMANN (Jahrb. Min. 1915. ii 109-132).-A detailed summary of the C. H. D. Mixed Crystals of Iron Ammonium Chloride. iiterature and of the views previchsly expressed by the aithor.L. 5. S. Synthesis of Smaltite and Lollingite. A. BEUTELL and FR. LORENZ (Centr. Min. 1916 10-22).-Smaltite and lollingite (A,,INORGANIC CHEMISTRY. ii. 1413 1915 ii 633) after being heated in a vacuum until no further loss of arsenic occurred were the materials experimented on the ratio of (Co Ni Fe) As and of Fe :As being thereby reduced t o 1 0.95 and 1 0.88 respectively. Thesel and also pure cobalt were heated in an atmosphere of arsenic a t various temperatures f o r prolonged periods until equilibrium was attained. Using pure cobalt the following arsenides were obtained the range of temperature through which they are stable in arsenic vapour being indicated in brackets (415-430°) and CoAs3 (450-618O). The iron arsenides obtained under these conditions were FeAs (335-385O) Fe,As3 (395-415O) and FeAs (430-618O).The varying compositions of the minerals smaltite chloanthite skutterudite and lollingite are explained by the mixture of these various arsenides. L. J. S. COAS (275-335') CO~AS (345-365') COAS~ (385-405') CO~AS The Explosive Property of Uranyl Nitrate. ARNO WLLER (Chem. Zeit. 1916 40 38-39).-The author was unable) t o confirm the detonation or decrepitation of preparations of uranyl nitrate crystallised from ether as specific properties of t h a t substance. In only three out of twenty experiments was any detonation observed on mechanical handling of the preparations after moistening with water and in no case with the violence described by Ivanov (A. 1912 ii 455) o r Andrews (A. 1913 ii 60).The phenomenon was never observed in the case of preparations recrystallised from water or prepared in the absence of free nitric acid and the opinion is advanced t h a t i t may be due t o the decomposition of an unstable compound of a lower oxide of nitrogen with a uranium-ether additive compound. G. F. M. Densities of Solutions of Uranium Nitrate in Water i n Alcohol and in Some Acids. W. CECIISNER DE COXINCK ( B d I . SOC. chim. 1915 [iv] 17 422-424).-The8 author has determined the densities of solutions of uranium nitrate in water alcohol (85%) commercial methyl alcohol acetic acid (D 1-055) nitric acid (D 1.153) sulphuric acid (D 1.138) and hydrobromic acid (D 1-21> containing varying percentages of the salt. The results are tabu- lated in detail in the original.W. G. The Preparation of Metallic Vanadium. R. EDSON and D. MCINTOSH (Trana. Roy. SOC. Canada 1915 [iii] 9 81-83).-The method describemd whilst inapplicable for the preparation of vana- dium on a large scale may be used with ,advantage in the labora- tory 0.r f o r demonstration in the1 lectureroom. A flask containing some vanadyl chloride is fitted with a platinum wire filament attached t o two heavy copper leads and also with inlet and exit tubes for the passage of a current of dry hydrogen. The filame8ntl is made to glow by passing a current through it and the vanadium is deposited smoothly on the platinum as a silvery-grey coating. The experiment may be carried out either in a vacuum or in an atmosphere of hydrogen a t low pressure. As soon as the filamentii.144 ABSTRACTS OF CHEMICAL PAPERS. reaches a white heat the deposition begins and can be continued until the wire burns out. The vanadyl chloride is made by heating a mixture of the pent- oxide arid charcoal in a stream of chlorine and need not be purified from any vanadium tetrachloride i t contains. T. S. P. Antimony Pentachloride and Iodine. OTTO RUFF [with J. ZE~DNER and LEOPOLD HECHT] (Bey. 1915 48 2068-2076).-1n an earlier paper (A. 1909 ii 1023) it was meiitioned that antimony pentachloride reacts with iodine but not with bromine. The author hoped to make a complete study of this reaction but has had t o desist because of the effect of the vapours on the' respiratory organs. Recently however Moles (A. 1914 ii 812) has studied the depres- sion of the freezing point of antimony pentachloride when iodine iodine monochloride or iodine trichloride are dissolved in it and his results help t o elucidate the above reaction.Three main reactions proceed as indicated by the equations (I) SbC1 + 2 1 = SbC1 + 2IC1; (11) 2SbCl + 2 1 = SbC1,,2ICl+ SbCl ; (111) 3SbC1 41 = SbCl,,3IC1+ 2SbC1 + IC1. Equation I repre- sents the reaction which takes place when less than 1.5% of iodine is dissolved in the antimony pentachloride. Some iodine trichloride antimony tri-iodide and possibly a chloro-iodide of quinquevalent antimony are formed in addition but no evidence can be adduced of the formation of a compound SbClJ analogous t o SbF,I. The compounds SbC1,,2ICl and SbC15,31C1 may be isolated by sublimation from a mixture of antimony pentachloride (10 grams) and io'dine (4.3 o r 8.6 grams) under 15 mm.pressure from a bath a t 30-35O. They form bluish-black crystals stout prisms o r needles m. E. 62-63O which fume in the air and dissolve readily in carbon tetrachloridc o r chloroform but sparingly in antimony pentachloride. Temperature-concentration diagrams of mixtures of antimony pentachloride and iodine monochloride were also made in order t o confirm the existence of the above double compounds. I n the solutions they are strongly dissociated. J. C. W. Presence of Platinum in Spain. DOMINGO DE ORUETA and S. PIRA DE RUBIES (Gompt. rend. 1916 162 45-46. Compare this vol. ii 106).-The Ronda chain occurring in Andalusia between Malaga and Gibraltar is constituted by a series of rocks very similar in constitution and distribution t o those forming the Ural platiniferous beds.The central zone of peridotites is 72 kilometres long by 20 kilometres broad and is surrounded by other smaller ones. llilicroscopic examination further confirms the analogy between these rocks and those of the Urals particularly in the case of the dunite. The mean of fifty analyses gives the platinum content as 3 grams per cub. metre of platiniferous sand the varia- tion being from traces up t o 28 grams. IDE KOIFMANN. (Arch. Sci. phys. nut. 1915 [ivl 40 509-513).-The action of nitric acid on silver-platinum alloys was investigated ; the alloys W. G . Silver-Platinum Alloys and their Analysis.MI N ERALOGZCAL CHEMISTRY. ii. 145 used contained from 0,219 t o 5.162% of platinum and were p8re- pared by heating together mixtures of silver and platinum for twenty minutes a t a temperature above the fusing point of silver the mixtures being covered with a layer of pure sodium chloride. The preparation of the alloys confirmed the slight solubility of platinum in silver and i t was impossible t o make an alloy contain- ing much more than 5% of platinum. When these alloys were boiled wiZh nitric acid of varying concentrations a brown-coloured solu- tion was obtained together with a more or less voluminous black sediment and the latter always yielded a brown-coloured solution when treated with water. The author considers that silver and platinum in an alloy cannot be separated by means of nitric acid; part of the platinum forms a colloidal solution in the nitric acid and the remainder also passes into solution when treated with a sufficient quantity of water. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005136

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 145 Errors in Silicate Analyses Composition of Alkali-free Aluminous Augites. G. TSCHERMAK (Centr. Mz’n. 191 6 L-9)- General remarks on the errors in the methods used in analysis personal errors and erxors due t o impurities of the material. Analyses made by-different authors on the same sample of material o r of a mineral from the same occurrence are compared and criti- cised. A further reply t o Boeke (A. 1911 ii 283) regarding the components assumed to enter into the composition of the alkali-free aluminous augites and a criticism of the analvses plotted in his diagrams many of which are rejected as untrustworthy. The author still maintains that the condition p=q+r holds in the formula pSi0,,qMg0,rCa0,sA1203. L. J. S. Identity of Kalk-Cancrinite and Meionite. L. H. BORGSTROM (Jahrh. 3Ji17. 1915 ii Ref. 310; from Ofz1cr.s. Fitiskn V e t . SOC Pb?h. 1915 57 ,4fd. A No. 6 l-3).-TJemberg’s (1876) analysis of kalk-cancrinite from Vesuvius agrees very closely with Borg- strorn’s carbonate-meionite CaCO,,SCaAl,Si,O (A. 1915 ii 836). The physical characters and paragenesis are also in agree- ment. L. J. s. F. JADIN and A. AXTRUC (Compt. re17d. 1916 162 196-197).-The authors have examined the waters from fifteen springs in the Alps for man- gailesel and find that they are on the whole poorer in manganese than the1 natural waters of the Central Plateau but richer than those of the Vosges mountains (compare A. 1914 ii 378 739). The presence of iron exerts a marked influence on the manganese content increasing i t considerably. Manganese in Some Springe in the Alps. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9161005145

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 146 ABSTRACTS OF CHEMICAL PAPERS Analytical Chemistry. Use of Centrifugal Apparatus in Chemical Analysip. OTTO NOLTE (Landw. Versuchs-Stat. 1915 87 449-457).-The author gives many instances in which the centrifugal apparatus possesses advantages over the filter f o r the separation of precipitates from liquids; in many cases precipitates can be much more rapidly and accurately separated by centrifugal action than by filtration. A centrifugal apparatus is described in which the separations are effected in small silica beakers o r other vessels suitable mountings being provided f o r these in the centrifugal drum. New Form of Gas Burette. HARXRIERMANX ( C ' h e m Zezt. 1916 40 84).-A gas-measuring burette) and a levelling tube are con- nected at their lower ends with a Y-tube the stem of which is fitted into one neck of a three-necked Woulfe's bottle; the centre opening of the latter carries a three-way tap connected with a caoutchouc pressure bulb and a thermometer is fitted into the other neck. The Woulfe's bottle is filled with the absorption solution; this is forced up into the burette and levelling tube by means of the pressure bulb; the tap atl the top of the burette is then closed and the level of the solution is adjusted by means of the tap on the centre neck of the bottle( this also serving for the escape of air from the bottle when the gas under examination is admitted t o the burette.W. P. S. A tubulure is provided a t the bottom of the bottle. w. P. s. Potassium Hydrogen Carbonate as a Staadard in Acidi- metry and Alkalimetry. G.INCZE ( Z c i t . anal. Chem. 1915 54 585-602) .-Potassium hydrogen carbonate is most readily pre- pared by passing a current of carbon dioxide into an alcoholic solution of potassium hydroxide ; the salt is then recrystallised by treating its aqueous solution with alcohol. It should be stored in well-closed perfectly dry bottles and under these conditions does not undergo any change; in the presence of moisture how- ever it loses carbon dioxide. On account of its high molecular weight and thk readiness with which i t may be obtained in a pure condition the salt forms a suitable basis for standardising acid solutions. w. P. s. Estimation of Oxygen (in Water) by Winkler's Method. 11. G. BRUHNS (Chem. Zeit. 1916 40 45-46 71-73. Compare this vol. ii 47).-The following modifications of this method are recom- mended Manganous sulphate solution (1 1) is used in place of manganous chloride solution and potassium hydroxide-sodium hydroxide solution (1 1 2) in place of sodium hydroxidepotassium iodide solution.After the water has been treated with 10 drops of each of these solutions and the precipitate has settled potassium iodide is added either in the form of crystals o r as a concentratedANALYTICAL CHEMISTRY. ii. 147 solution. The mixture is then acidified with dilute hydrochloric acid (1 1) o r sulphuric acid (1 3) a de'finite volume of the water is withdrawn from the flask by means of a pipette and the remain- der is titrated with thiosulphate solution in the usual way. The influence of nitrites etc.may be eliminated by adding solid potassium hydrogen carbonate after the manganese oxide precipi- tate has settled collecting the precipitate on a filter and t'hen treating i t with potassium iodide and acid. If the water contains ferric salts phosphoric acid should be used instead of hydrochloric acid f o r acidifying the mixture; the water should be treated previ- ously with permanganate if it contains ferrous salts. W. P. S. Estimation of Sulphuric Acid in the Presence of Phosphoric Acid. TH. VON FELLENBERG (Chenz. Zeizt7*. 1915 jj 1262 ; from M i t t . Lebensmittelunters. Hyg. 1915 6 191-195).-The author confirms a statement by Baragiola and Godet that the results obtained in the estimation of sulphuric acid are too high if phos- phoric acid is also present.The error may be reduced to a mini- mum if the barium chloride solution is added drop by drop in not too great excess t o the boiling sulphuric acid or sulphate solution which should contain about 0.13 C.C. of concentrated hydrochloric acid per 100 C.C. w. P. s. The Volumetric Estimation of Total Sulphur and Sulphates in Small Quantities of Urine. JACK CECIL DRUMMOND (Bi0~7zem. ,7. 1915 9 492-507).-The benzidine method of Rosenheim and Drummond (A. 1914 ii 455) for the estimation of urinary sul- phat,es can be carried out with as little as 2 C.C. of urine by titrating the precipitated benzidine sulphate with 0.02N-alkali provided certain details of technique especially in the' matter of filtration are followed. The method is also applicable to the estimation of total sulphur in small quantities of biological material by applying the precipitation of the benzidine sulphate to the solution of salts obtained after oxidation of the material by Benedict's method.W. D. H. The Analysis of a Mixture of Alkali Sulphides Thio- sulphates and Dithionates. J. A. MULLER (B2tl.Z. SOC. chinz.. 1916 [iv] 19 8-9).-Any sulphate present is first estimated by precipitation with barium chloride in a very dilute solution slightly acidified with acetic acid. The sulphur present as sulphide and thiosulphate is estimated by titrating an aliquot portion suitably diluted and feebly acidified with acetic acid with a standard iodine solution. Another portion is acidified with acetic acid and the hydrogen sulphide removed by evacuating the flask for ten minutes by means of a water-pump the residual liquid being titrated with the standard iodine solution.From a fourth portion of the liquid the sulphide is removed as described and the liquid then made alkaline with potassium hydroxide transferred to a silver capsule and evaporated to dryness with a little potassium nitrate the residue being gradually raised to a dull red heat. I n this residueii. 148 ABSTRACTS OF CHEMICAL PAPERS. the sulphate is estimated in the usual way. Owing t o the presence of an excess of alkali sulphides the only thionates likely t o be presentl are the dithionates and thus from the above data the neces- sary percentages can be calculated. Simple Method for the Estimation of Nitrogen in Urine. VICTOR C. MYERS (Chem. Zentr.1915 ii 858; from Munch. med. Tt'och. 1915 62 1076-1077).-A modification of Folin and Farmer's method (A. 1912 ii 702) is described. The colorations are compared in an Aut,enrieth-Konigsberger colorimeter (A. 1910 W. G. ii 910). w. P. s. A Modification of the Lunge Nitrometer. W. SENFTEN ( Chenz. Zeit. 1916 40 39-40).-1n order t o obviate the necessity of dissolving the substance in the cup of the nitrometer in its usual form the apparatus is modified by connecting the upper stop-cock with the decomposition tube with a ground glass joint. The stop- cock itself is triple bored and thO nitric oxide is measured externally by transference t o a gas burette. The substance is dis- solved in sulphuric acid in the decomposition tube in a vacuum if necessary after adjusting the mercury level to the stop-cock a t the base of the tube which is then turned off.When solution is complete the mercury is slowly admitted into the tube thus expel- ling the air through the upper stop-cock and the decolmposition is then conducted in the usual way. A special reversible gas-measur- ing burette is also described having a tap a t each end an snlarge- ment a t one end and graduate'd through its entire length. I f after absosption of one constituent of a gas mixture the remaining volume is so small that it is contained entirely within the enlarged bulb the burett.e is simply reversed and the volume can then be read off on the second reversed scale. G. F. M. Detection of Arsenic in Beverages. L. VUAFLART ( A m . 'Fnlsif. 1915 8 414-415).-The author states t h a t 1 mg.of arsenic per litre of liquid can be detected by means of Bougault's reagent.. To detect arsenic in beer 250 C.C. of the sample are treated with a few drops of b,romine filtered after twenty-four hours and the filtrate then mixed with 1 C.C. of saturated sodium phosphate solution 5 C.C. of magnesia mixture and 80 C.C. of ammonia. After twenty-four hours the precipitate is collected dissolved in 20 C.C. of nitric acid (I 4) the solution treated with 2 C.C. of 20% magnesium nitrate solution and evaporated to dryness. The residue is then ignited and heated with 10 C.C. of t h e reagent A similar process is used for the detection of arsenic in wines. w. P. s. Estimation of Arsenic in Urine Blood and Animal Organs. WILHELM KOSIAN (Chem. Zentr.1915 ii 1311 ; from P71nrm. Post 1915 48 321).-One hundred and fifty grams of urine blood or serum are evaporated t o a syrup and 50 grams of this or the same quantity of finely divided animal substance etc. are warmed withANALYTICAL CHEMISTRY. ii. 149 20 C.C. of hydrochlmic acid and a quantity of potassium chlorate; ths excess of chlorine is then expelled 10 grams of ferrous sulphate are added the mixture is transferred t o a distillation flask and diluted to 200 C.C. with hydrochloric acid. The cold mixture is saturated with hydrogen chloride and then distilled in a current of the same gas until 80 C.C. of distillate have been collected in a receiver containing 50 C.C. of water. The distillate is now diluted to 200 c.c. and 10 C.C. of i t are treated with 3 C.C.of concentrated hydrochloric acid methyl-orangs is added and the mixture is titrated with. N / 10- or N / 100-potassium bromate solution until it Formulae for Use in the Indirect Analysis of Generator Gas. FRITZ HOFFMANN (Chew. Zeit. 1916 40 81-82).-The following formulze are given f o r calculating the proportions of carbon mon- oxide hydrogen and methane in generator gas after the carbon dioxide and oxygen have been removed. Letl V bel the total volume of the three gases K the volume of the carbon dioxide formed when they are burnt together C the contraction in volume S the volume of oxygen required for the combustion then Being given ; V K C. K C S. c s v. S V K . is colourless (compare Gyory A. 1893 ii 554). w. P. s. A. B. C. D. CO = 2K/3+ V-2C/3 4K/3+CI3-rS 4V/3+S/3- C K-22513- V/3 Hg z= V-K C-Is c-s V-K CH,= 2K/3+2C/3- V S-KJ3-CJ3 22513- V13 2S/3-V/3 The formulze A and I3 are principally used since the values C and h' are determined directly in the course of the analysis.W. P. S. Fractional Combustion of Gases over Copper Oxide. E. TERRES and E. MAUGUIN (Chem. Zentr. 1915 ii 1309; from J . Gasbeleucht. 1915 58 8-ll).-Hydrogen is oxidised completely when passed over copper oxide a t 250-300° but carbon monoxide is oxidised a t 305O only to the extent of 90-94%. A mixture of equal volumes of hydrogen and carbon monoxide is burnt com- pletely a t 300'. Acetylene and ethylene even when mixed with hydrogen do not busn quantitatively a t 300O; a quantity of carbon separates. Benzene behaves in a similar manner.Methane begins to burn atl 310° and the presence of hydrogen lowers this tempera- ture by a few degrees. Pure methane is oxidised completely a t a red-heat and the presence of hydrogen is without influence. A mixture of carbon monoxide and methane cannot be separated by fractional combustion but this is possible in the case of a mixture consisting of equal volumes of carbon monoxide and hydrogen on the one hand and methane on the other. I n using the Drehsclimidt- Ubbelohde apparatus notice should be taken of the fact that at high temperatures copper oxide loses oxygen and that this may lead to error. w. P. s. A New Method for the Simultaneous Estimation of Carbon Hydrogen and Mercury in Organo-mercuric Compounds. V. GRIGNARD and A. ABELMANN (Bzcll. SOC. chim. 1916 [iv] 19 25-27).-The ordinary combustion tube A is modifisd as shownii.150 ABSTRACTS OF CHEMICAL PAPERS. in the sketch a t the) exit end. It is slight'ly constricted a t e just before i t leaves the furnace and then is allowed t o project 20 cm. beyond this. I n this external portion is fitted the tube B held in position a t the open end by a rubber stopper and a t the constric- tion by a cone of calcined asbestos. B contains a spiral of gold wire and is weighed before and after the experiment and during the combustion and is kept slightly heated to prevent t'he condensation of water. Ro'und the tube B by means of the narrow tube t is kept passing a slow current of dry oxygen a t a pressure slightly higher than that existing in the major part of A in order to prevent any leakage of water or mercury vapours through the asbestos stlopper a t e.The carbon dioxide and water vapour are collected and weighed as usual. Can Carbon Dioxide in Sea Water be Directly Estimated b-y Titration ? SERGIUS MORGULIS and EVERETT W. FULLER (J. Biol. Chem. 1916 24 31-35).-1n recent investigations of the metabolism of marine organisms Moorre and his collaborators have estimated the amount of carbon dioxide produced in the water by titration with a centinormal solution of an alkali. The authors believe that this method is so inaccurate as t o invalidate the conclu- sions based on its results and quote results of experiments which in their opinion show that only approximately one-third of the carbon dioxide can be determined under such conditlions.They also suggest that an indirect method of estimation based on precipitation of the carbon dioxide with N / 5-barium hydroxide solution and the titration of the excess of this reapent with NIlO- W. G. or AT/ 5G-acid is susceptible' of development t o greacer accuracy.' D. F. T. A Copper Cathode and Iron Anode in the Electro-analysis of Brass. J. GUZMLN and J. M. FERNANDEZ LADREDA (A?tuZ. Fis. Quim. 1915 13 308-315).-An account of t.he results obtained in the electrolytic analysis of cartridge cases. A. J. W. Analysis of Copper-Aluminium-Zinc Alloys. H. GRAEFE (Chem. Zeit. 1916 40 lO2).-The following method is suggested for the analysis of alloys consisting approximately of copper 25-27% aluminium 14-18% and zinc 54-57% together with traces of silicon cadmium tin lead and iron.A quantity of 0.5 gram of the turnings is dissolved in 15 C.C. of nitric acid (D 1-4) the solution is diluted and metastannic acid is separatd by filtration. The sodution is then dilubd t o 150 c.c. heated toANALYTICAL CHEMISTRY. ii. 151 60-70° and the copper and lead deposited electrolytically; with a current of 0.2-0.4 ampere and 2-3 volts these metals are deposited within forty-five minutes whilst the zinc remains in solution. The solution is next partly neutralised with solid potass- ium hydroxide aluminium zinc and iron are precipitated by the addition of Eodium carbonate the precipitate is collected washed with hot water and dissolved in a very small quantity of dilute (I :4) sulphuric acid. The solution is treated with an excess of potassium hydroxide and the cleas liquid (except for a small precipitate of ferric hydroxide) measuring about 150 C.C.is sub- mitted to electrolysis. The copper-coated cathode should be rotated a t 600-800 revolutions per minute and the current increased from 1 to 5 amperes in steps of 1 a.mpere every ten minutes. The zinc is deposited in forty minutes and without interrupting the current is washed dried with alcohol and weighed. The electrolyte con- tains the iron and aluminium and these two metals are then separated in the usual way. w. P. s. Sensitive Clinical Method for the Detection of Mercury in Urine. 31. PERELSTEIN and J. ABELIN (Chem. Zmzlr. 1915 ii. 1027; from Munch. med. Woch. 1915 62 1181-1183).-Five hundred C.C. of the urine are treated with 10 C.C.of concentrated hydrochloric acid boile'd f o r one minute cooled 6 C.C. of ammonia 25 grams of sodium acetate and 10 C.C. of 10% ferric chloride solution are added and the mixture is again boiled. The precipi- tate formed is collected on a filter while the solution is still hot washed with a small quantity of hot water then dissolved in con- cenhrated hydrochloric acid and the mercury deposited on copper in the usual way. The deposited mercury may be identified by Qualitative Analysis of the Iron Group in the Presence of Phosphates. ROBERT GILMOUR (Chem. News 1916 113 1-3 ; 13-15).