摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON ORGANIC CHEMISTRY. H. RRERETON BAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CEOSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. BERNARDYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.R.S. F. R. S. T. M. LOWPLY D.Sc. A. bfCKENZIE M.A. D.Sc. P1i.D. W. H. PERKIN Sc.D. LL.D. F.R.8 J. C. PHILIP D.Sc. Ph.D. F. B. Powmi Ph.D. LL.D. A. SCOTT N . A . D.Sc. F.R.S. S. SMILES D.Sc. @bitox J. C. GAIN DSc. Ph.D. %dJ-dfbbitDr A. J. GREENAWAY. E. F. ARMSTRONG l’h.D. D.Sc. I?. BARROW M.Sc. Ph.D. R. J. CALDWELL D.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. P1i.D. W. H. GLOVER Ph.Z). W. GODDEN B.Sc. E. GOULDING D.Sc. JV. D. HALLIBUKTON M.D. F.R.S. T. A. HENRY D.Sc. H. R. HUTCHINSON P11.D. L. DE KONINGH. G. D. LANDER D.Sc. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. T. H. POPE R.Sc. T. SLATER PRICE D.Sc. Y1i.D. S . B. SCIIRYVER D.Sc. Ph.D. W. P. SKEHTCHLY. C. SMITH D.Sc. F. SODDY M.A. F.R.S. J. F. SPEXCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc. Ph.D. W. J. YOUNG M.s~. n.sc. 1913. Vol. CIV. Part I. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 1913.RICHARD CLAY & SONS LIX~TED BRUXSWICK STREET STAMFORD STREET S.E. AND BUXGAT SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91304FP001

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON PHYSICAL INORGANIC MINEIEALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. AND dommittae o f @ubtitrttion H. RRERETON RAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY n.Sc. Ph.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. I~ERNARD DYER D.Sc. hl. 0. FORSTER I).&. Ph.D. F.R.S. F.R.S. E. F. AHMBTROKG. Ph.D. T. M. LOWRY D.Sc. A. MCKENZIE M.A. D.Sc. Ph.D. W. H. PERKIN Sc.D. LLD. F.R.S. J. C. PHILIP D.Sc. Ph.D. F. B. POWER Ph.D. LL.D. A. SCOTT M.A. D.Sc. F.R.S. S. SMILES D.Sc. @hAK J. C. CAIN D.Sc. Ph.D. A. J. GREENAWAY. S,ub.-Qbitor 8bdrattarw D. Sc. F. BARROW M.Sc1 Ph.D R. J. CALDWELL D.Sc. H. M. DAWBON Ph.D. D.Sc. C. H. DESCR D.Sc. P11.L). W. H. GLOVER Ph.D. W. GODDEN R.8c. E. GOULDINO D.Sc. W. D. HALLIBURTOK BI.D. F.R.S. T. A. HENRY D.Sc. H. B. HUTCHINSON Ph.D. I,. DE KONINGH. G . D. I,ANDER. D.Sc. 1’. H. POPE 13.S~. T. SLATER PRICE D.Sc. Ph.D. S. B. SCHRYVER D.Sc. Ph.D. W. P. SKERTCHLY. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STAXFORD M.Sc. 1’h.D. D. F. Twiss D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS P1i.D. c. SMITH D.Sc. H. WREN M.A. D.Sc. Ph.D. \Ir. J. YOUNG M.Sc. D.Sc. F. M. G. MIC~LETHWAIT. N.H. J. MILLER Ph.D. I - 1913. Vol. CIV. Part 11. LONDON GURNEY L JACKSON 33 PATERNOSTRR ROW E.C. 1013.RICHARD CLAY & SONS LIMITED BRUNSWICK STREET STAMFORD STREET S.E. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91304FP003

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 39 The Behaviour of Water as a Liquid and in Five Solid Modifications Under Pressure. P. W. BRIDGMAN (Zeitsch. anorg. Chem 1912 77 377-455).-The behaviour of water has been examined under higher pressures than in previous experiments liquid water being studied between - 20' and + 80° up to 12,800 kilograms per sq. cm. and solid water between -80' and 97s' up to 20,500 kilograms per sq. cm. Two new modifications of ice one of which is capable of existing above O' have been discovered. Five of the six stable triple points have been found and ten of the eleven trans- formation lines have been followed. In addition to the five stable solid modifications two exist which have no range of stability. All with the exception of ordinary ice are denser than water.The temperature of maximum density of water is independent of the pressure but the maximum disappears at high pressures ; a new anomaly appears however between - 1 5 O and - 20° a t a pressure of 5000 kilo- grams. The increased compressibility a t high pressures suggests a possible compressibility of the atoms as well as of the molecules but the data are still insufficient to construct an equation for the behaviour of liquid water. The results with the solid phases confirm and extend those of Tammann The oquilibrium curve between ice I1 and 111 which was not found by Tammann has now been determined. The water isii. 40 ABSTRACTS OF CHEMICAL PAPERS. enclosed in a vessel filled with light petroleum and the pressure is measured by the change in resistance of a manganin wire.I n order to determine the curve 11-111 along which the volume changes are very small a different mothod has t o be adopted the temperature being varied a t constant volume and the changes of pressure ob- served. Ice VI which is formed at temperatures above 0' under high pressure has the greatest range of existence as regards both tempera- ture and pressure and the form of the curve is such as to indicate that further modifications are not formed. The existence of two modifications having no range of stability is inferred from the occurrence of volume changes which do not lie on any of the equilibrium curves. The observations confirm the impossibility of superheating a solid phase with respect to the liquid whilst undercooling readily takes place and many of the curves have been prolonged into the region of instability but an unstable triple point has not yet been realised and indications of a metastable limit have not betn found.Nuclei of a previously existing phase appear to persist even in a solid phase. The velocity of tiansformation even in solid phases is extrerriely high in the neighbourhood of a triple point but diminibhes rapidly with falling temperature. Thebearing of these results on the theory of the solid state is discussed. A New Modification of Sulphur. A. H. W. ATEN (PYOC. K. Wetensch. Amstsrdum 1912 15 572-583 ; Zeitsch. physikul. Chem. 1912 81 257-280).-1f a solution of rhombic sulphur in sulphur chloride saturated a t the ordinary temperature is heated a t about 150' and then cooled it is found that a further and considerable quantity of sulphur may be dissolved in the liquid.It is shown that this cannot be due to the formation of 8 from S' for the solubility of 8 in sulphur chloride is very small at the ordinary temperature and if solutions saturated with S a t a higher temperature are cooled down this separates out quite readily. I n order to ascertain whether this phenomenon is due to the forma- tion of a new modification of sulphur or to the combination of sulphur with the sulphur chloride systematic determinations have been made of the solubility of rhombic sulphur in sulphur chloride which has been heated with varying proportions of sulphur a t a definite tem- perature and then cooled to either 25" O' or - 60'.The data thus obtained point to the formation of a new variety of sulphur. If this conclusion is correct i t should be possible t o obtain some indication of its formation in the absence of sulphur chloride. This is actually the case for if sulphur is heated alone to 125' and rapidly cooled and its solubility in sulphur chloride examined it is found that the solubility is distinctly greater than that of unheated rhombic sulphur. C. H. D. H. M. D. Tho Relation between the Sulphur Modifications. H. I;. DE LEEUW (Yroc. IT. Akad. Wetensch. Amslerdcm 191 2 15 584-593). -If the sulphur contained in a dilatometer tube is heated t.0 its boiling point and then rapidly cooled so that a large proportion of theINORCANIC CHEMISTRY. ii. 41 S formed remains intact it is found that the temperature of conver- sion of rhombic into monoclinic sulphur is lowered from 95-45' to about 71".As the proportion of S present decreases the transition temperature rises until it reaches 95*45O which must be regarded as the true unary transition point. Kruyt's work (A. 1911 ii 879 ; 191 2 ii 1051) on the dynamic allotropy of sulphur is criticised adversely and in particular it is shown that there is no evidence for the assump- tion of a region of partial miscibility in tbe liquid phase. The occurrence of two liquid layers is due to differences in tempera- ture and when the thermal conductivity is increased by the introduction of platinum wire or gauze the phenomenon in question is only observed very indistinctly or not at all. Alleged Complexity of Tellurium.WILLIAM C. MORGAN (J. Amw. Chenh. SOC. 1912 34,1669-1675).-Flint (A. 1910 ii S45 ; 1912 ii 1051) has stated that by fractional hydrolysis of tellurium tetrachloride he obtained two fractions one giving the atomic weight 124.3 and the other which was still impure the atomic weight 128.85. This work has now been repeated with a large quantity of material biit the results do not show progressive diminution of the atomic weight and thus fail to confirm Flint's conclusion. I n view of these experiments and those of other investigators the author considers that the evidence for the homogeneity of tellurium is quite convincing. [Compounds of Tellurium and Iodine.] FRANS M. JAEGER and J. B. MENKE (Zeitsch. anorg. Chem. 1912 77 320. Compare A. 1912 ii 344)-It is not possible to determine the freezing point of mixtures containing more than 70% of tellurium in an open vessel and mixtures rich in iodine boil.The compound TeI dissociates when heated in carbon dioxide. The Ternary System Tellurium Tetra-iodide-Hydrogen Iodide-Iodine and the Estimation of Tellurium by means of Hydrazine Hydrate. J. €3. MENKE (Zeitsch. cmorg. Chem. 1912 77 282-28s. Compare Jaeger and Menke A. 1912 ii 344).- Tellurium tetra-iodide prepared by melting together its components is heated wit,h hydriodic acid and iodine in a sealed glass tube ten days being allowed for the attainment of equilibrium in each experi- ment. The only solid phases found are TeI4,HI,8H,O and iodine. A hexa-iodide is thus not obtained either by fusion or from solution.'l'he double compound resembles iodine in appearance. For analysis the free iodine is titrated with thiosulphato after neutralisation with sodium hydrogen carbonate ; the total iodine is estimated as silver iodide after removal of most of the tellurium by alkali sulphite. The method of Gutbier and Flury (A 1902 ii 653) is not applicable to tellurium tetra-iodide and the reduction of tellurium by means of sulphur dioxide is not exact as the fine amorphous tellurium readily oxidises. Precipitation by means of hydrazine hydrate is usually incomplete as the filtrate contains colloidal tellurium. In acid solution the precipitation is almost complete but the excess of acid must be noutralised before filtration otherwise the precipitate partly redissolves. H. M. D.E. G. C. H. D. C. H. D.ii. 42 ABSTRACTS OF CHEMICAL PAPERS. The Validity of Werner's Theory of Subsidiary Valencies for Ammoniates. WALTER PETERS (Zeitsch. anorg. Chern. 1912 77 137-190).-The addition of ammonia to inorganic salts has been studied by means of the apparatus of Ley and Wiegaer (A. 1905 i 749). After saturating the solid with ammonia it is weighed trans- ferred to a vacuum until the weight is constant and again saturated. Addition takes place more readily the second time and in some cases a further quantity of ammonia is added. The number of molecules added depends on the degree of saturation of the salt molecule and on the residual affinity of its ions and when salts with the same anion but different cations are compared analo- gies corresponding with the periodic system are observed.The number of molecules of ammonia is most frequently R ~ X or a multiple of six which is in accordance with Werner's hypothesis. The following new compounds have been prepared CuC1,3NH3 ; CuBr,3NH3 ; CuI,3NH3 ; CuCN,$NH ; Cu(NO3),,5NH ; AgCl,SNH ; AgBr,Z$NH ; AgI,+NH ; AgCNO,NH,; AgCNS,ZNH,; AgNO3,3NH,; KAuU1,,3NH3; IT Au(CNS)~,~NH ; ZnS04,H20,6NH,; K2Hg14,2NH3 ; BaHg14,8NH,; Cu,HgI,,GNH,; CdHgl4,6NH,; CrCl,,GNH,; Hg(CBs),,4NH3 ; Hg(C,H302)2,4NH ; Hg(C,H,02)p4NH3 ; UC1,,3NH3 ; UG2C1,,2NH3 ; Mn6I296NH3 ; Mn12,6NH ; MnSO,,fiNH ; iSlnS0,,H20,5NH ; FeS04,H,0,5NH ; Zn2Fe(CN),,7NH3 ; Mn2Fe(CN),,2NH3 ; Cd,Fe(CN),,7NH3 ; Co,Fe(CN),,3NH3 ; Ni2Fe(CN),,7NH3 ; Mn,[Fe(CN),],,GNH ; CLI,[F~(CN)~],,~ 6NH ; Cd,[Fe(CN),]2,1SH20 ; Co,LPe(CN),],,SNH ; Na,FeNO(CN),,ZNH ; Ni(SCN),,GNH ; NiS,O6,6NH3 ; Co(CN),,2NH3 ; Co(SCN),,6NH3 ; RuC1,3NH3 ; RuBr,,3NH3 ; RhC1,,4NH3 ; PdCj2,5NH ; PdI,,6NH3 ; Na2PdCI,,5NH3 ; ( NH4),PdC1,,5NH ; PtC1,,5NH3; Pt12,6NH ; Na2PtC1,,4NH ; Ag,PtCl,,GNH,(7~NH3 at low temperatures) ; K,Pt(CK)),,NH ; KNaPt(CN),,2N& ; CuPt(CN )".4NH0 Zn3[Fe('N),]2,12NH3 ; Ag,Pt(CN),,5NH3 ; MgPt(CN)i,4N'$ ; E;Pt(CN),,GNH ; ZnPt(CN),,4NH ; CdPt(CN),,CiNH ; MnPt(CN)4,4N€I ; FePt (CN),.4NH0 NiPt(CN),,GNH ; CoPt(CN),,6NH;'; Cal%(CN),,3NH3 ; K2Pt( S(?N),,2NH ; CuPt(SCN),,8XH3 ; Ag2Pt(SCN),,6NH ; PtCl,,GNH ; PtBr4,6NH ; Na2PtC1,,6NH3 ; Ag2PtU1,,8NH (lONH a t - 10') ; CuPtC16,18NH3 ; CaPtC1,,12NH3 ; BaPtCI,,GNH ; ZnPtCI6,11NH ; CdPtCl 182JM ; RtnPtC1,,1 lNH,; NiPtC1,,12NH3 ; CoPtC16,12NH,( 18NH a t - 20' ; Na,PtBr6,6NH ; K,Pt(SCN),,lBNH ; (NH,),Pt(SCN),,15NH3 ; CuPt(SCN),,15NH3 ; Ag2Pt(SCN),,14NH ; hu2[Pt(S(11N),],,30NH3 ; BaPt(SCN)6,1 2NH ; ZnPt(SCN)6,15NH ; CdPt(SCN),,18NH3 ; TI,Pt(SCN),,gNH ;INORGANIC CHEMISTRY.ii. 43 MnPt(SCN),,lSNH ; NiPt(SCN),,lSNH ; CoPL(SCN),,14NH3 ; K,Pt( SeCN),,GNH,. Hydrogen chloride and hydrogen phosphide are not absorbed by any inorganic salts under similar conditions. The absorption spectra of aqueous solutions of the compounds CuCI,,GNH and CuPtC1,,18NH3 show that both the long visible waves and the ultra-violet are absorbed the transmitted band being narrower in the case of the double salt. Determinations of the vapour pressure of several of the compounds have been made by means of a tensimeter. C. H. D. Revision of the Atomic Weight of Phosphorus.111. Analysis of Phosphorus Trichloride. GREGORY P. BAXTER and CHARLES J. MOORE (J. Arner. Chem. Soc. 1912 34 1644-1657).-1n earlier papers (Baxter and Joned A. 1910 ii 288; Baxter Moore and Boylston A 1912 ii 347) accounts have been given of determinations of the atomic weight of phosphorus by the analysis of silver phosphate and phosphorus tribromide. The investigation has now been extended to the analysis of phosphorus trichloride. Phosphorus trichloride was prepared and analysed by methods similar to those employed in the case of the tribromide. The product was freed from the pentachloride by distillation in a vacuum. Two series of fractions were collected and analysed in the usual way after decomposition with water and oxidation of the phosphorous acid produced.From the average of twenty-four analyses the value for the atomic weight of phosphorus was found to be 31.018 (Ag= 107*880 ; C1= 35.457) as compared with 31.04 obtained from the analysis of silver phosphate and 31.027 from that of phosphorus tribromide. The averdge of the results from the tribromide and trichloride is 31.023. E. G. The Density of Phosphorus Vapour. ALFRED STOCK GEORGE E. GIBSON and ERICH STAMM (Ber. 1912 45 3527-3539).-A membrane-manometer which is a special modification of the spiral manometer of Ladenburg and Lehmann (Bsr. Deut. physikal. Ges. 1906 4 20) and is to be described in another paper was used to determine the vapour density of phosphorus; the manometer is sensitive to 0.5 mm. difference in pressure.Purified red phosphorus which can be obtained in a purer condition than colourless phosphorus was used in the experiments at the t'emperature of which i t was completely transformed in to vapour. At temperatures between 500" and 700" the vapour density corre- sponds exactly with the forrnult P,. At higher temperatures dissociation takes place but even at 1200" it is only 61% under a pressure of 175 mm. Calculations made on the assumption that the dissociation which occurs is in accordance with the equation P 2P give a very good agreement between theory arid experi- ment. Under atmospheric pressure the degrees of dissociation at 800" 1000° and 1200" are respectively 0.01 0.1 and 0133 ; under aii. 44 ABSTRACTS OF CHEMICAL PAPERS pressure of 0.25 atmos.the degree of dissociation is almost 0.66 at 1200O. Calculation of the heat of dissociation gives values varying from -49,200 to -60,300 cals. The above results do not agree with previous measurements but various measurements were so concordant that there is every probability of their accuracy. The experiments of Preuner and Brockmolier (A 1912 ii 1146) are probably untrustworthy because they used ordinary commercial phosphorus. T. S. P. Boron Hydrides. ALFRED STOCK and CARL MASSENEZ (Be?.. 1912 45 3539-3568).-The boron hydrides obtained by the authors have been prepared by the action of hydrochloric acid on magnesium boride. Full details are given of the conditions needful for the preparation of a satisfactory sample of magnesium boride from magnesium and boron trioxide.The decomposition of the boride with acid was carried out in an apparatus similar to that used in the preparation of antimony hydride (A. 1904 ii 246) the boride being dropped continuously into t h e acid whilst a slow stream of hydrogen is passed through the apparatus. The decomposition is carried out at 50° using 4N-hydro- chloric acid. The evolved gases are passed through U-tubes im- mersed in liquid air a snow-like deposit forming whilst hydrogen passes on. The first portions of gas escaping from the U-tube smell strongly of boron hydride but as soon as the solid forms i t prevents the escape of any more hydride. The deposit consists of boron hydrides together with silicon hydrides and carbon dioxide from impurities in the materials used It is fractionally distilled at varying pressures and temperatures in order to remove the impurities.Hydrogen and traces of silicon hydride are removed by evacuating at the temperature of liquid air. The temperature is then raised to -SOo when the solid Melts to a colourless strong refracting liquid having a pressure of 250 mm. The pressure can be rnpidly diminished t o a few millimetres whereby silicon hydridw carbon dioxide and any traces of hydrogen phosphide or sulphide which may be present are removed. As soon as the gas is free from silicon hydride it is collected separately a t a pressure of less than 3 mm. the temperature of the room in which the distillation is being carried out being maintained above 20° otherwise liquid hydride would be coudensed in the mercury pump used.The gas collected a t this pressure and temperature consists of the boron hydride B,H,,. The residue is then warmed to -40' and dietilled until the pressure falls to 14 mm. the temperature further raised to Oo and distillation proceeded with until the pressure falls to 9-10 mm. in order to remove all the hydride B4Hlo. The remaining iiquici on Turther distillation gives the boron hyiricle B,Hl the pressure falling below 5 mm. Two hundred grams of magnesium boride give about; 100 C.C. of the pure hydride B4H10 and 60 mg. of the hydride B,H,,. Owing to the fact that these hjdrides possess compositians veryINORGANIC CHEMISTRY. ii. 45 different from what was to be expected t h e j were i~nalysed by a numbor of different methods. The hydride B4HIo was analysed as follows (1) a known volume was decomposed by passing slowly through a weighed quartz tube at 500' and the hydrogen collected. The boron was weighed directly and also oxidised to boric acid and estimated volumetrically; (2) atl room temperature the gas is slowly decomposed by water with liberation of hydrogen and formation of boric acid.The results are in accordance with the equation B,HIo + 12H,O 4B(OH) + 1 IH,. (3) Decomposition also takes place in the presence of sodium hydroxide the results according with the equation B,Hlo + 4NaOH + 4H,O = 4NaB0 + 1 lH,. The vapour density agrees with the formula B,H1,. The boron bydride B,H is a colourless liquid b. p. 16-17'/ 760 mm. m. p. ca - 1 1 2 O ot a peculiar and most disagreeable odouv. A few bubbles of the gas affect respiration and cause headache.It is a very unstable substance decomposing at the ordinary tem- perature after a few hours and quicker a t higher temperatures giving rise t o a whole series of new hydrides which await investi- gation. It takes fire spontmeously in the air or in oxygen burning with a green flame. Water and dilute hydrochloric acid decompoEe it and it is oxidised by concentrated nitric acid with explosive violence. It is rapidly absorbed by aqueous sodium hydroxide the solution slowly evolving hydrogen in accordance with the equation already given. It is probable that an intermediate hypoborate corresponding with the oxide B,O (compare Travers and Ray A. 1912 ii 938) is formed since when brought into contact with solid potassium hydroxide the latter becomes coated with a thick layer of a whito salt in the form of a loose powder.Ammonia gives a solid light brown substance insoluble in water whilst alcohol decomposes the hydride with evolution of hydrogen. The solution in benzene is very stable towards oxygen. The hydride B6H12 was analysed similarly t o the hydride B4HIo by decomposing it by heat. The vapour density corresponds with the forruula B,H,,. It is a colourless liquid b. p. 10'115 mm. ca 100°/760 mm. possessiug a highly disagreeable odour and taking fire spontaneously in the air. It is more sensitive towards water and moisture than the hydride B,HIo. With aqueous alkalis hydrogen is immediately evolved. The composition of the above hydrides is not in agreement with that of the boron alkyls nor with the results obtained by Jones and Taylor (T.1881 39 213) Sabatier (A. 1891 979) and Ramsay and Xatfield (P. 1901 1'7 152). A critical examination of the experi- ments of these various investigators shows that no trustworthy conclusion can be drawn from them as t o the composition of boron It is similarly decomposed by electric sparks. hy dride. T. s. P. Condition Diagram of Carbon Dioxide. GUSTAV TAMMANN (Chem. Zentr. 