-The solution from which the metals of the silver and copper groups have been removed is boiled to expel hydrogen sulphide and the alkaline earths are precipitated as sulphates by means of sulphuric acid and alcohol.The precipitated sulphates are converted into carbonates and analysed according t o a method described previously (A. 1915 ii 486). The filtrate from the sulphates is evaporated t o expel alcohol sodium hydroxide is added followed by an excess of sodium peroxide the mixture is boiled for some minutes and filtered. The filtrate contains aluminium chromium and zinc a-nd most of the phosphate; the precipitate consists of hydroxides and phosphates of iron nickel cobalt man- ganese and magnesium. After the precipitate has been dissolved in hydrochloric acid the solution is evaporated t o dryness the residue dissolved in water and iron and phosphate separated by the basic acetate process. The filtrate from this precipitate contains nickel cobalt manganese and magnesium ; it is boiled treated with hydrogen sulphide and the nickel and cobalt sulphides are separated bj filtration.The filtrate is rendered ammoniacal the converting i t into mercuric iodide. w. P. s.ii. 152 ABSTRACTS OF CHEMICAL PAPERS. manganese is separated as sulphide and tl10 magnesium subse- quently as snimonium magnesium phosphate. w. P. s. Rapid Estimation of Iron in Presence of Organic Substances F. FERRARI (Ann. Chim. Applicata 1915 4 341-343).-The pre- liminary destruction of the organic matter usually effected when iron is t o be estimated in solutions containing hydroxylic organic acids polyhydric alcohols sugars etc. may be avoided by the following melhod. To the solution which is made up to a t least 150 C.C.and contains hydrochloric acid in excess (10.15 C.C. of the concentrated acid) chlorine water is added in small po,rtions until a faint odour of the halogen persists. A cold clear 6% solution of " cupferron " is then added drop by drop in amount a t least one-fifth greater than that necessary for the complete precipitation of the iron the liquid being kept in motion meanwhile. After fifteen t o twenty minut'es when the pulverulent precipitate has mostly collected into large friable crystalline masses these are broken up with a glass rod and the liquid filtered by aid of a filter pump the suction at first gentle being continued until the precipitate is dry when i t is washed twice with cold water acidified with hydrochloric acid and afterwards with water alone until the filtrate loses its acidity; i t is then treated several times with ammonia solution and finally washe$ again with water.After thorough drying and cautious heating t o redness in a covered plakinum crucible the precipitate is calcined in the air and the residual ferric oxide weighed. The whole of the opesations require about one and a-half hours. The method gives exact results but is not applicable in presence of copper silver lead mercury tin bismuth titanium or zirconium all these giving insoluble salts with " cupferron." T. H. P. Separation and Estimation of Nickel. T. L. WALKER (Tyans. Roy. SOC. Canada 1915 [iii] 9 93-97).-The following method has been investigated far the separation of iron from nickel and cobalt The hot solution containing iron nickel cobalt copper and lead chlorides is oxidised with a few drops of hydrogen peroxide in order t o convert all the iron into the ferric condition.After nearly neutralising with sodium carbonate xed lead is added gradually to1 the boiling solution until i t is seen t o be in excess by the distinct re'd colour of the precipitate which is heavy and granular. The separation of the iron is complete in a few minutes. After collecting the precipitate the lead and other metals are precipitated f8rom the filtrate as sulphides after which the fresh filtrate is concentrated tlo 100 c.c. 3 C.C. of concentrated sulphuric acid and 30 C.C. of strong ammonia added and the nickel and cobalt deposited on a revolving cathode. It is found that nickel and iron can be separated satisfactorily in this way but not cobalt and iron there being about a 10% loss with cobalt. Litharge does not give1 any better result with cobalt than does red lead.ANALYTICAL CHEMISTRY.ii. 153 Neumann's method (Chem. Zeit. 1901 25 731) fw the separa- tion of nickel from iron in steel and matte is found to be unsatiS- factory. Cobalt may be deposited successfully from chloride solutions under the following conditions To the solution of cobalt chloride containing 0.13 gram of cobalt are added 3 C.C. of concentrated sulphuric acid 30 C.C. of strong ammonia solution and water to 150 C.C. Deposition is complete in twenty minutes a t a revolving cathode using 4 amps. and 5 volts. The accuracy of the dimethylglyoxime method for nickel is about the same as the red lead method.T. S. P. Rapid Analysis of Commercial Antimony Sulphide. A. HUTIN (,4nn. ChZm. aital. 1916 21 3-7).-Moisture and calcium sulphate are estimated by the usual methods and free sulphur by extracting the sample with acetone. Commercial antimony sulphide consists chiefly of a mixture of the tri- and penta-sulphides; these are converted into antimony tetroxide when ignited j n the presence of mercuric oxide and their quantity can be calchlated from the weight of tetroxide obtained. The total quantity of antimony can also be estimated by reduction in a current of hydrogen. Samples which contain antimony tetroxide are not completely soluble in JAROSLAV M~LBAUER ( C h r n . Zeit. 1916 40 l08).-Antimony glass consists essentially cf antimony oxide (90.5%) and antimony sulphide (8-7%) and these two constituents may be estimated as follows 1 gram of the finely divided material is boiled f o r five minutes with 100 C.C.of dilute hydrochloric acid (1 :4) the liquid is filtered through asbestos the insoluble portion washed first with the dilute acid then with water dried and weighed. The insoluble portion is now washed with a mixture of concentrated t'artaric acid solution and dilute hydrochloric acid and after the total filtrate has been neutralised with sodium hydroxide sodium hydrogen carbonate is added t o the solution and the latter titrated with N/lO-iodine solution. The1 result gives the quantity of antimony oxide present. The insoluble residue of antimony sulphide is then dissolved in concentrated hydrochloric acid the solution boiled t o expel hydro- gen sulphide and titrated with / 10-iodine solution undm the same conditions. w.P. s. boiling hydrochloric acid. w. P. s. Rapid Analysis of the So-called Antimony Glass. Estimation of Titanium in Ferrotitanium. G. EOHL (Chem. Zeit. 1916 40 105-106).-Gooch7s method as modified by Thorn- ton (A 1912 ii 1000) was found to yield concordant results but these were lower by about 0.8% than those obtained by volumetric methods. Of the latter thO methylene-blue process (A. 1913 ii Estimation of Methyl Alcohol in Ethyl Alcohol. G. REIF (Chem. Zentr. 1915 ii 1056-1057 ; from Arbeit. H. Gesundh.- *4mt. 1915 50 50-56).-The method depends on the fact that VOL CX. ii. 7 1079; 1914 ii 73) is rapid and accurate. w. P. s.ii. 154 ABSTRACTS OF CHEMICAL PIPEKS.methyl iodide reacts with methyl sulphide in the cold to form tri- methylsulphonium iodide according to the equation Me1 + SMe = S1Lle31 wliilst the cosresponding ethyl compound is not formed a t the ordinary temperature if the quantity of methyl iodide in the mixtiire of methyl and ethyl iodides is not too small but in this case its formation can- be prevente'd by the addition of ether. The trimethylsulphonium iodide behaves as a salt of hydriodic acid and can be estimated volumetrically. The mixture of the alkyl iodides is obtained as described by Wirthle (A. 1912 ii 607) and the specific gravity of the mixture will indicate approximately the quantity of methyl iodide present. Two C.C. of the iodide mixture are placed in a 20 C.C.flask and if the quantity of methyl iodide exceeds 5% 2 C.C. of methyl sulphide are added; otherwise only 1.5 C.C. of methyl sulphide and 0.5 C.C. of dry ether are added. The flask is closed placed in a desiccator a t 20° for twenty-four hours the trimethylsulphonium iodide is then rinsed on t o a dry filter with dry ether and washed with the same. The crystals are now dissolved in water and titrated with silver nitrate solution. One mol. of silver nitrate corresponds with 1 mol. of methyl alcohol. F o r the estimation of methyl alcohol in brandy a preliminary test is first made as described by Wirthle (Zoc. czt.) t o detect the actual presence of this alcohol. One hundred C.C. of the sample are then treated with 10 C.C. of N/1-sodium hydroxide solution and distilled in an apparatus fitted with a Le Be1 still-head the quantity of distillate collected being 10 C.C.more than the amount of alcohol present. The quantity of total alcohol is now estimated in the distillate and from the result is calculated the number of C.C. of the distillate corresponding with 10 C.C. of alcohol. This quantity of the distillate is used for the preparation of the mixed iodides; the boiling point observed during the distillation will indicate the proportion of methyl alcohol present and consequently the quan- tities of iodine and phosphorus t o be used but an excess of 1 gram of iodine per 10 C.C. of the alcohols is without influence. When large quantities of methyl alcohol arel present i t is recommended that the boiling point of the brandy should be closely observed so that a distillate containing approximately 10% of methyl alcohol may be obtained.The mixed iodides are then treated as above described. w. P. s. Estimation of Methoxyl in Compounds Containing Sulphur. ALFRED KIRPAL and THEODOR BUHN (Monatsh. 1915 36 853-863. Compare A. 1914 ii 497).-The authors describe improvements in their modification of the Zeisel method for the estimation of methoxyl. They find that i t is not necessary to use hydrogen and t h a t a current of carbon dioxide gives satisfactory results. The pyridine to absorb the methyl iodide is now enclosed in two small bubbling tubes wholly composed of glass the only necessary con- nexion being for the attachment to the remainder of the apparatus. After evaporating off the pyridine in a dish the remaining meth- iodide is dissolved in w a k and titrated with N / 1 0 silver nitrate solutioa using sodium chromate as an indicator.ANALYTICAL CHEMISTRY.ii. 155 With this modification of the Zeisel process there is no need for a pure hydriodic acid because the common impurities for example hydrogen sulphide and phosphine do not affect the pyr- idine. The new method is also applicable t o the estimation of the methylimide group but is of no value for the estimation of ethoxyl as ethyl iodide is only partly absorbed by the pyridine. This method is also satisfactory f o r methoxyl estimations in sulphur compounds but here the advantage over the Zeisel process is not so great as a t first appears because the latter can be made t o give accurate results if the mixture of gas and vapour from the digestion flask is first passed through a slightly acidified solution of cadmium sulphate before reaching the silver nitrate solution.I n this case any hydrogen sulphide is precipitated as cadmium sulphide. The unf avourable and inaccurate results obtained by Benedikt and Bamberger (A. 1891 1296) who endeavoured to effect a similar result by the use of cadmium iodide solution is explained by the fact t h a t with this reagent the cadmium sulphide produced tends t o remain in part in colloidal solution in which form i t is more active and reacts with the methyl iodide giving methyl mercaptan. Experimental results are given indicating the applicability of the Zeisel method with the use of cadmium sulphate t o the estimation of methoxyl and ethoxyl groups in compounds containing sulphur in various states of combination.Detection of Glycerides by the Magenta-Sulphurous Acid Reagent. MAURICE FRANSOIS ( J . Phnrm. Chim. 191 6 [vii] 13 65-77).-A modification of a test for glycerol described recently by Franqois and Boismenu (A. 1915 ii 110) may be used for the detection of glycerides in the presence of paraffins waxes resins etc. The substance mixed with sand is heated in a test-tube for ten minutes nearly t o redness and the vapours produced are con- ducted into another test-tube containing a quantity of the magenta reagent (sulphurous acid 220 c.c. 0.1% magenta solution 30 c.c. and concentrated sulphuric acid 3 c.c.) ; white fumes produced a t the commencement of the heating should be prevented from coming into contact with the reagent by removing the source of heat for a few moments a t a time.The tesbtube containing the reagent is then heated in a boiling water-bath for fifteen minutes. If glycerides are present in the substance tested the reagent is coloured red while cold and the coloration changes to blue on heating; paraffins waxes resins and caoutchouc yield vapours which give a red coloration with the cold reagent but the latter becomes colourless when heated. The author also discusses the mechanism of the formation of the red and blue colorations. G. ADANTI (Boll. Chin2. Farm. 1916 55 33-35).-The method described by the author is identical with Bertrand’s method (A. 1907 ii 136). D. F. T. w. P. s. Indirect Estimation of Sugars.T. H. P. The Fehling-Soxhlet Method of Estimating Sugar. RUOSS (Zeitsch. anal. Chem. 1916 56 1-23).-The author gives 7-2ii. 156 ABSTRACTS OF CHEMICAL PAPERS. tables sliowiiig the quantities of sugar solutions (containing from 0.1 t o 1% of reducjiig sugar) required t o seduce 10 C.C. of Fehling’s solution. I n the titration of Fehling’s solution with the sugar solution the end-point is found by filtering the solution after the bluish-green coloration has disappeared acidifying the filtrate with acetic acid and testing with potassium ferrocyanide solution. If a brown coloration is obtained the titration is repeated adding more of the sugar solution until the filtered solution ceases t o give a coloration with f errocyanide. If the sugar solution contains nitro- genous substances the end-point is ascertained by acidifying the solution with acetic acid containing sodium chloride and adding a small quantity of potassium thiocyanate. The cuprous salt forms a precipit’ate whilst any cupric salt remains in solution and gives a coloration on the addition of ferrocyanide solution.I n solutions containing from 0.01 t o 0.1% of reducing sugar 10 mg. of sodium potassium tartrate should be added to the sugar solution in order to prevent the precipitation of cupric oxide from the Fehling’s solution. Iodometric estimation of the excess of cupric salt remain- ing after Fehling’s solution has been partly reduced by a sugar solution yields untrustworthy results owing t o the action of oxidised sugar compounds on the liberated iodine.w. P. s. Comparative Action of Sucrose and Invert-sugar on the Cupropotassic Solution. L. MAQUENNE (Coin@. !~-eiad. 19 16 162 145-149. Compare this vol. ii 56).-A study of the varia- tion of the reducing powers of invert-sugar and sucrose with varia- tions in temperature and duration of heating. Starting from 70Q there is a very slight steady rise in the reducing power of invest- sugar with rise in temperature but f o r sucrose the increase is much more marked particularly from 90° to looo. Working with mixtures of these sugars the most satisfactory temperature is 70° where under the given conditions the reducing power of invert- sugar is eight to ten thousand times greater than that of sucrose. For temperatures above 6 5 O the time of heating has very little effect on thel reducing power of invert-sugsr but in the case cf sucrose the duration of heating has a very marked influence on the reducing power which f o r temperatures in the neighbourhood of 70° is almost exactly proportional to the time of heating.W. G. The Estimation of Reducing Sugars In the Presence of an Excess of Sucrose. L. MAQUENNE (Compt. rend. 1916 162 207-213. Compare Saillard this vol. ii 55).-The author has studied the effect of temperature and duration of heating on the estimation his conclusions being in agreement with those of Saillard (7oc. cit.). He has also examined the effect of varying the amount of sucrose present on the estimation of small quantities of reducing sugars. The results show that in the) case of products poor in invert- sugar 20 grams of sugar should be used when working with an external temperature of 6 5 O o r looo and 10 grams when working with boiling solutions the total volumes of liquid used being 42.5 C.C.and 36.2 C.C. respectively. The method of estimationANALYTICAL CHEMISTRY. ii. 157 should be adapted to the case under examination using the metho,d based on the separation of the cuprous oxide f o r products rich in invert-sugar and the thiosulphate method f o r products poor in invert-sugar. It is necessary to carry out the reduction as soon as possible after the sugar is dissolved and t o titrate immediately after the reduction and cooling. W. G. Use of Yeast for tbe Invereion of Sucrose and the Estima- tion of the Latter Polarimetricallg or Chemically.H. PELLET (BuZZ. A ssoc. C'him. Sucr. Dist. 1915 33 29-30).-The addition of sodium salicylate prevents alcoholic fermentation when sucrose is inverted by yeast and since larger proportions of yeast may b0 used the time required for the inversion is shortened. The results obtained in the estimation of sucrose in molasses when the sugar lias been inverted with yeast treated with sodium salicylate agree with those found by the ordinary inversion method. W. P. S. Preparation of Very Active Salioylated Yeast for the Inversion of Sucrose. H. PELLET (Bdl. Assoc. Chinz. Suer. Dist. 19 15 33 30-33).-Yeast is liquefied immediately when treated with 756 of its weight of sodium salicylate; the solution thus obtained retains its activity (inverting power on sucrose) f o r several months and a quantity of it corresponding with 3 grams of yeast is capable of inverting 3.5 grams of sucroge within twenty minutes. w.P. s. Uee of Different Substances in the Preparation of Invertase Solution. Possible Eources of Error. H. PELLET (Bzdl. Assoc. Chim. Sucr. D i d . 1915 33 33-34).-Thymol chloroform and formaldehyde have been used in the preparation of invertase solution from brewers' yeast; whilst the former is optically inactive and does not reduce Fehling's solution the last two in dilute solution alt'hough optically inactive reduce1 Fehling's solution. An error may therefore be1 introduced in the estimation of the cupric- reducing power of sugar solutions t o which invertase solution con- taining either of these substances has been added.Sodium sali- cylate is to be preferred t o any of the above substances in the w. P. s. preparation of invertase solutions. Estimation of Raffinose by Means of Different Yeasts. H. PELLET (Bit!!. ,4ssoc. Chim. Suer. Dist. 1915 33 41).-The different' actions of top and bottom fermentation yeasts on raffinose noted by Hudson (A. 1914 i 1147) have been investigated by the author and found t o be as stated; the method of estimating raffinose described by Hudson and Harding (A. 1915 ii 803) may be used far the analysis of molasses containing a small quantity of raffinose. It is mentioned that 1 gram of anhydrous raffinose when inverted with hydrochloric acid yields 0.765 gram of reducing sugar; inverted with top fermentation yeast i t gives 0.745 gram and with bottom fermentation yeast 0.965 gram of reducing sugar all expressed in terms of invert-sugar.w. 9. s.ii. 158 ABSTRACTS OF CHEMICAL PAPERS. Detection of Small Quantities of Oxalic Acid in Wine. HANS KREIS and W. I. BARAGIOLA (Chem. Zentr. 1915 ii 810-811 ; from Schweiz. Apoth. Zeit. 1915 53,397-400).-0xalic acid is added occasionally t o wine to decrease the quantity of calcium salts present and t o increase the " residual acidity"; even when the quantity of oxalic acid added is insufficient t o precipitate the whole of the calcium a small quantity of oxalic acid remains in solution owing t o the solubility of calcium oxalate in the presence of tartaric acid. To detect a small quantity of oxalic acid in wine 50 C.C. of the sample are heateld to boiling 3 C.C. of 5% calcium chloride solution are added and the mixture is rendered ammonia- cal; acetic acid is now added t o the hot solution until the latter is just' acid in reaction (an excess of acid must be avoided) the mixture is cooled submitted t o centrifugal action and the sediment examined under the microscope.Characteristic crystals of calcium oxalat'e will be observed if tlhe wine contained as little as 0.02 gram of oxalic acid per litre. Still smaller quantities (0.01 gram per litre) of oxalic acid may be de€ected by treating 50 C.C. of the wine (cold) with 2.5 C.C. of 5% calcium chloride solution 2.5 C.C. of acetic acid and 5 C.C. of saturated sodium acetate solution. After twenty-four .hours the mixture is shaken in order to disturb the sediment of calcium oxalate (if present); the greater part of the precipitated calcium tartrate adheres t o the bottom of the vessel.The liquid is now submitted to centrifugal action the sediment transferred to a small drawn-out tube again submitted t o centri- f ugal action and examined microscopically. The calcium oxalate contained in the cell tissue of grapes does not find its way into the) must o r wine. w. P. s. Acidimetric Estimation of Oxalic Acid Using Methyl- orange aa Indicator and its Estimation by t h e Iodide-Iodate Method. G. BRUHNS (Zeitsch. a?znZ. Chewz. 1916 55 23-51).- Oxalic acid may be titrated accurately with alkali solutions using methyl-orange as indicator provided that an equivalent quantity of calcium chloride1 solution is added when the acid has be'en almost completely neutralised. Without the addition of calcium chloride the end-point of the titration is not shasp owing to the tendency of the added alkali t o form hydrogen salts with the acid.The iodide-iodate method is not satisfactory when applied to oxalic acid; the liberation of iodine is extremely slow towards the end of the reaction and if calcium chloride is added the results obtained are slightly too low. w. P. s. Modification of the So-called Mohler's Reaction for Benzoic Acid. J. GROSSFIELD (Chem. Zentr. 191 5 ii 1313-1314 ; from Zeitsch. Nahr. Genussm. 1915 30 271-273).-Von der Heide and Jacob's method (A. 1910 ii 359) of carrying out Mohler's test (compare Robin A. 1908 ii 1078) is trustworthy but somewhat hdious and the reduction of t'he dinitrobenzoic acid with ammon- ium sulphide has little advantage.The author modifies the method as follows The dry alkali benzoate residue is mixed with 0.1 gramANALYTICAL CHEMISTRY. ii. 159 of potassium nitrate and 1 C.C. of concentrated sulphuric acid the mixture is heated for twenty minutes on a boiling water-bath then cooled diluted with 2 C.C. of water again cooled and treated with 10 C.C. of 15% ammonia and 2 C.C. of 2% hydroxylamine hydro- chlmide solution. A red coloration devedops more o r less rapidly according to the amount of benzoic acid present; the coloration develops more quickly if the mixture is heated and reaches it6 greatest intensity when the mixture is cooled. I n the colorimetric estimation a standard iron solution (containing 1 mg. of Fe,03 per c.c.) mixed with thiocyanate solution may be used for the com- parison.w. P. s. Analysigl of Medicated Drinks. B. H. ST. JOHN ( J . SOC. Chem. Itzd. 1916 35 68-69; from J . Assoc. Off. Agric. Chem. 1915 1 343-345).-The acidified sample is extracted with a mixture of chloroform and alcohol and the acids present are transferred to aqueous solution by washing the extract with sodium carbonate solution. Caffeine if present is then estimated by evaporating the washed chlcrof o m solution to dryness. I n the sodium carbonate extra& salicylic acid is estimated by adding an excess of iodine and after warming for an hour collecting and weighing the precipitate; its weight multiplied by 0.4657 give6 the amount of sodium salicylate present. Saccharin ” and bennoic acid which are also present in the sodium carbonate extract are estimated the one by conversion into its silver salt and the other by eteam distillation.Phosphoric acid is precipitated directly from the beverage as ammonium magnesium phosphate which is converted into phosphomolybdate and back again to ammonium magnesium phosphate and weighed as pyrophosphate. Glycerol is estimated by the American official method f o r the estimation of this substance in wines but since the residue of glycero’l obtained may contain caffeine and other substances it is oxidised with permanganate and the glycerol calculated from the amount of oxalic acid pro- duced. G. F. M. Melting Point of Salicylic Acid and a Test for the Presence of p-Hydroxybenzoic Acid. HENRY L. SMITH (Analyst 1916 41 3-5) .-Salicylic acid prepared from different sources and dried over sulphuric acid under reduced pressure had m.p. 158.5O; p-hydroxybenzoic acid melted a t 213.5O the same melting point being obtained after crystallisation and drying over sulphuric acid. For the detection of phydroxybenzoic acid in salicylic acid the formation of basic calcium salicylate which is leas soluble than the calcium salt! of p-hydroxybenzoic acid may be employed to concen- trate the latter acid. The salicylic acid to be tested is mixed with an excess of calcium hydroxide and water evaporated to dryness and the residue extracted with water. The aqueous extra& is acidified extracted with ether and the ethereal extract evaporated. When an ethereal solution of this residue is allowed to evaporate on a microscope slide the phydroxybenzoic acid crys-ii.160 ABSTRACTS OF CHEMICAL PAPERS. tallises in tufts which are quite different in appearance from the crystals of salicylic acid seen a t the same time. w. P. s. New Reaction of Picric Acid and its Application. J. CASTETS ( J . Pkarm. Chim. 1916 [vii] 13 46-49).