1912 ii 598; from Nuchi*. K. Ges. Wiss. Gatt. 1912 446-452).-The author had observed previously that liquid carbonii. 46 ABSTRACTS OF CHEMICAL PAPERS. dioxide a t temperatures ranging from - 56.7" to - 7.5" and pressures between 5.1 atm. and 2800 kg. per sq. cm. deposited n different crystalline species from that obtained at higher pressures.Repetition of the experiments up to 4000 kg. pressure showed that a triple point does not occur in the melting curve (compare A. 1912 ii 29). T. A. H Carbon Subsulphide C,S,. ALFRED STOCK and PAUL PRAETORIUS (Bey. 1912 45 3568-3578).-1n the preparation of carbon telluride (A. 191 1 ii 722) a substance possessing a very penetrating odour was always an accompanying product. This has proved itself to be the tricarbon disulphide C,S first obtained by Lengyel (A 1894 ii 90) which the authors propose to call carbon subsulphide from analogy to carbon suboxide. Lengyel's method of preparation (Zoc. cit.) is not a convenient one and the authors have sought for a better. The compound is produced when an arc is formed between carbon electrodes under liquid carbon disulphide but i t is accompanied by many by-products.It is also produced when carbon disulphide is passed through a heated quartz tube the most favourable temperature being 1000-~lOOo ; carbon is deposited in the tube at the same time and diminishes the yield of subsulphide. If the quartz tube is filled with a spiral of iron wire the formation of subsulphide takes place below 800° but i t soon ceases owing to the formation of iron sulphide. The action of metals led the authors to investigate the formation of subsulphide by the disintegration OF metals by means of an arc under liquid carbon disulphide the disintegration of the anode exposing fresh hot surfaces continually to the carbon disulphide. Iron copper and aluminium electrodes gave no eubsulphide whilst electrodes of arsenic bismuth lead tin antimony cadmium or zinc yielded the required compound large quantities of the metallic sulphides being formed a t the same time. The best results were obtained with a carbon cathode and an anode consisting of antimony mixed with 7% of carbon.The brownish- red solution obtained is filtered and then shaken with mercury and phosphoric oxide to remove sulphur and polysulphides and water. A solution of carbon subsulphide in carbon disulphide is thus obtained from which by distillation finally under a high vacuum the pure substance is obtained in a receiver cooled to - 40" as a yellowish-red solid. At the ordinary temperature i t forms a bright red strongly refracting liquid the vapour density of which corresponds with the formula C,S,; the m. p.is -0-5' and the substance possesses normal molecular weight in carbon disulphide solution. The alcoholic solution decomposes after a short time. Dilute solutions in carbon disulphide are salmon-coloured stronger solutions yellowish-brown ; above 1% strength the solutions gradually deposit black polymerisation products even in the dark ; solutions below 1% strength are stable in the dark but not in sunlight. Carbon disul- phide solutions have no action on copper or mercury but are decom- posed by the sulphides of these metals owing probably to the formation of additive products. The polymerisation at 90' is a reaction of the second order andINOKGANIC CHEMISTRY. ii 47 can be readily measured by observing the diminution in pressure ; the reaction takes place at the surface of the containing vessel.Carbon subsulphide can be considered as the anhydride of thio- malonic acid (compare carbon suboxide) since with aniline it readily gives thiomalonanilide. Its constitution may therefore be expressed as S:C:C:C:S. The black polymerisation product is not affected by water sodium hydroxide hydrochloric acid or chlorine water. Heated in a vacuum it gives carbon disulphide and a black residue which still contains 39% of sulphur. H. VON WARTENBERG (Zeitsclh. ccno~g. Chem. 191 2 79 71-87).-Platinum is often attacked when heated in a silica vessel in a reducing atmosphere even if not in contact with the silica indicating the formation of either silicon vapour or silicon hydride. The disociation of silicon hydride (prepared by the action of alcohol on purified silicon-chloroform followed by decomposition of the ester by sodium) has been studied.It is necessary to use a catalyst and the nickel used in Sabatier's method of reduction has proved to be suitable. Without a catalyst decomposition is hardly measurable below 350° even after several days. Measurements up to 380' give the result SiH,=Si+2H2 - 8700 cal. From 100' to 150' the pressures observed are higher than would be expected probably owing to the occurrence at the lower temperature of the reaction BSiH = Si,?? + 2H,. The volatilisation of crystallised silicon in a stream of hydrogen has been measured up t o 1315". Silicon hydride is not to be detected in the issuing gas. The experiment has been repeated with argon io place of hydrogen with similar results the diminished loss of silicon being accounted for by the formation of a thin protecting layer of the nitride Si,N as nitrogen is not completely removed from argon even by passing over heated likhium.The value SiH,= Si (vapour) + ZH - 44,000 cal. is calculated. The reduction of silica by hydrogen has been studied at 1350-1400" a t which temperature silica is not volatile. The observed sublimation at lower temperatures is therefore due to reduction followed by oxidation. Carbon monoxide and graphite are also capable of reducing silica. The Velocity-of Crystallisation and Crystallieing Power of Silicates. ERWIN KITTL (Zeitech. ccnorg. Chem. 1912 77 335-360). -The crystal!isation of a number of silicates has been examined in relation to the viscosity.Crystallisation takes place on the heating stage of a microscope and the growth of the crystals which usually form radiating groups of needles is measured by means of a micro- meter eyepiece. The linear velocity of cry stallisation varies with the undercooling in the manner described by Tammann for organic substances. The horizontal maximum of the curve is often very short or diminished to a point and is best marked in silicates of low viscosity. Olivine bronzite and hypersthene show sharp maxima whilst polysilicstes show a low flat curve. The maximum is usually 20-30' below the initial temperature of crystallisation. Metasilicates T. S. P. The Reduction of Silica. C. H. D.ii. 48 ABSTRACTS OF CHEMICAL PAPERS. form the longest needles the larger number of centres in orthosilicates causing in terforence.Orthosilicates of the alkalis form glasses without crystallising with the exception of lithium orthosilicate which cryst.allises if cooled slowly. Simple and mixed magnesium calcium ferrous and manganous silicates crystallise readily. Alkali metasilicatea with the exception of litbium form only glasses. The simple metasilicates of the metals mentioned above crystnllise readily whilst the mixed ruetasilicRtes remain partly glassy. Polydicates e~pecially those of complex constitution tend to form glasses. C. H. D. The Proportion of Potassium Chloride in Potassium Chlorate and the Nephelouetric Control. FRIEDRICH MEYER and ARTHUE STAIILER (Zeitsch. ano7.g. Chem. 1912 77 255-256.Compare A. 1911 ii S d l ; Guye A. 1912 ii 552).-The criticism of Guyeoverlooks the fact that the solution in the nephelorneter is not one of silver chloride in pure water but contains an excess of either silver or chloride considerably diminishing the solubility. I n the case of potassium chlorate the error cannot affect more than the sixth decimal place in the atomic weight of chlorine or potassium. C. H. D. Molten Carnallite. KURT ARNDT and HEINRICH Huao KUNZE (Zeitsch. Elektrochem. 1912 18 994-99S).-Determinations of the density electrical conductivity and freezing point of carnallite and mixtures of carnallite and potassium chloride are given. The carnallite used was prepared artificially by mixing magnesium chloride and potassium chloride in the requisite proportions.In all experiments decomposition of the magnesium chloride was prevented by the constant and careful addition of small quantities of ammonium chloride. The freezing points were deduced from cooling curves obtained by the use of a thermocouple and are as follows pure carnallite 496'; carnallite + 6% KC1 493' ; carnallite + 12% KC1 484' ; carnullite + lS% KCl 4'70' ; carnallite + 24% KCL 460' and carnallite + 30% KCl 436'. The density determinations were made by weighing a platinum sinker in the molten mixture (compare Brunner A 1904 ii 244). Tables of results are given which show that at 550° 650' and 750° the addition of potassium chloride up to 30% causes a slight decrease in the density of the mixture. Pure carnallite has the density a t 570° 1.711 ; 600° 1.698 ; 650° 1.678 ; TOO' 1.658; 7509 1.638 and 780' 1.625.It is shown from the density determinations that carnallite and potassium chloride form no definite compounds. Tho conductivity measurements were made by the method described by Arndt (A. 1906 ii 418) and the following specific conductivities obtained %-Excess of potassium chloride. - + Temp. 'i0.3-20.5. 10.4-10'7. 0*8-1'0. 550" 600 650 700 750 0 '96 0.92 0 *87 1 '07 1.03 0.9s 1'18 1 *14 1-09 1 '29 1-25 1'20 1'40 1-36 1.31INORGANIC CHEMISTRY. ii. 49 By extrapolation from the above figures the specific conductivity of pure carnallite was deduced. The values are at 570° 0.92; 600° 0.97 ; 650° 1.08 ; 700° 1-20 and 780° 1-37. J. F. S. Thermal Analysis of Binary Mixtures of Alkali Nitrites with Other Salts of the Same Metals.D. MENEGHINI (Gazxettcc 1912 42 ii 47%-479).-'I!he paper deals with the thermal analysis of the syatems KN0,-KNO NaN0,-NaCI and NaN0,-NaBr. Fused mixtures of potassium nitrite and nitrate in the interval from 10% to 100% of nitrate give an uninterrupted series of mixed crystals whilst at the ordinary temperature between the same limits of concen- tration there is no miscibility. I t is imposaible t o obtain nitrite free from nitrate. The experiments with sodium nitrite were carried out with a nitrite containing 15% of nitrate The diagrams of the systems NaN02-NaC1 and NaN0,-NaBr belong to Roomboom's type 111. R. V. S. The Action of Ozone on Alkali Hydroxides. WILHELM TRAUBE (Ber. 1912,45 3319-3320. Compare A. 1912 ii 844).- The previous work of Manchot and Kampschulte (A 1908 ii 101) on the same subject is acknowledged.T. S . P. The Electrolytic Preparation of Sodium Hypoohlorite. PAUL H. PRAUSNITZ (Zeitsch. Xkltrochem. 19 12 18 1025 -1 080).- After careful consideration of the theory of the electrolytic production of sodium hypochlorite from sodium chloride the paper deals first with an experimental examination under laboratory conditions with enclosed cells of the various factors which influence the reaction. I n the second part the results are applied to the technical conditions the author using in this connexion working models of the best known technical electrolysers. The experiments were all made except where the contrary is stated with 5N-solutions of sodium chloride t o which a 0.2N-solution of potassium chromate had been added The reactions were studied with regard to the maximum concentration of available bleaching chlorine obtainable and the current efficiency. The first section includes (a) The influence of the anode current density (Dn) and the anode shape The best results were obtained with a short bright platinum anode in the form of a wire in which case a maximum concentration of 88 grams per litre of available bleaching chlorine was obtained with a current density D = 14.3 amperes per sq.cm. Massive platinum anodes (sheets or wires) are far more efficient than gauze electrodes. Platinised platinum anodes showed a slight superiority over bright anodes for current densities up to Da=0*44 ampere per sq. cm. but abovo this value there was no advantage gained by platinising the electrodes.With D =2 0.44 ampere per sq. cm. using platinised electrodes a maximum concentration of 48 grams per litre available bleaching chlorine was obtained with a current efficiency of 91%. The platinised electrodes showed their superority .especially when they had been previously cathodically polarised. Grey platinum electrodes behaved similarly to the platinum- black electrodes. VOL. civ. ii. 4ii. 50 ABSTRACTS OF CHEMICAL PAPERS. ( 6 ) Influence of temperature. The best results were obtained a t the ordinary temperature. A t 30' the concentration of hypochlorite mas diminished whilst at 0' and 15' the formation of chlorine hydrate (CI,,lOH,O) on the anode interfered with the process. ( c ) Influence of stirring the electrolyte.The effect of stirring is to reduce the maximum concentration of the hypochlorite. (d) Influence of dilution of the electrolyte. The salt concentration was changed from 5N to 2N and l.1N; in each case there was a decrease in the maximum concentra- tion of the hypochlorite and of the current efficiency. (e) Influence of the addition of various substances to the electrolyte. The object of the addition was to prevent cathodic reduction. The experiments were carried out with carbon anodes in addition to platinum which had hitherto been used. The results are (I) Potassium chromate pre- vented reduction almost entirely ;. (11) the addition of calcium chloride and Turkey-red oil (sulphonated castor oil) allowed a reduction of 20% although a 30% higher maximum coneen tration of hypochlorite could be obtained.The action of the Turkey-red oil is probably the forma- tion of an anode coating which causes a great increase of the current density. The best results are obtained by combining the chromate and Turkey-red oil additions; in this way for example 62 grams per litre of available bleaching chlorine was obtained with a 62% current efficiency. By using Portland cement to make the cell malls of from which something is dissolved an improvement of both anode and cathode actions was effected. Wheat starch and soluble starch gave much inferior results. The author experimented with models of the apparatus used in the old Kellner process the new Kellner process the Schuckert process and the Weichert process.Working with the old Eellner process it was found that the highest Concentration of hypo- chlorite obtainable was 12-20% below that given in closed vessels. This is attributed t o the influence of the carbon dioxide from the air and to the circulation of the electrolyte over the anode. I n the new Kellner process it was found that the maximum hypochlorite concen- tratiou was independent of the current density and the rate of flow of the electrolyte. The anode in this process must be placed beneath the cathode for the best results. The yield is increased by the addition of potassium chromate and Turkey-red oil to the electrolyte and in this case a concentration of 68 grams per litre available bleaching chlorine was obtained from a 5N-solution of sodium chioride with a 41% current efficiency.I n the Schuckert process the current density has but little iufluence on the concentration of the product; the best results were achieved by adding potassium chromate to the electrolyte. The addi- tion of calcium chloride and sodium resinate gave less favourable results. I n the Weichert process using a dilute sodium chloride solution ( 5 5 O Be) with the addition of 0.2% potassium chromate a yield of 8-10 grams per litre of available bleaching chlorine was obtaiued when working with a current of 14 amperes at 95 volts and with the electrolyte floLving through the cell a t 40 litres per hour. J. F. S. Crystallographic Study of Lithium Chlorate. (Mlle.) H. BKUHL (BUZZ. SOC. frang. Min. 1912,35 155-165).-Lithium chlorateii. 51 INORaANlC CHEMISTRY.was prepared by mixing solutions of lihhium sulphate and bsriam chloritte. It is extremely deliquescent and is very soluble in alcohol the latter property affording a means of purifying the salt. Under the microscope the anhydrous salt LiCIO (m. p. 125-127*5") was observed in three different crystalline modifications. There is also the hydrate Li,UlO,,&H,O (m. p. 63-65') which forms plates with secondary twin-lamellE. L. J. S. REZSO BALL^ and EMIL UITTLER (Zeitsch. nnorg. Chem. 1912 77 456. Compare A. 1912 ii 758).-The biaxial modification of lithium metltsilicnte previouily described is already known and is probably monoclinic. Its pro- The Binary System Zi2SiO3-Al,(SiO,),. perties persist in -its solid solution - with aluminium metasilicnte. C.H. D. The Carbonic Acid of Natural Waters which is Able to Attack Calcium Carbonate. J. TILLMANS and 0. HEUBLEIN ( C / L R ) ~ . Zen.fr. 1912 ii 1355-1396 ; from Gasundheits-lny. 19 12 35 669-677).-A certain amount of carbonic acid is necessary to pro- tect calcium hydrogen carbonate from decomposition so that although " free," it does not attack calcium carbonate. Thus a soft water mill attack limestone f a r more than a hard water containing the same amount of free carbon dioxide. A curve has been made connecting calcium hydrogen carbonate with the carbon dioxide which is necessary for its protection. Having found the amount of combined carbon dioxide and the total free carbon dioxide in a water i t is thus possible to say how much of the latter is capable of attacking calcium carbonate.Small amounts of magnesium carbonate do not seriously affect the results. J. C. W. Physical Action of Neutral Reagents on the Tribasic Alkaline Earth Phosphates. Investigation of the Colloidal State. WILLIAM OECHSNER DE CONINCK (Rev. Gen. Chim. Y u w App!. 1912 15 285-886).-1f the normal phosphates of calcium strontium and barium are shaken up with water methyl alcohol or ethyl alcohol for several days colloidal solutions are obtained which can be s2parsted from the excess of phosphate by filtration through filter paper. I n this way the author has prepared colloidal solutions of calcium phosphate in water and methyl alcohol and of strontium phosphate in methyl aud ethyl alcohol. The solutions are unstable and on this account the solutions of barium phosphate which appear t o be formed in methyl and ethyl alcohole are coagulated during the process of filtra- tion.H. M. D. The Ternary Alloys of Magnesium Zinc and Cadmium. GIUSEPPE BRUNI and CARLO SANDONNINI (Zeitsch. anorg. Chem. 1912 78 273-297):-The portion of this system which includes the con- stituents Zn-Cd-MgZn2 has been described previously (A . 19 10 ii 954). Cadmium retains up to 3 atomic % of zinc in solid solution. The crystallisation-interval i s very small throughout the magnesium- cadmium series. A transformation curve for the compound DlgCd is 4-2ii 52 ABSTRACTS OF CHEMICAL PAPERS drawn showing a eutectoid point; near 80 atom. % Cd traces of a eutectoid structura being recognisable in slowly-cooled alloys having about this composition. The compounds MgZn and MgCd form a simple eutectiferous series.The entire triangular diagram is divided into two parts by a continuous eutectic curve connecting the two eutectic points of the magnesium- zinc system and separating the MgZn area from that of solid solutions and from that of zinc. This curve passes through amaximum. The curves of secondary and eutectic crystallisation have been completely traced. It appears that the P-solid solutions retain zinc in solution at high temperatures but that its solubility disappears at about 250'. The alloys are best etched by means of nitric acid in alloy1 alcohol. The photo-micrographs illustrate the whole series of ternary alloys and serve t o fix the limits of stability of the solid solutions. C.H D Action of Potassium Amide on Thallium Nitrate in Liquid Ammonia Solutions. EDWARD CURTIS FRANKLIN (J. P l y i c a l Chem. 19 12 16 682-703).-The author describes in detail the preparation and properties of thallium nitride and potassium ammonio- thallite which have already been briefly mentioned (A. 1912 ii 452). The interaction in liquid ammonia solution of thallium nitrate and potassamide according to the equation 3TlN0 + 3KNH2 = TI,N + SKNO + 2NH yields a a dense black precipitate of thallium nitride ihich is readily soluble in excess of potassamide and also in liquid ammonia solutions of ammonium nitrate. I n the latter case the thallium nitride is reconverted into nitrate thus Tl,N + 3NH,N03 = 3TlN0 + 4NH From the solution in excess of potassamide well formed golden- yellow crystals are deposited.These consist apparently of iso- morphous mixtures of potassamide and dipotassium ammoniothallite with ammonia of crystallisation. The potassamide may be eliminated by contact with excess of thallium nitride or by repeated crystallisation. Dipotassiurn ammoniothallite when freed from excess of ammonia in a vacuum a t - 40° has the formula TlNK2,4NH3 or TlNH,,2KN H2,2N H 3 At + 20° in a vacuum ammonia is given off and the yellow substance TlNK,,2NH3 or T1NH,,2KNH2 results. On further deammoniation a t + 100' the substance turns black and approximate3 to the composi- tion TINK l$NH8 alternatively written Tl,N,6KNH2 or as a simplo mixture (T1,N + GKNH,). TINH 2 KNH,,2NH3 is more reasonable in view of the isomorphous mixed crystals with potassamide but on the other hand thallium amide is unknown in the free state.The extreme composition observed in the mixed crystals was T1NK2,4NH 3*6KNH and the higher the proportion .of potassamide the greater the solubility. The ammonia of crystallisation was always proportional to the thallium content the proportions being T1 4NH and TI 2NH in preparations dried at - 33' and + 20' respectively. Thallium nitride and potassium ammoniothallite and its mixtures The alternative formula for dipotassium ammoniothallite,INORGANlC CHEMISTRY. ii. 53 explode with great violence when subjected to heat shock or the action of water or dilute acids. They were hydrolysed for analysis by means of water vapour. No evidence could be obtained of the formation of an.amide or imide of thallium even at - 33". R. J. C The Quaternary System KCI-CuC12-BaC12-H20. FRANS A. H. SCHREINEMAKERS and (Miss) W. 0. DE BAAT (Proc. Lz. Ahad. Tetensch. Amsterdam 191 2 15 467-472).-The equilibria occurring in this quaternary system have been examined at 40" and 60". The choice of these temperatures is determined by the fact that the ternary system KCI-CuC12-H20 is characterised by the formation of only one double salt 2KC1,CuCl2,2H2O below 57O whereas a further double salt KCl,CuCl may occur between 57" and 92". The experimental data may be conveniently represented by means of a tetrahedron the four apices of which correspond with the fow components. The spacial model for 40" shows saturation surfaces corresponding with KCI BaC12,2H,0 CuC12,2H20 and 2KCl,CuCl2!2 H20 whereas that for 60" show an additional surface corresponding with KC1,CuC I 2.The temperature corresponding with the disappearance of this surface has been found to be 5 5 * 7 O and this temperature corresponds with the reversibility of the change represented by BaC1,,2H20 + CuC1,,2H20 + 2KCI,CuCJ2,2H2O KCI,CuCl + solution. H. M. D. Mutual Solubilities of Cuprous Chloride and Ferrous Chloride as also of Cuprous Chloride and Sodium Chloride and the Transformation Point of FeC1,,4H20 FeC1,,2H20 + 2H20. ROBERT KREMANN and F. Noss (Monutsh. 1912 33 1205-1215).'At 21.5" the solubility of cuprous chloride is increased by tho addition of ferrous chloride as also that of ferrous chloride by the addition of cuprous chloride the solid phases in equilibrium with the solution being respectively cuprous chloride and ferrous chloride ; there is no formation of a double salt.The solution saturated with respect t o both the salts contains 73.20 grams of ferrous chloride (anhydrous) and 23-20 grams of cuprous chloride in 100 grams of water. The system cuprous chloride-sodium chloride-water a t 26.5' behaves similarly to the system ferrous chloride-cuprous chloride- water. At the point where it is simultaneously saturated with respect to the individual salts i t contains 5'7.21 and 44.14 grams of cuprous chloride and sodium chloride respectively per 100 grams of water. FeC1,,4H20 as determined by cooling curves was found to be 65.2'. T. S. P. The transformation point of the system FeCI2,2H2O + 2H20 Ammoniacal Sodium Cuprous Trithionate.KSHITIBEIUSHAN BHADURI (Zeitsch. anorg. Chem. 1912 78 327).-Copper sulphate is precipitated with ammonia and the precipitate is washed and dissolved in ammonia. Sodium thiosulpbate is added and after remaining over- night blue crystals are obtained the solution becoming colourlees.ii. 54 ABSTRACTS OF CHEMICAL PAPERS. The product after washing with water and alcohol and drying forms sky-blue crystals soluble in water or more readily in ammonia and giviag the reactions of a trithionate. The salt has the composition 3Cu2S,06,2Na2S30,,9N H,. C. H D. The System HgC12-CuC12-€€20. FRANS A. H. SCHREINEMAKERS and J. C. THONUS (Proc. K. Akad. JVetensch. Amsterdam 1912 15 472-474).-1n order to ascertain whether mercuric chloride and cupric chloride form a double salt the form of the solubility isotherm has been determined by a series of solubility deasurements at 35".The composition of the residual '' solid phase" as well as that of the solution was determined and the numbers so obtained show that no double salt is formed at this temperature. A solution containing 21.5% of cupric chloride and 50.5% of mercuric chloride is saturated both with respect t o cupric chloride (CuC1,,2H20) and to mercuric chloride. The middle portion of the isotherm where two solid phases coexist is of very limited dimensions. The data show that the solubility of mercuric chloride is greatly increased by the addition of cupric chloride. Whereas in pure water the solubility amounts t o 8*5% it increases to 52.8% in presence of 18.06% of cupric chloride.When the quantity of cupric chloride present is further increased a slight diminution occura in the percentage amount of dissolved mercuric chloride. H. M. D. The Acid Dissociation C o n s t a n t of Aluminium and Zinc Hydroxides. ROLAND EDGAR SLADE (Zeitsch. anoyg. Chern. 19 12 77 457-460. Compare P. 1910 26 236; Klein A. 1912 ii 351; Hantzsch ibid. 644).-An approximate calculation shows that aluminium liydroxide must have an acid dissociation constant of a t least 10-10 and probably higher and that zinc hydroxide in its most stable form must have a corresponding constant of.not less than 0.5 x 10-12. C. H. D. Ultramarine Compounds. L. WUNDEB (Zeitsch. anorg. Chem. 191 2 '77 209-23S).-The replacement of sodium in blue ultramarine by other metals has been studied by Heumann (A.1877 ii 572 ; 1878 113; 1879 437 692 ; 2880 217-367) and has now been further developed. The material is heated with the [reacting solution to 120-180" in a closed glass tube enclosed in sand in a steel cylinder. Mercurous nitrate yields a greyish-blue mercuro-ultramarine which loses mercury on heating and leaves a pure blue residue which becomes yellow on heating and again blue on cooling this change being capable of being repeated indefinitely. The product is very stable towards acids. Mercuric salts are reduced by ultramarine. Cadmium yields :in olive-green product whilst lead replaces the sodium completely. Lithium ammonium and calcium ultramarines have also been prepared. The decomposition of ultramarine by alum solutions is not due to the acidity of tho latter but to the intermediate formation of an aluminium derivut ive.Chromium has the same effect. Ferrous ultramarine is dark greyish-blue and is readily decomposed by acids.INORGANIC CHEMISTRY. ii. 55 Yellow phosphorus reduces ultramarine to a leuco-compound which again becomes blue if heated in air. Red ultramarine is decomposed by acids without evolution of hydrogen sulphide and is not changed by alum solution. Red ultramarine is best prepared by the action of nitric oxide on the blue compound sulphur being removed in the process. Violet ultramarine is decomposed by alum and also by acids sulphur dioxide being evolved. Dry hydrogen reduces it sulphur being removed as hydrogen sulphide. Red ultramarine is regarded as an acid the sodium salt of which is the violet compound The blue compound contains the group A1-S-Na which is absent from the red.Formulae are proposed for all these compounds. C. H. D. The Heusler Ferromagnetic Alloys of Manganese. EDGAR WEDEKIND (Zeitsch. angew. Chem. 1912 25 2524-2526).-A claim for priority against Heusler (ibid. 2253) in respect to manganese borides and the magnetic properties of binary compounds of manganese. C. H. D. Ternary Alloys of Iron-Manganese-Copper. NICOLA PARRAVANO (Gaxxetta 1912 42 ii 513-531).-0f the three binary systems comprised in the tornary system Fe-Mn-Cu the system Fe-Cu has been studied by Sahmen (A.? 1908 ii 186) and the others by the author (A 1912 ii 1175 and this vol. ii 58). The system Fe-Mn-Cu belongs to type I of the cases of solubility gaps in ternary systems discussed by Parravano and Sirovich (A 19 1 1 ii 705) and in a theoretical discussion the author applies the con- clusions there set forth to the construction of diagrams from the experimental results in the present instance.I n addition to the diagrams photographs are given of a number of the ternary alloys which are thus shown to have the structure to be expected from their position in the space diagram. R. V. S. Revision of t h e Atomic Weight of Iron. V. Analysis of Ferric Oxide. GREGORY P. BAXTER and CHARLES RUGLAS HOOVER (J. Amer. Chern. SOC. 1912 34 1657-1669).-From analyses of ferric oxide by reduction with hydrogen at 900° Richards and Baxter (A. 1900 ii 407) obtained the value 55.88 for the atomic weight of iron.Baxter (A 1904 ii 177) analysed ferrous bromide and found the value 55.845; on repeating this work with purer material Baxter Thorvaldson and Cobb (A. 1911 ii 287) obtained the result 55.838. Baxter and Thorvaldson (A. 1911 ii 288) further proved t h a t meteoric and terrestrial iron give identical values. I n the present investigation ferric oxide was prepared by igniting carefully purified ferric nitrate in a current of air. A weighed quantity of the oxide was reduced to the metal by heating it in a current of hydrogen at 1050-1 100' for several hours. Two specimens of ferric nitrate were employed one containing iron of terrestrial origin and the other meteoric iron. The average of twelve analyses yielded 55,847 as the atomic weight of iron (0 = 16.000).This when combined with the result obtainedii. 56 ABSTRACTS OF CHEMICAL PAPERS. from the analysis of ferrous bromide (Baxter Thorvaldson and Cobb Zoc. cit.) gives the value 55.84. The identity of terrestrial and meteoric iron was confirmed. E. G. The System Iron-Carbon. 111. ANDREAS SMITS (Zeitsch. Elektrochern. 1912 18 1081-1086. Compare A 1912 ii 165 769).- An answer to Ruff (A 1912 ii 917; compare also A. 1911 ii 897). The remainder of the paper is a theoretical consideration of the results of Wittorf (A 1912 ii 259) who shows that the system iron-carbon undergoes two inverse separations by raising the temperature namely C -+ Fe,C -+ FeC -+ Fe,C -+ C. In this connexion the author discusses the relations of the separations of the substances C FeC FeC C which he shows are successively deposited on raising the temperature.PZ' curves of the system are given in which two quadruple points are indicated at both of which graphite FeC solution and vapour are in equilibrium. On raising the temperature a t the lower point FeC is formed at the expense of the graphite whilst at the higher point graphite is produced at the expense of the FeC. The thermal relationships of the various changes are considered. J. F. S. The System Iron-Iron Sulphide. RICEARD LOEBE and E. BECKER (Zeitsch. anorg. Chern. 1912 7'7 301-319. Compare Treitschke and Tammann A. 1906 ii 547).-Ordinary ferrous sulphide always contains free iron and also oxide. A product contain- ing 98.72% FeS is obtained by repeatedly melting natural pyrites.The mixtures are made by fusing this product with Swedish iron in porcelain tubes using a kryptol furnace. The equilibrium diagram shows a freezing-point curve of simple form the two branches meeting in a eutectic point at 985O and 85% FeS. The solid components are practically immiscible on the iron side whilst solid ferrous sulphide retains about 1%Fe in solution. The formation of two liquid layers and the occurrence of a crystallisation interval are not observed. The transformations in the solid state have been examined by the differential method and it is found that the sulphide is without influence on the transformation points of iron. A polymorphic trans- formation of ferrous sulphide occurs at 298O and has been studied by the dilatometric method using mercury as the filling liquid.The transformation a t 1 3 8 O is also observed in all mixtures containing more than 7% Fe (compare Rinne and Boeke A. 1907 ii 471). The brittle- ness of iron containing sulphide is due to this transformation. Photo-micrographs of the alloys are given. The eutectic tends to become segregated in mixtures rich in sulphide. Alloys which have been in contact with oxygen contain a new eutectic. Fusion of iron sulphide with iron oxide however leads to the elimination of sulphur and formation of ferrite and the structure is better developed by fusing the sulphide in contact with air. The composition of the eutectic is uncertain. The brittleness of iron containing sulphur at a red heat is due to the absorption of oxygen in this form.C. H. D.INORGANIC CHEMISTRY. ii. 57 Stability of the Oxides of Cobalt in the Interval from Co,O to COO. SIEGFRIED BURGSTALLER (Chern. Zentr. 1912 ii 1525-1526 ; from Abhandl. Beut. naturwiss.-med. Ver. Bohrnen 1912 3 83-143).- The stability of the oxide of cobalt has been followed dynamically in view of the numerous oxides mentioned in the literature and of the statical measurements of the dissociation pressures made by Richards and Baxter (A 1900 ii 78) and by Smith and Foote (A. 1908 ii 847). By means of baths of diphenylamine b. p. 301*9'/760 mm. anthra- cene b. p. 339*8O/760 mm. and anthraquinone b. p. 377*2'/760 mm. the dissociation temperature of cobaltic oxide has been narrowed down to 372-373O/760 mm. Above this temperature the reduction of the oxide has been followed in a sulphur bath and in an electric oven and after allowing for the possible sources of error (such as the time taken in warming up and in cooling down) the alteration of the oxygen con- centration of the oxide with time by rising or falling temperature has been graphically portrayed. From the dissociation temperature of cobalic oxide to a point between '705.5" and 869O cobalto-cobaltic oxide is stable above which the region for cobaltous oxide occurs.The transition points cannot be determined however because regions of solid solution of one oxide in the otber must be passed through. From the reactions curve of the oxidation of cobalt in air i t is also seen that between 300' and 431° cobalto-cobaltic oxide is formed and that at 869' the region of solid solution between Co,O and COO is entered.The existence of solid solutions and the fact that the speed of the dissociation becomes very slow after a short time explain the numerous references to improbable oxides of cobalt. The Replacement of Metals from Aqueous Solutions of their Salts by Hydrogen at High Temperatures and Pressures. IV. VLADIMIR IPATIEV and B. ZRJAGTN (Ber. 1912 45 3226-3229. Compare A. 1912 ii 50).-In solutions of 2N- and 0.2N-cobalt sulphate and initial pressures of 100 atmos. of hydrogen no formation of a precipitate takes place within twenty-four hours at 103". A t 145-1 50' a rosy-violet coloured crystalline precipitate is formed having the composition CoS0,,H20 ; metallic cobalt also separates. If nitrogen or air is used instead of hydrogen the 2N-solution gives only the salt CoSO,,H,O.When a quartz tube is used instead of aglass one the reaction is not complete at 150" within four days cobalt sulphate still remaining in solution. A glass tube could not be used for so long a time without being attacked. A t 150° 2"- and 0.2N-cobalt nitrate solutions bebave similarly to the sulphate solutions a t 103'. At 205-210' a crystalline brownish- black precipitate- of cobaltic oxide which is contaminated with silicic acid from the glass tube is formed within a day (compare nickel nitrate A. 1912 ii 51). A similar result is obtained with N-solu- tions both in glass and quartz tubes whereas N-solutions oE nickel nitrate give a small quantity only of a green crystalline precipitate containing 52*90-53.36% of nickel. J.C. W.ii. 58 ABSTRACTS OF CHEMICAL PAPERS Solutions of cobalt chloride behave similarly to those of nickel chloride (Zoc. cit.) the reaction being reversible iarnely CoCI + H 3 Co + 2HC1. T. s. P. The Origin of the Colour Produced by Cobalt Solutions in Certain Mineral Colours. SIEGFRIED BURGSTALLER (Chem. Zentr. 1912 ii 1523-1525; from Abhandl. Deut. natuywiss.-med. Ver. Bollmen. 191 2 3 57-80).-The coloured residues obtained by moistening certain inorganic oxides with cobalt solutions and then igniting are shown to be solid solutions in which a white substratum such as alumina does not modify the blue or red colour of the cobalt ion whereas a yellow oxide such as hot zinc oxide produces a mixed colour. Rinmann’s green prepared at 750-760° from zinc oxide moistened with cobalt nitrate was extracted with ammonium carbonate in which a solid solution of 7.05 mol.COO to 100 mol. ZnO dissolved whereas free cobaltous oxide was insoluble. Thhard’s blue obtained by evaporating aluminium nitrate with cobalt nitrate solution and igniting the residue also contained cobaltous oxide. No solvents could be found which would separate the solid solution from the free oxide and other methods for investigating its constitution are being pursued. J. C. W. Ternary Alloys of Nickel-Manganese-Copper NICOLA PARRAVANO (Gazzettcc 19 12 42 ii 385-394).-The paper contains an account of this ternary system derived from the results of its thermal analysis and from the thermal analysis of the three con- stituent binary systems.Of these the system Ni-Mn has been previously described by the author (A. 1912 ii 1175) and the remaining two by other writers. The results of some new experi- ments with the system Cu-Mn are also given. The nature of the ternary system is exhibited in diagrams and photographs are reproduced of a number of the ternary alloys prepared. The Constitution of the Halogen Compounds of Bivalent Molybdenum. IVAN KOPPEL (Zeitsch ccnorg. ClLem. 