-The reaction depends on the formation of 2-bromo-4 6-dinitrophenol and the red coloration which this substance gives with ammonia vapour or potassium cyanide. A solution containing picric acid is treated with bromine water heated t o boiling cooled and extracted with ether. The ethereal solution is separated and divided into two portions one of which is evaporated and the residue treated with ammonia vapour; a red coloration is obtained which is destroyed by an excess of ammonia o r by the addition of water.The other portion is evaporated drop by drop on a piece of filter p a p r ; a red coloration is obtained if the paper is then treated with ammonia vapour or with a drop of potassium cyanide solution and again dried. For the detection of picric acid in urine 100 C.C. of the sample are acidified with 2 C.C. of hydrochloric acid and extracted with chloroform. The chloroform solution is evaporated the residue dissolved in water treated with bromine and the test carried out as described. I n the case of beer the liquid is evapor- ated the1 residue treated with alcohol f o r twelve hours the alcoholic solution then decanted filtered evaporated the residue dissolved in water the solution acidified and treated as described for urine.The test will detect the presence of 5 mg. of picric acid per litre of urine. w. P. s. Estimation of Uric Acid in Blood. CARL MAASE and HERMANN ZONDEK (Cherri. Zentr. 1915 ii 858-859; from Miinch. med. T170ch. 1915 62 1110-llll).-Fivel C.C. of the blood are boiled with the addition of 25 C.C. of iV/lOO-acetic acid the hot mixture is filtered the coagulum is washed with 60 C.C. of boiling water containing 0.5 gram of sodium acetate the filtrate is acidified with 2.5 C.C. of 50% acetic acid and evaporated tlo a volume of 5 C.C. This residual solution is neutsalised with sodium carbonate solution transfe'rred t o a flask 2.5 C.C. of saturated sodium carbonate solution and 1 C.C. of Autenrieth's phosphotungstic acid reagent are added the mixture is diluted to 25 c.c.and after ten minutes the colora- tion is compared with a standard scale in the Autenrieth-Konigs- berger colorirneter (A. 1910 ii 910). To correct f o r the influence of other blood constituents (tyrosine and peptone) 0.5 mg. is deducted from the result obtained. w. P. s. Sensitive Method for the Examination of Oils. A. MAZZARON (Chem. Zentr. 1915 ii 1316-1317; from Staz. sperim. agrar. ital. 1915 48 583-594).-The method depends on the measurement of the quantity of sulphur dioxide evolved when an oil is treated with concentrated sulphuric acid. Twenty C.C. of the oil are placed in a flask connected with an absozption vessel containing a definite quantity of N/lO-iodine so'lution and 5 C.C. of sulphuric acid (D 1.8417) are added to the oil.A current of air is drawnANALYTICAL CHEMISTRY. ii. 161 through the apparatus the mixture in the flask is shaken for fifteen seconds and the current of air continued until all the sulphur dioxide has been absorbed by the iodine; the excess of iodine is then titrated with thiosulphate solution. The reaction should be carried out a t a temperature of 20°. The number of C.C. of N / 10-iodine solution required to oxidise the sulphur dioxide evolved from 20 C.C. of an oil is termed the sulphur dioxide number of the oil. This number f c r various oils was found t o be as follows Olive oil 2.4; sesame oil 49-5; cottonseed oil 137.5; maize oil 65; soja-bean oil 223; r a p oil 15; earthnut oil 7. There does not appear t o be any definite relation between the sulphur dioxide number and the sulphuric acid thermal number of the oils.w. P. s. EJtimation of Fat (in Animal Substancep etc.). HELMAN ROSENTI-IAL and P. F. TROWBRIDGE ( J . Biol. Chem. 1915 20 7 11-7 17).-Whilst Soxhlet’s method (simple extraction with ether) yields trustworthy results in the case of such substances as pork fat where! the fat is the only soluble substance present it is not trustworthy f o r the estimation of fat in blood liver etc. and for the latter ,purpose the authors prefer the following modification of a method proposed by Liebermann and Szekely (A. 1898 ii 655). The sample (20 grams of blood or 10 grams of liver) is heated on a water-bath f o r two hours with 30 C.C. of 20% sodium hydroxide solution the warm solution then transferred to a separ- ating funnel acidified with 35 C.C.of 20% hydrochloric acid (I) 1*1) cooled and extracted with ether. The ethereal solutions are evaporated the residue is dissolved in about 25 C.C. of light petroleum (b. p. 30-50°) 15 C.C. of 95% alcohol are added and the solution is titrated with AT/ 20-alkali solution using phenolphthalein as indicabor. The result is calculated into neutral glyceride. The authors also prefer this method t o that of Kumagawa and Suto (A. ,1908 ii 331) as in the latter there seem t o be many possibilities of e.rror in the separation of the unsaponifiable substances. w. P. s. Estimation of Formaldehyde in the Presence of Acetone. J. BOES and H. WEYLAND (Chem. Zentr. 1915 ii 982-983; from Hyg. Rundschau 1915 25 657-663).-A definite quantity of the f ormaldehycle solution containing acetone is treated in a stoppered flask with an exces of neutralised ammonium chloride solution ; litmus solution is added followed by an excess of N/1-sodium hydroxide solution and after one hour the mixture is titrated with N / 1-acid.The reaction proceeds according to the equation 4NH4C1+ 6CH20 + 4NaOH = C,H,,N + 4NaCl+ 10H,O. w. P. s. Analysis of Vanillin. J. F. SACHER (Chem. Zentr. 1915 ii 1027 ; from Deutsch. Parfumerie Z e i t . 1915 1 187-188).-The method propoeed depends on the fact that vanillin in alcoholic solution can be titrated with N/lO-mdium hydroxide solution usingii. 162 ABSTRACTS OF CHEMICAL PAPERS. phenolphthalein as indicator ; the end-point of the titration is sharp. The result of the titration will indicate whether or not small quantities of foreign substances are present. w.P. 8. Significance of the Strophanthin Reaction which is Obtained by the Action of Sulphuric Acid on Stropbauthus Seeds. ALESSANDRO BALDONI (Chem. Zentr. 1915 ii 984-985 ; from Arch. Farmacol. sperim. 1915 19 511-528).-Fresh strophanthus seeds (St. Komb6) give a green coloration when t,reated with con- centrated sulphuric acid but the reaction is not obtained with old seeds. I n some cases where a reaction is not obtaine'd with the concentrated acid a coloration is given when 80% acid is used; 50% sulphuric acid never yields a reaction. Exposure of the seeds to sunlight causes a decrease in the intensity of the coloration. The substance in the seeds which gives the reaction can be extracted partly by means of ether or 95% alcohol but not by light petroleum.Although the reaction will not distinguish between the various strophanthins it is useful in conjunction with other tests. w. P. s. Estimation of Urea and Extractives in Urine by the Xanthhydrol Method. L. MAESTRO (Chem. Zentr. 19 15 ii 984 ; from Arch. Farmacol. sperim. 1915 19 572-576).-A modifica- tion of this method (A. 1914 ii 506 593) is described. One C.C. of the urine is mixed with 9 C.C. of water and 20 C.C. of glacial acetic acid and 5 C.C. of at 6% solution of xanthhydrol in glacial acetic acid are added in five equal portions a t intervals of ten minutes. After one hour the precipitate is collectesd washed with methyl alcohol dried and weighed; its weight multiplied by 142.857 gives the quantity of urea per litre of the urine.The extractives may be estimated in the filtrate. w. P. s. Purification of the Residues of the Ether and Chloroform Extracts in the Forensic Detection of the Alkaloids. A. CARDOSO PEREIRA (Chem. Zeit. 1916 40 39).-The residues from the ethereal or chloroform extracts in forensic analysis may be completely freed from ptomaines by boiling the original tartaric acid extract after extraction with ether with a few C.C. of per- hydro1 for a few minutes and then proceeding with the analysis in the usual way. Strychnine nicotine and coniine are unaffected by t'his treatment but marphinel is converted into oxidation products. G. F. M. G. FENDLER and W. STUBER (Chem. Zentr. 1915 ii 1315; from Zeitsch.ATahr. Genussm. 1915 30 274-277. Compare A. 1914 ii 757).-A method described by Burmann (A. 1910 ii 465) was found to be untrustworthy. w. P. s. Estimation of Caffeine in Coffee. Detection of Safflower -in Saffron. G. VICARI (Chem. Zentr. 1915 ii 1318; from Mitt. Lebensmittelunters. Hyg. 1915 6 195-197).-The phoecpho'mdybdic acid test described by Verda (A,,ANALYTICAL CHEMISTRY. ii. 163 1914 ii 305) is useful for the detection of safflower (Carthamus tinctorius) in saffron; the latter gives a hlue coloration whilst Distinction between Erythrosin and Rose-Bengal. Estima- tion of their Commercial Value. ALEXAXDRE LEYS ( A m . Chi1)z. anal. 1916 21 25-32).-Erythrosin the sodium salt of tetra- iodofluorescein contains 57.7% of iodine and is free from chlorine; its solutions are practically free from fluorescence. It is however rarely met with in a pure state in commerce a portion of the iodine being replaced by chlorine ; these mixed halogen compounds may exhibit fluorescence particularly when the halogens are attached to both the phthalic and resorcinol nuclei.Rose-bengal the sodium salt of tetraiododichlorofluorescein contains 53.53% of iodine and 7.48% of chlorine and is less valuable than erythrosin. Estimations of the iodine and of the ratio of iodine t o chlorine in a sample will give information as t o whether it is pure erythrosin. The matesial should be extracted with alcohol t o separate mineral substances the alcoholic solution then evaporated and the residue dried a t looo. A weighed portion of this residue is fused with a mixture od potassium hydroxide and sodium carbonate cooled d i s solved in water and an aliquot portion of the solution titrated in the usual way with silver nitrate solution; the iodine is then estimated in another portion of the solution the potassium nitrite safflower yields a red coloration.w. P. s. method being used for the purpose. w. P. s. Simple Apparatus for the Estimation of Small Quantities of Albumin. RICHARD WEISS (Chenz. Zciztr. 1915 ii 81 1-812 ; from Miinch. med. Woch. 1915 62 1010).-Five C.C. of phospho- tungstic acid reagent (phosphotungstic acid 1.5 gram ; hydrochloric acid 5 c.c.; and 95% alcohol 95 c.c.) are placed in a specially con- structed albuminometer and filtered urine is added until a distinct turbidity is produced.The reagent will give a turbidity with as little as 0*0001 gram of albumin and the quantity of urine added t o produce a turbidity will consequently contain this amount of albumin. The apparatus is graduated so t h a t the quantity of urine used may be noted. w. P. s. Estimation of Albumin in Urine. W. AUTENRIETH and FRIEDA MINK (Chem. Zentr. 1915 ii 1265; from Miinch. med. Woch. 1915 62 1417-1421).-A colorimetric method based on the biuret reaction is described; the albumin is first precipitated by warming the urine with the addition of acetic acid. The Auten- rieth-Koenigsberger colorimeter (A. 1910 ii 910) is used for w. P. s. Rapid Methods for the Estimation of Albumin and Sugar in Urine. EMIL LENK (Chenz. Zentr. 1915 ii 1265 ; from Deutsch. med. Woch. 1915 41 1281).-For the estimation of albumin the urine is diluted so that it contains not more than 0.4% of albumin and is filled into an Esbach tube up to the mark comparing the colorations obtained.ii.164 ABSTRACTS OF CHEMICAL PAPERS. U ; Esbach’s reagent is theii added up t o the mark K a small quantity of powdered pumice-stone is introduced the tube is closed and inverted about ten times but not shaken. The mixture becomes clear within two minutes and the estimation can be com- pleted in ten minutes. Sugar is estimated by titration against Eehling’s solution potassium ferrocyanide solution acidified with acetic acid being used as an external indicator in determining the end-point of the titration. w. P. s. Test for Drobilin in Urine and Faeces. ADOLF EDELMANN (Chem. Zentr. 1915 ii 1059; from Wien. ?din. TVoch. 1915 28 978-979).-The test depends on the formation of a red compound when urobilin is treated with mercuric chloride. Five C.C. of a 10% alcoholic mercuric chloride solution are added to 10 C.C. of the urine and the mixture is shaken with amyl alcohol; the amyl alcohol layer is then transferred to1 a test-tube and mixed with a few C.C. of clear filtered 10% alcoholic zinc chloride solution. If large quantities of urobilin are present the amyl alcohol solution will exhibit a red colour and a green fluorescence appears on the addition of the zinc chloride; with a small quantity of urobilin the green fluorescence is seez only when a ray of light is projected through the clear liquid. The reactiotn is not affected by any of the other constituents of normal or pathological urine. F o r the detec- tion of urobilin in fzces a few grams of the latter are mixed with a \-ery small quantity of water an excess of alcoholic mercuric chloride solution is added the mixture filtereld and the filtrate is treated with a few C.C. of alcoholic zinc chloride solution; a green fluorescence is seen if urobilin is preselnt. w. P. s. Detection of Bile in Soaps. F. STEINITZER (Chem. Zentr. 1915 ii 810; from Chem. Rev. Fett. Harzdnd. 1915 22 69-70). -Five grams of the soap are dissolved in hot water the solution is filtered and the filtrate treated with dilute sulphuric acid. After cooling the cake of fatty acids is separated dried between filter- paper then heated a t 70° in a test-tube with 10 C.C. of sulphuric acid (1 l) and the hot mixture treated with a few drops of 10% sucrose solution. If biliary acids are present a red to violebred coloration develops on keeping thel mixture a t 70° f o r a few minutes (Pettenkofer’s reaction). w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005146

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 165 General and Physical Chemistry. Atomic Refraction of Phosphorus in Certain Organic Phos- phorus Compounde. A. E. ARBUZOV and A. A. IVANOV ( J . Russ. Y h y s . Chem. SOC. 1915 47 2015-2027).-The results obtained by Zecchini (A. 1893 ii 353 354; 1894 ii 221) and by Kovalevski ( J . Russ. Phys. Chem. SOC. 1897 29 217) are discussed. I n the authors’ measurements the index of refraction was determined a t 20° f o r the D Ha H and H hies and the values of M(n2- 1)/ DT ( ~ 2 + 2) calculated. The values of the atomic refraction of phos- phorus are given for the D line (1) according t o Conradi; with the three compounds containing quinquevalent phosphorus the values are calculated also on the assumption t h a t all the oxygen is singly linked to the phosphorus; (2) according to Traube.The results are as follows Atomic refraction of phosphorus (D). M(n2- 1 ) <-A- -. Compound. Line. D( n2+ 2) Conradi. Traube. 42-78 42.57 43.33 P( OEt) I”H 7.45 7.12 ......... \g 43.79 D 40.67 For 0’ 40.50 5.34 41.08 For 0” 41-43 4-57 3 1.75 For 0’ 31.61 5.62 32-08 For 0” 32.35 4-86 41.90 For 0‘ 41-74 5.05 42-32 For 0’’ 42.66 4.28 5-01 ... ki POEt(OEt) D 5.47 ... POH(OEt) D 4.64 ...... PO(OEt) For the atomic refraction of phosphorus f o r the D line calculated according t o the Lorenz and Lorentz formula Kovalevski (Zoc. cit.) found from PCl,*OMe 7-72 ; PCl,*OEt 8-22 ; PCl,*OPr 8.01 ; PCl,*O*C,H 8-04 ; and PCl,*O*C,H, 7.60. The atomic refraction calculated from Zecchini’s results f o r a compound regarded by this author as P(OEt) is 2.97 ; according to Arbuzov’s results (A.1907 i 8 174 275) this compound is probably impure diethylphos- phorous acid OH*P(OEt) and recalculation of Zecchini’s result o n this assumption gives the value 4.96 f o r the atomic refraction this number agreeing well with the author’s value 4.86. F o r the four compounds of the table given above t h e authors have determined the values of D;‘’. the molecular volume and the atomic volume of phosphorus according to Kopp’s data; the last of these magnitudes has the values 32-25 26.55 27.38 and 32.79 for P(OEt) POEt(OEt) POH(OEt) and PO(OEt) respectively VOL. cx. ii. 8ii. 166 ASSTtlACTS OF CHEMICAL YAP EKS. For the same four compounds the ratio of the molecular volume to the molecular refraction f o r the D line has the values 4.77 4-88 4.89 and 5-07 the mean being 4.9.Further the ratios of (1) the molecular volumes and (2) the molecular refractions are fox P(OEt),/POEt~(OEt) (1) 1.03 (2) 1-Q5 ; f o r P(OEt),/ YOH(Oht) (1) 1.31 (2) 1-35 ; and for P(OEt),/YO(OEt) (1) 0.96 (2) 1.02. The ratios 1.03 1.05 1-31 1.35 and 0.96 1.02 have the approximately equal values 0.98 0.97 and 0.94. T. H. P. The Neutral Atom and the Poeitive Ion as Carriers of the Band Spdctrum and of the Series Spectrum of Hydrogen. J. SIraRIc ( A ) z n . Physik 1916 [iv] 49 179-200).-The conditions under which the many-lined (band) and the series spectra of hydrogen are emitted lead to the view t h a t the series spectrum is emitted by positively charged hydsogen ions and the band spectrum by neutral hydrogen atoms.The fact t h a t the lines of the band spectrum show no appreciable canal ray Doppler effect affords evi- dence t h a t high-speed neutral atoms are not present in any measur- able quantity in hydrogen canal rays. It is probable that these lines are emitted as a result of collisions with the canal says. H. M. 1). The Single-line Spectra of Magnesium and otner Metals and their Ionising Potentials. J. C. MCLENNAN ( J . E’~~uddin Inst. 1916 181 191-207.* Compare A 1915 ii 657).-Previous experi- ments have shown t h a t the vapours of mercury cadmium and zinc give rise t o spectra which consist of a single line when tha heated vapours are bombarded by electrons the energy of which lies within certain well-defined limits. It has now been found t h a t magnesium vapour behaves similarly the wave-length of the singleline emission being h 2852.22.The wave-lengths of the single-lines in the emission spectra of mercury cadmium and zinc have been found to be identical with those of bands in the corresponding absorption spectra and this re’lation is also shown by magnesium the absorption spectrum of which contains bands atl ~2852.22 and h2073.36. Since these lines are the first members of Paschen’s combination series v = 2,p2 - m,S and v = 1.5,s - m,Y respectively it. follows t h a t the absorption spectrum of magnesium is analogous to the spectra of the vapours of mercury cadmium and zinc. On the assumption t h a t this analogy extends to calcium stron- tium and barium and thallium it is calculated t h a t the single-line emission spectra which would be emitted by these vapours when suitably bombarded by electrons should have the wave-lengths h 4226.91 h 4607.52 h 5535.69 and h 5350.65 respectively.According to Franck and Hertz (Ber. Deut. physikal. Ges. 1914 ‘11 512) the8 single-line frequency of mercury is identical with t h a t calculated from the minimum ionising potential on the basis of the quantum theory. By the same method the author has calculated the minimum ionising potentials of all the metals referred to above. ’ and Proc. Roy. SOC. 1916 [A] 92 305-312.GENERAL AND PHYSICAL CHEMISTRY. ii. 167 It is considered however that this method of correlating single-line frequencies with minimum ionising potentials is difficult to reconcile with Bohr’s theory. A Comparison of the Arc and Spark Spectra of Nickel Produced under Pressure.E. G. BILHAM (Phil. Nag. 1916 [vij 31 163-170).-According to Duffield (A 1915 ii 658) the dis- placements per atmosphere of reversed nickel lines are greater for the arc spectrum than for the spark spectrum. I n view of the fact that the pressure of 10 atmospheres which were employed in the author’s observations on the spark spectrum coincides with a region in which Duffield’s observations on the arc spectrum show ail abnormally high rate of shift per atmosphere it has been con- sidered advisable to subjectl the data to a more rigorous comparison. The conclusion reached is t h a t the behaviour of lines easily reversed o,r tending towards reversal is approximately the same for both arc and spark liims.Differences are shown on the other hand by unreversed lines. This result is exactly the opposite of that reached by Duffield in his analysis of the data. The High Frequency Spectra of the Elements from Gold to Uranium. MANNE SIEGBAHN and EINAR FRIMAN (PhysikuZ. Zeitsch. 1916 17 17-18 *).-Measurements have been made of the wave- lengths of the stronger a-line in the X-ray spectra of the1 elements gold mercury thallium lead bismuth thorium and uranium. The relation between the atomic number and the square root of the frequency is found to be linear as required by Moseley’s formula if the atomic numbers assigned to thorium and uranium are 90 and 92 respectively. H. M. D. Absorption Spectra of the Vapours of Inorganic Salts. E. J. EVANS (Phil. Mag. 1916 [vi] 31 55-62).-The examination of the absorption spectra of the vapours of ammonium chloride mercuric and inercurous chloride cadmium chloride bromide and iodide has shown thatl the vapours have no well-defined absorption lines or bands in the region h 2500 t o h 6700.With the possible exception of ammonium chloride the salts show general selective absorption in the ultraviolet which in the case of the cadmium salts is greater for the iodide and bromide than f o r the chloride. H. M. D. H. M. D. H. M. I>. The Rotation Dispersion of Hydrogen. PAUL SCIIERREH (Physil~al. Zeitsch. 1916 17 18-21).-A theoretical paper in which i t is shown that the observed rotation of the plane of polar- isation exhibited by hydrogen in a magnetic field can be calculated on the assumption that the changes prolducd in the interior of the atom by the application of the magnetic field are in accordance with the requirements of Newtonian mechanics.The Magnetic Rotation of the Plane of Polarisation in Titanium Tetrachloride. 11. L. H. SIERTSEMA (Proc. K. AkacZ. Wetensch. d msterdarn 1916 18 925-932. Compare A. 1915 ii H. M. D. * and Phil. Mag. 1916 [vi] 31 403-406. 8-3ii. 168 ABSTRACTS OF CHEMICAL PAPERS. 610).-Thes experimental observations on the magnetic rotatory dispersion of titanium tetrachloride1 are1 shown to be in agreement with thel requirements of Lorentz’s theory. The Life of Radium. ELLEN GLEDITSCH (Amer. J. Xcz. 1916 [iv] 41 112-124).-Boltwood’s method of finding the period of radium by separating the whole of the ionium present in a uranium mineral and determining the rate of grolwth of the radium from i t in terms of the equilibrium amount of radium in the mineral has been repeated. I n the first place a solution more than six years old prepared by Boltlwood was found t o be generating radium a t the same rate as i t had done six years prelviously showing that the rate of change of ionium is very small.Four minerals were used (1) Uraninite N. Carolina containing 69.4% uranium very purs and free from alteration products. (2) Cleveite from Saetersdakn Norway containing 10% of rare earths. (3) Broggerite Raade Norway; (4) the same a very pure specimen. The ionium was removed from the solution by precipitating rare1 earths mostly thorium by oxalic acid in (1); by means of hydrofluoric acid in (2); by oxalic acid and thorium in (3); and by rare earths and hydrofluoric acid in (4).Several successive precipitations were employed the final being kept separately as a test solution so that if no radium were generated in it all the’ ionium must have been removed in the previous precipitations. The values for the radio- active constant h(year)-1 and f o r the half-period of radium from these four preparations are shown below H. M. D. I. 11. 111. IV. A X lo4 ..................... 3.71 3-90 4.22 4.14 Half period (years) ... :.. 1865 1777 1642 1774 The last two results are considered the most satisfactory I being a preliminary test and I1 being slightly uncertain on account of an accideat. The mean of I11 and IVY 1660 years agrees excel- lently with Rutherford’s value 1690 years deduced from his experiments with Geiger on the1 counting of the number of a-par- ticles emitted per second per gram of radium.I?. s. The Laws of Radioactive Transformation. A. DEBIERNE (Ann. Physique 1916 [ix] 4 309-322).-The general equation of radioactive change dn2= Alnldt -Ah,n,dt where n1 and n2 are the numbers of atoms of any two successive produds of radioactive constants A and A and the usual resulting integrations are con- sidered from a fresh point of view in which each atom is regarded as spending times t t t . . . in t’he successive forms A B C . . . A so-called ‘‘ equation of destiny” is so obtained which permits the various problelms of radioactive change t o be treated generally in a simple manner. Considerations on the Mechanism of Radioactive Changes and the Constitution of Atoms.A. DEBIERNE ( A m . Physique 1916 [ixl 4 323-345).