19 12 7’7 289-300).-The compounds having the empirical composition AIoC1 and MoBr are known to react in n manner which indicates a more complex constitution. The properties are now reviewed and con- stitutional formulae are proposed. The most important properties are the existence and stability of the radicles (Mo3R?)” the formation of ;t crystalline hydroxide the resistance to oxidation the difference in solubility between the anhydrides and the hydrates and the arnphoteric character of the radicles.The formulae given assume a co-ordination number 4 the insoluble hydrates for example being [Mo3CI,R,,2H20]H,0 where It is a halogen. The amphoteric hydroxy-compound is . represented as [Mo,C1,(OH),,2H20] and the formation of salts from it is necessarily Molybdates. GEORG WEMPE (Zeitsch. ccnoyg. C l m ~ . 1912 78 29S-326).-Ammonium tetramolybdate i s best obtained by the R. V. S. accompanied by isomeric change. c. H. n.INORGANIC CHEMISTRY. ii. 59 action of warm hydrochloric acid on the ordinary molybdate and forms transparent triclinic crystalp (NH,),0,4M00,,2H20 of which 3.67 grams dissolve in 100 C.C.of water at 18". Further decom- position gives the trimolybdate ( NH,),0,3Mo0,,H20. Sodium tetra- molybdate Na20,4Mo03,6H,0 obtained by the action of nitric acid on the ordinary salt is much more soluble than the ammonium salt. The trimolybdate is obtained with 6 or 9 H,O from the mother liquor. Potassium tetramolybdate has not been obtained the corresponding solutions yielding instead the trimolybdate K,0,3M00,,3H20. The potassium hydrogen tetramolybdate has the composition K,O H20,8Mo03 12 H,O. Lithium tetramolybdate obtained from Rammelgberg's salt and hydrochloric acid forms triclinic crystals Li,O 3H,O 16M00,,6~5H20 from which a trimolybdate is obtained with 2 or 4 H,O. A second tetramolybdate is Li,0,H20,8M00,,1 OH20. The mbidium tetra- molybates obtained are Rb20,4Mo03 ; Rh20,H20,8M00,,3H,0 ; Rb,0,Mo0,,Rb20,3Mo0,,5H,0 ; and Rb,0,4Mo03,4H20 whilst the trimolybdate has been obtained with 3H,O.The caestum salts are Cs,0,4Mo0,,3H20 ; 5Cs20,12Mo03,1 lH,O ; and Cs,0,Mo03,Cs2~,3Mo03,4~5H20. The calcium Ca0,2H20,1:!Mo0,,~1H,0 and Ca0,H,0,8Mo03,16H20 ; barium Bit0,H20,8RIo0,,1 4H20 and qBa0,4Mo03),7 H,O ; strontium 2Sr0,3H20,20Mo03,21H20 ; thallous 'l'1,0,41!Co0,,H20 ; silver Ag,0,4Mo03,6 H ,O ; cadmium Cd0,1T20,8M00,,6H20 ; magnesium Mg0,H,0,8M00,,20H20 ; and zinc Zu0,H20,8M00 1 4H20 salts have also been obtained. C. H. D. Iso- and Hetero-poly-acids. VI. Hydrates of Same Hetero-poly-acids. ARTHUR ROSENHEIM arid JOHANNES JAENICKE (Zeih3cl~ anwg. Chem. 1912 77 239-251. Compare A. 1911 i 109 265 ; ii 116 612).-The following new hydrates of 12-phospho- tungstic acid have been prepared H,[P( W207),],28H,0 which is metastable at the ordinary temperature and passes into the stable 22-hydrate.The transformation point must be below 0". The addi- tion of concentrated nitric acid t o the solutions of ptecipitates the 1 %hydrate. 12-Silicotungstic acid also yields two new hydrates H@( W,0,),]33H,O which is stable below 29" and the 22-hydrate which is stable between 29' and 53'. 12-Borotung~tic acid forms H,[B( W2(/7)6],28H,0,. which does not pass into a 32-hydrate when heated. Nitric acid precipitates a 10-hydrate. The 22-hydrate previously described is hexagonal and is derived from an acid isomeric with that of the 28-hydrate thu two hydrates crj-stallising simultaneously from solution.Metatungstic acid which is also H 12-hetero-poly-acid yields only a single hydrate HI,[ H,( W20,),],22H,O. 12-Phosphoruolybdic acid yields a 28-hydrate H7[P(Mo,0,)6],28H20 which apparently yields a 12-hydrate on dehydration but the individual character of this hydrate is uncertain. A 22-hydrate is obtained by precipitation with nitric acid. 13-Silicomolybdic acid also forms a H,[%( h~020,),],28H20 fromii. 60 ABSTRACTS OF CHEMICAL PAPERS. which nitric acid precipitates a 12-hydrate but a 22-hydrate has not been obtained. C. El. D. Action of Acids on Uranous Oxide. A. COLANI (Compt. rend. 1912 155 1249-1251).-Usin,a uranous oxide prepared by reduction of the green oxide with hydrogen the anthor bas obtained results widely different from those of Raynaud (A.1912 ii 166 948). Whilst but a small amount of the uranous oxide goes into solution with sulphuric acid a considerable amount is converted into the sulphate and as such remains in the insoluble portion. Uranous oxide only dissolves slowly in hydrochloric acid the amouut dissolved in a given time varying widely with the mode of preparation of the oxide. Solution is continuous over a very long period of time. Asserted Explosibility of Uranyl Nitrate. LAUNCELOT W. ANDREWS (J. Amer. Chent. ~ o c . 1912 34 1686-1687 ; Chem. Zed. 1912 36 1463).-With reference to the statement of Ivanov (A. 1912 ii 455) on the explosibility of uranyl nitrate the author records the explosion of a quantity of uranyl nitrate in the preparation of which ether bad been employed.On adding strong solution of potassium hydroxide t o some of the salt which had escaped decom- position a marked odour of ether was produced whilst another specimen when disFolved in water gave a deep blue colour to Congo- red paper indicating the presence of nitric acid. It is considered that in this case the explosion was due to the water of crystallisation of the uranyl nitrate CJr02(N03)2 6H20 having been replaced by ether and nitric acid and it is regarded as probable that Ivanov's explosion was due to the Fame cause. VC'. G. E. G. The S y s t e m Tin-Iodine. WILLEM REINDERS and S. DE LANGE (PYOC. K. Akad. Wetensch. Amsterdam 1912 15 474-481*C).-The freezing-point curve for mixtures of iodine and stannic iodide consists of two branches meeting a t a point corresponding with 19.6' and 60% by weight of stannic iodide.The corresponding boiling-point curve which has been determined for atmospheric pressure shows neither maximum nor minimum. When stannic and stannous iodide are heated together a t 350° two liquid layers are formed one of which consists of almost pure stannic iodide whilst the other layer represents stannous iodide together with at most 6% of stannic iodide. When iodine is melted in contact with a small excebs of tin the product firbt formed is almost exclusively stannic iodide. The reaction SnI + Sn = 2Sn12 takes place extremely slowly and even a t 350' the velocity of t h i s change is comparatively small. Pure stanriic iodide melts at 143.5' and boils at 340° the corres- ponding temperatures for the stannous salt being 320' and 720".H. M. D. The Volatisation of Vanadic Acid by Halogens. ERNST 13. AUERBACH and K. LANCE (Zeitsch. angew. Chew%. 1912,25 2532-2523). -The observation of Ephraim ( A . 1903 ii 48'7) that vanadic acid * and Zcitsch. anorg. Chenh. 1912 79 230-238.INORGANIC CHEMISTRY. ii. 61 volatilises with hydrochloric acid is confirmed. The loss when vanadic acid is heated with sodium chloride is also appreciable. When barium chloride is used i t is found that the greater part of the chlorine may be driven off with very little loss of vanadium the chloride first formed being decomposed by the atmospheric moisture. If heated in a stream of dry carbon dioxide red vapours are obtained which condense to an oily liquid of unknown composition containing vanadium. It is necessary in the estimation of vanadium by means of mercurous nitrate that chlorides should be absent.C . H. D. Hetero-poly-acids Containing Vanadic Acid. WILHELM PRANDTL (Zeitsch. ano3.g. Chcm. 1912 79 97-124. Compare A. 1912 ii 167).-The author's view that compounds of this kind are derived from a hexa-vanadic acid is contrasted with the formulation due to Miolati (A. 1908 ii 595) and Rosenheim (A. 1911 i 109 265; ii 116 612 ; this vol. ii 59). Most oE the well-defined COM- pounds of this class may be represented as additive compounds of 4 or 6 mols. of molybdate and 1 mol. of hexavsnadate. Ammonium paramolybdate 3( NH4)20,7M003,4H20 is regarded as a compound of 1 mol. of diammonium trimolybdate with 4 mols. of ammonium hydrogen moly bdate ( NH4),E4M03012 4NH4H MOO,.Acids remove ammonia from the monomolybdate molecule which then polymerises to the trimoly bdate from which the hexamolybdate is obtained by elimination of water. [With SIGJIUND P ~ a ~ o w s ~ ~ . ] - T h e following new salts have been obtained KVO3,K,MoO4,4H?0 or K3V,0,,3K2Mo04,1 2H2O,. the normal salt of the series which is pale yellow and very sensitive to acids. Na4V,Ol7,6NaHMoO4,l 2H20 also yellow. Na6V60 s 6 Na,H,Mo30i 36H20 pale yellow. B~,V,O,,~GN~,H,MO~~~~ 2OH,O or 74 H,O according to the conditions ot precipltation. Na H,V,017 Nn2H,Mo3012,4NaHMo0 1 6H,O ; ~3HV60,7,2KHMo04,2K,H4Mo,0,,,6H,0 which are more deeply coloured. (NH,),v,o, 2NH4HMo04,2 ( NH,),H4Mo,0,,,8H,0 ; (NH4),HV60,,,2 ( NH4),H,Mo3O1,,4N H4H Mo04,6H20.These salts are tabulated and correlated with others of the same series described in the literature. Chemical Reactions of @Gold and Crystallised Gold. MAURICE HANRIOT and FRAN~OIS RAOULT (Conapt. rend. 1912 155 1085-1088. Compare A. 1911 ii 791).-Contrary to general belief ordinary gold as well as the brown (p) modification is attacked by nitric acid the amount dissolved whilst small varying with the concentration of the acid the @modification being readily acted on. Fuming hydrochloric acid in the presence of oxygen also has a marked solvent effect. The best solvent for /3-gold is a hot solution of auric chloride containing hydrochloric acid. On cooling the solution the dissolved gold crystallises out in the metallic state and a determination of its magnetkation coefficient shows that in this form it consists almost entirely of the @-variety.This solvent h j s a much more marked action on the brown than the yellow gold and it is the P-variety which passes into solution thus leaving the insoluble residue C. H. D.ii. 62 ABSTRACTS OF CEEMICAL PAPERS. enriched with the a-variety. This fact is borne out by comparison of the magnetisation coeficients of the origins1 brown gold the crystallised gold and the insoluble residue. 'CV. G. The Preparation and Application of Colloidal Platinum Metals ALADAR SKITA and W. A. MEYER (Ber. 1912 45 3579-3589).-See this vol. i 53. Osmium Tetroxide as an Oxygen-carrier and the Activation 3329-3336).-1n the presence of about 1 mg. of osmium tetroxide per 500 c.c. 1% solutions of p-leucaniline and leucomalachite-green become strongly coloured after a few hours on shakiog in the presence of air.Under an oxygen pressure of 10 atmospheres and temperatures of 50-100° the following oxidations take place in the presence of 0.01 gram of osmium tetroxide per 200 C.C. of liquid 40% alcohol is oxidised in three to four hours to acetic acid and aldehyde or acetal traces of crotonaldebyde also being formed ; 50% methyl alcohol gives formaldehyde and formic acid. The action on the aldehydes takes place very slowly or not a t all; €or example paracetaldehyde and acetal shows no signs of oxidation within eight days at 20'; vanillin only after twenty-four hours. The acids formic acetic and oxalic are very stable towards osmium tetroxide. Aniline sulphate is readily oxidised and anthracene gives anthraquinone in acetic acid solution. The following oxidising actions of potassium chlorate in neutral or slightly acid solutions take place very readily in the presence of osmium tetroxide but not at all or only extremely slowly in its absence arEenic to arsenic acid hypophosphorous acid to phosphoric acid ; hydrazine sulphate quantitatively t o nitrogen indigo-carmin to indigo- white quinol to quinhydrone aniline to emeraldin; mono- and di- methylaniline are oxidised ; benzidine to diphenoquinone-di-imide p - leucaniline and leucomalachite-green t o the dyes ; catechol resorcinol and tannin are oxidised anthracene to anthraquinone ethyl alcohol to acetal no chlorination taking place ; slightly acid potassium formate to carbon dioxide. Substances containing the ethylene linking such as ethylene propylene amylene indene r-pinene and dichloroethylene CHCl:CHCl are readily oxidised ; trichloroethylene CHCKCCI is only slowly oxidised and perchloroethylene not a t all. Ally1 alcohol is much more readily oxidised than ethyl alcohol ; isoeugenol is readily oxidised whilst vanillin is not. Benzene containing thiophen gives a reaction due to the presence of the thiophen. Benzoic acid bromobenzoic acid naphthalene and saturated ketones O f ChlOrate Solutions. KARL A. HOFBIANN (i?e!r. 1912 45 Acetylene is oxidised. T. s. P. are not affected and benzaldehyde only very slowly.

ISSN:0368-1769    

DOI:10.1039/CA9130405039

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Miner a 1 o gi c a1 C h e mi 8 t r ye ii. 63 Origin of Native Sulphur. A. W. KRUEMMER and R. EWALD (Centr. Jlin. 1912 638-640).-A large cavity in gypsum met with in the Barsinghausen mines was lined with bitumen resting on which mere large crystals of sulphur. Between the gypsum and the bitumen was a zone of calcium carbonate; and the gases in the cavity contained hydrogen sulphide and hydrocarbons. The sulphur had no doubt been formed by the reducing action of the hydrocarbons on the gypsum for example I. CaSO + CH4 = CaS + CO + 2H,O = CaCO + H2S + H,O. 11. H,S + H,O + 0 = 2H,O + S. The deposits of sulphur in Sicily which are associated with gypsum and outbursts of gas containing hydrocarbons and carbon dioxide have probably been formed in a similar manner.I,. J. S. Asphalt Theory of the Formation of Naphtha. K. W. CHAKITSCHKOV (Chem. Zeit. 1912 36 1402).-The author finds that the decomposition products of Russian asphalt exhibit similarity to many Russian mineral oils. Specimens of the former yield when distilled paraffins oils and residues analogous to and in approxi- mately the same amounts as the mineral oils as shown in the appended table B. p. Decomposition product. Mineral oil (Groeny). t o 110" 5.72% (D 0.720) 4'78% (D 0.705) 110-150" 10.63% (D 0.765) 10'45% (D 0.7443) 150-220" 26.5 % (D 0.8108) 16.2 % (D 0.7219) The author is k d to the conclusion that naphtha is a product of the decomy;osition of asphalt. H. W. Vrbaite a New Thallium Mineral from Allchar Macedonia. B. J E ~ E K (Zeitsch. Kryst. Milt.1912 51 364-378). Chemical Examination of Vrbaite. FR. KkEmfK (Zbid. 379-3S3).-The new mineral was found as small (about 1 mm.) crystals embedded in realgar and orpiment. The crystals are orthorhombic u b c = 0.5659 1 :0.4836 with a tabular or pyramidal habit and a good brachypinacoidal cleavage. The mineral is opaque with a metallic to semi-metallic lustre and a greyish-black colour but in thin splinters it is dark red and translucent; the streak is bright red with a tinge of yellow. H = 38 D 5.30. It is readily fusible before the blowpipe and is easily soluble in nitric acid. Analysis gives the formula TlAs,SbS representing a thallous salt of the acid HAs,S in which one atom of arsenic is replaced by antimony Ti. Sb. As. S. Fe. Total. 29.52 18'34 24.06 25-20 1-55 98-97 L.J. S.ii. 64 ABSTRACTS OF CHEMICAL PAPERS. Iron Sulphide in the Miocene Clays of Govt. Samara Ruaeia. BRUNO Doss (Jahrb. Min. 19 12 BeiZ.-Bd. 33 662-7 13). -In boring for artesian water on the estates of the Brothers Melnikov in the Novo-Usensk district outbreaks of natural gas containing 67.65% CH 20.70% N were encountered. The clays in these borings are impregnated with a black very finely divided iron sulphide which differs from the hydrated iron sulphide met with in the black mud of lakes and ponds. The material is magnetic D 3.57-4-16 (the true value being probably 4-2-4.3). Analysis gave Fe 46.24 ; S 51.92 ; insoluble 3*95% corresponding with the formula FeS,. I n another analysis the figures correspond with Fe,S7. The material is soluble in cold dilute hydrochloric acid with evolution of hydrogen sulphide and i t is much more readily attacked by various reagents (potassium cyanide potassium hydroxide iodine solution etc.and even by boiling water) than is iron-pyrites. The material is regarded as a labile phase of iron disulphide and is named melnikovite. Its mode of origin is discussed; it is regarded as having been derived from a colloidal form of iron sulphide. Bauxite of the Croatian Karst and its Origin. MIJAT KIBPATIC (Jahrb. Nin. 1912 Beit?.-Bd. 34 513-562).-Twenty analyses are given of bauxite from various localities in Croatia and also in Dalatuatia and Bosnia; the extreme values shown are quoted under I and 11. Analysis I11 is of the bauxite (" wochenito") from Wochein Carniola L.J. S. SiO,. TiO,. ZrO,. A1,0,. Fe,O,. MnO. CaO. Ign. Total. I. 0.87 nil. nil. 24'54 1-80 nil. nil. 8-11 - 111. 61.31 trace trace 16.95 12.46 trace - 6'40 99.75 11. 33.00 8'51 2.71 66.68 26.89 1-21 6.79 19.97 - At these localities the bauxite occurs as beds in limestone and dolomite; i t is dull red in colour and usually oolitic i n structure. Microscopical examination shows that the main constituent has the form of minute isotropic granules ; this material is named sporogelite (compare Tudan this vol. ii 69) and to it is assigned the com- position Al,0,,H20 corresponding with the crystalline diaspore. This colloidal material is sometimes white but usually it is coloured by intermixture with colloidal iron oxide and hydroxide. Other minerals present although usually only in small amounts include diaspore hydrargillite quartz felspar amphi boles felspars micas epidote rutile zircon etc.The same materials were obtained when the limestones and dolomites were dissolved in acid ; and it is considered that these bauxites as well as those from some other localities (France Italy Georgia etc.) represent the insoluble residues resulting from the weathering of these rocks. On the other hand certain other bauxites (from the Vogelsberg) and laterite are the products of decomposition of basalt and other silicate rocks. L. J. S. A New Deposit of Chrome-iron-ore in Northern Caucasus. N. BESBORODKO (Jahrb. Min. 1912 ; Bed.-Bd. 34 783).-Veins of compact to granular chrome-iron-ore have been discovered in serpentineMISERALOGICAL CHEMISTRY.ii. 65 about 18 km. south of the village Psemjonowka in prov. Kuban. Analysis I of an ore sample corresponds with about 85% of chromite. ‘Secondary minerals occurring in the serpentine (an altered olivine- rock) include chrysotile antigorite chrome-chlorites (kaemmererite and kotschubeite) revdinskite carbonates and quartz. The revdinskite {anal. 11) is apple-green with brownish patches and occurs sparingly as a thin coating on the serpentine. SiO,. Cr,O,. A1,0,. FeO. NiO. MnO. JIgO. CaO. H20. Total. 11. 20 5 - 25‘.0 6.2 - 29.9 - 23.4 102.0 I. 1’66 59.09 8.08 18.43 - 0.20 12.47 0.91 0.80 101’04 I n the same district chromium and nickel minerals respectively fuchsite and millerite were detected in a contact-metamorphic rock (silicate hornfels).L. J. S. Carboniferous Limestones of the Avon Gorge Bristol. MILDRED B. CHAPNAN (Geol. ilfay. 191 2 [v] 9 498-503).-Tmenty- one analyses are given of limestones from the various fossiliferoua zones. The extreme values are CJO 29-38-5.5*63% ; RlgO 0-16*76% ; CO 24.62-44*72% ; Fe,O + Al,O 0.08-5.S7:$ ; insoluble in hydro- chloric acid 0.02-43.99% ; P,O 0-0.14%. The insoluble residue consists of quartz black carbonaceous mhtter chalcedony weathered felspar zircon and tourmaline. Those limestones which have been formed under coral-reef conditions contain very variable amounts of insoluble residue whilst those which were r.tpidly deposited near a coastline are more pure. L. J. S. Tsumebite a New Lead Copper Phosphate. KARL Busz (Iiestschrijl Deut. Nccturf. Aertze illunster 19 12 188- 185).-The new mineral occurs as small emerald-green crystals with cerussite and chessylite on snow-white calamine (ZnCO,) the littter cementing fragments of reddish-brown dolomite in the mines at Tsumeb Otavi German South-West Africa.The crystals are monoclinic with (6 b c = 0.9974 1 0.8215 ; p = d1°44’. Analysis agrees with the formula P205,5(Pb,Cu) 0,8H,O PbO. CuO. P,05. H,O. Total. Sp. gr. 63.77 11‘79 12.01 012.33 99.90 6.133 L. J. S. Ludlamite from Ashio Japan. NOBUYO FUKUCHI (Beitr. ) A . Japan 1912 No. 4 192-194).-This iron phosphate is found in tilo Ashio copper mines prov. Shimotsuke as druses of light green trans- parent crystals with a bright vitreous lustre. It is associated witti crystals of vivianite and it sometimes foras pseudomorphs after vivianite.The crystals are monoclinic and have the form of thick six-sided tablets with a perfect basal cleavage. H = 3& ; streak white. Analyses give the formiila Fe,(OH),( P0,),,7H20 FeO. P,OP H,O. Insol. (in HCl). MnO h1,Q3 Ca0,MgO. 53‘21 32-03 14‘60 trace traces 50.54 31-38 13.79 3.67 - L J. S. VOL. CIV. li. 5ii. 66 ABSTRACTS OF CHEMICAL PAPERS. The C o n s t i t u t i o n of Some ‘‘ Salic ” Silicates. HENRY S. WASHINGTON (Amer. J. Sci. 1912 [iv] 34 555-571).-Accepting Streng’s and Groth’s suggestion that the quinquevalent groups ( R’Si)v and (R”Al)Y and in some caFes the decioalent group (CaSi,)” are present in certain silicates the author shows that the constitution of all the members of the felspar leucite nephelite and scapolite groups and nearly all the zeolites can be interpreted in such a way as to explain readily their composition mutual relations poly- and iso-morphism resistance to acids and their relation t o the mutually common end alteration product kaolinite.The felspar~ lenads (felspathoids including leucite nephelite and their congeners) and most zeolites are regarded as salts or isomorphous mixtures of salts of an alurnino-silicic acid H,AISi,O or most probably of a polymeride of this the five hydrogen atoms being isomorphously replaced by the groups (RSi)” (R”Al)’ and (R”Si,)” R’ being K Xa and Li and R” being Na K Ca and rarely Ba and Sr. The scapolites are interpreted as salts of a different aIumino- silicic acid H,oAISi,O, the hydrogens being entirely xeplaced by t h e radicles (NaSi) and (CaAl)2.DENZ~ SAT^ (Beitr. Min. Japan 1912 No. 4 139-141).-The water issuing from the hot springs of Obama prov. Hizen is clear and odourless with a slightly alkaline reaction and a temperature of looo. Three analyses of water from different springs are given that from the Funtfi-yu contains per litre CaCO 0.32150; FeCO 0,01626 ; Na,SO 0.63517 ; NaC1 5.66341 ; KCI 1.63388 ; MgCl 0.53582 ; CaCI 0.2’7539 ; SiO 0.21800 ; total solids 9.20390. Analysis of a snow-white incoherent hinter forming a small cone around the orifice of this spring gave SiO,. Fe,O,. A1,0,. MnO. CaO. MgO. K,O. Na,O. CO,. C1. Ign. Total. 16‘59 0‘41 0-18 1-80 38’28 7’28 0.20 0.89 23.28 1.03 10’46 100.40 T. S. P. Sinter from the Geyser of Obama Japan. D15’5 1.006. L. 3. s. A Felspar of Porto-Scuso (Sardaigne).GIUSEPPE CESARO (Bull. Acud. roy. BeZg. 1912 553-569).-A detailed account of the crystal- lographic examination of a felspar from Porto-Scuso which analysis shows t o be a sodium orthose with two molecules of sodium oxide and one of potassium oxide. The numerical data are tabulated. The author discusses the effect of the replacement of potassium by sodium on the values of the fundamental angles and from his results calcu- lates the values of these angles for a purely sodium orthose. At the end of the paper he gives an account of a method for measuring under the microscope the angle of the optical axes in a section passing through the obtuse bisectrix and inclined t o the acute bieectrix. The error for the method is calculated t h a t for 2t,b being 30’ that relative t o a being 2’ ; for 2V 22’ to 24’.Sericite from North Wales Penninite and Labradorite from Ireland. ARTHUR HUTCHINSON and WALTER CAMPBELL SMITH (Min. Mag. 1912 16 264-2’il).-Sericite (anal. I) occurs as talc-like W. G.MINERALOGICAL CHEMISTRY. ii. 67 aggregates of pale-green flakes in quartz veins intersecting dolerite and slate at Tan-y-Bwlch Merionethshire. Refractive indices @ = 1.589 y=1*594 2E=6B050'. I n composition i t conforms with type I of Clarke's formula Al(Si0,)3A12R3'. Ponninite (anal. 11) forms colour- less to pale brown hexagonal plates in the ophicalcite ("Connemara marble ") which is quarried at Recess Co. Galway. In composition H,,Mgl,A1,Si,0,9 it approximates to pseudophite. Labradorite (anal. 111) occurs as large porphyritic crystals in dolerite dykes at St.John's Point near Ardglass Go. Down. The optical constants are a= 1.5630 p= 1-5665 y = 1.5712 2V=8lo48' extinction on (001) - 1l0 on (010) - 23" ; angle (001) (010) = 85'57'. 33NaA1Si30,,5KA1Si30,,62CctA1,Si,0,. Formula H,O. H,O. SiO,. A120,. Fe,O,. FeO. CaO. NgO. K20. Nn,O. (> 105"). (105"). Total. Sp. fir. I. 46.51 36.58 0.51 0.48 0.44 0.46 7.84 1.77 5.03 0.11 99.73 2.798 11. 34.81 16'21 1-09 0.36 0.75 30.05 1'85 - 12.71 1.89 99'72 2.619 111. 52-33 30.22 0.40 - 12.52 - 0-55 3.62 0 3 6 100.30 2'706 Laumontite from Ashio Japan. NOBUYO FUKUCHI (Beitr. Min. Jcqmn 1913 No. 4 190-192).-A vein of lsumonite occurs in lipnrite the country-rock of the Ashio copper mines prov. Shimotsuke. Crystals are perfectly colourless and long-prismatic in habit.Analysis of the fresh crystals gave the following results corresponding with the formula H,CaA1,Si,01,,2~H20 ; other determinations of water varied from 16.02 to 16.43%. v L. J. s. SiO,. A1,0,. CaO. H20. Na,O,I<,O,MgO etc. 50.79 18'49 10'69 16-20 3-53 On exposure to the air the crystals soon fall to a white powder in which was found only 14.44% water corresponding with the formula H,CaAl2Si4Ol,,2H,O. The latter formula is the one usually given for laumontite. L. J. S Minerals of Taiwan ( = Formosa). Y~HACEIIR~ OKAMOTO (Beitr. Min. Japccn 1913 No. 4 157-188).-Fifty-one species of minerals (including petroleum and coal) are described ; analyses are given of the following. Hornblende as black crystals in the horn- blende-pyroxene-andesite of the Daiton volcanic group (anal.I and 11). Fuller's earth (?) white greyish-blue or yellow and more or less greasy from Hbko-tG (anal. 111) ; hygroscopic water 10.50", ; portion soluble in hydrochloric acid 64.96%. SiO,. AI,O,. Fe,O,. FeO. MnO. CaO. MgO. Na,O. K,O. Ign. I. 43'99 15-04 13'76 - 0'52 10.55 11-35 0.34 0.19 3'44 11. 41-67 14'14 - 16.18 0.69 11.10 14-16 1.98 nil. 111. 56'06 19-72 11'35 - - - '2.25 not det. - Alunite occurring as crystals (up to 2 em. across) with auriferous enargite and native sulphur in the Kinkwaseki gold mines; IV. of pale violet and V of white alunite. -+ SO:;. Also,. Fe,O,. MgO. K,O. H,O. Insol. Total. Sp. gr. IV. 34.90 37'40 trace nil. 6.18 13.24 7.42 99-14 2.787 V. 38.65 35-88 0.69 6.09 Il'tjO 6'42 99'33 - VOL.civ. ii. 6ii. 68 ABSTRACTS OF CHEMICAL PAPERS. A radioactive mineral consisting of barium and lead sulphate is deposited together with native sulphur etc. by the Hokuto hot springs in the Daiton volcanic group. The water has a strong acid taste (containing free hydrochloric acid) an odour of hydrogen sulphide and a temperature of 80-90°; i t contains in 1000 parts Na,S04 1.9055 ; NaCI 0.9990 ; AI,(S04) 0.6588 ; KCI 0.7130 ; NH,Cl 0.6073 ; CaSO 0.4787 ; FeSO trace ; Fe,(SO,) 0.5420 ; MgSO 0.2024 ; AI,(HP04)3 0*0012 ; BaSO 0.0007 ; PbSO trace ; H2Si0 0.2174; HBO 0.0710; HCI 1.9596. D?$ 1.0150. The radioactive material forms a coarsely fibrous crust (anal. VI) or clusters of brown rhombic plates (anal. VII). These crystals are zoned and have angles agreeing approximately with those of barytes and anglesite ; D 6.1; the a-ray activity is 0.0366 that of uranium oxide. Analysis VIII is of an accompanying dirty-grey crust of siliceous sinter.PbO. BaO. SrO. CnO. SO;. Fe20y. 9lzO3. Mg.0. KzO. NazO. HzO. Ign. P,05. 9iO.L. Totnl. VI. 21'96 32.04 0'93 0.51 3031 3'93 0'8s 1'04 nil. 0.53 2'53 - 0.01 1'27 96'44 VI1. 19'3s 42'27 trace 0'17 31 70 0.43 0.4s 0% 0 14 1.53 - 2'74 nil. 0.97 1(,0'09 VIII". - - - 0 13 2 4S 2.11 2.27 0.30 0'14 0 73 - 14'04 trace 77'10 100'20 Ti02 trace. L. J. S. The Tourma line Group. WALDEMAR T. SCHALLER (Zeitsch. K r p t . Min. 1912 51 331-343).-The following determinations of the physical constants and analyses mere made on crystals of tourmaline Locality. Colour. Sp. gr. Axis c. W . F.W-E (Ka). I. Nba ..... .................. Pale red 3.05 0'4448 1.651 1.630 0,021 11. Mesa Graude California Red 3.04 0'4479 1,647 1.628 0'019 111. Y > ' 7 7 ) Palegreen 3.04 0.4489 1.646 1.628 0.015 IV. Ramona California ...... Black 3-22 0.4534 - - _- V. L o s t Valley Califorilia Black 3.16 - - - - Total less I. 37'89 10 2s 43 S.5 0'04 0.11 0.11 0'07 - - 2 43 1% 3'47 0.10 !M*97 11. 37.57 10 65 42.18 trace 0.19 0'24 1.20 - - 2.05 1.92 3'38 0'39 99.80 TI I . 36.72 lO'(i0 41.27 O ' O ( i 1'13 1.48 0.57 - - 2.23 1.76 3.33 0'31 (39'03 I V . 35'21 10 43 36.07 0.23 11'11 0'98 0'25 0.19 - 1.92 trace 3 51 - 99.90 V. 39'96 10% 93.28 0.36 11 04 0'13 0'42 3.48 - 2.16 - 3.31 - 100 75 SiOF D203. hI2O3. Ti203. FeO. MnO. CaO. MgO. KzO. KazO. Li20. Hz0. F. 0 for F. These new analyses conform very closely with Penfield and Foote's general formula HzoB2Si,0z1 (A 1899 ii 304).Together with some earlier analyses they are discussed in detail. The ratio of (H,O + 4F) SiO ranges from 3.72 12 to 4.17 12 and in the special formuh proposed water is given as 3H20. Further the alumina varies inversely in amount with the other bases (R = Fe" Mn" Ca Mg K2 Na Li and H2 in excess of the 3H,O). The end com- ponents as plotted on a curve are 12Si0,,3B,O3,8A1,0,,3RO,3H,O and 1 2Si0,,3B,03,5A1,0 1 2R0,3H20. I n analysis I of Elbn tourmaline still more alumina is present and the component 128i0,,3B20,,9A1,0,,3H20 is assumed. There may also be several other members of the series for example 1 2SiO 3 B,O 7 A1 203 6 R 0 3 H ,O. Other special types are introduced by replacing KO by MgO Li20 etc.MINERALOGICAL CHEMISTRY. ii.69 The composition of Ramona tourmaline (anal. I V ) is for example expressed by the mixing of the following three components 1 2Si 0 3B20 8A I2O3 3 H,O 3 H,O 12SiO 3B,03,7A120,,6Fe0,3H,0 1 2Si0,,3B203,5A120 1 2Na,0,3H20. Comparing the chemical composition and the physical constants it is noticed that the specific gravity crystallographic axis c refractive indices and double refraction reach a maximum with AI,O 35-36% and that this point separates two series of tourmalines. Magnesia- free-tourmalines contain more and magnesia-tourmalines less than this amount of alumina. The former occur in pegmatites whilst the latter are usually found in metamorphic rocks and are brown or black in colour.L. J. S. Minerals from the Pegmatite of Ampangabe’ Madagascar. ALFRED LACROIX (Bull. Xoc. Jranf. itfin. 1912 35 180-199. Compare A 1912 ii 1182).-The pegmatite of Ampangab& near Miandrarivo consists of microcline quartz and muscovite and is exploited for beryl of gem-quality. This beryl is of the prismatic type very poor in alkalis D 2*713-2*721. The gem materialbis of a fine blue colour but delicate pink colourless yellow and green stones are also found. Other minerals present in the pegmatite include monazite in crystals columbite crystals D 5.52 (anal. 1 by Pieani) ampangabeite (A. 1912 ii 567) striiverite etc. The striiverite is found as large tetragonal crystals (up to 6 kilos.) which are usually elongated in the direction of a pyramid-edge (1 11 I1 l) and sometimes twinned on (101)) giving them an orthorhombic aspect.These crystals are optically uniaxial and positive and have angles very close to the angles of rutile. The material is iron-black with a conchoidal to uneven fracture D 4.91 ; anal. I1 by Pisani. TiO,. Ta,O,. Cb,O,. SnO,. FeO. MnO. AI,O,. Total. I. - 12.60 64.60 0’40 15.00 7.30 - 99.90 11. 71.15 10’14 - 0.05 15’84 - 1.80 98-98 I n SL beryl-bearing pegmatite from the west of Miaidrarivo is a fresh monazite which in thin flakes is transparent and clear yellow U 5.1 1 anal. 111 by Pisani. Loss 011 P,O,. Ce,O,. (La Di),Os. (Y,Er),O,. Tho,. A1,013. Fr,O,. ignition. Total. 27’45 31.85 27’90 2.93 9‘15 0.21 0‘42 0.74 100‘65 L. J. S. N a t u r e and Origin of “Terra roma.” FRAN. TU~AN (Jahrb. Min. 1912 Bed.-Bd. 34 401-430).-Terra rossa occurs in the crevices and cavities of the bare corroded limestones and dolomites of the Karst district and i t represents the insoluble residue left by the denudation of these rocks.It consists mainly of minute amorphous particles of aluminium hydroxide A1203,H20 ; and for this colloidal mineral (corresponding with the crystalloid diaspore) the name sporogelite is proposed. The red colour is due t o colloidal ferric hydroxide ( 2Fe2O,,3H,O) ; and various accessory minerals are present as minute grains namely quartz mica epidote hydrargillite diaspore amphibole felspar garnet rutile etc. The residues (averaging 0.32%) 6-2ii. 70 ABSTRACTS OF CHEMICAL PAPERS. obtained by dissolving the limestones in dilute acetic acid or the dolomites in dilute hydrochloric acid have the same reddish colour and are identical in mineralogical composition with the terra rossa.Analysis of terra rossa from various localities gave K20,h'a20 Si02. Ti&. Zr02. A120,;. Fe203. MnO. CaO. MgO. 1&0. HzO. COz. Total. I. 0.37 8-51 0-45 55.37 21-76 trace trace trace trace 13.45 - 99.91 11. 26-20 0.51 0.81 39-14 14.03 1.45 - 18.14" - 100.28 111. 35.42 0.30 0.10 32-89 15-03 0.93 0.43 trace 15.32 0.23 100.55 IV. 43.61 trace trace 27.80 11.75 trace 1-64 15.43" - 100.23 V. 47.89 0.96 24.38 12.63 1-18 0.68 {-b2 11.86 0.39 100'29 VI. 46-27 0.80 26.61 12.64 0'12 1'13 ) trace 13'32" - 100.89 VII. 26.47 trace 20.19 18.03 1.32 13.19 11'24 9-12 99-56 VIII. 32.11 25'69 6.20 - 14'44 0.48 11-33 10.77 100.97 IX.66.57 O'i2 0.09 21-87 5.72 - - - 5*58* - 99.95 ' Loss 011 iguitioii. Analysis I of the purest material from iupanjac Bosnia is interpreted as sporogelite 70.38% ; colloidal ferric hydroxide 22.025% ; rutile 6.88%; zircon 0.48%. I n the other analyses the silica is present partly as quartz and partly as colloidal silicic acid the latter being soluble in dilute hydrochloric and nitric acids. I n anal. 11 for example 8.99% of the silica is soluble and represents 43089% colloidal silicic acid intermixed with 39.54% of sporogelite. The sporogelite is regarded as an original constituent of the lime- stones and t o have been precipitated as such from the sea-water at the time that t h e limestones were deposited. The bauxites oE the same region are identical chemically and mineralogically with the terra rossa but they are of earlier date (compare KGpatie this vol. ii 64).L. J. S. Analysis of Red Earth from the Floor of an Ancient Hut. JOHN 0. HUGHES (Chern. News 1912 106 247)-A reddish- brown earth obtained from the floor of one of the ancient huts forming the stone fortress on the top of Penmaenmawr Carnarvonshire was found to have the following composition substances insoluble in hydrochloric acid silica etc. 83.82% ; alumina 2.47% ; iron oxide 4-7 1 % ; magnesia 1-457L ; sodium and potassium oxides 052% ; phos- phoric anhydride 1.2274 ; sulphur trioxide 0.13%; water (at l l O o ) 1.86% ; loss on ignition 3070% ; manganese oxide calcium oxide carbon dioxide and chlorine traces. Embedded in the earth were a few small pieces of charcoal The author is of the opinion that the earth is the ash of some combustible substance (possibly peat) mixed w.P. s. MASUMI CHIKASHIGB and TADASU HIKI (Zeitsch. ccnorg. Chem. 1912 '77 197-199).-A meteorite which fell in 1904 at Okano in the province of Tamba Japan has been examined. The meteorite which weighs 4742 grams contains Fe 94*S5% ; Ni 4.44% ; Co 0.48% ; P 0.23%; Cu trace and has D 7.98. The ground-mass consists of nickeliferous iron showing Neumann's lines on etching. The phosphide occurs as distinct 1 he bdite crystals. Heating at 1300O for thirty minutes causes granulation of the mass and the Neumann's lines disappear. witli a portion of the surrounding soil. A New Fall of Meteoric Iron in Japan. C. H. D.MINERALOGICAL CHEMLSTRY.ii. 71 Meteoric Fall near Holbrook Arizona. GEOI~GE P. MERRZLL (Smithsonian MiscelZ. Collections 1912 60 No. 9 1-4. Compare Foote A. 1912 ii llSS).-The stones of t h i s recent and remarkable fall resemble in lithological character those of the Pultusk (Poland) shower of 1868 and in Brezina's classification belong to '( spherulitic chondrite crystalline Cck." The material consists of orthorhombic with occasional monoclinic pyroxenes and of olivine with small scattered masses of metallic iron and iron sulphide ; numerons chon- drules are set in a loose aggregate of particles The iron sulphide forms granules up to 8 mm. across and resembles pyrrhotite in its bronzy lustre ; it is however non-magnetic Dz'c = 4.61 and analysis I1 gives the formula FeS proving the material to be troilite.The stone has D22'G = 3.48 and contains silicates 87.48 ; metal 4-85 ; troilite 7.56 ; schreibersite 0.1 1%. Analysis by J. E. Whitfield of the metallic portion gave I the sulphide 11 and of the silicate portion the results under 111. Fe. Xi. Co. Cu. S. Total. I. 90.50 8-68 0'64 0.29 - 100*11 11. 63'62 nil. 36'50 100*12 SiO,. A1,03. FeO. CaO. MgO. MnO. NiO. Na,O. Total. 111. 41.93 4'30 21.85 2'40 29.11 0'25 0.08 trace 99'92 L. J. S. Meteoric Stones of El Nakhla El Baharia (Egypt). GEORGE T. PRIOR (Mi@ gag. 1912 16 274-281. Compare A 1911 ii 1106 ; 1912 ii 361).-One of the stones weighing 274 grams of this recent fall was examined. Thin sections show a holocrystalline aggre- gate of green diopside and brown olivine (there being no hypersthene as stated in previous accounts) with a little interstitial matter consisting of felspar laths.The diopside shows " herring-bone " struc- ture and its optical constants are a =; 1.685 = 1.69 y = 1.72 2V = 44-4So c L - 40-44' ; its composition I1 (calculated from I and 111) corresponds with 3MgSi0,,3CaSi0,,2FeSi03. The olivine is characterised by the presence of dark brown to black enclosures with a definite crystallographic orientakion ; a = 1.75 p = 1.785 y = 1.80 2V = 67'; analysis I11 is of selected grains and IV of the portion of the stone soluble in hydrochloric acid corresponding with ZFe,SiO,,Mg,SiO,. This olivine is near to hortonolite and is much more ferriferous than any meteoric olivine previously described. The bulk analysis of the meteorite is given under I corresponding with the following mineral composition diopside 76.70 ; olivine 13.25 ; felspar 6.76 ; magnetite 1.87 ; ilmenite 0.73 ; chromite 0.49 ; troilite (?) 0.17 ; water 0.24%.Si02 A1,0,. Fe,O,. FeO. CaO. NgO. Total. Sp. gr. I." 48'96 1'74 1-29 19'63 15.17 12-01 100.45 3-47 11. 52'73 - - 14-93 1 9 2 2 13.12 100*00 3'42 111. 32.59 - - 51.80 1.11 15'60 101-10 3.98 * Also TiO 0.38 ; Cr20 0.33 ; MnO 0.09 ; Na,O 0'41 ; K20 0'14 ; S 0'06 IV. 33.06 - - 51.67 1.86 13.03 99'62 - H20 0'24.ii. 72 ABSTRACTS OF CHEMICAL PAPERS. Consisting mainly of monoclinic pyroxene and olivine with no metallic iron this meteorite approaches most closely to the angrite group. L. J. S. Meteorite Fall in Central Japan. TETSUQORO WAKIMIZU (Beis-. Min. Japan 1912 No. 4 145-150).-A fall of stones was observed on July 24 1909 near the town of Gifu prov. Mino. Twenty-four stones the largest weighing 4039 grams were picked up over an area of 12 x 5 km. The material D 3-57 is classed as a white chondrite with very little nickel-iron and iron sulphide. Under the microscope it is seen to be holocrystalline and to consist essentially of olivine and bronzite. Analysis gave SiOa. PzOs. Ti02. Fe2O~ Fe. Ni. Mn. CaO. MgO. S. SO3 C. Hz0. Total. 41'013 0.455 0'1lG 5'170 30'5S3 0'1S3 0'910 2.76s 24.707 2.185 0.231 trace 0.331 99.227 1,. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9130405063