-It is supposed that in each at<om there exists gtn element of internal disorder. I n the law of F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 169 a unimolecular chemical change which is formally that of radio- active change the element of disorder is sought in thermal agita- tion. I n radioactive change there is supposed to' be something analogous in the interior of the atom to the decoordinated motion of the molecules of a gas. This idea is discussed generally a t con- siderable length. F. 8. The Distribution of the Active Deposit of Thorium in an Electric Field. (2. H. HENDERSOX (Tmzs. LNovn Scotinn Inrt. Xci. 1914-1915 14 1-16).-A convenient form of apparatus f o r the investigation of the distribution of residual atoms in an electric field is described.Observations made with thorium in dry air show that the1 percentage cathode activity increases with the applied potential the curve expressing the relation having a close resem- blance t o the ionisation saturation curve. With an applied poten- tial of 12,000 volts the cathode activity is 100% within the limits of experimental error and there i& no evidence of the existence of neutral residual atoms. I n ethyl ether vapour on the other hand the whole of the residual thorium atoms are initially uncharged. I n mixtures of ether vapour and air the proportion of charged atoms depends on the composition of the' gas. A similar variation is indicated by the results obtained in experiments with moist air.The Branching Point of t h e Thorium Series. STANISLAW LORIA (Physikal. Zeitsch. 1916 17 6-9).-The result of Barratt and Wood (A 1914 ii 606) puts in doubt the generally accepted scheme of disintegration of the thorium series and the position of the branching point and their explanation and scheme are contrary t o the Soddy-Russel-Fa jans generalisation. The result has been confirmed but the explanation has been shown to be untenable. A well-marked inflection in the curve connecting the volatility of thorium B+C with temperature occurs a t 920° when some 35% has been volatilised. An identical behaviour is shown however by the radium8 curve. Since here the proportion between the two branches is 0.03 99.97 it follows that the explanation advanced as to the inflection a t 35% in the case of thorium namely that the number giving 35% of the a-rays of thorium-C is a distinct sub- stance so that the branching must occur before its formation does not explain the inflection.The cause of this is regarded as of chemical rather than radioactive origin and possibly is due t o the formation of several oxides of thorium-C analogous t o those of the isotope bismuth only stable within certain ranges of temperature. There is a difference in the volatility curves the same for both thorium-G and radium-C according as the active deposit is obtained directly or by electrolysis which mav be due t o formation of alloys with the supporting metal. H. M. D. This view is being further tested. F. S. The Question of Isotopic Elements.11. K. FAJANS (Phzisikal. Zeitsch. 1916 17 l-4).-Thel author now agrees with Hevesy and Paneth in their point of view as regards the potential of aii. 170 ABSTRACTS OF CHEMICAL PAPERS. metal immersed in a solution of its isotope but regarding this as merely a special electrochemizal problem proceeds to criticise the general view of isotopes taken by these’ authors. The chief subject discussed is whether the interpretation of Hevesy and Paneth with regard to their electrochemical experiments is “ new,’’ or differs merely as t o expression from the practice “ a s old as the estab- lishment of the existence of chemically inseparable elements,” of regarding 2 mixture of isotopes as one element which has been repeatedly applied by the author in describing precipitation experi- ments.Only in the case of a metal immersed in a solution of its isotope have He’vvesy and Paneth gone’ further than has been cus- tomary in regarding a mixture’ of elements as one element. Such a system however is thermodynamically indefinite and the line of argument deduced from the application of Nernst’s formula can only be applied with caution. Itl is appropriate t o designate the properties of isotopes not as identical but as equal and there remains the important task of establishing the limits within which this equality holds. F. S. The Question of Isotopic Elements. 111. G. VON HEVESY and F. PANETH (Physikal. Zeitsch. 1916 17 4-6).-With the admission by Fajans of the definiteness of the electrode potential measured by the authors the only dispute as to facts vanishes. Soddy has not raised the question as t o how a system will behave in which the isotopes are not mixed initially and it was only after the authors had .successfully isolated visible quantities of radium-D that such a case could be experimentally studied.This is an impor- t a n t supplementation but no one but Fajans would be under the impression that the authors had ascribed Soddy’s fundamental idea of isotopy to themsellves. Words such as “ our mode of representa- tion” merely arise from the fact that Fajans had attacked not Soddy but the authors. The test now applied-measurement of the electrode potential between pure’ isotopes-enables chemical indi- viduality t o be1 recognised in a much more lucid manner than in the case of the precipitatioas of mixtures of isotopes which are subject to suspicion owing t o adsosption processes and the authors’ results lead t o the conclusion that radium-D and lead are actually “ practically identical in chemical properties.” The authors prefer their term ‘‘ substitutional,” rather than “ identical ” or “ equal ” in the definition of isotopes but to pursue the problem of definition further would be t o cause the controversy to assume the aspect of a mere quibble.F. S. Electrical Resistance of Some Rare Metals ; Thermo-electric Power and Rectifying Action of Germanium. CARL RENEDICKS ( I n fern. Zeitsch. illetallographie 1916 7 225-238).-A specimen of massive cerium free from pores is found to have a specific resistance of 78.Praseodymium and neodymium give the values 88 and 79 respectively. The specific resistance1 of ruthenium is probably about 9 the actual value1 found beling higher on accountGENERAL AND PHYSICAL CHEMISTRY. ii. 171 of porosity. Uranium has a lower resistance than bismuth but the metal is not readily obtained free from carbide. The specific resistance of germanium lies between the values for silicon and tin. Measurements of the tlierrnoelectric power of gerinanium give as the value of the coefficient a against copper - 380 rt 40 microvolts per degree. Germanium has thus next to silicon the highest known thermoelectric force against copper. The fact t h a t silicon occasionally gives positive values is attributed to allotropy as grey tin is found t o be1 positive whilst ordinary t i n is negative.Germanium like silicon exhibits a marked rectifying effect. The thermoelectric current passes much more readily in one direction than in the other especially when the contact surface is fresh and the pressure light. This happens even when the point and plate in contact are of the same metal. The direction of the effect makes a purely thermoelectric explanation inapplicablel. C. H. D. Contact Electricity of Solid Dielectrics against Conducting and Non-conducting Liquids. ALFRED COEHN and JOSEF FRANKEN (A72n. Physik 1915 [iv] 48 1005-1033).-A method is described by means of which it. has been found possible to measure electrostatically the1 charge which solid dielectrics acquire when brought- into contact with aqueous solutions The contact electrical effect increases with time but' reproducible end-values are readily obtained .Solid paraffin was employed as dielectric substance and the influ- ence of electrolytes and non-electrolvtes on the contact effect was examined. The influence of electrolytes on the charge acquired by the dielectric is similar to that' which has been previously found in experiments with gases bubbled through the aqueous solutions but in the case of paraffin the electrolyte concentrations required f o r a given reduction in the magnitude of the contact effect are1 much greater than in the case of eases. This parallelism shows itself in the much greater influence of the hvdroqen ion as compared with other ions. I n all the experiments with acids i t was found possible to bring about a reversal of siqn of the contact.effect 7nv increasinq the concentration of the solutions. The difference in behaviour between acids and neutral salts is also shown in the temperature-coefficient' of the contact effect in t h a t temperature has little influence in the case of neutral salts and alkalis whereas the influence of acids increases rapidly with rise of temperature. Non-electrolytes in dilute solution have no appreciable influence cn the contact effect; a resnlt which was also obtained in experiments with gases. H. M. D. The Electrical Resistance of Acetic Acid in the Solid and Liquid Phases. J. H. L. JOHNSTONE (Tmizs. ATOWL Scoticcu Inst. Sci. 1912-1913 13 191-208).-The influence of temperature on the electrical resistance of acetic acid has been examined over the range - 8 O O to 27O and the influence of small quantities of water on the resistance determined.The acetic acid was pre'pared by fractional freezing of a sampleii. 172 ABSTRACTS OF CHEMICAL PAPERS. which contained 99.55% of acetic acid but it is not claimed t h a t water was completely eliminated by this treatment. The presence of water is indicated by thel fact t h a t a sharp change in the resist- ance was observed a t the eutectic temperature (- 26.55O) as well as a t the melting point of the acid. For a particular sample! of acid the resistance changed suddenly from 1O1O below to 8.8 x 108 above the euhctic temperature and from 1-27 x l o 9 below to 3-52 x lo7 above the) m. p. The variation of thel resistance in the interval between the eutectic temperature and the m.p is anomalous b u t can be explained in terms of the changing concentration of the liquid phase which is present. The conductivity ob the acid in this region is due almost entirely to the prenence of traces of water. H. M. D. Galvanic ( ( Exaltation” of Metals by Alcohol. CII. M. VAN DEVENTER (Ghem. TVeelcblad 1916 13 173-183).-A further con- tribution to the author’s theory of the leaking insulator. A. J. W. New Thermoelectric Method for the Study of Allotropy of Iron or Other Meta-1s. C. BENEDICKS (Cowzpt. re?zd. 1916 162 297-299. Compare) J . Iron Steel Inst. 1914 1 434).-The metal was examined in the form of a fine wire which was drawn a t a constant. velocity of 1.6 mm. per second through a small electric furnace maintained a t a constant temperature measured by a Le Chatelier couple.Ileasurements were made of the E.M.F. developed a t different. temperatures. The curve for the sample of iron examined which was remarkably pure showed a marked dis- continuity corresponding with the point A b u t for the point A no discontinuity was found. The curves obtained for this effect resemble the dilatation curves. W. G. Magneto-chemical Effect. A. N. SCHTSCHUKAREV ( J . Rws. Phys. Chem. SOG. 1915 47 1644-1668).-The author assumes t h a t tho process of chemical combination or in general of the mutual action between two impinging molecules is equivalent to an electric discharge so t h a t the medium in which such chemical process takes place will represent a collection of such discharges proceeding in all possible directions.In a magnetic field there should be an increase in the number of discharges perpendicular to the lines of the field and therefore a temporary difference’ of potential in the same direction. I n a vessel situate in a magnetic field were arranged parallel t o the lines of the field two similar pieces of platinum foil perfectly identical as regards electromotive force’. When these plates were connected through a galvanometer and the vessel was charged with ferric chloride solution no deflection was observed but addition of potassium iodide to the liquid caused an immediate deflection. This phenomenon of chemical polarisation accompanies many other and possibly all reactions. As a rule the smaller of the platinum plates becomes negatively and the larger positively electrified.With one and the same pair of platinum plates hhe deflection gradually diminishes owing to their exhaus- tion but the latter effect may be reduced by occasional immersionGENERAL AND PHYSICAL CHEMISTRY. ii. 173 of the plates in concentrated hydrochloric acid. Thus the initial magnitude of the current of chemical polarisation varies but in every case the current exhibits a very gradual diminution which probably extends over the whole time occupied by the reaction. The existence of the current of magnetic polarisation referred to1 above has been actually observed (1) with reactions proceeding freely and (2) with reactions taking place a t electrodes during electrolysis. The results obtained appear t o indicate a connection between this magnetic effect and diminution in valency.The magnetic effect is indeed o'bserved only with reactions in which there takes place a lowering of thO valency of one of the reacting ions such as occurs in the reactions between ferric chloride and potassium iodide chromium trioxide and hydriodic acid and vana- dium tetrachloride and potassium iodide. If hcwever the libera- tion of iodine takes place notl on account of the depression of the' valency of one of the reacting ions but' on account of the decom- position of a complex ion o r a non-ionised compl.~x or if the diminished valency of one of the reacting ions is compensated by increased valency of another as in the reaction 2FeCl,+ SnCl no magnetic effect is observed. Examinat'ion of a number of cases in which the magnetic effect accompanies electrodic changes leads t o the following coiiclusions Complex ions which on separation react only with water such a s OH NO SO CH,*CO CN S,O ClO give no magnetic effect but when ions f o r instance SO separating from an -ous salt unite immediately with the dissolved salt forming an -ic salt a marked magnetic effect is observed.Zn" and Fe" give no magnetic effect but Fe"' gives a very strong effect which changes its sign. With rare exceptions the1 sign of the magnetic effect is constant f o r a given reaction o r for the separation of a given ion. It appears strange that Ca" gives no effect whereas with Mg" the effect is very marked. Particularly int'ense magnetic effects are given by reactions accompanied by separation of ions of the halogens ; with bromine and iodine an almost constant negative1 effect is observed with a normal field and this is also the case with the separation of chlorine ions from a whole series of salts although with another series of chlorides a marked positive effect is observed.No effect is produced in cases where the liberated chlorine undergoes immediate combination; this is the case f o r instance with the reaction SnCl + C1,= SnCl or when a small proportiop of ally1 alcohol is added to a solution of barium chloride. T. H. P. Thermal Expansion and Compressibility of Liquids at Low Temperaturea. W. SEITZ H. ALTERTHUM and G. LECHNER (Ann Physik 1916 [iv] 49 85-92).-1n the expectation that the pro- perties of liquids would show a tendency t o approximate a t low temperatures to those characteristic of solids measurements have been made of the' change of the specific volume of a number of liquids o'f low freezing point.For isopentane and ethyl ether the coefficient of thermal expansion diminishes with falling temperature down t o -120° the lowest temperature a t which observations were 8*ii. 1‘14 ABSTRACTS OF CHEMICAL PAPERS. made. For methyl alcohol and ethyl alcohol the coefficient decreases a t first attains a minimum a t about -40° and a t lower tempera- tures increases. Carbon disulphide was found t o behave similarly the minimum in this case corresponding with a temperat’ure between -70° and -8OO. H. M. D. Thermal Expansion and Compressibility of Liquids at Low Temperatures. W.SEITZ and Q. LECHNER ( A ~ L ~ L . Yhysik. 1916 [iv] 49 93-115. Compare preceding abstract).-The compressi- bility of isopentane ethyl ether methyl alcohol ethyl alcohol and carbon disu!phide has been determined a t temperatures between Oo and -110” and at pressures up to 1000 atmospheres. As the pressure increases the tendency of the coefficient of expansion t o increase with falling temperature becomes much more marked than a t atmospheric pressure. H. M. D. [Determination of the Velocity of Sound in Gases.] C. DIETERICI (Ann. Physik 1915 [iv] 48 1122-1124).-A reply t o Schweikert’s criticism (this vol. ii 79) of the results obtained in previous measurements of the velocity of sound in gases. The results in question are shown t o be in good agreement with Schwei- kert’s own data.H. M. I>. A Criticism of van der Waals’s Equation and Some New Equations Derived Therefrom. JAMES KAM (Phil. Mag. 191 6 [vij 31 22-36).-From a consideration of the influence of a and 6 on the pressure-volume relations the author arrives a t the formula Y+a/(V+ b)2=R2’/ V as an alternative to the van der Waals’s equation. According to this formula an actual gas of density 1 / (I’ + 0) exerts the same pressure1 as an ideal gas of density 1/ V . The analysis of the formula leads to the conclusion that the density in the critical condition is for all substances two-thirds of the density of an ideal gas which a t the same volume exerts a pressure equal to the critical plessure a t the critical temperature. If the internal pressure is denoted by Pi so that the total pressure ir = P + Pi then i t is shown that the critical values of P and 1’ are equal or Y =PI$ and further that Y = 12T,/d Vc and 7rc = 11!f’,/ V according t o which the ideal gas law is applicable t o the critical condition.Experimental data in support of the validity of this relation are cited. The equality of P and Pi is supposed t o be connected with the disappearance of the surface tension and of the latent heat of vaporisation a t the critical point. When this equality obtains the cohesive f o r e s are exactly counterbalanced by the thermic pressure and the transference of a molecule from the interior of the liquid t o the space above it requires no expendit,ure o,f energy. H. M. D. The Variation of Surface Tension with Temperature.ALLAN FERGUSON (Phil. Mag. 1916 [vi] 31 37-47).-1t is shown that the variation of the surface tension of liquids with temperatureGENERAL AND PHYSICAL CHEMISTRY. ii. 175 can be represented by the! equation T=T,(l -bB)n in which T is the surface tension a t t'emperature 6 To the tension a t Oo and b and ? L are constants characteristic of the substance. Since T = O a t the critical temperature 6 it follows that 8 = 1 / h. The critical temperatures calculated in this way are found t o be in close agree- ment with the) observed values f o r some fourteen non-associated liquids which have been examined. The value of h varies from 0.002793 f o r clilorobenzene to 0.005155 f o r ethyl ether but 'IL varies very little from the mean value of 1.210. This mean value may be employed generally without seriously detracting from the accuracy of the formula.I n the group of esters R-CO,R the value of b diminishes with increase of R o r R and is greater f o r an iso-compound than for the corresponding normal ester. Moreover R and R cannot be intar- changed without alteration in 6 and this has the greater value when the more complex radicle is associated with the carbonyl group. I n esters of the series R-CO,Me the value of b is apparently con- nected with the boiling point 6 of the ester as expressed by the equation b = c / ( d - ? ~ ) 6 - 273c in which c and d are constants and / I is the number of carbon at'oms in R. The empirical relations connecting the temperature-coefficient of the surface tension of a liquid with its critical temperature which have been pointed o a t by Walden (A.1909 ii 1221 are discussed in relation to the author's formula. H. M. D. Thermodynamics and Fractional Distillation. E. CHENARD (Bull. Assoc. chim. Suer. Dist. 1916 33 47-55).-A discussion of the influence of various factors on the separation of the components of binary liquid mixtures by fractional distillation with special reference t o mixtures of ethyl alcohol and water. It is pointed out t h a t the rate of flow of the vapour and the difference in density of the components exert an influence on the fractionation which is of practical importance and may lead t o results which are quite different from those anticipated from a consideration of the thermo- dynamic equilibrium between thel liquid and vapour phases.For the construction of improved forms of distillation apparatus i t is shown that the design must be such as t o permit of free passage of the vapour and rapid removal of the condensed liquid. The frac- tionating column should be disposed horizontally or nearly so and the number of fractionating elements should be considerable. Actual elxperiments with apparatus constructed on these lines have shown t h a t much better results can be obtained than by the use of apparatus of the' usual type. H. M. D. Heats of Formation of Additive Organic Compound@. IV. Picrates. B. L. VANZETTI rmd V. GAzz.4~1~ ( 8 t t i R. Accnd. Lime; 1915 [v] 24 ii 527-532; Gnzzettn 1916 46 i 145-151. Com- pare A. 1913 ii 296).-Them heats of formation of the picrates of certain bases of the pyridine group now given indicate clearly the differences existing between compounds of picric acid with tertiary amines s ~ c h as pyridine and quinoline and those of the same acid 8"-2ii. 1'76 ABSTRACTS OF CHEMICAL PAPERS.with the corresponding hydrogenated secondary basw in which the nitrogen-containing group has lost completely the aromatic char- acter. The following are the mean molecular heats obtained in large caloriels pyridine picrate (m. p. 164O) 13-84 ; piperidine picrate {m. p. 151-152O) 20.56; quinoline picrate (m. p. 204O) 13.2; tetrahydroquinoline picrate (m. p. 141*5O) 9.9. Physico-chemical Force of Attraction. 11. N. A. KOLOSOVSKI ( J . Buss. Phys. Chem. Soc. 1915 47 2035-2037).-Reply to Gur- vitscli (A. 1915 ii 747). HENRY LE CHATELIER (Cornpi.rend. 1916 162 245-246).-A reply to Colson (compare this vol. ii 129). W. G. T. H. P. T. H. P. The Law of Solubility. Ultramicroscopy of Crystallisation Phenomena. I. P. P. VON WEIMARN ( J . Buss. Phys. Chem. Soc. 1915 47 2140-2163).- After discussing the capacity of highly disperse particles for vec- torial growth etc. experiments are described on the formation and disaggregation with the disperse particles of skeletons of sodium chloride in silicic acid gels. From the results obtained under different experiineutal conditions and the microscopic and ultra- microscopic appearance of the crystalline systems obtained a number of general conclusions are drawn. Crystalline skeletons and dendritic growths resulting from the prevention of regular crystal- line development by marked initial supersaturation or obtained in a disperse medium may be regaxded as coalitions of disperse par- ticlee which are to some extent irregularly orientated t o one' another. These1 crystalline systems in consequence of the great delvelopment of their external and internal surfaces the latter the result of rupture of the crystalline' homogeneity exhibit instability and break down into disperse particles od a different degree of dispersion ; this disaggregation is accelerated by small oscillations of the temperature.The disperse systems thus formed undergo gradual diminution of their dispersion and the disperse particles then tend t o consume) one another and thus yield crystals with com- plete outlines. The capacity for vectorial growth shown by large crystals is inherent in particles of all degrees of dispersion includ- ing those a t the extrelme limit of ultramicroscopic visioln.Precipi- tates formed by the disaggregation of dendritic systems and consist- ing of particles which do not reveal their crystalline form when examined ultramicroscopically are still undoubtedly crystalline. When dissolved these crystalline formations characterised by marked development of their external and internal surfaces o r by rupture of the crystalline homogeneity undergo disruption into disperse particles this procws preceding solution. T. H. P. Materials for Experiment ~1 Dispersoidology. I. Prepara- tion of any Substance in any Degree of Dispersion. P. P. VON WEIMARN ( J . Russ. Phys. Chem. SOC.1915 47 2133-2139).-The author d i s c u m the colloidal condition a8 a general property ofGENERAL AND PHYSICAL CHEMISTRY. ii. 177 matter (compare A. 1910 ii 940) and describes again the elxperi- ments with sodium chloride (A 1913 ii 31). Further results are given in succeeding papers. T. H. P. Materials for Experimental Dispersoidology. 11. Gels and the Process of Gelatinisation. P. P. YON WEIMXRN ( J . Rziss. L'hys. Chew. SOC. 1915 47 2163-2176).-m7hen a gel is formed by the more or less uniform gelatinisation of a liquid throughout its entire mass the. author terms i t reticulated and whe'n the gela- tinisation takes place at' definite surfaces within the liquid coarsely- cellular. A gel of the1 latter type is obtained f o r instance# when saturated aqueous barium thiocyanate is added t o saturated man- ganous sulpliate solution every drop or stream of the added liquid becoming coated with a transparent membrane of gel.Systems analogous t o coarsely-cellular gels are obtainable with ice by pouring drops of water into alcohol cooled in a mixture of carbon dioxide and ether o r in liquid air; it is difficult t o fix the gelatinous form of the ice membranes for any length of time but the structure of these1 membranes may be examined microscopically and ultramicro- scopically and is found to be identical with that of gelatinous mem- branes of barium sulphate. The formation of membranes in this case is due t o the fact that a t such low temperatures the water is able to diffuse scarcely a t all into1 the alcohol and is almost instan- taneously solidified in a highly disperse state.Reticulated gels of ice are obtainable particularly easily near the' eutectic point of the water-alcohol syskem. Membranes of coarsely-cellular gels are closely comparable with sections of correspoading thickness of reticu- lated gels cut by means of a microtome. Many observations confirm the view that the process of gelatinisation and the formation of distinctly niicrocrystalline precipitates are essentially identical and differ only in degree. The swelling spontaneous dispersoid solution and gelatinisation of sodium oleate in toluene xylene and benzene have been investi- gated the observations made being in complete agreement with those' of the same processes with barium sulphate gelatin alumin- ium hydroxide etc.confirming the conclusion that a gel is a sponge composed of highly disperse crystalline granules soaked in dispersive medium. T. H. P. Materials for Experimental Dispersoidology. IV. Disperre Systems of Cupric Chloride in Benzene P. I?. VON WEIRIARN and I. B. KAGAN ( J . Rms. Phy:. Ghem. SOC. 1915 47 2215-2251).-The conditions of formation and certain properties of the following disperse systems have been investigated With the liquid disperse phase zH,O + yHC1; with the solid disperse phase CuCl ; with the solid disperse phase aCnC1 + yCuCl2,2H2O ; with the solid disperse phase CuC1,,2H,O this being the first example found of a typical crystallo-hydrate in the disperse state; with t,he solid disperse phase CuC1,.2H,O and the complex liquid disperse phase (rH,O + yMCl + zCuC1,) and (xR,O + yHC1) ; with the solid disperse phase (xCuC12 + y copper oleate) ; with the solid disperseii.178 ABS'l'ICACTS OF CHEMICAL PAPERS. phase (xCuC12,2H,0 + y copper oleate). Confirmation is obtained of the theory according to which in a medium either almost com- pletely passive o r very active the stability of dispersoid solutions is small. The colour of dispersoid solutions is nearly identical with that of true solutions and that of coarse disperse phases but is less intense than thel latter and with a sufficiently high degree of dispersion is turbid; i t is hence possible t o judge by the colour of the course of chemical and physical transformations of disperse phases. T. H. P. Nature of the Elastic and Plastic Conditions of Matter.I. I. OSTROMISSLENSKI (2. Russ. Phys. Chern. SOC. 1915 47 1995-2014) .-The two new constants for colloids namely the elasticity point and the fatal temperature (this vol. i 54 55) permit of the characterisation of two new states of aggregation of matter (1) the plastic state in which a substance exists in the interval of temperature between the elasticity and fatal points and (2) the elastic statel corresponding with the interval between the elasticity point and the melting point. The supposition that these states of aggregation are properties of all colloids is confirmed experimentally and since the colloidal condition is common t o all forms of matter the elastic and plastic states are general forms of aggregation. The normal course of the changes in the condition of aggrega2n is expressed by the scheme solid plastic t elastic +- liquid S gats.. Many substances follow exactly this scheme1 of transformations bef ore1 reaching the temperatures a t which their molecules undergo decomposition but others melt with previous conversion into only one of these intermediate states or into neither of them.Such substances correspond with the following in- complete schemes solid = plastic = liquid solid = elastic f liquid o r solid liquid and cannot be1 obtained in the plastic or elastic condition by simple change of t'emperature. The methods availablel f o r obtaining matter in the' plastic o r the elastic state are1 as follows (1) By changel of temperature. Various individual compounds and mixtures such as caoutchouc and some of its homologues polymeric acrylic esters factis gels of gelatin etc.exist in the1 elastic condition at the ordinary temperature and others such as guttapercha camphor copper oleate paraffin wax ozokerite etc. in the plastic state. The transformation from the elastic t o the plastic state is always realisable since i t accompanies lowering of temperature but that from the plastic to the elastic condition by rise of temperature does not always occur since fusion o r decomposition may take place before the elasticity point is reached. I n such cases one of the two following methods mustl be employed. (2) By introduction of a foreign liquid. This liquid must be able to act as a medium in which the given colloid elither dissolves o r swells the process of solution being intimately con- nected with the plastic condition of matter and that of swelling with the elastic state.Solids which neither dissolve nor swell in liquid media cannot be obtained in elither the elastic or plastic state by this method. For example caouprene chloride readily swells inGENERAL AND PHYSICAL CHEMISTRY. ii. 119 carbon disulphide a t the' ordinary temperature giving an elastic substance possessing all the properties of natural caoutchouc but exhibiting instability owing t o the ease with which the carbon disulphide is lost. Again the1 compound of isoprene with sulphur dioxide (S02)nln(C5H8)S is a typical solid with a fatal temperature above the ordinary temperature; when heated i t is converted first into the plastic condition and then approximately into the elastic form but a t this point decomposition begins.If however this compound is precipitated by alcohol from its solution in hot aniline i t yields the complex n(C,H,),,(SO,) + pNH,Ph + cyEt*OH which a6 the ordinary temperature exhibits qualitatively and quantita- tively the association of elastic properties of ordinary caoutchouc its elasticity point being below Oo. (3) By supercooling liquid masses. By rapid and intense1 supercooling for instance t o - looo a liquid or fused solid may be obtained in an elastic o r plastic modi- fication a t a temperature corresponding normally with the solid form alone. This method is generally known and is used princi- pally for obtaining substances in amorphous solid vitreous modi- fications; the plastic and elastic states represent intermediate stages.Thus by rapid and profound cooline water is obtained first in the elastic then in the plastic and finally in the vitreous modification and similar behaviour is shown by almost all liquids. Substances in the plastic o r elastic condition are not to be regarded as mere mechanical mixtures of a solid and a liquid although their peculiar properties are due t o mutual action of a solid and liquid. When a liquid o r fused substance is rapidly and intensely cooled the low temperatiire1 causes reduction in the velocity with which its solid phase appears so that part of the' substance retains its liquid consistency ; into this portion the nascent solidified part swells the elastic o r plastic modification being thus obtained a t temperatures correspondinq normally with the solid phase.The following principles are deduced (1) The trans- formation of a solid into a liquid usually commences considerably below its melting point. (2) Every given temperature of a sub- stance corresponds with a definite stable equilibrium between its solid and liquid phases. With this equilibrium there corresponds with any substance a definite association of elastic o r plastic pro- perties ; in particular f o r a certain temperature interval the propor- tion of one of the phases may be zero. A colloidal solution of a solid substance! containin? the latter partly in the solid state should when heated behave in a definite manner independently of the nature of the solvent. Since also with everv temperature there corresponds a definite equilibrium between the solid and liquid phases the solid will be Converted successively into the plastic elastic and liquid states indenendentlv of the condition of xqgregation of the sin-roundinq medium; this Drocess should therefore take place both in a gaseous medium and in colloidal solution.It has been already foiind that the elasticitv point amd the fatal temnerature may be determined by means of either the substance in t.he free state or its colloidal solution. The melting points of colloidal substances are also measurable in anii. 180 ABSTRACTS OF CHEMICAL PAPERS. analogous manner t h a t is by the change in direction of the curves expressing the dependence of physical properties on the temperature (this vol.i 55). Tlie temperature thus determined would corre spond with the disappearance of the solid phase in the given colloidal solution and in reality it may be accompanied by either (1) separa,tion of the solution into two layers or (2) its conversion into a molecular disperse solution o r (3) the formation of a colloidal solution of a liquid in the same solvent. T. H. P. Non- Uni- and Bi-variant Equilibria. IV. F. A. H. SCIIREINE- MAKERS (Proc. K . Akad. TVeteilzsch. Amsterdam 1916 18 1018-1025. Compare this vol. ii 19).-A further consideration of types of equilibrium in heterogeneous systems with special refer- ence t o the general case of a syste'm of ?z components. The n + 2 equations which are required to define the univariant equilibria are not independent of one another.TWO of these equations only are required for the determination of the remainder. H. M D. Non- Uni- and Bi-variant Equilibria. V. F. A. H. SCIIREINE- MAKERS (I'roc. K . Akad. TVetensch. A msterdam 1916 18 6026-1037. Compare preceding abstract).-It is shown t h a t the different types of pressure-temperature diagram corresponding with any system of TL components may be deduced without a knowledge of tlik concentration diagram or the composition of the phases. H. M. D. Determinations in the System Lead Sulphate Sulphuric Acid and Water. A. D. DONK (Chenz. TVeekbZad. 1916 13 92-97).-An application of Schreinemakers's graphic method t o mixtures of lead sulphat,e and dilute sulphuric acid. A. J. W. Swelling of Hides in Presence of Hydrogen Ions.G. POVARNIN ( J . Buss. Phys. Ghem. Soc. 1915 47 2064-2073).-The work of other investigators notably Paessler and Appelius (Gerber- Zeit. 1902 45) in this direction is discussed. Tlie velocity with which hide-material swells in pure water is expressed by the equa- tion log [ M / ( M - Q)] = 0 4 3 4 3 4 t (l) and the swelling in presence of acid depends on the following considerations ( a ) The velocity of swelling is directly proportional t o the velocity of the acid ions in penetrating the membrane (hide) and this velocity is propor- tional to d? as was shown by Morsel and Pierce (A. 1904 ii 14) for gelatin; in absevlce of acid the swelling is proportional t o the velocity with which the ions of water pass through the membrane t h a t is t o t . ( b ) The' rate of swelling is inversely proportional t o the quantity of the1 hide-material dissolving a t the surface of contact of hide and liquid and since' this swelling is directly pro- portional to the time the rate of swelling is invers2l-y proportional to t . ( c ) The maximum swelling Jf for a given acid is equal to some constant maximum M multiplied by Lo which is a ccefficient varying with the nature of the acid; it may be assumed that k1 of equation (1) is in general equal t o some magnitude k/2.(d) TheGENERAL AND PHYSICAL CHEMISTRY. ii. 181 rate of swelling is proportional t o the index of basicity n of the acid if the latter is completely dissociated and in general it should be proportional t o the number of free hydrogen ions in the solution of the given acid.On these1 theoretical foundations the equation log [ X / (ill - Q)] = 0.4343nJc d j is constructed. It is found that Paessler and Appelius's results for five acids a t concentrations of 0*1-0*6% are' expressed satisfactorily by this equation 0.4343k having the value 0.274 whilst n is equal t o 1 or with strongly dissociated dibasic acids 2 ; M is a variable magnitude depending on the character and concentration of the acid. T. H. P. Interaction of Benzoyl Chloride a.nd m-Xglene in Presence of Haloids of Various Metals of the Second Group. B. N. MENSCHUTKIN ( J . Rprss. Phys. Clzem. SOC. 1915 47 1853-1884).- By absorption of the hydrogen chloride liberated in potassium hydroxide solution the author has measured the velocity of the reaction Pli-COCl+ m-C?H4Me = C,H3Me2Bz + HC1 a t 1 5 8 O in pres- ence of varying proportions of hzloids of metals of group 11.The following considerations have a bearing on the results obtained. When antimony trichloridel or tribromide is present (compare A. 1914 i 188 673) this forms a molecular compound with the aromatic hydrocarbon readily soluble in the latter so t'hat the re'action with the chloroanhydride proceeds in a perfectly homo- geneous medimi. The halogen salts now investigated with the possible exception of tQhose of zinc and mercury are quite insoluble in either benzoyl chloride o r sn-xylene o r in mixtures of the two and as far as can bel seen enter into reaction with neither of the relacting compounds; in these cases then the media are hetero- geneous. Further although most of the salts are kept thoroughly mixed with the liquid by a current of air passing through the latter this is not the case with such heavy salts as mercuric chloride and bromide; in these instances then the values of the velocity constiants obtained are lower than the true values.The values of the velocity constant obtained when approximately 0.5 o r 1.0 mol. of the haloid is taken per 1 mol. of each of the reacting compounds are as follows the first. figure in each case giving the absolute value followed by the relative value in brackets lCaCl X 0.0515 (1) ; 0*94CaBr 2Kz 0.0514 (I) ; 0*98SrC1 K2 0.0563 (5) ; 0*5SrBr X 2 0.0423 (16) ; 0*48BaC1 X 0.0578 (6) ; O*5BaBr K 0.0413 (9) ; 0*57CdC1 KO 0*0462 (44) ; O*5lCdBr X 0.0417 (12) ; 0*49MgCI K 0.0415 (11) ; h*51HgCI2 KO 0.0334 (243) ; l-OSHgBr K 0*0245 (3214) ; 0*53ZnCI R 0.0110 (7857) ; 0*52ZnBr2 R 0.0121 (8643).I n presence of the zinc and mercuric salts the velocity constant increases only t o a maximum value given above these maxima being obtained with 0*38ZnC12 0*26ZnBr 0~18HgCI and 0*26HgBr respectively. The values of K2 corresponding with the presence of 1.03 0.53 0.5 0.38 0.27 0.105 and O*O13ZnCl are 0.0125 0*0110 0.0106 0.0112 0.0071 0.0047 and 0.00021. The variation of IT with the concentration of the halogen salt is here quite different from t#hat found when varying proportions of antimony trichloride are present since K is then almost exactlyii. 182 ABSTRACTS OF CHEMICAL PAPERS. proportional to’ the square of the concentration of the trichloride (Zoc.cit.). The use of zinc chloride and bromide in organic syn- theses is now undelr investigation. T. H. P. Velocity of Decomposition of Electrolytes in the Light in Relation to their Degree of Electrolytic Dissociation. C. BONGIOVANNI (Gnzzetta 1916 46 i 127-135).-The fact that the instability of perchloric and nitric acids is not shown by aqueous solutions of these acids o r by the corresponding salts Ostwald (“ Principles of Inorganic Chemistry ”) regards as due to the occur- rence in the latter cases of the stable perchloric or nitric ion which is not present in the anhydrous acids. The author considers this conclusion unfounded and points out that water often has a positive or negative1 catalysing influence on the decomposition of compounds dissolved in it and further that the latter often combine with the water yielding compounds differing in stability from the anhydrous compounds.A number of cases are quoted in support of this view. The results of the author’s own experiments are as follows. -* I The velocity of decomposition of oxalic acid in dilute aqueous solution by the action of sunlight is considerably diminished by the presence of sulphuric acid and the depression of the freezing point of the solution containing the two acids is far less than the sum of the depressions observed with solutions of the two acids taken separately. According to Ostwald’s hypothesis similar behaviour should be shown by solutions of oxalic acid and potassium oxalate. I n this case however the presence! of potassium oxalate causes marked retrogression of the degree of dissociation of oxalic acid but this is not accompanied by any variation in the stability of the acid towards sunlight.Thew results appear t o exclude1 the assumption that the molecule1 of oxalic acid exhibits a stability towards light different from that of its ion. T. H. P. A Kinetic View of Catalysis. H. J. PRINS (Chenz. Weekblnd. 1916 13 127-131).-A theoretical paper. A. J. W. The Influence of Different Surfaces on the Decomposition of Methane. WILFRID ERNEST SLATER (T. 1916 109. 160-164) ,-The influence of different surf aces on the thermal decomposition of methane has been investigated in comparative experiments a t 910° in which the gas was exposed t o equal surfaces of different substances f o r equal intervals of time and the decom- position measured by the amount of hydrogen in the1 residual gas.The various substances examined were used in the form of fine powders which had been sifted through fine gauze and were disposed in two porcelain boats placed end to end along the middle portion of the electrically heated porcelain tube. The results obtained with silica alumina magnesium oxide calcium oxide barium oxide wood charcoal graphite csrborundum iron and copper show that the rate of decomposition of methaneGENERAL AND PHYSICAL CHEMISTRY. ii. 183 depends not only on the e’xtent of the hot surface which is exposed to the gas but; also on the nature of the substance concerned. H. M. D. Velocity of Hydrogenation of Fumaric Acid with Colloidal Palladium as Catalyst.A. KOREVAAR (C7zcm. Weekblad. 191 6 $13 98-107).-The author points out that the velocity of hydro- genation of fumaric acid with colloidal palladium as catalyst is dependent on the rapidity of revolution of the stirring apparatus and describes a form of stirring gear with which the velocity of revolution can be measured and controlled. A. J. W. The Metastability of the Elements and Chemical Com- pounds in Consequence of Enantiotropy or Monotropy and its Bearing on Chemistry Physics and Technics. I. ERNST COHEN (Proc. I!. ,4 Icad. Wetenseh. Am.sterdnm 1916 18 961-965). -Observations on the enantiotropic yellow and red modifications of thallous picrate are described which show that the dry substances may be heateld o r cooled far above o r below the transition tempera- ture without change.I f traces of a solvent such as water ethyl alcohol methyl alcohol o r ether are added the retardation pheno- mena are not observed. It is suggested that arrested transformation may be of frequent occurrence amongst the non-metals and chemical compounds and that’ this property is not confined to the metals. Integral Atomic Weights. I. and 11. FRANK WILLIAM DODD (Trans. iVoua Scotia Tnst. Sci. 1912-1913 13 216-221 223-227). -1. It is suggested that the properties of the elements are func- tions of integral atomic numbers which are greater than the accept’ed atomic weights t o an extent depending on the density of the element in accordance with the relation I . N-A . W = 1.8D where I . N is the integral atomic number A . W the atomic weight and l3 the density. Such properties are the specific heat and the m.p. 11. To meet the1 criticism that the relation between integral atomic number atomic weight and aensity will depend on the temperature at which the density is measured i t is suggested that each element has a natural density any departure from which is more or less accidental. LEONARD DOBBIN (Chem. News 1916 113 85) .-Avogadro’s hypothesis (1811) which was not generally accepted until some years after the publication of Cannizzaro’s ‘‘ Sunto di un corso di filosofia chimica ” in 1858 was clearly stated by Prout in his “Chemistry Meteor- ology and the1 Function of Digestion considered with reference t o Natural Theology,” which was published in 1834. Prout’s views which were adopted without knowledge of the essays of Avogadro Arnp&re and Dumas were criticised by W. C. Henry (Phi7. Mng. 1834 [iiil 5 33) but were not otherwise noticed until 1904 (see A. N. Meldrum (( Avogadro and Dalton ”) H. M. D. H. M. D. Prout in Connexion with Avogadro’s Hypothesis. N. H. J. M.ii. 184 ABSTRACTS OF CHEMICAL PAPERS Valency of the Elements. 111. G. POVARNIN (J. Rz~ss. Phys. Chem. SOC. 1915 47 1737-1769. Compare A. 1915 ii 761).- The author develops further his theory of polar affinities and dis- cusses the views of Tschitschibabin who states (“ Investigations on Teirvalentl Carbon”) ‘‘ Valency is a number denoting how many atoms are in immediate union with the given atom.” “Valency and also the degrees of saturation that is tlie store of chemical energy of an individual atom is a function of the atoms and groups entering into Combination with such atom.” “ The strength of the separate valency of each atom is not a constant magnitude but varies . . . in dependence on the remaining radicles united with the atom.” The insufficiency of these views is maintained parti- cularly with reference tot various points connected with derivatives of “ tervalent ’) carbon and i t is claimed that the author’s hypo- thesis gives more reasonable explanations of such points. T. H. P. Stesm Apparatus with Constant Water Supply. J. TRAMBICS (Chem. Zed. 1916 40 128-129).-A simple apparatus consisting of a boiler of thin metal provided with a constant level tube similar t o that used for water-baths except that’ i t is attached to’ the water- tap and has two tubes cdnnecting it with the boiler one! below and the other above tlie water level; the outlet is connected with a U-tubs which gives a pressure in the apparatus corresponding with the column of water. A mercury regulator is employed for tlie gas supply. A sketch of the apparatus is given. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9161005165