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 72 ABSTRACTS OF CHEMICAL PAPERS. An alg tic a1 Chemistry . The Estimation of W a t e r and of Carbon Dioxide i n Minerals and Rocks. MAX DITTRICH and W. EITEL (Zeitsch. anorg. Chem. 1912 77 365-376. Compare A. 1912 ii 804).-It has not been found practicable to estimate water and carbon dioxide in minerals and rocks by fusion with sodium metaphosphate or borax as a constant weight is not obtained in blank experiments. On the other hand heating the material in a stream of dry air in a silica tube is found to be satisfactory. The air supply tube is also of silica and is ground in and held by springs. A spiral of silver gauze is used to retain sulpbur. I n the case of minerals which lose water with difficulty the final heating is performed by means of the blow-pipe. Rocks contain- ing epidote mica or hornblende often do not lose the whole of their water through these minerals becoming enclosed.Much better results are obtained by the use of a platinum electric furnace sur- rounding the silica tube. The water is then driven off completely except in the case of materials containing much fluorine. Calcite does not lose its carbon dioxide completely unless first mixed with powdered quartz with a blowpipe but is completely decomposed in the electric furnace a t 1100O. The silica tubes last well a t 1000° but devitrifg at higher temperatures By the use of a platinum-iridium tube and a boat of the same material the most refractory rocks lose their water and carbon dioxide completely at 1250-1300'. C. H. D. New Reagent for Chlorine and Bromine Free and- Com- bined.GEORGES DENIQES and L. CHELLE (Compt. relad. 1912 155 1010-1012. Compare A. 1912 ii 1208 ; Guareschi ibid. 989).-The reagent is prepared by the addition of 10 C.C. of a solution of magentaANALYTICAL CHEMISTRY. ii. 73 (1 in 1000) to 100 C.C. of sulphuric acid (5% by volume). This is then mixed with an equal volume of acetic acid and 4 C.C. of strong sulphuric acid are added. This solution is coloured yellow by chlorine and reddish-violet by bromine the colour being best shown by shaking with chloroform. If the halogens are combined as metallic salta the solution is acidified the iodine removed by a ferric salt the bromine liberated by the addition of potassium chromate and tested for and the chlorine then liberated by potassium permanganate and separately tested for.The vapours are absorbed in dilute alkali before applying the test. The method can be applied quantitatively for dealing with small quantities of bromine as in natural waters and is more delicate than the methods at present in use. The Iodic Acid Process for the Estimation of Bromine in Halogen Salts. FRANK A. GOOCH and P. L. BLUMENTHAL (Amer. J . Xci. 1912 [iv] 469-474).-A criticism of Bugarszky’s process (boiling the solution containing bromides and chlorides with potassium iodate and dilute sulphuric acid and determining the loss in iodine A 1896 ii 216). The authors find that although the process was thought to be an ideal one it is vitiated by secondary effects. The latter may be reasonably attributed to the action of small amounts of iodine monochloride or monobromide formed in the interaction of iodic acid and free iodine with hydrochloric acid and hydrobromic acid Substitution of chloric acid for iodic acid cannot be recommended.L. DE I(. W. G. Oxidisable Substances in the Air. L. SCHWARZ and GEoRa MUNCHMEYER (Chern. Zentr. 1912 ii 1695 ; from Zeitsch. Hyg. Imfekt.-Krankh. 1912 72 371-384).-Henriet and Bouyssy’s method (A. 1911 ii 532) whereby the titration of condensed water is taken as a measure of the degree of vitiation of an atmosphere is criticised. Such condensed water gives different readings at different tem- peratures and would only give a correct value if all the moisture in the atmosphere could be condensed or if it contained oxidisable substances to the same extent as the collected water which is not the case.J. C. W. An Apparatus for Microanalysis of Blood Gases and Micro-respirometry. HANS W INTERSTEIN (Biochem. Zeitsch. 19 12 46 440-449).-The apparatus (which is figured) is a combination of the Barcroft-Haldane and Petterson systems. It consists essentially of two pear-shaped flasks one of which is a compensation flask and the other serves for the actual analysis. They communicate by means of three-way stopcocks either with the outer air or with one another. The latter communication is through an etched capillary tube containing an oil drop. The analysis flask communicates furthermore with a manometer of which the narrower limb which is nearer the flask is a capillary graduated in millimetres. The outer limb is broader and is closed by a piece of indiarubber with a screw-clamp and a piece of solid glass rod.The flasks communicate ; the meniscus of the oil drop in the capillary connecting the twoii. 7’4 ABSTRACTS OF CHEMICAL PAPERS. flasks is brought to a certain point by turning the screw-clamp on the indiarubber and the height of the mercury in the graduated limb of the manometer is then read. This takes place with the same materials in each flask and the whole apparatus is kept in a water- bath. If the measurement to be carried out consists in the deter- mination of the oxygen content Haldane’s ferricyanide method is employed the reagent being kept in spoons fused on to the stoppers. The apparatus after the first reading and adjustment is then removed from the water-bath and shaken so as to bring the ferri- cyanide into the blood and ammonia mixtures whilst the two flasks are kept closed and out of communication with one another.They are then brought back to the water-bath brought into communication the position of the oil drop in the communicating flask is readjusted and the height of the manometer is read. The difference between this and theGrigina1 reading gives the amount of oxygen evolved. 3. B. 8. Estimation of Tellurium by means of Hydrazine Hydrate. J. B. MENKE (Zeitsch. anorg. Chenz. 1912 77 282-288).-See this VOI. ii 41. Detection of Nitrogen in Organic Substances H. ZELLNER (Pharm. Zeit. 1912 57 979-980).-For the detection of small quantities of nitrogen or when the amount of the substance to be tested is not large the following modification of the usual test may be employed.The substance is fused with potassium the fused mass is dissolved in water and the solution is warmed after the addition of ferrous sulphate. The solution is then filtered and the filtrate is poured on the surface of ferric chloride solution acidified with hydro- chloric acid. If nitrogen is present in the substance a blue zone appears at the junction of the two liquids. w. P. s. A New Gas-analytical Method for the Estimation of Nitric Oxide. I. OSKAR BAUDISCH and GABRIEL KLINGER (Ber. 1912 45 3231-3236).-The method depends on the fact that when air is passed into nitric oxide standing in contact with solid potassium hydroxide nitrogen trioxide (N,O,) is formed and immediately converted by the hydroxide into potassium nitrite there being no formation of nitrogen dioxide.Four-fifths of the contraction thereby caused is due to nitric oxide as expressed by the equation 4N0 + 0 + 4KOH = The analysis is carried out in Fuller’s gas-analysis apparatus ; the pipette contains slightly moistened stick potassium hydroxide with which the nitric oxide is in contact before air is passed in and all measurements are carried over mercury. Before passing the nitric oxide into hhe pipette the latter is completely filled with mercury. The method gives accurate results even in the presence of nitrous oxide or hydrogen. The reverse method of passing the nitric oxide into air standing over potassium hydroxide cannot be used since a mixture of N20 and NO is formed 4KN0 + 2H20.T. S. P.ANALYTICAL CHEMISTRY. ii. 7 5 Detection of Nitrous Acid in Water. PRIMOT (Chevz. Zentr. 1912 ii 1546-1847; from Bull. Sci. PharntacoZ. 1912 19,546-547). -To 10 C.C. of the water 4 or 5 drops of a 1-1*5% solution of benzidine o-tolidine or dianisidine in 30 -40% alcohol are added. The mixture is then acidified with 5 or 6 drops of acetic acid and shaken when the development of a yellow cclour which deepens in time shows the presence of a nitrite. Benzidine is the least sensitive reagent. The limit of sensitiveness is below 0.01 mg. of nitrous acid per litre. J. C. W. LUIGI ER~IANNO CAVAZZA (C?hem. Zentr. 1912 11 1061-1062; from Atti 11. Congr. Nax. Chifiz. uppZic. 1912j.-Ten grams of powdered pure indigo are intro- duced (with cooling) in small quantities into 50 C.C.of fuming sulphuric acid and after forty-eight hours the solution is diluted t o a litre. Fifty C.C. of the liquid are then diluted so that 10 C.C. corres- pond with 0.001 gram of nitrogen pentoxide. When dealing with nitrates a stronger solution may be employed. Organic matters if present should be removed by adding to 25 C.C. of the solution the requisite amount of potassium permanganate (previously determined) ; 30 C.C. of sulphuric acid are added and the whole heated over a small flame and titrated. When the liquid turns bright yellow the heating is discontinued and the titration rapidly brought to an end. I n testing ordinary water concentration by evaporation is not necessary as the GEORG LoCIiEMANN (Chem. Zed. 1912 36 1465-1 466).-Historical. The original Marsh apparatus and Estimation of Nitrates with Indigo. end reaction is so very sensitive.1,. DE K. The Marsh Arsenic Test. modifications of it are described. L. DE I(. Estimation of Small Quantities of Carbon Monoxide. OTTO BRUNCK (Zeitsch. angew. Chum. 1912 25 2479-2481).-A suitable flask of known capacity (say a litre flask) is fitted with a doubly perforated rubber cork closed by means of rods. After filling the flask with the air to be examined 50 C.C. of sodium palladium chloride (1 C.C. =5 0.004762 gram of palladium) are introduced from a pipette (while gently loosening the second rod) followed by 2.5 C.C. of 5% solu- tion of sodium acetate; the volume of liquid ip of course deducted from the volume of the gas tested. After an hour’& action with frequent shaking the palladium which has deposited owing t o the reducing action of the carbon monoxide is collected and ignited with the usual precautions; 1 gram of metallic palladium = 0.2624 gram or 210 C.C.of carbon monoxide. Hydrogeu and the unsaturated hydrocarbons should be absent as Simple Apparatus for the Estimation of Carbon Dioxide. W. R. FORBES (CIhem. News 1912 106 284).-The apparatus consists essentially of an inverted V-tube closed at either end and provided in the middle with a ground stopper carrying a delivery tube and tap. In use the acid is placed in one limb and the carbonate in the other. Beaction is started by suitably inclining the apparatus. they also exert a reducing action. L. DE K. H. W.ii. 76 ABSTRACTS OF CHEMICAL PAPERS. Cobaltinitrite Method of Estimating Potassium.F. H. MACDOUGALL (J. Amer. Chern. Soc. 1912 34 1684-1686).-1n the estimation of potassium by the cobaltinitrite method i t is usual to boil the yellow precipitate with excess of N/10-potassium permanganate then add dilute sulphuric and oxalic acids and finally to titrate with N/10-permanganate. The oxidation of the nitrite thus takes place in alkaline solution and the permanganate is reduced to manganese dioxide. The latter reacts but slowly with the oxalic acid added subsequently since the mixture is so dilute. The author has therefore studied the effect of adding dilute sulphuric acid to the yellow precipi- tate before oxidising it with perrnanganate. It has been found that accurate results can be obtained in this way but that a different factor must be eniployed in the calculation ; accord- ing to the usual method 1 C.C.of lY/lO-permanganate is equivalent to 0.0007111 gram K or 0,0008564 gram K,O whilst with the modified method 1 C.C. of N/lO-permanganate corresponds with 0.0006518 gram K or 0.0007850 gram K,O. IE. G. Determination of the Sensitiveness of the Hydroxide Re- actions for the Common Metals. LOUIS J. CURTMAN and A. D. ST. JOHN (L Amer. Chern. Soc. 1912 34 1679-1684).-A study has been made of the sensitiveness of the hydroxide test for metals. The experiments consisted in treating a solution of a salt of the metal with 10% ammonia or sodinm hydroxide the final volume being 5 C.C. I n the following cases ammonia was used as the precipitant and the limiting concentrations of the metals a t which a precipitate was visible were lead 1-6500 ; mercury (in the mercuric state) 1-13,000 ; bismuth 1-10,000 ; iron 1-80,000 ; aluminium 1-100,000 ; chro- mium 1-170,000 ; zinc 1-80,000.For the following metals sodium hydroxide was employed as the reagent and the limits found were silver 1-40,000 ; mercury (in the mercurous state) 1-200,000; copper 1-10,000 ; cadmium 1-40,000 ; nickel 1-80,000 ; cobalt 1-80,000 ; magnesium 1-10,000. I n the case of manganese either ammonia or sodium hydroxide can be used the limiting concentration in each case being 1-170,000. Estimation of Lead in Lead Paints. FRANZ UTZ (Chern. Zentr. 1912 ii 1788 ; from Fas.benxeit. 18 18-20).-The nitric acid solution of the lead compound is electrolysed at 60-65' by a current of 0.05-1.5 amperes using gauze electrodes and the lead dioxide is washed without breaking the current and then dried a t 200O.E. G. J. C. W. Cuprous Iodide. MORITZ KOHN and ARTHUR KLEIN (Zeitsch. anorg. Chem. 1912 77 252-254).-Cuprous iodide may be analysed by the method of Baubigny and Chavanne for iodine in organic substances (A. 1903 ii 510; 1904 ii 203). One to 1.5 gram of silver nitrate is dissolved in 40 C.C. of concentrated sulphuric acid in tl flask and after cooling 5 grams of pure potassium dichromate are added. This is then dissolved by warming and the whole is again cooled. After adding 0.3 gram of the substance the flask is warmedANALYTICAL CHEMISTRY. ii. 77 and shaken until the svolution of oxygen begins. The silver iodide formed a t first dissolves as iodate.After cooling the contents of the flask are poured into 80 C.C. of water reduced by sodium sulphite and allowed to remain until t h e silver iodide has settled. This is collected on a Gooch filter after the addition of nitric acid dried a t 130° and weighed. Copper is estimated by heating 0-5 gram of the substance with 15-20 C.C. of nitric acid (1 l) converting into sulphate and precipitating as sulphide. Like potassium bromide (Kohn A. 1909 ii 891) ammonium bromide solutions dissolve cuprous iodide the solubility increasing rapidly with the concentration. Sensitiveness of the Bead and Lead Dioxide Tests f o r Manganese with Special Reference to the Interference of Iron. LOUIS J. CURTMAN and A. D. ST. JOHN ( J .Amer. Chern. Soc. 1912 34 1675-1679).-A study has been made of the sensitiveness of the bead and lead dioxide tests for manganese and the influence of iron on these tests. The results show that the lead dioxide test is not trustworthy in presence of 300 or 400 parts of iron to 1 part of man- ganese unless as much as 0.2 mg. of manganese is present but that the bead test is efficient with larger quantities of iron provided that as much as 0.005 mg. of manganese is introduced into the bead and certain specified precautions are observed. F. KONIG (Cliern. Zentr. 1912 ii 1064 ; from Apoth. Zeit. 2’7 536-’537).-Klut’s nitric acid process (ibid. 1909 ii 1076) for the colorimetric estimation of iron in waters gives good results with samples absorbing not more than 80 mg.of potassium permaaganate per litre. When this amount is exceeded the iron should be estimated colorimetrically in the residue after Reagent for D e t e c t i n g Small Quantities of Nickel. V. FORTINI (Chem. Zed 1912 36 1461).-The following solution is recommended for the detection of nickel in plated wares and nickel alloys. 0.5 Gram of dimethylglyoxime is dissolved in 5 C.C. of 98% alcohol and 5 C.C. of ammonia are added. After rinsing the surface with ether a drop of the reagent is applied when a rose-coloured spot mill form should nickel be present. Previous heating in the oxidation flame mill render the test still more delicate. The presence of other metals usually present does not interfere. The spot formed may be Test for Methane. I. OTTO HAUSER and H.HERZFELD (Ber. 19 12 45 351 5 -35 16).-Methane and ozonised oxygen react with each other with the formation of formaldehyde which reaction may be used as a very delicate test for methane. The gas t o be tested is mixed with ozonised oxygen and the mixture passed through a tube containing moistened glass wool which is afterwards extracted with water and the solution tested for formaldehyde with morphine and sulphuric acid C. H. D. E. G. Estimation of Iron in Water. ignition. L. DE K. easily removed with a towel. L. DE K.ii. 78 ABSTRACTS OF CHEMICAL PAPERS. Methane is the only hydrocarbon which gives formaldehyde. Ethane gives acetaldehyde or acetic acid but the reaction is much slower than with methane whilst acetylene is oxidised explosively to carbon dioxide.The reaction with acetylene takes place also i n acetone solution and is accompanied by a beautiful green luminescence. Toluene is oxidised by ozone with formation of formic acid. T. S. P. Analysis of Hydrocarbon Mixtures. OSCAR ROUTALA (Chem. Zelztr. 1912 ii 638; from Ann. AcacZ. Sci. FennicaB A. 2 No. 13 19 pp.).-The iodine absorption process for the testing of petroleums is too much affected by the personal equation and reports founded on it should be accompanied by a careful description of details of analysis including time of action temperature exposure to light and volume of iodine solution added. Frank's bromine process (Chem. I d 1901 24 263) may be successfully applied when small quantities of the substance are t o be tested also when the refining degree of colourless or pale petroleum products has to be determined or when the degree of purity of olefines has to be ascertained.From the bromine number the percentage of the olefine is calculated directly by the formula A = [K+ (.n - 5)c].G in which A = % of the olefine K= a constant n the mean number of carbon atoms for the olefine boiling at between the limits of temperature (at least 5) c = a constant ( =Om8750) and G the bromine number. For amylene K = 0,4375 ; for hexylene 0,5950 ; for heptylene 0.6075 ; for each additional CH,-group the constant increases on the average by 0*@€375 To show the accuracy of the formula a bromine number was taken of a mixture of amylene and isopentane and the result agreed with the sulphuric acid process and the density. L. DE K.Methoxyl Estimation with Hydriodic Acid and Phenol. FRITZ WEISHUT (Monatsh. 1912 33 1165-11~2).-1t is found that many substances which fail to give satisfactory results for the estima- tion of the methoxyl group even in the presence of acetic anhydride can be made to do so by using a mixture of hydriodic acid with approximately one-quarter its volume of phenol. I n most cases the reduction is complete in about one and a-half hours but methyl nitroanisate required five and a-half hours. D. F. T. Estimation of Higher Alcohols in Wine. THEODORE VON FELLENBERG (Chem. Zentr. 1912 ii 1851 ; from Mitt. Lebensmitt. Hyg. 3 231-235).-The colour reaction which higher alcohols give with salicylaldehyde and concentrated sulphuric acid (A. 191 1 ii 667) has been applied to wine. Natural wines are found to contain about three parts per 1000 of higher alcohols which suggests that the accepted value for cognac (1 per 1000) is very low. THEODORE VON FET'LENBERG ( C h m .Zentr. 1912 ii 1850-1851; from Mitt. Lebensmitt. Hyg. 3 228-231).-A colour reaction which phloroglucinol gives with vanillin and hydrochloric acid is also obtained with wine which J. C. W. A Colour Reaction of Wine.ANALYTICAL CHEMISTRY. ii. 79 probably contains therefore an unsaturated alcohol. may be matched against a standard solution of acid magenta. The red colour J. C. W. Examination of Lead Rrecipitates in Wine; Pentose and Methylpentose Estimations in Grapes and Wine. THEODORE VON FECLENBERG (Chem. Zentr. 1912 ii 1850 ; from Mitt. Lebensmitt. Hyg. 3 213-217).-After precipitation with just the required amount of lead acetate (found by a series of preliminary tests) there are still some substances in natural wines although scarcely at all in sophisticated wines which may be precipitated by basic lead nitrate.The precipitate contains succinic acid inositol pectin pentosan and methylpentosan. The pectin of grapes contains pentose and methyl- pentose but does not account for the whole of these sugars which are present both in the free state unprecipitable by basic lead nitrate as well as in the form of pentosans. J. C. W. A Simple Method of Characterising Acraldehyd 8. WILLIAM OECHSNER DE CONINCK (BUZZ. h a d . roy. Belg. 1912 534).