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i. 176 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. The Controlling Influence of Carbon Dioxide. 111. The Retarding Effect of Carbon Dioxide on Respiration. FRANKLIN KIDD (Proc. Roy. doc. 1916 89 [B] 136-156).-Previous work has shown that the resting-stage of the moist seed is primarily due to the narcotic action of carbon dioxide. It is now shown that the rats of anaerobic production of carbon dioxide is depressed by carbon dioxide; this passes off when the concentration of carbon dioxide is lowared. The1 same occurs in aerobic respiration; when the oxygen is deficient carbon dioxide has no retarding effect. The production of carbon dioxide in both conditions is regarded as having a genetic relationship in normal respiration the r a b of the anaerobic process acting as the limiting factor.It is “floating respiration ” (Blackman) which is retarded by carbon dioxide. W. D. H. The Action of Chlorine on the Blood. WILSON HAKE (Lancet July 10 1915).-The addition of chlorine t o blood causes the ab- sorption bands to disappear. A few bubbles of the gas renders the blood colourless the filtrate being as clear as water. Chlorine water produces a brown filtrate. When chlorine is used protein is precipitated and this is destitute of colour. The iron goes into solution as a ferric salt. W. D. H. The Effect of Isotonic Ringer’s Solution on Blood-corpuscles. 3’. H. SCOTT ( J . Physiol. 1915 50 128-139).-1sotonic Ringer’s solution and solution of sodium chloride are not indifferent liquids but dissolve out from the corpuscles protein and non-protein nitrogen.The corpuscles are thus permeable to these two kinds of nitrogenous compound. The non-protein nitrogen is probably chiefly amino-acid and urea; the protein material dissolved is not precipitable by half saturation with sodium sulphate a t 3 5 O but it. is precipitated by trichloroacetic acid. W. D. H. The Time Required by Reduction of Oxyhzemoglobin in Vivo. D. FRASER HARRIS and H. J. M. CREIGHTON ( J . Biol. Chem. 1915 23 469-470).-The oxyhzemoglobin bands seen in the red glare between adjacent fingers fads after bandaging the wrist in 18-26 seconds and in the rabbit’s ear in 40 seconds. Reductase in vitro requires more than 2 minutes. W. D. H. Blood-fat. 11. Fat Absorption and the Blood Lipoids. W. R. BLOOR ( J . Biol. Chem. 1915 23 317-326).-The fatty acids of the blood are increased in alimentary lipzmia but the extent of the increase) varies in different animals and in the same animal a t different periods even when the amount and kind of fat are the same.Cholesterol variations are small and irregular andPHYSIOLOGICAL CHEMlSTRY. i. 177 this substance takes a t most a minor part in the phenomena of fababsorption. Lecithin was increased in all experiments (average 20%) butr this does not run exactly parallel with the1 fatty-acids. This favours Leathes’ view that lecithin is a stage through which fats must pass before they cttn be utilised in metabolism; according to Leathes the synthesis cccurs in the liver and the presence of fat droplets in the liver during fat-absorption supports this.On the other hand the passage of the fat vid the thoracic duct into the general circulation appears t o have f o r its object the avoidance of the liver altogether. It is however well known that the fat of the thoracic duct does not accouni f o r all the fat absorbed so i t is possible that the) residue’ (30% t o 40%) passes t o the liver by the portal vessels and d’Errico showed t h a t during fat absorp- tion portal blood is richer in fat than jugular blood. It is also possible that the intestine may synthesise lecithin as it does fat but this view is not pressed. W. D. H. Blood-fat in Relation to Heat Production and Depth of Narcosis. J. R. MURLIN and J. A. RICHE (Proc. SOC. Expt. Bid. M e n . N ~ u ) Yof.L* 1915 13 7-8).-An emulsibii of lard was intro- duced into the circulation of dogs; heat production rises and the respiratory quotient falls indicating that combustion of the fat takes place.Chloretone was given t o ensure complete muscular rest and i t was found that the deeper the narcosis the more the blood-fat falls. As narcosis passes off the heat production rises. Similar results were obt,ained with morphine. W. D. H. The Acid-base Equilibria in the Blood after Para- thyroidectomy. D. WHIGIIT WILSON THORNTON STEARXS and MADGE DE G. THURLOTV ( J . Biol. Chem. 1915 23 89-121).-After parathyroidectomy in dogs alkalosis may develop which is neutral- ised by the acid products formed by the muscular activity incident to tetany and after acute tetany acidosis may be the ultimate result. Periodic variations in the “ non-volatile ” acid-base equi- librium seem t o accompany the periodic attacks.The acidosis is associated with relief from tetany. Calcium salts when injected into animals in tetany lower the value of the dissociation constant of oxyhaemoglobin and the alveolar carbon dioxide pressure an effect similar to that brought about by the introduction of acids. W. D. H. A Comparison of the Effects of Dextrose and Meat Feediog on the Non-protein Nitrogen of the Blood and the Duration of Life in Experimentel Renal Insufficiency. J. H. AUSTIN and S. S. LEOPOLD (Proc. Soc. Expt. Biol. MPcZ. n’ew Pork 1915 13 3-4).-Renal insufficiency was produced in dogs by ligature of both ureters; some of these animals were given meat the others dextrose. Forty-five hours later the loss of weight in the dextrose animals was the greater and the non-protein nitrogen of the blood lower.Sixty-nine hours after the operation only one of the meat- fed dogs survived whereas those in the dextrose group were all VOL CX. i. hi. 178 ABSTRACTS OF CHEMICAL PAPERS. alive; the lower nitrogen figure appears t o be favourable for dura- tion o’f life. W. D. H. The Residual Nitrogen of the Blood. I. IVAR BANG (Bioclzem Zeitsch. 1915 72 104-118).-A series of researches has been carried out by the author with the object of estimating the amino- acids and carbamide in the blood under various physiological and pathological conditions for which purpose he has employed his own micro-methods published in a monograph (Wiesbaden 1915). The content of amino-acid and nitrogen in the human subject lies between 3 and 22 mg..per 100 grams of blood with a mean value1 of 12. The carbamide nitrogen lies between the numbers 6 and 20 with a mean value of 12. The total residual nitrogen averages about 25 with the extreme variations of 19 and 36 mg. The numbers obtained f o r ox-blood do not differ very greatly from those of the human subject; the few experiments made with the blood of sheep pig and horse yield substantially the same numbers. I n the case of rabbits on the other hand the numbers found are appreciably higher. The total residual nitrogen yields the mean value of 33 with variations between 24 and 47; f o r carb- amide nitrogen the mean is 16 (varia,tions from 8 t o 33) and f o r amino-acid nitrogen 17. The residual nitrogen of the corpuscles does not differ markedly from that’ of the plasma; the carbamide nitrogen is generally the same and where there is a difference in the amino-acid nitrogen the corpuscles in most cases contain more than the plasma.S. B. S. The Residual Nitrogen of the Blood. 11. TVAR BANG (Biochem. Zeitsch. 1915 72 119-128).-The residual nitrogen of rabbits’ blood increases during starvation ; the increase is due entirely t o the! larger amount of carbamide as the content in amino- acids remains practically constant. The carbamide rapidly dimin- ishes in amount after feeding. The increased amount of carbamide nitrogen in starvation in the blood is due to want of water and can be prevented by administration of large amounts of liquid. An increase in residual nitrogen in the blood (in dog and man) also results from a diet containing excessively large amounts of protein which is also due only t o an increase in the carbamide; the amino-acids on the other hand tend t o diminish in quantity and in some cases even entirely disappear.The alimentary “ hyper- carbamidaemia ” is produced only after diets containing an exces- sively large quantity of proteins and does not. follow an ordinary mixed diet. It is of short duration only and has generally com- pletely disappeared after nine hours. The Reeidual Nitrognn of the Blood. 111. IVAR BANG (Biochem. Zeitsch. 1915 72 129-138).-’Whilst the administra- tion of moderate amounts of protein t o rabbits dces not produce an increase in the amino-acids in blood this is not the case when the amino-acids themselves are given.The increase in the amino- S. B. S.PHYSIOLOGICAL CHEMISTRY. i. 170 acids in the blood is observed about one hour after the administra- tion. The increase is much more marked in fasting than in well- fed animals. A considerable amount of the amino-acid is excreted in the urine. The increase in the amino-acids in the blood following their ingestion is compared and contrasted with alimentary glyco+ uria. It is shown that the onset of the latter condition is much more rapid than the increase in the amino-acids of the blood. From the results of estimations of the amino-acids in the blood and in the urine after injection of glycine the inference is drawn that the amino-acids are in part retained in the tissuea and are then gradually released and pass into the blood-stream.The increase of amino-acids in the blood of a dog after their ingestion is relatively small. I n man on the other hand the increase is relatively large as it is in the case of rabbits. The Residual Nitrogen of the Blood. IV. IVAR BANG (Biochem. Zeitsch. 1915 72 139-145).-Experiments were carried out to determine the effects of the administration of carbamide. The most striking effect is the great toxicity of the substance especially when administered to starving animals. A rapid rise in the amount of carbamide in the blood also follows the adminis- tration which reaches its maximum in between one and two hours. This phenomenon is in marked contrast to the effect produced by amino-acids (see preceding abstract) where the increase in these acids in the1 blood is not observed until about two hours after their ingestion.Carbamide is not (JO toxic when administered intra- venously. It is rapidly excreted by the kidneys but a hyper- carbamidzemia exists f o r some time a fact which is taken to indicate that the kidneys become fatigued and bhat the excretion of carbamide is an active secretory process and not a mere filtration. The experimentti also indicate that carbamide is taken up by the tissues. The toxic symptoms produced by carbamide are described and their similarity t o those of urzemia and of ammonia poisoning is noted. An analysis of the blood of animals poisoned by carb- amide shows that this fluid contains abnormally large amounts of ammonia and the results leave little doubt that the carbamide is decomposed into ammonia the latter substance being the true cause of the toxic effects.S. B. S. The Residual Nitrogen of the Blood. V. IVAR BANG (Biochem. Zeitsch. 1915 72 146-168).-The effect of nephritis experimentally produced in rabbits by mercuric chloride potassium chromate and tartaric acid was studied. A dose of 15 mg. of mercuric chloride is necessary to produce toxic symptoms in a well-nourished rabbit whereas one-third of this dose is toxic to starving animals. I n both cases the effect is accompanied by a large increase in the carbamide of the blood. There is no parallelism bet'ween this increase and albuminuria. I n the case of the well-fed rabbits poisoned with large doses i t is conceivable that the hypercarbamidEmia was associated with starvation as in this case animals refuse food after administra- tion of the drug.As furthermore as has been already pointed S. B. S. VOL. CX. i. ii. 180 ABSTRACTS OF CEEMICAL PAPERS. out by the aLthor starvation liypercarbamidzemia is connected with the want of water numerous experiments were carried out to1 ascertain the effect of administration of water on the toxic symptoms produced by mercuric chloride. The results indicate that the retention of carbamide in the blood is not entirely or even primarily due to starvation. On the other hand water has a con- siderable influence on the course of the intoxication. It appears that in order to produce injury t o the kidneys the drug must have a certain higher limit of concentration.When administered to a well-nourished animal with a plentiful store of water in the body the drug is diluted as it passes through the kidney and pro- duces a relatively small effect. On the otlier hand when once the kidney has been injured by the action of mercuric chloride (passing through this organ in relatively high concentration as would happen with large doses or with small doses given to a starving animal) subsequent administration of water has little effect on the course of the toxic symptoms. Itl is found furthermore that the ingestion of food after injury to the kidney produces some curative action. It has not yet been discovered what constituent of the diet produces this specific effect but it is noticed that feeding caused a dirliinution of the hyper- carbamidzmia which is regarded as a measure of the efficiency of the organ.The results of chromate nephritis were not so constant as those produced by mercuric chloride. They show also a marked want of parallelism between albuminuria and 1iypercarbamidEmia. Tar- trate nephritis is similar t o that produced by mercuric chloride. Attention is called by the author to certain clinical aspects of his results. He1 also draws the conclusion that they support the secre'tion rather than the filtration theory of the action of the kidneys. The effect of phosplicrus poisoning is to produce a large increasel of the amino-acids in the blood accompanied by a relatively small increase of the carbamide. The animal dies fro'm uraemia which is ascribed to ammonia poisoning.Attention is called t o the fact that all cases of ummia cannot be' ascribed to ammonia pcisoning although this is the probable cause of toxic sympt,oms in eclampsia and in phosphorus poisoning. S. B. S. The Effect of Ingested Purines on the Uric Acid of the Blood. W. DENIS (J. Biol. Chem. 1915 23 147-155).-1n normal men no increase in the circulating uric acid is produced by the ingestion of large quantities of purines but a rise occurs in cases of renal insufficiency. The Action of Blood Serum after Intravenous Injection of Sucrose. F. ROHJHANN (Biochem. Zeitsch. 1915 72 26-100).- Details are given of numerous experiments which amplify the observations already publishe'd of the author and by Kumagai on the changes produced in the serum by the injection of sucrose (A.1914 i 766). They confirm the statement that the serum of W. D. H.PHYSIOLOGICAL CHEMISTRY i. 181 animals (rabbits and dogs) after parenteral administration of this sugar acquires the power of converting sucrose into dextrose and laevulose and of converting these liexoses into lactose. This property is however only acquired after administration of large doses of sugar and the results even then are not quite constant. The “ passive immuiiisation ” of animals is also confirmed. The relationship of these phenomena to those of ordinary protein iminunisation are discussed. Details of experiments on about fifty animals are given in the paper. S. B. 8. Reduction of Oxyhzemocyanin in the Serum of Limulus polyphemus L. CARL L. ALSBERG ( J . Biol. CIienz. 1915 23 495-503).-The view is advanced that the reduction which occurs in this serum on keeping which is slow is due t o microbic action. W.D. H. So-called Protective Enzymes. VIII. The Mechanism of Anapbylaxis and Antianaphglaxis. J. BRONFENBRENNER (Proc. ,Sot. e x p f . Biol. Med. New YorX. 1915 13 19-21).-The inter- action between an immune serum and its substratum or antigen leads to tlie formation of toxic fission products which originate from the serum itself. The serum normally contains proteolytic enzymes which require special conditions to exhibit their activity ; normally their action is restrained by the colloids present but in wit yo one can alter the colloid concentration thus diminishing the antitryptic (inhibiting) power and setting the enzymes free.One result of the interaction of antigen and its anti-substance is an influence on the colloidal conditions which allows the enzymes to act. I n anaphylaxis this also takes place and the antitryptic power of the serum falls; this allows the enzyme t o act toxic products are formed and anaphylactic shock follows; the shock may be prevented by increasing the antitryptic power of the animal’s serum. The introduction of the poisons in amounts in- sufficient to kill the animal is followed by the death of the tissues immediately affected and the intercellular enzymes are set free. Thess enzymes possibly with the aid of those thrown out by the surrounding fixed cells blood-serum and leucocytes dispose of the dead material and some of the fission products of digestion together with some non-protein constituents (lipoids 1) of these cells exert an antitryptic action and inhibit the activity of the proteolytic enzymes. The preliminary injection of the poison thus causes an increase in the protein fission products in the animals’ circulation and the resulting change in colloidal dispersion paralyses the activity of proteolytic enzymes which are liberated 011 tlie subsequent introduction of a lethal dose of the antigen into the sensitised animal.This theory makes active immunity and anaphylaxis part of the same process the difference being only in tile rapidity and extent- of proteolysis induced by the specific combination of antigen with its anti-substance in viuo. W. D. H. i 2i. 182 ABSTRACTS OF CHEMICAL PAPERS. The Ammonia of the Gastric Juice.HARRY L. HUBER (Proc. A'oc. Expt. Biol. Med. New l-l'c.rk 1915 13 13-15).-The occur- rence of ammonia in the gastric juice of men and dogs was noted by Carlson; in dogs with Pavlov stomachs the amount varied from 0.5 to 3.5 mg. per 100 C.C. of juice; this rises when ammonium chloride is added to the food or if ulceration is produced; if the dog refuses to eat the amount is also increased. The figure in normal men was the same as in dogs; on a low protein diet the amount fell and the urinary ammonia rose; on a high protein diet the ammonia both in the juice and the urine rose. Excess of alkali in the food did not affect the ammonia of the juice but that in the urine fell immediately; during ingestion of acid the juice ammonia remained normal whilst that in the urine was increased.I n twenty-six patients with gastric disturbances (supposedly ulcers) a rise in the ammonia of the juice was noted in only five (two of cancer and three of simple ulcer). W. D. H. Gastro-intestinal Studies. XI. The Relative Digeetibility of Lard and Hydrogenated Vegetable Oil. C. A. SMITH RAYMOND J. MILLER and PHILIP B. HAWK (Proc. Soc. Bxpt. Bio7. Med. New York 1915 13 13; J . Biol. Chem. 1915 23 505-511).-By examination of the faxes in t,wo men it appears that the two kinds of fat given are equally satisfactorily digested and utilised. W. D. H. The Behaviour of Some Hydantoin Derivatives in Meta- bolism. 111. Parabanic Acid. HOWARD B. LEWIS ( J . BzoZ. Chem. 1915 23 281-285).-As parabanic acid does not yield its nitrogen by the urease method metabolism experiments on its fate are now possible; these were performed on rabbits and a dog.No toxic symptoms followed its administration and no conversion of any significant amounts into urea t'ook place. Perf usion experiments on the liver also showed no such conversion. Parabanic acid therefore is probably not an intermediary metabolic stage in the conversion of uric acid into urea. W. D. H. The Metabolic Relationship of the Proteins to Dextrose. 111. Formation of Dextrose from Human Proteins. N. W. JANNEY and N. R. BLATHERWICK (J. Riol. Chern. 1915 23 77-80).-The ratio of dextrose t o nitrogen in the urine is not always a certain basis f o r calculating the amount of sugar formed from protein in the body. This does not apply t o the observa- tions of Benedict and Lewis on a case of phloridzin diabetes in the humaii subject; there the diet was free from carbohydrate and the D:N ratio was 3*6:1.About the same value is reported in severe diabetes mellitus. In the present experiments phloridzinised dogs were fed on human muscle and nearly the same figure obtained. namelv. 3.4 1. Statements in the literature of much J' higher ratios such as 5:1 can no longer be accepted. W. D. H.PHYSIOLOGICAL CEEMISTRY. i. 183 The Fate of Ingested Sodium Nucleate in the Human Subject. MAURICE H. GIVENS and ANDREW HUNTER (J. Biol. Chem. 1915 23 299-309).-Even though the purine nitrogen given is completely absorbed and promptly re-excret,ed only a fraction reappears as uric acid. From this Schittenhelrn argues that uric acid cannot be a terminal metabolic product in man but that it must be transformed into some other compound presumably urea since the human organism is admittedly incapable of making allantoin from uric acid.If this is admitted the present experi- ments show that the liunian “uricolytic index ” must vary from 29 to 94. I n the lower animals this index is almost a constant for the species; the more plausible explanation now suggested is that purines entering o r liberated in the intestine undergo before absorption a varying degree of bacterial destruction. W. D. H. The Physiology of Nutrition of Domestic Animals Especially of the Ox. WILHELM KLEIN (Biochenz. Zeitsch. 1915 72 169-252). -An improvement in the Zuntz method f o r determination of the gaseous metabolism is described and also a modification of the Tigerstedt method by means of which mean values taken over longer and shorter periods of observation can be obtained.A method for the estimation of small amounts of combustible gaqes is also described. The three main methods fox determination of €110 respiratory exchanges (those of Zuiitz Pettenkofer and Regnault- Reiset) give results in concordance with one another. The1 energy balance of tlie organism as calculated from the results of measure- ment of respiratory exchanges agrees with that got by the chemical analysis of the iiigesta and egesta. Calculations were made as to the amount of energy consumed in tlie process of chew- ing the cud and of digestion and the results agree with those obtained by Pachtner and Dahm.The estimation of the respira- tion by the skin and intestine of ox was made and found to amount to 14% of the total (of carbon dioxide). The energy con- sumed in the act of standing of the animals was also determined. The energy needs of the animal a t different ages as found from the experiments of tlie author a i d others are shown t o bs nearly proportional t o the body surface. The author calls attention tlo the practical value of the work on respiratory exchanges f o r agri- cultural and other purposes. s. 13. s. The Cause of the Loss of Nutritive Efaciency of Heated Milk. E. V. MCCOLLUM and MARGUERITE DAVIS (J. BioZ. Chenz,. 1915 23 247-252).-Skim-milk powder loses much of its efficiency to promote growth after prolonged boiling especially a t 15 lb.pressure,. Wheat embryo does not deteriorate from this point of view after the same treatment. Skim-milk free from protein also remains active so does whey freed from albumin. Lactose contaminated with the water-soluble accessory after heat- ing still behaves like the unheated product. Heating caseinogen in an autoclave a t 15 lb. pressure for an hour destroys its bio-i. 184 ABSTRACTS OF CHEMICAL PAPERS. logical value as a complete protein. Heated caseinogen and heateJ milk powder have little or no toxicity; the deterioration is due t o a loss of value of the protein fraction of the ration through changes produced in the caseinogen. The Dietary Deficiencies of Rice. E. V. MCCOLLUX and MARGUERITE DAVIS ( J . Bid. Chem. 1915 23 181-230).- Polished rice cannot be made t o induce growth by the addition of purified protein gro'wth-promoting fat or salts.If the salt content of milk powder (or desiccrtted egg) plus dextxin is altered to imitate that in rice there is no loss of growth promotion in the mixture. Polished rice even when employed to the extelnt of S0-90% in a growth-promoting food is harmless. Even 2% of a growth-pro- rnoting food mixture furnishes enough of an essential accessory t o induce growth. This accessory aside from that in buttex-fat is present in aqueous and alcoholic extracts of wheat embryo and egg-yolk; i t is thermostable. The amount of aqueous extract (freed from protein) necessary t o supply enough of this accessory carries nitrogen equivalent t o about 1% of the total nitrogen of the ration; about one-third of this suffices in the case of the alcoholic extract.The accessory is not the same as that in butter; addition of 20% of biitter-fat does not induce growth unless the other is presetit also; both must be present before growth can proceed. W. D. H. E. V. MCCOLLUM and MARGUERITE DAVIS c.7. BioZ. Cheni. 1915 23 231-246).-The value of lactose in growth promotion is due to the fact that most preparations contain as an impurity the water- alcohol soluble accessory ; the same is true f o r most preparations of caseinogen and this substance is also usually contaminated with the fat-soluble accessory. A method is described of obtaining caseinogen free from both accessories. Both must be present in small quantities but growth and prolonged maintenance are in some measure proportional t o the amount supplied. Etudies on Growtb.11. The Probable Nature of the Substance Promoting Growth in Young Animals. CASIMIR FUNK and ARCHIBALD BRUCE MACALLUM (c7. B i d . GJLPII~. 1915 23 413-421).--Neither butter nor purified butter (free from vitamine) promotes growth in pigeons or rats; the addition of yeast is howcver efficacious. Whether yeast without butter will produce normal grcwtli in rats and whetlier there are one or more compounds in the yeast which promote growth are still under investigaticn. W. D. H. The 'Resumption of Growth after Long-continued Failure to Grow. THOMAS B. OSBORNE and LAFAnwrE B. ENDEL EL [with EDNA 2. FERRY and ALFRED J. WAKEMAN) ( J . Bid. Chens. 1915 23 439-454).-The capacity to grow can be retained and exercised a t periods beyond the age when growth usually ceases.I n albino rats this latter age is 300 days but resuinptioii may be induced at W. D. H. The Eesential Factors in the Diet During Growtb. W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 185 550 days. Growth can also be normally stimulated after stunt- ing due to underfeeding or to feeding on imperfect proteins. This resumption of growth under the influence of a suitable diet is accompanied by a restoration of the procreative functions. Further work is in progress. W. D. H. The Relationship between the Content of the Perspiration in Chlorine and Nitrogen and the Diet. ELMER BERRY (Biochenz. Zeitsch. 1915 72 285-302).-During work more urine is excreted even with intense perspiration than during rest; its specific gravity is however smaller and on this fact diet exerts no influence.The urine excreted during work is less acid and less coloured than that excreted during rest. The nitrogen excreted is nearly proportional t o the timel both during work and during rest and the form of diet is without influence on this factor. Urine excreted during rest nearly always contains a larger amount of nitrogen than that excreted during work. The excretion of chlorine during work is enormously increased. I n 21% of the time during which work was performed 40% of tIhe total chlorine of a twenty-four hours' period was excreted. I n other experiments even higher amounts were observed. Diet has no influence 011 this excretion. I n spite of its lower specific gravity the urine excreted during work always contains a higher percentage of chlorine than that excreted during rest'.It appears that diet does not have an essential influence on the chlorine and nitrogen coii- tents of the perspiration. From 2-5*6% of the total nitrogen and from 13-30% of the t o t d chlorine excreted appear in the perspira- tion under the conditions of experiment described. S. B. S. The Apparent Change of the Osmotic Pressure of the Cell- contents with the Osmotic Pressure of the Surrounding Medium. JACQUES LOEB and HARDOLPH WASTENEYS ( J . Biol. Chem. 1915 23 157-162).-The osmotic pressure of the contents of Fuitdrtlus eggs curresponds with a freezing-point depression of 0*76O and is the same whether the eggs are fertilised or not. When the egg is washed or kept in solutions of different concentrations the osmotic pressure of the expressed juice varies somewhat with the outer fluid.It must be assumed that the outside solution adheres to the meshes of the outer part of the membrane without entering the egg. W. D. H. The Influence of Electrolytes on the Diffusion of Potassium out of the Cell and into the Cell. JACQUES LOEB and MCKEEN CATTELL ( J . BioZ. CAem. 1915 '23 41-66).-Hearts (like Elu~d2i.lics eggs) after being poisoned by potassium chloride recover quickly when placed in salt solutions; the efficiency of the salts used depends (1) on their concentrations within certain h i t s and (2) on the valency of the anion. Fu~~durTrts eggs stained with neutral-red do not give up the stain to distilled water but they do so when a trace of acid or some salt is added.The diffusion out both of potassium and the dye presupposes their combinationi. 186 ARSTRACTS OF CHEMICAL PAPERS. with the colloidal anion of the membrane; this is counteracted by the presence of an excess of anions (especially bivalent and ter- valent anions) in the outer solution or by a trace of acid. The colloid in the membrane which unites with the potassium or the dye is probably an amphoteric electrolyte which through the addition of acid is transformed into a salt in the dissociation of which the colloid forms a cation which is no longer able to bind other cations. Previous immersion in distilled water delays the poisonous action of potassium; traces of the water must get into the membrane and this acts as a barrier blocking the further diffusion of potassium into the cell.The R81e of Electrolytes in the Diffusion of Acid into the Egg of Fundulue. JACQUES LOEB (J. Bid. Chenz. 1915 23 139-144).-SaIts inhibit the toxic action of acids on Fuizdulus embryos. This is a function of the anion as well as the cation. Thio- cyanates acetates sulphates and tartrates inhibit strongly ; chlorides bromides and nitrates less ; and iodides least. Calcium strontium and to a less degree magnesium inhibit. more strongly than univalent cations. The antagonistic action of the anions is due to retardation of the rat& of diffusion of acid through the egg-mem- bsane. I n the adult fish tartrates and thiocyanates are too toxic to be of use in inhibiting the action of acids.Calcium in Permeability and Irritability. JACQUES LOEB ( J . BioZ. Chem. 1915 23 423-430).-The variation in the amount of calcium or of caIcium plus magnesium required t o antagonise various concentrations of sodium chloride or of that salt plus potassium chloride was investigabed both as regards permeability and irritabiIitly in barnacle larvae. I n regard t o irritability the calcium required varied in direct proportion to the concentration of salt (Weber’s law) but in regard to permeability the amount varied approximately with the square of the ratio of the concen- tration of the sodium chloride. W. D. H. Xanthophyll the Principal Natural Yellow Pigment of Egg-yolk Body-fat and Blood-serum of the Hen. The Physio- logical Relation of the Pigment to the Xanthophyll of Plants.LEROY S. PALMER ( J . Biol. Chem. 1915 23 261-279).-!L’he natural pigment of egg-yolk body-fat and blood-serum of the hen is physiologically identical with the carotin and xanthophyll pig- ments of plants with the latter present in excess. I n the cow however carotin is the predominating pigment of milk serum and adipose tissue. I f xanthophyll is reduced in the hen’s food there is no appreciable decrease in the amount of pigment carried by the blood and deposited in the yolk. But if the rations are relatively free from both carotin amd xanthophyll this amount is much reduced. W. D. H. The Action of Certain Inorganic Salts and Quinine on the Activity of the Mammalian Heart. F. B. HOFMAN and T. SAKAI (Zeitsch. Biol. 1915 66 293-325).-Diminution of the sodium W.D. H. W. D. H.PHYSZOLOGICAL CHEMISTRY. i. 187 chloride in Locke’s perfusion fluid to 0*5-0.2% (keeping it iso- tonic by the addition of sugar) causes the ventricle to become more excitable and contractile after the division of the auriculo- ventricular bundle; still further reduction of the salt stops €he ventricle; the auricle acts similarly but is more sensitive; if the heart is intact the auricles stop and the ventricles beat slowly. Increase of the potassium lessens excitability and inhibits ‘I extra systoles.” I n some cases there is a preliminary stage of increased frequency; under these conditions the optimum of calcium is high but varies. Quinine inhibit8 (( extra systoles.” W. D. H. The Influence of Adrenaline on the Coronary Circulation of the Monkey.HENRY G. BARBOUR and ALEXAKDER I;. PRINCE (?7. e x p t . Med. 1915 21 330-337).-The experiments were made on isolated hearts perfused with Locke’s solution. I n dog cat rabbit ox sheep and pig the addition of adrenaline dilates the coronary vessels but in the monkey constriction occurs; there is 801120 evidence that man and monkey are alike in this particular and the1 conclusion is drawn that in these two species the coronary arteries are supplied with vaso-constrictor nerves. W. D. H. Vagus Stimulation of the Adrenalised Heart. M. KUROUA and YAS KUNO ( J . Physiol. 1915 50 154-156).-The cardiac vagus is rende;red inexcitable by the injection of adrenaline; it is doubtful if this is due to a direct effect of adrenaline’ or to the increased intracardiac pressure which it causes.Bessmertny con- cluded in favour of tlie former because “ emostasin ” raises the pressure as much as adrenaline but does n o t affect the vagus. I n the present expesiments on the (‘ heart-lung preparation,” the pressure was raised by (1) increasing the venous supply and (2) by adrenaline without any increase in the venous supply. Fre- quently vagus stimulation was ineffective when the arterial pres- sure was raised to I e s than twice its normal height by adrenaline. This abolition lasts longer than in the intact animal. W. D. H. The Action of Caffeine and Adrenaline on the Vagus Nerve. HENRY G. BARBOUR and SIMON B. KLEINER (J. Pharmacol. expt. Ther. 1915 7 541-544).-Both drugs accelerate the heart but this may be masked by central stimulation of the vagus.If the vagi are cut increase of the heart’s rate is always obtained. When either is perfused through the frog’s heart vagus stimula- tion usually produces no inhibition ; after caffeine recovery is more complete than after adrenaline. The effect of adrenaline is due to depression of the vagus endings in the heart; this may be partly true for caffeine but here there is an additional factor iiamely increased irritability of the cardiac muscle. W. D. H. The Action of Phenylethylamine on the Heart. HENRY G. BARBOUR and EDWARD M. FRANREL (J. Pharmacot. e z p t . Ther. 1915 7 511-527).-Phenylethylamine is a cardiac poison in small amounts stimulating and in large amounts depressing thei. 188 ABSTRACTS OF CHEMICAL PAPERS. mammalian heart.I n the frog the stimulating effect does not occur. It also stimulates constriction of the coronary arteries. The effects are reversibIe and disappear on perfusion with Clark’s or Locke’s modification of Ringer’s solution. The Production of Atrio-ventricular Rhythm in Man after the Administration of Atropine. FRANK N. WILSON (Proc. SOC. Expt. Biol. U e d . N e w Yort? 1915 13 17-18).-Several types of disturbed cardiac rhythm were observed in men (both healthy and affected with heart disease) after a dose of atropine which are explained by assuming t h a t this drug releases the A-V tissues from vagus control before it releases t,he sinus node. W. D. H. W. D. H. The Action of Heavy Metals on the Isolated Intestine. WILLIAM SALANT and C. W. MITCHELL (Proc. Soc.Expt. Biol. Me& New Pork 1915 13 15-16).-Very low concentrations of zinc salts depress the muscular activity of the intestine (Magnus’s method) ; some recovery occurs in Locke’s solution unless the injury is too pronounced. Nickel acetate produces temporary depressiou followed by recovery and sometimes stimulatioii. Recovery even after strong solutions is complete in Locke’s solution. The re- action to pilocarpine and to barium in these experiments points t o more resistance in the muscle fibres than in the nerve-endings. W. D. H. The Response of the Surviving Uterus to Morphine and Scopolamine. HENRY G. BARBOUR and NAT H. COPENHAVER (J. Ph~rriitcicol. expt. Ther. 1915 7 529-539).-Morphine (0.05 t o O.Ol% and sometimes 0.002%) stimulates the isolated uterus of cat and guinea-pig t o an increase of tone.Scopolamine acts in the same way but is ten times more powerful. Inhibitory effects with large doses as described by Kehrer were not obtained. W. D. H. The Action of Morphine and Scopolamine on the Intact Uterus. HENRY G. HARBOUR ( J . Phurmncol. expt. Ther. 1915 7 5 4 7-5 5 5 ) .-I ri t 11 e i 11 tact a 11 i m a 1 (d ec er e b r a t ed) m o r p h i 11 e a 11 cl scopolamine cause a temporary increase of tone in the pregnant or non-pregnant animal. That large doses iiiliibit is not. due t o their action on the uterus itself but any delay in labour they produce is due entirely t o their cerebral action. W. D. H. The Occurrence of Pituitrin and Adrenaline in Foetal Pituitary and Suprarenal Glands. . CAREY PRATT MCCORD ( J .Biol. Che?77. 1915 23 435-438).-Bovine organs were used and the extracts were physiologically active during all developmental stages in which the suprarenal and pituitary glands were inicro- scopically recognisable ; for the pituitary this is from the eighth week and f o r the suprarenal from the sixth week of intra-uterine life. The f e t u s is thus not merely under the iiifluence of the niateriial internally secreting organs TV D. H,PHYSIOLOGICAL CHEMISTRY. i. 189 Failure of Pituitrin to Sensitise the Sympathic System. R. G . HOSTSINS (Proc. SOC. Expt. Biol. Med. flew Yorb. 1915 13 16-1 7).-Kepinov states that small quantities of pituitary extract * * sensitisle ” the point of attack of adrenaline (the sympatlietic endings) so that small doses of the latter will thus produce large effects.The present experiments fail t o support this contention. W. D. H. The Influence of Pancreatic Extracts on the Production of Lactic Acid in Surviving Muscles. GEORGE WINFIELD and F. GOWLAND HOPKINS (Proc. physiol. Soc. 1915 v-vi; J Physiol. 50).-Pancreatic extracts were added to minced muscle and the yield of lactic acid compared with that in similar preparations with- out such adciitions. Those with the added extract showed less lactic acid. This inhibitory action is not confined to the action of the pancreas on the aut.ogenous muscle but> is produced by preparations f roin widely different sources. The responsible factor is thernio- stable and is thus similar to Cohnheim’s glycolytic factor. W. D. H. Biochemistry of Iodine.11. The Distribution of Iodine in Plant and Animal Tissues. A. T. CAMERON ( J . Biol. Cheiii. 1915 23 1-39).-1odine is always present in marine a l p between the limits of 0.001% and 0.7%. Land plants contain much less; all sea animals contain iodine. As one rises in the animal kingdom differentiation occurs and the iodine is localised in certain organs and the total in the whole system becomes less. Full details are given for sponges corals worms ascidians and molluscs. In ascidians the endostyle which represents the thyroid contains iodine but less than the thyroid of vertebrates does. 111 vertebrate tissues the thyroid alone is important as a storage place for iodine the percentage in the dry tissue varying from 0.01 t o 1-16. Other tissues contain less than O.OOl% except in the liver and kidney of fishes where the amount is slightly higher.Varia- tions in the iodine content of the thyroid can all be traced to differences in diet. I n elasmobranch fish there is no evidence that the thyroid tissue of females contains more iodine than the male tissue. In the analyses Kendall’s method was used The Non-destructibility of Uric Acid in the Human Organism. MORRIS S. FINE ( J . Biol. Chem. 1915 23 471-473).- Contrary to the findings of Schittenlielin and Wiener the present analyses show that uric acid can be demonstrated in considerable concentrations in human tissues ; the contention of these workers that human tissues decompose uric acid is not suprorted. W. D. H. W. D. H. The Salts Required for the Development of InsectP.J a c ~ u ~ s LOEB ( J . Bio!. Cheni. 1915 23 431-434).-The experiments show that an animal as highly orgaiiised as ths‘banaiia fly can be raised on a culture medium as siinple as that required by certaiii micro-i. 190 ABSTRACTS OF CHEMICAL PAPERS. organisms ; the liquid used contained dextrose sucrose ammonium tartrate citric acid dipotassium hydrogen phosphate and mag- nesium sulphate dissolved in water. W. D. H. The Preparation of Protein-free Milk. H. H. MITCHELL and R. A. NELSON ( J . Biol. Chem. 1915 23 459-467).-The protein is removed by trichloroacetic acid ; preliminary experiments indicate that such protein-free milk may be used with advantage as a basis of the ration in metabolic work. W. D. H. The Action of Animal Extracts on the Flow of Bile.ISAAC OTT and JOHN C. SCOTT (Proc. SOC. Expt. Biol. itfed. New York 1915 13 12).-In etherised cats equal doses of secretin cause equal increments in the flow of bile. Animal extracts were1 then added to the secretin ; extracts of parathyroid mammary gland thyroid and corpus luteum have little or no effect; t h s flow is increased by extract of tonsil and decreased by adrenaline pitui- trin and extracts of pancreas and of thymus. W. D. H. The Reaction of Bile. SEIZABURO OKADA ( J . Physiol. 1915 50 114 -118).-The reaction of bile from the1 gall-bladder and from the liver is different' the former being more variable and inclining more to the acid side; liver bile is alkaline; its H'-ion concentrat<ion is 1.5 x 10-8 a t 23O; i t turns red Iacmoid blue but does not turn phenolphthalein red.The reaction of bile from the liver during digestion corresponds with that of pancreatic and intestinal juices and with the optimal point for trypsin pancreatic lipase and erepsin. W. D. H. The Excretion of Acids and Ammonia after Para- thgroidectomy. D. WRIGHT WILSON THORNTON STEARXS and J. H. JANNEY jun. ( J . Biol. Chem. 1915 23 123-137).-Afhr parathyroidectomy in dogs there is usually a sudden diminution in the excretion of aci'ds and ammonia and a decrease in the ammonia ratio and the hydrogen ion concentration of the urine. With the development of tetany the elimination of acids and ammonia increases and the ammonia ratio and hydrogen-ion con- centration rises. This indicates that the alkalosis resulting from the operation is neutralised by the development of tetany.After acute or chronic tetany acidosis may occur. W. D. H. The Chlorides in Diabetes after Pancreatectomy. JAMES ELAZER LEBENSOHN (J. Biol. Chem. 1915 23 513-520).- Chloride metabolism in dogs after removal of the pancreas remains normal; so also does t,h0 permeability of the intestine as regards the absorption of chlorides. TN. D. H. The Supposed Acid Intoxication of Diabetic Coma. E P. POWLTON (Proc. physiol. SOC. 1915 i-iii; J . Physiol. SO).- I n the acidosis of carbohydrate starvation the hydrogen-ion con- centration of the blood remains constant for the increase in acidPHYSIOLOGICAL CHEMISTRY i. 191 is compensated for by lessening of carbon dioxide; but the qucstion is open whether in the severe type of acidosis in diabetes this holds good; the general belief is that acid intoxication occurs.The present observations were on eight patients with varying severity of the symptoms. When the coma was deep (two cases) the hydrogen-ion concentration was distinctly higher than normal but the fact that in the other cases where there was definite drowsiness the blood reaction was normal argues against diabetic coma being due to acid intoxication. After severe muscular exercise the acidity of the blood is greater than in the depth of diabetic coma but there are no signs of acid intoxication. W. D. H. Experimental Study of Fever. JUDAH LEON JONA (J. Hyg i e w 1916 15 169-194).-A definite rise of body temperature occurs in rabbits after injecting a minute amount (0.00004 gram) of cultures of Bacillus coli com~nu~zis or B.typhosus in Ringer’s solu- tion. Larger doses cause collapse and even death. The substances to which this is due are soluble in water and saline solutions insoluble in ether and in alcohol. Their potency is lessened by contact with alcohol. They may be separated from the solutions by filtering through a collodion filter. They are therefore colloidal or adherent to colloid materials. They are not destroyed by boil- ing or by dry heat a t l.lOo. The fever lasts a few hours and is due t o diminution in the loss of heat; heat production is unaffected o r may be increased. The fall of temperature in collapse is accom- panied by decrease of both production and loss of heat. I n animals in which the brain stalk has been severed distal to the optic thalamus no fever was caused after the injection of the ordinary pyretic dose.W. D. H. I cterus. A Rapid Change of Haemoglobin into Bile-pigment in the Pleural and Peritoneal Cavities. C. W. HOOPER and G. H. WHIPPLE (Proc. SOC. Expt. Biol. &fed. iVew Pork 1915 13 22-23) .-The introduction of solutions of haemoglobin into the blood-vessels of dogs thO livers of which have been excluded from the circulation is followed by a prompt formation (within two hours) of bile pigment in which the liver can have no part. The same is true when the haemoglobin is introduced into the pleural or peritoneal cavities. The endothelial linings are probably responsible for the transformation; the power may be however a general property of all protoplasm.Botassium in Normal and Nephropathic Kidney Cells. WM. DEB. MACNIDER (Proc. Soc. Expt. Biol. Med. New Pork 1915 13 10-12).-Potassium was determined microchemically by Macallurn’s method in dogs. Normally the kidney cells show only traces the nuclei possessing none. I n nephritis produced by uranium nitrate the amount rises and some is present in the nucleus; this is most marked in the cells of the convoluted tubules. W. D. H. W. D. H.i. 192 ABSTHACTS OF C ii EMlCAL PAPERS. The Interpretation of a Positive Nitrogen Balance in Nephritis. HERMAN 0. MOSENTHAL (Proc. Soc. Expt. Bz’ol. 3 h I . N e w York 1915 13 g-lO).-Retention of nitrogen in nephritis is usually due t o renal insufficiency but the present results show that this is not necessarily followed by a rise in the non-protein nitrogen of the blood.Uric Acid Urea and Creatinine of the Blood in Early and Late Nephritis. V. C. MYERS M. S. FINE and W G. LOUGH ( I ’ m - . ,Cot. h’xpt. Niol. dlurl. X e w Y o r k 1915 13 5).-In early nephritis the blood resembles t h a t found in gout in a rise of uric acid but as the disease progresses and the permeability of the kidney is lowered the urea rises and lastly the creatinine follows suit; the rise in creatiiiiiie may near death be twenty times the normal. W. D. H. W. D. H. The Action of Barium Chloride on the Circulation; the Antagonistic Action of Nicotine and Curare. E. P. CATHCART and G. H. CLARK (e7. Physid. 1915 50 119-127).-Tlie antagon- istic action of nicotine and curare in skeletal muscle (Langley) holds good also for the muscular tissue of the arterioles.Nicotine inhibits o r abolishes the rise of blood-pressure produced by barium chloride ; curare then restores or may even intensify its pressor action. Barium chloride probably does -not act on the muscle itself but it acts on a different part of the apparatus from that on which adrenaline acts. W. D. H. The Pharmacological Action of Tetra-alkyl Ammonium Compounds. 11. and 111. C. R. MARSHALL (Trans. Roy. Soc. Bdin. 1915 50 379-398; 481-516).-11. The most prominent symptoms produced on frogs by the action of tetraethylammonium chloride are the following. The injection into the dorsal lymph sac produces muscular contractions and tremors. These symptoms are accompanied by some loss of co-ordination a varying degree of paralysis with diminution or absence of reflexes or cessation of the respiratomry movements.Doses of 2 mg. per gram of body- weight are lethal. The lethal dose for rabbits was found t o be about 0.05 gram per kilo. of body-weight. The injection of 0.1 gram per kilo. into the ear vein produced a t first deep convulsive breathing follo’wwed by convulsive movements and paralysis of the hind limbs; the heart became weaker and weaker. The action of the drug on isolated nerve and muscle was studied in detail. Both muscular contractions and paralysis were found t o be peripheral in origin. The tremors can be inhibited by the action of calcium salts when these are perfused through the animal (frog). Immersion of isolated muscle in a solution (1 in 1000) produces contracture which is due to the presence of free acid in the com- mercial sample of the drug employed.The drug produces in- creased irritability or paralysis on the motor nerve-endings of mammals the effect varying with the magnitude of dose and method of injection. I n contradistinction t o tetramethyl-PHYSIOLOGICAL CHEMISTRY. i. 193 ammonium chloride tetraethylammonium chloride exerts no dis- tinctive action on the circulation. Injections produce a transient fall of blood-pressure in rabbits the amount of which varies with the dose; this fall appears t o be due to a vascular effect. I n cats the effect is less than t h a t in rabbits. The effect on the respira- tion in mammals is also comparatively small and is much below t h a t produced by tetramethylammonium chloride.111. The relative pharmacological actions of the various methyl- ethylammonium compounds are compared. The methylethyl- ammonium compounds have actions intermediate between those of the tetraethyl and tetramethyl derivatives. When injected into the dorsal lymph-sac of frogs trimethylethylammonium chloride produces paralysis and rarely a few muscular twitches. Dimethyl- diethylammonium chloride produces chiefly paralysis but there is distinct evidence of increased irritability of the nerve-endings. Methyltriethylammonium chloride caused slight irregular muscular movements and tremors followed when sufficient doses were given 11y paralysis. The effect on tadpoles was similar to that on frogs. When tested on the mammalian circulation the following were tlie broad effects produced. Methyltriethylammonium chloride is similar to but slightly more powerful than the tetraethyl coin- pound whereas trimetIiylethylammonium chloride is similar to 11 u t 1 ess p ow er f ul than t e t r amet h y 1 ammonium chloride w h i c h as mentioned in previous communications has a more marked action on the respiration and circulation than the corresponding ethyl derivative. TLe dimethyldiethyl compound has an intermediate action. The effects of these drugs on tlie isolated muscle of frog have been investigated i n detail and are illustrated by numerous tracings. In conclusion attention is called to the fact that the most important action of quaternary ammonium compounds is on the myoneural junction and the mode of action is fully discussed by the author. The Elimination of Picric Acid by the Urine. M. MURAT and J. DURAND (J. Pharm. Chim. 1916 13 18-23).-Picric acid is but little toxic; dos’es of 1 gram are well borne and except for a slight feeling of fatigue produce no symptoms. The colour of the urine resembles t h a t in jaundice ; elimination begins six hours after the dose and continues for about twelve davs. The smallest S. B. S. dose necessary to produce the pseudo-icterus is 0 . i gram. W. D. H. Mercuric Chloride Poisoning in Animals Treated Unsuccess- fully by Hall’s Antidote. HENRY G. BARBOUR (J. Amer. Med. Assoc. 1915 64 736).-W. A. Hall recently suggested the treat- ment of cases of mercuric poisoning by a reversal of Mayer’s reaction namely the employment of an alkaloid dissolved in potassium iodide solution which would precipitate mercuric chloride. I n the present experiments quinine was selected as the alkaloid and appropriate doses were given subcutaneously to mice and rabbits poisoned with mercuric chloride ; the treatment was quite ineffectual. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9161000176