-The acraldehyde vapour is condensed in distilled water through which a slow stream of oxygen is then passed until the solution is strongly acid.On dissolving freshly precipitated silver oxide in this liquid and concentrating the clear solution silver acrylate crystallises out in the pure state. W. G. A Bromometric Estimation of Formic Acid. H. MADEH (Chem. Zentr. 1912 ii 1401 ; from Apoth. Zeit. 1912 27 746-747). -A method for the estimation of formic acid is given; it depends on the oxidation of the acid by bromine. The solution is left for twelve to fifteen hours with bromide and bromate of potassium and phosphoric acid in a stoppered bottle when the unused bromate is decomposed by potassium iodide and estimated with thiosulphate. J. C. W. The Detection of Acetoacetic Acid by Sodium Nitroprusside and Ammonia. VICTOR JOHN HARDING and ROBERT FULFORD RUTTAN (Bio-Chem.J. 1912 6 445-45O).-Le Nobel’s test for acetone in the urine in which the urine is treated with acetic acid sodium nitro- prusside and ammonia mas found to give a less distinct reaction with urine to which acetone had been added than in natural acetonuric urines ; furthermore in the latter cases the reaction was less distinct in distillates containing relatively large amounts of acetone than in the original urine. The authors show now that the Le Nobel test is really a reaction for acetoacetic acid and not for acetone and as such it is capable of detecting 1 part of this acid in 30,000 whereas the ordinary ferric chloride test fails when the dilution is only 1 in 7000. s. B. s. Detection of Benzoic Compounds. OTTO SCHNATOLLA (Pharna. Zeit.1912 57 947).-Twenty C.C. of a solution t o be tested for the presence of benzoic acid are mixed with 5 C.C. of hydrogen peroxideii. 80 ABSTRACTS OF CHEMICAL PAPERS. and a solution prepared by dissolving 5 grams each of ferrous sulphate and boric acid in 100 C.C. of water is added until the mixture no longer becomes darker in colour. Should benzoic acid be present a dark bluish-green coloration develops with a few seconds. The test will detect the presence of 1 part of benzoic acid in 15,000 parts of solution. A similar reaction is given by all benzoic compounds hippuric acid etc. Benzoic acid however may be separated from hippuric acid in mixtures of the same by extracting the former acid with light petroleum. By means of suitable solvents benzoic acid may be separated from salicylic acid and then identified by the above reaction.w. P. s. Nature of the Reactions of Naphthenic Acida. I(. W CHARITSCHKOV (Chem. Zeit. 1912 36 1378. Compare A. 1910 ii 549 ; 1911 ii 543)-The reactions OF naphthenic acid described previously with copper sulphate ferrous salts cobalt nitrate and hydrogen peroxide are characteristic of cycEopentanemonocarboxylic acids and are not shown by acids which contain the cyclohexane ring such as cyclohexylacetic acid. H. N7. A New Method f o r the Colorimetric Estimation of Uric Acid in Urine. OTTO FOLIN and A. B. MACALLUM jun. (J. Bid. Chenz. 1912 13 363-370).-The method is based on the colour produced by the action of phosphotungstic acid. W. D. H. Detection and Estimation of Arachie Oil. NORMAN EVERS (Analyst 1912 37 487-492).-After trying various methods already proposed the author gives the following process 5 grams of the sample (say olive oil) are saponified with 25 C.C.of alcoholic potassium hydroxide (80 grams in 80 C.C. of water and diluted to a litre with 90% alcohol) in a reflux apparatus. To the hot soap solution are added 7.5 C.C. of dilute glacial acetic acid (1:2) and 100 C.C. of 70% alcohol containing 1 vol.% of hydrochloric acid and the liquid is then cooled to 12-14' for a n hour. The deposit is collected and washed with the acid alcohol (temp. 17-19") until the filtrate gives no turbidity with water the washings being measured. The precipi- tate according t o its bulk is dissolvod in 25 to 70 C.C. of hot 90% alcohol and cooled tc 15-20'.If abundant crystals appear then after one to three hours they are collected and washed first with 90% alcohol (about half the volume used for crystallisation) and finally with 50 C.C. of 70% alcohol. The crystals are now dissolved in hot ether and this is then distilled off in a weighed flask; the residue is dried at 100' and weighed. Should the m. p. be lower than 71° the acid should be recrystallised from 80% alcohol. A correction for solubility should be made for which a table is given. If no or but few crystals are obtained from the 90% alcohol a sufficient quantity of water is added to reduce this to 70% strength. Any deposit then formed within an hour at 17-19' is collected washed with 70% alcohol and weighed as before applying the correction for solubility.It must be re- crystallised if the m. p. is below 71'. The following 4.54 Grams of crystals= 100 grams of arachis oil.ANALYTICAL CHEMISTRY. ii. 81 oils gave no crystals olive oils including three superfine Maloga and eight of unknown origin almond poppy and rape oils. 5 L. DE K. E s t i m a t i o n of Cyanogen Compounds in Gas-Liquors. FRANZ WEISSEB (Chem. Zeit. 1912 36 1285-1287).-Estimatiorr 01 ammonium cyanide.-This is found by difference from the total cyanogen and that present as ferrocyanide. Totul cyanogen.-500 C.C. of the liquor are mixed with 50 C.C. aqueous potassium hydroxide (1 1) and 50 C.C. 10% ferrous sulphate and heated for one to two hours on the water-bath. After cooling and diluting to a litre 100 C.C. of the filtrate are acidified with hydrochloric acid and 5 C.C.of 10% ferric chloride are added The Prussian-blue formed is collected and then again decomposed with dilute aqueous potassium hydroxide. The filtrate which contains all the cyanogen as ferrocyanide is evaporated with excess of sulphuric acid and the residue is gently ignited. The residual iron oxide is then estimated as usual by titration with pernianganate. One C.C. of N/lOO-permanganate = 0.00156 gram of cyan og en. Ammonium ferrocynnide.-l00-500 C.C. of the liquor are evaporated and the residue is gently ignited. The iron is then titrated as usual; 1 C.C. of N/100 permanganate = 0.00334 gram of the ferrocyanide. Ammonium thiocyanak-The author has slightly modified Pfeiffer’s colorimetric process. Fifty C.C. of the sample are diluted with 50 C.C.of water and evaporated on the water-bath to 30 C.C. so as to expel the free ammonia. After diluting to 100 c.c. 20 C.C. of the solution ( = l o C.C. of sample) are mixed with 10 C.C. of ferric chloride solution (5 parts of the salt made up to 100 parts with 10% hydro- chloric acid) and diluted to 500 C.C. An aliquot part of the liquid is then matched as usual with a solution of ammonium thiocyanate of known strength. L. DE K. Estimation of Scatole and Indole in Faeces. CURT MOEWES (Chem. Zentr. 1912 ii 1702 ; from Zeitsch. expt. Path. Ther. 11 555). -The scatole and indole obtained by extracting the steam distillate with light petroleum are precipitated by dirnethylaminobenzaldehyde and the dye is dissolved in water and compared in a Plesch chromo- photometer with a test solution of 1 100,000 made from equal parts of indole and scatole.Values of 0*008-0-024 gram per 100 grams of fsecal matter were obtained J. C . W. Action of Activated Aluminium on Alkaloidal Extracts Its Use in Toxicology. XMILE KOHN-ABREST (Comnpt. rend. 19 12’ 155 1179-1181. Compare A. 1912 ii 645-768).-A study of the behaviour of the more common vegetable alkaloids pure or mixed with viscera in the presence of activated aluminium. The hydrated oxide formed from the activated aluminium only fixes a certain small proportion of alkaloids such as strychnine puinine and cocaine in alcoholic solution acidified with tartaric acid whilst on the other hand it retains almost all the nicotine. Data are given for some fourteen alkaloids.Alcoholic extracts of viscera containing morphineii. 52 ABSTRACTS OF CHEMICAL PAPERS. and strychnine after treatment with activated aluminium are obtained in a state of great purity wherein the alkaloids can be readily detected and estimated. W. G. Distinction between Cocaine and its Substitutes. D. SCHERBATSCHEV (Chem. Zentr. 1912 [ii] 386 ; from Apoth. Zait. i912 27 441. Compare Hankin A. 1911 ii 162).-The appearance under the microscope of solutions of /3-eucaine nirvanine alypine holocaine and novocaine when solutions of ammonia (lo%) potassium hydroxide (lo%) or sodium hydrogen carbonate (saturated) are added to them is described T. A. H. Gravimetric E s t i m a t i o n of Quinine as Nitroprusside. P. J. KRUYSSE (Pharm. Weekblad 1912 49 11 17-1120).-Quinine nitro- prusside is obtained as a crystalline precipitate when a neutral solution of a quinine aalt is treated with sodium nitroprusside; its solubility is less than that of the tartrate or oxalate 100,000 parts of water dissolving 39 parts of the salt.For the estimation of quinine in powdered cinchona bark 5 grams of the latter are mixed with 3.5 C.C. of water 1 C.C. of ammonia and 2.5 grams of slaked lime and the mixture is extracted in a Soxhlet apparatus for two hours with acetone. After the acetone has been evaporated from the extract the residue is dissolved in 25 C.C. of 2% hydrochloric acid the solution is filtered rendered alkaline and shaken with ether. The ethereal solution is then shaken with dilute hydrochloric acid the separated acid solution is neutralised diluted to 50 c.c.heated t o 90° and treated with 0.5 gram of ammonium oxalate. After cooling the pre- cipitate is collected on a filter washed with a smallquantity of water and then dissolved in 5 C.C. of 2% hydrochloric acid. This solution is nearly neutralised and the excess of oxalate is removed as calcium oxalate. The solution is now neutralised with ammonia diluted to 70 c.c. heated to boiling and treated with 0.5 gram of sodium nitro- prusside. After cooling the precipitate is collected washed with water dried at looo and weighed. The treatment with ammonium oxalate is for the purpose of separating cinchonine from the quinine. w. P. 8. Estimation of Quinine Sulphate in Cinchona Bark. P. J. KRUYSSE (Pharm. Weekblad 1912 49 1135-1136).-The author (preceding abstract) regrets he was not acquainted with the work of Kramers (A.1897 ii 83) who however did not succeed in applying the nitroprusside reaction quantitatively. L. DE K. Hyposulphite in Volumetric Analysis. I. WILHELM SIEGMUND (Monatsh. 1912 33 1431-1445).-The hyposulphites give stable compounds with the ketones which in contradistinction to the form- aldehyde-hyposulphites act as reducing agents in the cold. Solutions of these compounds may therefore be used as standard reducing agents in volumetric analysis. The author finds that a convenient solution has the following composition 10 grams of sodium hyposulphite 15 C.C. of acetone and 35 C.C. of ammonia (D = 0.91) to one litre ofANALYTICAL CHEMISTRY. ii. 89 water. The solution is kept under a layer of paraffin oil in a stock bottle from which a burette can be filled automatically; the top of the liquid in the burette is covered with toluene to prevent contact with the air.The tip of the burette is connected with the titration flask by means of a piece of glass tubing which is bent twice a t right angles and passes through the rubber stopper of the flask. The stopper also contains inlet and exit tubes for a current of oxygen-free carbon dioxide and a thermometer. The solution of the hyposulphite is standardised by means of iron alum or an oxidised solution of ferrous ammonium sulphate using ammonium thiocyanate as indicator and in the presence of sulphuric acid. The titration is carried out in the cold with vigorous shaking; the sulphite formed has no action on the ferric salt.The solution is fairly stable but should be standardised daily. &Experiments mitb a large number of azo-dyes dyes which form leuco-compounds and nitro-colouring matters show that they are reduced quantitatively by the above hyposulphite solution. T. s. P. Methods of Estimating Saponins. (Mlle.) MARIE KORSAKOV (Compt. rend. 1912 155 844-846).-A critical study of the methods at present employed for estimating saponins. Christophson's method based on the precipitation of the saponin as a barium compound is inaccurate since the whole of the saponin does not separate and further the barium hydroxide precipitates from plant extracts other substances than saponins which on hydrolysis yield dextrose. A modification of Kruskul's method gives good results.The plant is dried finely powdered and extracted with boiling alcohol (60%). The extract is filtered the alcohol distilled off and the residue evaporated on the water-bath with calcined magnesia. The resulting paste is extracted with boiling alcohol (80%) the extract filtered and precipitated with ether. The precipitate is dissolved in 3% sulphuric acid and hydrolysed in an autoclave a t 105' for one hour the sapogenin liberated being washed with water dissolved in absolute alcohol and weighed after distilling off the alcohol. W. G. A Delicate Test for the Detection of Albumin in Urine. ADOLF JOLLES (Zeitsch. physiol. Chm. 1912 81 205-206. Compare A 1896 ii 344).-The reagent is composed of mercuric chloride 10 parts citric acid 20 parts sodium chlorate 20 parts water 500 parts.Five C.C. of the filtered urine are added to each of three test-tubes. To (1) and (2) 1 C.C. of 30% acetic acid is added 5 C.C. of the reagent are put in (l) and the other tubes are filled with water t o the same level. The tubes are observed against a black background (3) being placed in the middle. The reaction is sensitive to 1 part of albumin in 120,000 E. F. A. Chemistry and E s t i m a t i o n of Gelatin. M. BERRAR (Biochent. Zeitsch. 1912 47 189-214).-Gelatin forms saturated solutions in water in the following strengths 0.62% a t 21° 0.60% at lS" and 0.56% a t 17". If the concentrations only slightly exceed these pro-ii. 84 ABSTRACTS OF CHEMICAL PAPERS portions a gel is formed. Gelatin cannot be precipitated quantitatively by alcohol or by metaphosphoric acid as it completely dissolves in excess of the latter reagent the proteins being only partly soluble in excess.A t room temperature it is not precipitated quantitatively by picric acid but at 8' precipitation is complete when a gelatin solution is mixed with a saturated aqueoussolution of the acid. The acid com- bining power of gelatin was estimated by precipitation with potassium- mercuric iodide and picric acid solutions. Hydrocbloric acid could not be used for this purpose as the precipitate dissolves in excess of the acid. By this means i t W A S found that 1 gram of gelatin combines with the equivalent of 11.3 C.P. N/lO-acid which corresponds with a molecular weight of 823. The picric acid precipitate of gelatin dissolves in alcohol and in 2% urea solution containing sodium chloride. If a mixture of 1 part of saturated aqueous solution of picric acid and 4 parts of alcohol are added to a gelatin solution the gelatin is not precipitated whereas other proteins are.The gelatin is however pre- cipitated quantitatively from this gelatin-picric acid solution in alcohol by the addition of excess of aqueous picric acid solution in the cold. The precipitate again dissolves on warming to 40° or treating again with absolute alcohol. On these reactions a method is based for estimating quantitatively gelatin in the presence of other proteins. It was incidetltally observed that the nitrogen in picric acid can be quantitat'ively estimated by Kjeldahl's process if it is first reduced by iron and glacial acetic acid. S. B. S. The Rideal- WGlker Phenol Control. A Possible Discordant Factor in the Standardisation of Disinfectants. J. T. AINSLIE WALKER and JOHN 31. WEISS (J. Frank& Inst. 1912 101-112).- The accnracy of the Itideal-Walker process depends on the purity of the phenol which is employed as the standard. Ordinary crystallised phenol is usually contaminated by cresols to such a n extent as t o render it unsuitable for the purposes of bactericidal control ; four specimens of phenol examined by the authors were found to contain from 1 * 1 to lams% of cresols. As cresol has approximately three times t h e bactericidal e6ciency of phenol the error from this cause may be very considerable. The purity of the phenol should be ascertained by a determination of its solidifying point and phenol having a lower solidifying point than 40' should be rejecked. Synthetic phenol prepared by the authors showed a solidifying point of 40.5'. The bromine titration method does not yield trustworthy results as regards the purity of the phenol but i t may be employed for checking the strength of the 5% stock solution prepared from pure phenol. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9130405072