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 184 ABSTRACTS OF CHEMICAL PAPERS Inorganic Chemistry. Bromine Ion Content of Sea-water. L. W. WINKLER (Zeitsch. angew. Chem. 1916 29 68. Compare this vol. ii 109).-Water from the Adriatic was found t o contain 63-81 mg. of bromine per litre; the chlorine amounted to 18375 mg. per litre. W. P. S. Catalytic Method for the Separation of Solid Iodine from Solutions. L. PISARSHEVSKI and N. AVERKIEV ( J . Ruvs. Phys. Chem. SOC. 1915 47 2057-2060).-The action of chloric acid on iodine ions in an acid solution resulting in the deposition of iodine thus 6H' + GI' + C10,/.= 3H,O + C1' + 31 is greatly accelerated by the presence of ferri-ions in small concentration which act as a catalyst; the iodine is precipitated as a fine powder or as more or less large well-formed crystals according to the concentration of the iodine solution the amount of catalyst added the composition of the liquid and certain other factors.The ferri-ions are converted into ferro-ions according to the equation Fei'" + I/=Fe" +I theINORGANIC CHEMISTRY. ii. 185 ferro-ions being then oxidised thus 6Fe" + 6H' + C10,' = 3H,O + C1'+ 6Fe"'. The method is applicable t o the separation of iodine not merely from solutions of pure iodides but from the brine obtained on leaching with water the ashes of seaweed and is carried out as follows To the iodide solution acidified with excess of sulphuric or hydrochloric acid are added (I) potassium chlorate in the proportion indicated by the above equation o r a greater propor- tion if other substances capable of oxidation are present and (2) a small volume of a solution of a ferric or ferrous salt in three times its weight of water T.H. P. Electrolytic Method of Obtaining Solid Iodine from Solution. L. PISARSHEVSKI and S. TJELNI ( J . Russ. Phys. Chem. SOC. 1915 47 2060-2063).-Tlie authors describe preliminary attempts t o devise a method of separating iodine electrolytically from solutions containing iodides bromides and chlorides (compare Specketer A. 1899 ii 123). Lead electrodes or a lead anode and a carbon cathode give good results; the lead anode becomes coated with a thin layer of lead iod-ide which prevents further combination with the iodine the latter being depositeld in a crystalline crust easy t o remove. T. H. P. Materials for Experimental Dispereoidology. 111. Goloured Solutions of Sulphur.P. P. VON WEIMARN ( J . Russ. Phys. Chenz. SOC. 1915 47 2177-2214).-The author gives first a summary of the literature dealing with coloured solutions of sulphur and then his own investigations which lead t o the following results Sulphur dissolves with an indigo o r blue coloration in water ethyl propyl isobutyl and aniyl alcohols acetone glycerol and ethylene glycol if these solvents are rendered alkaline; with the last two solvents i t is indeed unnecessary to add alkali but this may come from the glass. When the above solvents are neutral o r acidified no blue colour appears. Any solution of a polysulphide becomes blue when heated if the solvent is not acid in charact'er and does not decompose sulphides in general and by variation of the concentra- tion and temperature such solutions may be obtained of any colour in the spectrum. The blue d o u r observed in the above cases and that exhibited by fused potassium chloride and sulphur solutions of sulphur in ammonia or sulphur trioxide etc.occurs when the linking of the sulphur in these compounds which are classed together as " sulphydrates," is weakened that is when the sulphur atoms approach a condition of freedom from combination. The blue colour may appear over an interval of temperature ranging from -8OO to +800°. T. H. P. Black Phosphorus. I. A. SMITS G. MEYER and R. PEL BECK (Proc. K. Akad. Wetensch. Amsterdam 1916 18 992-1007). -The black phosphorus obtained by Bridgman (A. 1914 ii 647) has a much greater density (2.69) than that found for violet phos- phorus (2*21-2*34) and this would seem to support the view that i t represents a new modification.ii.186 ABSTRACTS OF CHEMICAL PAPERS Attempts to compare the vapour pressures of black and violet phosphorus gave unsatisfactory results on account of the difficulty of removing from the former the kerosene which had been used as pressure-liquid in its preparation. A t temperatures below 550° the vapour pressure of black phosphorus did not reach a constant value. A t somewhat higher temperatures a constant value was reached and this was very nearly equal t o the vapour pressure of violet phosphorus. A t 570° the black modification has a higher vapour pressure than the violet form. I n presence of iodine as catalyst the melting points of the black and violet forms were found to be 587*5O and 589.5O respectively.The relation between the two modifications is discussed with especial reference t o the fact that it has not yet been found possible t o convert violet into black phosphorus even under pressures up t o 12,500 kilograms per cm.2. Molecular Volumes of the Hyponitrites of the Alkali Metals and Metals of the Alkaline Earths. PRAFULLA CIIANURA RAY and RAJENURALAL DE (T. 1916 109 122-131).-The densi- ties of the solid subst'ancea were determined by means of a pykno- meter with xylene as filling liquid. The molecular volumes of the anhydrous sodium silver and mercurous salts are 42.98 47.96 and 62.76 respectively and of the calcium strontium and barium salts 39.61 55-05 and 50.75 respectively. The molecular volume of the strontium salt is evidently anomalous in that i t is much larger than t h a t of the barium salt. This anomaly is not met with when the volumes of the nitrites and nitrates are compared.It may be con- nected with the fact that strontium hyponitrite loses its water of crystallisation much more readily than the calcium and barium salts. The latter two crystallise with 4H20 but the strontium salt crystallises with 5H20. The molecular volumes of the crystalline hydrates were1 also measured giving 93.83 109.3 and 98.26 for the calcium strontium and barium salts respectively. H. M. 1). H. M. D. The Structure of Silver Crystals. L. VEGARD (Phil. Mag. 1916 [vi] 31 83-87).-Rontgen-ray analysis of the structure of stlver crystals has shown that the atoms are arranged according to the simple f ace-centxed lattice which is identical with the arrange- ment fiund by Bragg (A. 1914 ii 775) f o r crystals of copper.- H. M. D. Investigations in the Field of Silicate Chemistry. IV. Data for the Meta- and Ortho-silicates of the Bivalent Metals Glucinum Magneeium Calcium Strontium Barium Zinc Cadmium and Manganese. F. M. JAEGER and H. S. VAN KLOOSTER (Proc. K . Akad. Wetensch. Amsterdam 1916 18 896-913. Compare A 1914 ii 363 810).-The silicates were pre- pared synthetically by heating together pure finely-powdered quartz with the1 pure oxides or carbonates of the metals in iridium-free platinum crucibles and repeating the process after the addition of silica or metallic oxide until the finely-ground product was found bylNORGAN IC CHEMISTRY.ii. 187 aiialysis t o be of the right composition. The inelting points densi- ties and refractive indices were measured and tlie data are given in the following summary glucinum metasilicate m. p. >1750°; strontium metasilicate rap. 1 5 ‘ 7 8 O 3.6.52 ?zl 1.620 7Z2 1.590 ; strontium orthosilicate m. p. >1750° ; barium metasilicate m. p. 1604O Df“ 4.435 7zl 1.6‘70 i z 2 1.667 ; barium orthosilicate m. p. >1750° ; zinc metasilicate m. p. 1437O UF 3.52 n1 1.623 7Z2 1.616 ; zinc orthosilicate m. p. 1509*5’ n1 1.719 n2 1-697 ; cadmium meta- silicate ni. p. 124Z0 Uy 4.925 i z l and 7 1 ~ >1.739 ; cadmium ortho- silicate m. p. circa 125d0 n1 and 7z2 >1.iY9 ; manganese nietasilicate m. p. ld’i3” Dfj 39’16 7z1 1.739 7z2 1.733; manganese orthosilicate (tephroite) in.p. 1290-ldOOo UT 4.044 7z1 and ia2 >1*739. By comparison with previous data for the calcium and magnesium silicates it is found that the m. p. of calcium strontium and barium inetasilica tes increase regularly with increasing atomic weight of the metal whilst the dat’a f o r the metasilicates in the series mag- nesium zinc cadmium show a regular decrease with increase in the atomic weight. H. M. D. Action of Boiling Acetic Propionic and Butyric Acids on Aluminium with a Note on the Action of Formic and Some Higher Acids. KICIIARD SELIGMAN and PERCY WILLIAMS (J. SOC. Chem. Iiad. 1916 35 88-93).-The corrosion of alumin- ium by the acids of the acetic acid series is conditioned largely by tlie concentration of the acid in question.The rate of dissolution falls as the strength of the acid increases a 99% acetic acid having only about one-tenth of the action of a 90% acid. With a perfectly anhydrous acid however the rate of dissolution increasw a hundsed- fold. I n these circumstances a crystalline acetate is formed contain- ing more acetic acid than the least basic acetate hitherto described and the increased action is apparently due either to the smaller protection afforded t o the surface of the metal by the crystalline acetate than by the basic gelatinous acetate formed when moisture is present or t o the formatioii of a protective coating of oxide when water is present which retards a normal high rate of dissolution of the metal in these acids. The behaviour of propionic and butyric acids is analogous t o that of acetic above described.Formic acid of 77% strength rapidly attacks aluminium a crystalline f ormate being formed which unlike the other salts is not decomposed by the water present into a gelatinous basic salt. All the above acids in a diluted form attack the metal rapidly because the solubility of the basic salts increases rapidly as the strength of the acid falls. With stearic and other higher fatty acids moisture also appears t o play a part. Below 300O the metal is unattacked; above this tem- perature action is rapid and continues when the temperature has fallen even t o looo. A t this lower temperature stearic acid attacks amalgamated aluminium and i t is considered that this is due to the fact that a protective coating of oxide cannot be formed in presence of the mercury.G. F. M. V. VINCENT (Comyt. re?7d. 1916 162 259-261).-Manganese is present in Circulation of Manganese in Natural Waters.ii. 188 ABSTRACTS OF CHEMICAL PAPERS. solution in natural waters in the form of manganese hydrogen carbonate. Of the three oxides manganous oxide is most soluble in water saturated with carbon dioxide then comes the sesquioxide the least soluble being manganese dioxide. A humus solution only dissolves manganous oxide or manganese carbonate being without action on the sesquioxide and the dioxide. The naturally occurring oxide being the sesquioxide this explains tlie low content of man- ganese in natural waters the drainage1 waters from the experimental field being foucd to contaic only 0.01 mg. of manganese per litre.The action of the commonly used fertiliwrs is much inferior to that of carbon dioxide in dissolving the manganesel. W. G. Action of Certain Chlorinated Hydrocarbons on Some Metals in the Presence of Moisture. SOSALE GARALAPURY SASTRY (J. SOC. Ghem. Ind. 1916 35 94-95).-The corroding action of some of the technical chlorinated solvents on steel iron nickel copper aluminium and lead was studied by boiling thin strips of metal in the various solvents for periods of ten hours and determining the loss in weight. Di- and tri-chloroethylene were found t o cause the least corrosion in all cases the action of tetra- and pecta-chloroethane being much more pronounced and in the case of aluminium the metal was completely destroyed probably owing to the dissociation of the solvents into hydrogen chloride and chloroethylenes.The corrosive action is naturally increased in the presence of moisture. Towards tlie chlorinatled ethanes nickel was in general the most resistant. Carbon tetrachloride had no measur- able corrosive action under the above experimental conditions on any of the metals except copper and lead and then only to a very slight extent. G. F. M. Synthesis of Nickel Arsenides. A. BEUTELL (Ceyztr. Miiz. 1916 49-56).-Comparativel experiments were made by heating metallic nickel cobalt and smaltite in an atmosphere of arsenic a t temperatures of 300-450° (compare A. 1916 ii 142). Owing t o the fact that a skin of arsenide forms on the surface of the material i t is necessary t o continue the heating for many weeks and t'o re-powder the material several time's before a condition of equilibrium is attained.At 400° there is no marked diffesence between the behaviour of nickel and cobalt but a t 450° the sinter- ing of the nickel arsenide cause6 the reaction t o cease# whilst with cobalt it proceeds slowly. The highest nickel arsenide obtained was NiAs and there are no well-marked stages in the process between NiAs and NiAs2. Amphoteric Metallic Hydroxides. 111. JOHN KERFOOT WOOD and VERA KATHLEEN BLACK (T. 1916 109 164-171. Com- pare T. 1908 93 411; 1910 97 878).-In view of the inconclusive nature of the evidence afforded by previous observations on the acidic character of chromium hydroxide further experiments have been made in which chromic hydroxide prepared from chrome alum by precipitation with ammonia was eIxposed to the action of soh- L.J. S.INORGANIC CHEMISTRY. ii. 189 tions of sodium hydroxide a t 2 5 O for prolonged periods of time. I n these circumstances the solut'ions slowly acquired a yellow colour due to the formation of chromate. The observation is considered t o indicate the amphoteric character of chromium hydroxide the chromate resulting from the oxidation of the dissolved chromib. I n support of this view it was found t h a t no chromate was formed when the sodium hydroxide solution was made up with freshly boiled water and the containing vessel was completely filled. The ratel of formation of chromate1 increases with the concentra- tion of the alkali solution but these are not proportional and from this the authors draw the conclusion that the chromium hydroxide behaves as a polybasic acid.Attempts t o measure' the degree of hydrolysis of chromic chloride solutions by the ester catalysis method were unsuccessful. H. M. D. Experiments on the Separation of Vanadium from Crude Sodium Uranate. H. H. BARKER and H. SCHLUNDT ( J . Xoc. Ghem. Znd. 1916 35 175; from Met. and Chem. Eng. 1916 14 18-23).-The following methods are1 suggested for the direct separation of vanadium from the crude sodium uranate obtained as a by-product in the extraction of radium from carnotite (1) On a laboratory scale vanadium was completely volatilised by the action of gaseous hydrogen chloride and a residue was obtained consisting of sodium uranate and chloride and uranyl chloride from which 59-64% of the total uranium was recovered as pure oxide by boiling with ammonium chloride and igniting the ammonium uranate produced.By proper regulation of temperature vanadium could probably be removed directly and quantitatively from carno- tite by this method. (2) By heatinq the crude uranate with ammonium chloride and sufficient water to form a paste the vana- dium content was reduced from 8.5 t o less than 0.5% and the uranium was partly converted into oxide. (3) By dissolvinq the crude uranate in the least possible quantity of dilute hydrochloric or nitric or in some cases salphuric acid and boiling the solution the vanadium was completely co-precipitated with about 13% of the uranium and pure uraniurll oxide was obtained by adding ammonia t'o the filtrate and iqnitinq the ammonium uranate obtained.By this means from 5 8 O 6 t o 79% of the total uranium was recovered as pure oxide when dilute hydrochloric or nitric acid was employed. G. F. M. Atomic Weight of Bismuth. W. CECHSNER DT~ CONINCK and G~RARD (Compt. rend. 1916 162 252).-The bismuth used was freed from arsenic and sulphur by fusing it several times with potassium nitrate. It was then converted into its chloride which was used far the determination. The pure chloride was weighed reduced by pure hydrogen and the resulting metal weighed. The atomic weight was calculated from these two weights and the mean of four determinations gave the value 208.50 f o r the atomic weight of bismuth. W. G.ii. 190 ARSTRACTS OF CHEMICAL PAPERS.Subhaloid Compounds of Some Elements. IT. So-called Bismuth Subchloride a n d Sub-bromide. I;. MARINO and R. BECARELLI ( A t t i R. Acctxd. Lincei 1915 [v] 24 ii 625-631. Compare A. 1913 ii 227; A. 1915 ii 770).-When mixtures of bismuth with proportions of bismuth trichloride or tribromide varying from 5% to 85% are fused in the sealed tubes previously used by the authors two layers are obtained above 320° the upper one being black and the lower white with a metallic lustre. Lower- ing of thel temperature results in the formation (1) from one of the two strata of a crystallinel product melting over thel range 270-305O for the! bromide or 270-320° for the chloride; a t about 240° this is transformed into two other products ( a ) m. p. about 260° and ( b ) m. p.270-305° and 270-320° in the two cases; (2) from the other stratum the eutectic Bi-BiBr m. p. about 200° or Bi-BiCl m. p. about 180O. The authors regard the crystalline product as a series of mixed crystals formed with very little develop- ment of heat,. The melting points of these series are in all cases higher than those of the components b u t it has not been found possible( t o establish exactly the limits of their region of existence oh to ascertain if the equilibrium curve exhibits a maximum since the experimental results are complicated by the suhlimation of the tribromide or trichloride. Eggink's conclusions (A . 1908. ii 1043) are regarded as erroneous. Subhaloid Compounds of Some ElementP. 111 and IV. The So-called Bismuth Sub-bromide. 11. MARINO and R.BECARELLI ( A t t i R. Acccrd. Lincei 1916 [v] 25 i 105-111 171-177).-111. The experimental data obtained in the cryoscopic investigation of the system bismuth-bismuth tribromide (preceding abstract) are given. IV. From all the upper layers formed in different mixtures of bismuth and bismuth bromide a t 200° there drops in greater or less quantity according t o the composition of the mixture a liquid which on cooling forms the black hygroscopic substance' previously mentioned. F o r each of these strata there remains a crystalline network which melts between about 270° and 300-305O and is regarded as a series of mixe'd crystals which undergo transformation into a ,&form and then into a ./-form with pronounced development of heat. The melting point of the y-crystals is always above those of bismuth and bismuth tribromide and on fusion and cooling they yield a-crystals of different composition together with two liquid strata which reproduce1 this series of changes.A t 153O bismuth tribromide undergoes transformation into the solid form. Eggink's conclusions (A. 1908 ii 1043) appear t o call for revision. T. H. P. T. H. P. Rapid Method of Converting Scrap Platinum into Chloro- platinic Acid. J. BISHOP TINGLE and ALFRED TINGLE (J. SOC. Chern. Znd. 1916 35 77).-The conversion of scrap platinum into chloroplatinic acid is facilitated by alloying it with some base metal preferably zinc by fusion under a layer of borax. The alloy isMINERALOGICAL CHEMISTRY. ii. 191 treated with hydrochloric acid which dissolves out most of the zinc and leaves the platinum as a finely divided black powder which is almost instantly soluble in aqua regia. This solution contains some zinc and is accordingly treated either with a rod of pure zinc t o precipitate the platinum or with hydrogen sulphide the precipitated platinum sulphide being washed and ignited. The residue of platinum obtained in either case is dissolved in aqua regia excess of acid is expelled by evaporating t o dryness and the residue dis- solved in water forms a solution of pure chloroplatinic acid. G. F. M.

ISSN:0368-1769    

DOI:10.1039/CA9161005184

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 191 Melting Points and Boiling Points of Mineral Sulphidee Selenides and Tellurides of the Metalloids. L. H. BORGSTROM @ah?%. Mi?&. 1916 i Ref. 9-11; from ofversigt Finska Vetens.- SOC. J'tjrh 1915 57 Afd. A No. 24 l-l3).-The method of deter- mining the melting points of minerals from the heating and cooling curves necessitates the use of a considerable amount of material whilst the microscopic method lacks accuracy. The author has made use of a method employed f o r organic substances the1 subsbance being encIoaed in a capillary tube of silica-glass and immersed in a transparent bath of fused salts (mixtures of sodium and potassium nitrates sodium potassium and lithium chlorides and sodium sulphate in various proportions according t o the temperature required).The results obtained are tabulated below . Melting point. Boiling point. Realgar (ASS) ........................... 307-314" 589" Stibnite (Sb,S,3) ........................ 546-551 990 about Orpiment (As,S,) ........................ 320-325 690 Bismuth-glance (Bi,S,) ............... 717-720 _- Guanajuatite (Bi,$e,). ................. 690 Tetradymite (Bi,[Te,S],) ............ 593-602 - Molybdenite (MoS,) .................. infusible - Kermesits (Sb,S,O) .................. 516-518 - A connexion is traced bet'wween the melting points and the geolo- gical occurrence of these minerals those with higher melting points being found a t greater depths in the earth's crust. - L. J. S. Alotrichite from Rio (Elba). FEDERICO MILLOSEVICH (Atti R..4ccad. Lincei 1915 [v] 24 ii 501-503).-1n addition to the numerous sulphates which have been observed in the ferriferous deposits of Elba the author has now found two specimens of alotri- chite collecteid a t Rio. The mineral occurs in moderately compactii. 192 ABSTRACTS OF CHEMICAL PAPERS. masses of fibrous structure the fibres which have an almost parallel arrangement being whitel or faintly blue and of a silky lustre; Ill4 1.901 hardness about 2.5. Analysis gives the figures SO,. A1,0,. Fe,O,. FeO. CaO. H,O. Total. 35.40 11.97 0.67 7.49 trace 43.80 99.33 which are in fairly satisfactory agreement with the formula FeS0,,A12(S04),,24H20. The deficit of water is due t o partial dehydration which occurs a t the ordinary temperature' in a dry atmosphere and the excess of sulphuric acid t o the presence of ferric alumioium and calcium sulphates as impurities.The two specimens werel accompanied by small crystals of pyrites and scales of hEmatite. It is considered probable that the angle of extinction of alotrichites varies with the content of iron and possibly with that of water. T. H. P. New Mineral Occurrences from the Tintic District Utab. A. H. MEANS (Amer. J . Sci. 1916 [iv] 41 125-130).-The follow- ing mineral species present in mixed ore samples were deter- mined by qualitative tests geocronite adaniite daubreeite ( ?) (2Bi203,BiC13,3H20) as small yellowisli-brown rosettes of slender hexagonal prisms with brilliant lustre bismite ( 1 ) (Bi203) and jarosite. Bismutite (Bi20,,C02,H20) occurs in the Victoria mine as thin dark veinlets in an ore containing argentite barytes quartz etc.; analysis by R.C. Wells of the mixed mass gave I. Arseszo- bismite a new bismuth arsenate occurs in considerable amount in the Mammoth mine. The heavy yellow friable1 ore consists of a mixture of arseno-bismite limonite barytes erinite and mixite. Analysis 11 by R. C. Wells is of the heavy concentrate obtained by vanning. Deducting large amounts of impurities the formula is deduced as 2Bi,03,As20,,2H,0. The material forms yellowish- green crystalline aggregates; D 5.70 Bi,O.{. As,O,. F'e,O,. PbO. CaO. SO,. CO,. H,O. Insol. Total. I.* 18.07 0.05 0.92 0.31 0.76 0.58 2.48 - 66.10 96.99 11.1- 28.17 10.59 3.88 1.12 0.62 0.46 - 2.52 49.92 99.14 Also loss on ignition 3.57 Ag 4.15.Also A1,0 0.44 CuO 0.12 MgO trace P,O 0.04 Sb,O 1.26. The abo~7e formula deduced from this analysis approximates to those of atelestite and rhagite. L. J. S. Intumescent Kaolinite. W. T. SCHALLER wid R. K. BAILEY ( J . Washington Acad. Sci. 1916 6 67-68).-White7 glistening lumps from Back Bone Mountain Le Flore Co. Oklahoma consist of minute hexagonal cryst'als with refractive indices a 1.561 P 1.563 y 1.567. The results of analysis-SiO 46.55; A120 38.90; H20 14.04 = 99.49-agree very closely with the kaolinib formula. Loss of water a t 1 4 5 O 0.09%; a t 220° 0*11% and a t 330° 0.12%. The mineral only differs from ordinary kaolinit'e in the fact that it intamesoes strongly before the blowpipe. L. J. 8.ANALYTICAL CHEMISTRY. ii. 193 The Variable Composition of Melanochalcite.W. F. Hum and E. H. KRAUS (Amer. J . Sci. 1916 [iv] 41 211-214).-A lustrous pitcliy-black mineral occurring a t Bisbee Arizona as a banded coating on massive cuprite and penetrated by thread-like veins of chrysocolla and malachite closely resembles the melanochal- cite of G. A. Koenig (A 1903 ii 156) from the same locality. It differs from this slightly in the colour of its bsownish-black streak and in its sp. gr. of 4.704. It gave analysis I; Koenig's analysis is quoted under 11 CuO. SiO,. CO,. H,O. ZnO. Fe,O,. Total. I. 88-94 4.31 1.78 4.48 0.12 0.22 99-86 11. 76.88 7.80 7.17 7-71 0-41 0.07 100.04 Analysis I is interpreted as a mechanical mixture of tenorite (68*6%) chrysocolla (20%) and malachitel (11.4%); and I1 as a mixture of the same minerals in the respective amounts 30.876 30*8% and 38.4%. This view is support'ed by a microscopical exam- ination of the powdered mineral. Cold dilube acid dissolves the particles of malachite leaving the tenorite and chrysocolla. Melano- chalcite is therefore not a mineral species but a mixture. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9161005191

出版商:RSC    

年代:1916

数据来源: RSC