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 85 General and Physical Chemistry. N e w Observations R e l a t i v e t o the Zeeman Effect in the H y d r o g e n S p e c t r u m . F. CROZE (Compt. rend. 1912 155 lW7-1610. Compare A 1912 ii 613).-The author has extended his study of the Zeeman effect in the case of hydrogen to the 8-line and has made new measurements for this line and the a- /3- and yjines of the value of AX in a field of 24,122 gause. He maintains his previous view that these three rays furnish a pure triplet with normal deviation and replies to Paschen and Back (Ann. Physik. 19 12 [iv] 39 897) putting forward an explanation as to why their results differ from his. W. G. The Dispersion of C e r t a i n Metals in the Visible Spectrum. CONSTANTIN ZAKRZEWSKI (Bull. Acad Sci. C~acow 19 12 842-849).- A formula is deduced by means of which the optical constants of a metal can be calculated from the phase differences of the components parallel and perpendicular to the plane of incidence measured for two different angles of incidence This method of obtaining the constants does not like the usual method involve the preparation of highly polished metallic mirrors.The formula is applied t o dtlta obtained by the author for nickel and zinc and to Drude’s measurements for silver. €1. 11. D. E l e c t r i c Behaviour of C e r t a i n Vapours which E x h i b i t Absorption Bands. F. BURGER and JOHANNES KOENXGSBEHGER (Physikal. Zeitsch. 1913 13 1198-1199).-The nature of the process which gives rise t o banded emission and absorption is further discussed (compare A. 1912 ii 405).Bromine and nitrogen peroxide exhibit banded spectra and experiments with these substances are described which show t h a t the carriers responsible for the banded spectra in these two cases cannot be due either to electrons or free ions so far as the visible spectrum is concerned. An upper limiting value for the proportion of ionised molecules is calculated which also indicates that the bnnded absorption cannot be attributed to the occurrence of ionised molecules. The Absorption C u r v e of Colloidal S i l v e r Solutions. R. GANS (Phy~iknl. Zeitsch. 1912 13 1185-1186).-0n the assumption that the colloidal particles have the form of ellipsoids o€ rotation the author has calculated the form of the absorption curve for the region X = 4200 to X = 7500 for varying values of t h e axial ratios.As in the case of gold solutions (A. 1912 ii 508) the curve thus obtained may be utilised in the investigation of the geometrical form of the particles present in colloidal solutions of silver. H. A l . D. H. 111. D. The Influence of Acid Radicles on t h e Colour Intensity of Copper Salts. CHARLES SCOTT GARRETT (Zeitsch. Eleklrochenz. 1913 19 1-7).-The molecular extinction of a number of soluble VOL. civ. ii 7ii. 86 ABSTRACTS OF CHEMICAL PAPERS. copper salts was determined by means of a Hiifner spectrophotometer. The salts CuCI2 CuSr2 CU(KO~)~ Cu(C10,)2 CuCr,07 CnS04 and Cu(ClO,) were examined at concentrations from In- 0.01n. The experimental results are discusbed and interpreted on the basis of Baly's theory of the action of a solvent on a dissolved substance.It is shown (1) that when a concentrated solution is diluted a penetra- tion of the salt molecule system by the solvent molecule system occurs ; (2) the mean number of solvent molecules the fields of force of which penetrate the field of force of the dissolved molecule conditions the process of solution at a given concentration; (3) every vibration of the copper atom in the undibsociated molecnle which is active in the absorption of light is influenced by the free electric field of the typical atoms of t h e acid radicle; (4) the light absorption due to the copper is not specifically influenced by the presence of a coloured acid radicle a s is frequently the case with organic substances and (5) there is a strengthening of the light absorption when the free electric field of the acid radicle is negative.J. F. S. Absorption Spectra of Solutions as Affected by Tempera- ture and by Dilution. Quantitative Study of Absorption Spectra by meam of the Radiomicrometer. HARRY C. JONES and J. SAM GUY (Amer. Chenz. J. 1913 49 1-46).-1n a n earlier paper (A 1912 ii 70) a n account was given of a study of the effect of heat and of dilution on the absorption spectra of certain neodymium salts. The work on these salts has now been continued and the investigation has been extended t o Frafeodymium nitrate and chloride and to uranyl nitrate and sulphate. The radiomicrometer employed was a slightly modified form of that described previously. E. G. Quantitative Investigation of the Absorption of Ultra- viqlet Rays by the Fatty Acids and their Isomeric Esters.JEAN BIELECKI and VICTOR HENRI (Compt. rend. 1912 155 1617-1620. Compare A . 1912 ii 882).-The authors have made a more detailed comparison of the absorptive power in the case of three fatty acids and the esters isomeric with them and in the case of a number of groups of isomeric esters the absorption being measured in aqueous and alcoholic solutions and with rays of varying wave- lengths. Curves and tables are given and the results show that (1) the absorption spectrum of the various acids is different from that of the esters isomeric with them this difference being independent of the solvent; (2) the absorption of the ultraviolet rays is controlled by the molecular complexity and augments with increasing complexity.There is also a considerable variation in the absorption spectra of the isomeric esters dependent on the molecular arrangement as is shown by a study of the four esters butyl acetate prop91 propionate ethyl n-butyrate and methyl valerate. W. G. The Absorption Phenomena of Oxyhmnoglobin in the Grating Spectrum. OTTO SCHUMM (Zeitsch. pl~ycliol. C.henz. 191 3 83 1-24).-The spectrum obtained by a diffraction grating isGENERAL AND PEY SICAL CHEMISTRY. ii. 87 spoken of as the natural spectrum in contradistinction to that obtained by 5t prism. Careful measurements of tbe three bands (two in the visible one in the ultra-violet region) are given and the results figured in plates. Some variations occur even in the blood of the same species and it is not possible to distinguish the oxyhzmo- globin of different animals by any such spectrum differences.W. D. H. Long- and Short-waved Absorption and Fluorescence Bands of the Carbonyl Group. 39. GELBKE (Jcdwb. Radioaktiv. A’Zektvonik 1913 10 1-.34).-The ultra-violet absorption of a number of ketones has been examined the substances being dissolved for the most part in ethyl alcohol although in a few cases the substances were investigated i n the form of saturated vapour or dis- solved in water or n-hexane. From a comparison of the short- waved absorption bands of acetone and its substituted derivatives it is found that the acetone band which has its maximum a t A = 868pp is displaced in the direction of greater wave-lengths when one or more hydrogen atoms are substituted by alkyl halogen phenyl nitroso- or carbonyl groups.In the case of alkyl substitution the displacement of the maximum amounts t o 5-10pp whilst the effect of halogens the phenyl nitroso- and carbonyl groups is greater. The displacement of the band is accompanied by an increase in the absorption and also by R broadening of the band. From a comparison of acetone and cyclohexanone i t appears that the influence of r i n g formation is comparatively small. I n addition to the above-mentioned short-waved band acetono shows a band with a maximum a t about X=365pp. which extends from about A=327pp into the visible spectrum. A similar band is also found in the substituted derivatives of acetone and t h i s i t is which gives rise to the yellow colour exhibited by many such substances which contain the carbonyl group. From a comparison of the absorption spectra of dimethyl diketone and methyl ethyl diketone with that of acetone i t is found that the bhort- waved band in the a-diketones is shifted about 5-1Opp in the direction of longer wave-lengths and that the absorption is considerably inten- sified.I n regard to the longwaved band the shift exhibited by the two a-diketones amounts to about 30pp and the intensity is increased about forty times. In tho case of P-diketones the intensification of the long-waved absorption band is not nearly so great as that observed for the a-diketones. From a comparison of the spectra of methplheptenone mesityl oxide and phorone with that of acetone i t is fouud that both the short and long-waved bands are not appreciably shifted by a con- jugated ethylene linking although the intensity of the absorption ~ncreases very considerably in both cases.If the ethylene linking is not conjugated but separated from the carbonyl group by two methylene groups the absorption intensity of the short-waved band appears to be increased to a much smaller extent that when conjugation occiirs. The results of the spectrographic examination of the fluorEscence bands 7-2ii. 88 ABSTRACTS OF CHEMICAL PAPERS. of acetone dimethyl diketone and oxalosuccinonitrile have been pub- lished previously (A. 1912 ii 713) but a large number of other hub- stances have now been examined in regard to the emission of fluorescent light when subjectcd to the action of intense ultra-violet radiation These observations Lhow that the activity of the carbonyl group in this direction is quite general fluorescence being exhibited by both mono- and di-ketones and by both cyclic and acyclic compounds in which i t occurs.It is thus proved that the faculty of fluorescence is by no means confined to ring compounds. 8. M. D. Rotation Dispersion. ERNST DEUSSEN (J. pr. Chem. 1913 [ii] 87 96).-A correction. In reply to Tschugaev (this vol. ii 3) the author admits that the rotations for mercury light recorded in previous papers (A. 1912 ii 510 1020) refer to light of wavc-length 546pp and not 491 pp F. B. The Rotation Dispersion of Some Goloured Lactates. H. VOLK (Btr. 19 12,45 3744-3748).-Abnormal rotation dispersion of coloured asymmetric organic compounds which has hitherto only been studied in the case of somewhat complicated substances (Gross- mann A 1900 ii 372 and Tscbugaev A 1909 ii 631) has now been observed with the copper nickel and cobalt salts of I-lactic acid.A maximum rotation is found in each case in the region of selective absorption. Increase of temperature diminishes the rotation but does not affect the character of the dispersion. For the preparation of these salts zinc ammonium I-lactate (Purdie T. 1893 63 1143) which has a normal but comparatively high rota- tion-dispersion is boiled with baryta water t o expel ammonia and precipitate the zinc and after removing the excess of barium hydroxide by means of carbon dioxide the filtrate is treated with the equivalent amount of the metallic sulphate and allosed to crystallise.Copper 1-lactate Cu(C,H,O,) 1 H,O a light blue crystalline powder has a maximum rotation and absorption in yellow light ; [MI calculated for lactic acid falls from 18.5 in the green to 15.6 in the dark blue. A'ickel 1-lactate Ni(C,H,O,),QH,O a light green powder is remai kable in that it is Zaevo-rotatory in all parts of the spectrum; the maximum rotation [MI = - 0-S and strongest absorption are in t h e yellow. CobuIt IJactate Co(C3H,03),,2H,0 a light red powder has maximum absorption for green light in which [M]=30; the rotation falls towards either end of the spectrum and changes sign between light blue and dark blue. J. C. W. Sunlight. PAUL C. FREER and HARRY D. GIBBS (J. Physical Chem. 1912 16 709-738).-The influence of sunlight on chemical and physiological processes is supposed by some to be greater in the tropics than in temperate climates.On the assumption that the difference lies in the intensity of the ultra-violet radiation an investigation of the photochemical action of tropical sunlight should yield some information as to its probable physiological action. The effect of sunlight in Manila in promoting the coloration ofaENERAL AND PHYSICAL CHEMISTRY. ii. 89 a number of benzene derivatives such as cresol and aniline has been described from time to time by Gibbs. Since these reactions have large temperature-coefficients and the temperatures of solutions exposed to the sun in Manila may attain 50° Gibbs’ experiments gave no certain indication t h a t sunlight is abnormally active in the tropics. Measurements of the total insolation in heat units made with the Angstrom pyroheliometer a t various latitudes indicate trhat the heat intensity varies but little from place to place.The intensity of violet and ultra-violet radiation is conveniently measured by the rate of decomposition of oxnlic acid in presence of uranyl acetate. This reaction has a very smnll temperature-coefficient and when used under standard conditions gives useful comparative results. I n Manila the average amount of oxalic acid decomposed in one hour during one year was 12*45% the maximum being 17.8% and the minimum 1.15%. The average values obtained by other observers were as follows Bltguio (Philippine Is.) 14.2%; Honolulu 13.9%; *Kuala Lumpur (Malay States) 15.29% ; Khartoum 17.8% (using quartz flask) ; Washington 11.96% ; Tucson (Arizona) 13.0% ; Munich 8.39%. When the sky is clear the activity is almost the same everywhere and the lower averages in the higher latitudes may be ascribed to the higher percentago of dull days.Oxyhemoglobin is converted by ultra-violet light into methsmo- globin which can be detected in the blood of rabbits which have died by exposure to the sun. Nevertheless experimonts in which rabbits monkeys and men of different shade were exposed to the sun seem to lead to the conclusion that the ill-effects are wholly due to the rise in blood-temperature and that the resistance of an individual depends largely on his opportunity for cooling by radiation etc. and the per- fection of his heat-regulating system #of sweat glands; thus black.grey and white rabbits monkeys and men showed an increasing resistivity. Monkeys exposed to the sun in Manila died in less than two hours the blood temperature rising almost loo but when the animals were kept cool by a fan although exposed to tho full radiation including the ultra-violet no ill-effects followed. The brain in these experiments was to sorne extent protected by the hair on the head. R. J. C. Photochemical Reduction of Copper Sulphate. CHARLES W. BENNETT (J. Physical Chem. 1912 16 782-785).-The author propounds the theory that the light which is absorbed by cupric sulphate solution tends t o decompose it so that a reducing agent might be found which although without action in the dark would precipitate copper when assisted by radiations of appropriate wave- length.Xxperiments are cited to show that light reduces ammoniacal copper sulphate t o cuprous oxide in presence of hydrazine hydrate and that the precipitation of copper phosphide from 5% cupric sulphate solution by an ethereal solution of phosphorus (Mrs. Fulhame 1794) is accelerated by the light from a carbon arc I n the latter case a quartz vessel was used. R. J. C .ii. 90 ABSTRACTS OF CHEMICAL PAPERS The First Stages in the Photolysis of Ethyl Alcohol Acetaldehyde and Acetic Acid. DANKEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 1913 156 68-’71).-Of the three sub- stances studied. acetaldehyde is the only one which is act,ed on by sunlight (A > 0*3p) the alcohol and acid requiring radiations of shorter wave-length.There are four stages in the photolysis of acetaldehyde namely (1) gaseous decomposition into carbon monoxide and methane (compare A.? 1910 i 543). (2) Polymerisation and sub- sequent evoiution of hydrocarbons such as ethane etc. (compare A 1910 ii 814). (3) Formation of resinous products. (4) Conversion of the aldehyde into acetic acid. Only the first reaction is produced by initial ultra-violet rays the three others requiring the mean or extreme rays. The photolysis of ethyl alcohol consists fundamentally of the evolution of hydrogen and formation of acetaldehyde which is then further decomposed (compare A. 1911 ii 835). Acetic acid on decomposition by the rays from an Heraeus lamp gives a gaseous product containing carbon dioxide (44%) carbon monoxide (1 i%) and combustible gases (39%) (compare A.1910 ii 814). Water has no effect on the products of photolysis but lessens the rate of the reaction. W. G. Photolysis of Different Complex Sugars (Bioses and Trioses) by Ultra-violet Rays. DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 1912 155 1506-1509. Compare A 1912 ii 1120). - 9 study of the decompobition of the biosea maltose lactose trehalose and gentiobiose and the trioses raffinose melezitose and gentianose by ultra-violet rays of varying wave-length. I n the case of the trioses no first stage of formation of a monose and a biose could be detected. After the first stage in the decomposition the action was the same a s in the case of the monoses (Zoc. cit.). W. G. The Radio-elements the Periodic System and the Constitu- tion of the Atom.a. VAN DEN BROCK (Physikaz. Zeitsch. 1913 14 32-41).-This paper deals with recent work in the radioactive disintegration series and in the rare earth group with the intra- atomic charge and theories of the constitution of the atom and their connexion with the periodic lam in a manner unsuitable for abstraction. F. s. Evidence of Spontaneous Alterations of Concentration in Solutions and Gases. THEODOR SVEDBERG (Physikul. Zeitsch 1913 14 22-26. Compare A 1912. ii 905 906).-The question is discussed as t o whether the relative deviation of the number of a-particles produced in a volume element of a solution of a radio-active substance from the mean value should be theoretically greater than the corre- sponding relative deviation from the mean value in the case of the solid substance. It has been shown previously that the ratio of the mean deviations should be J2 1 and experimental observations indicate t h a t this is approximately the case.Further arguments areGENERAL AND PHYSICAL CHEMISTRY. ii. 91 now put forward in support of the correctness of the above theoretical conclusion. The question of the detection of spontaneous alterations in the concentration of solutions of other than radioactive substances is also examined with reference t o the negative results which have been obtained lip to the present. The author draws the conclusion t h a t such changes cannot be detected by the methods of examination which are a t present available. H. M. D. E x c i t a t i o n of y-Rays by a-Rays.JAMES CEADWICK (Phil. Mag. 1913 [vi] 25 193-197. Compare A. 1912 ii 1025).-Further eviderice is given that the impact of a-rays on metals of high atomic weight excites y-rays. A tube of such thin glass t h a t the a-rays escape containing radium emanation was surrounded with two con- centric tubes of metals of widely different atomic weights of thickness just sufficient to stop all the a-rays. Tho position of the two metals was transposed and the ionisation with the two arrangements accurately compared by a balance method. Always when the metal of high atomic weight was next the emanation tube and bombarded by a-rays the ionisation current was slightly greater than when the metal bombarded was of low atomic weight. The effect was much increased by filling the ionisation chamber with vapour such as carbon disulphide or methyl iodide.The ratio of the ionisation in these vapoura t o t h a t in a i r by X-rays of low penetrating power is much greater than for X-rays of high penetrating power and it was to be expected that the y-rays generated by a-rays would have a milch lower penetrating power than the primary y-rays and that the part of the effect due to them would be greater in a heavy vapour than in air. If a thickness of light material was placed round the tube sufficient to absorb the a-rays the effect disappeared. That i t was not due to very soft P-rags was proved by experimenting in a powerful magnetic field sutlicient to coil up the P-rdys and prevent them from reaching the metal. This did not cause any change in the effect With outer tube of aluminium the inner tube being of the followiog materials gold silver copper aluminium paper ; the relative ionisations in carbon disulphide vapour were respectively 104.8 102.5 301.2 100 and 99.7. This shows t h a t the excitrition of y-rays by a-rays increases with tho atomic weight of the material bombarded.A rough estimate of the coefficient of absorption of the excited y-rays was 8 (cm.-l of aluminium). I n con6rmation i t has been shown with A. S. Russell that ionium and polonium which give a-rays without P-rays give-y-rays in amount sutticient t o be studied in detail. F. s. Retardation of a-Particles by Metals. E. MARSDEN and H. RICHARDSON ( P I d . Mug. 1913 [vi] 25 184-193. Compare Taylor A. 1908 ii 783 ; 1909 ii 850)-The “air-equivalent ” of a metal foil is the distance in cm.by which the range OF an a-particle at 76 cm. and 15’ is reduced in passage through the foil and is for materials of atomic weight greater than that of air the less the less the velocity of the a-particle or the nearer it is to the end of its range. This variation has been studied for the a-rays OF radium-Cii. 92 ABSTRACTS OF CEEMICAL PAPERS by a scintillation method which offers advantages only the fastest a-particles that is those which have not been scattered being observed. A zinc sulphide screen is rigidly attached in the focus of the microscope and is carried by the rack axid pinion to any required distance from the source of a-rays. Between on a separate rack and pinion the foil is mounted and the air-equivalent of the foil studied a t various parts of the range of the a-particles. Tables are given for the variation of the air-equivalent which is considerable especially near the end of the path with the range and also a curve from which the air-equivalent of any thickness of foil (Au Ag and Al) a t any part of the range can be deduced.A brightening of the screen just outside the extreme range of the a-particles themselves which is unaffected by a transverse magnetic field was observed and is ascribed possibly to y-rays excited by a-rays (see preceding abstract) F. S. Absorption of /3-Rays. J. A. GRAY (Proc. Roy. Soc. 1912 A 87 487-489).-Two experiments on the absorption of the P-rays of radium-E by paper show that the rays become more and more absorb- able practically none passing 56 sheets weighing 8.77 mg.per cm.2 the percentage transmitted by 5 sheets decreasing from 50 to 10. These results are explained on the view that P-rays are both retarded and stopped by mattor and when the velocity of the surviving rays falls below the previous mean velocity the exponential law can no longer hold. F. S Similarity in Nature of X - and Primary 7-Rays. J. A. GHAY (Proc. Roy. Xoc. 1912 A 87 489-501).-The absorption of the primary y-rays of radium-E and of the y-rays excited in lead by the /$rays of radium-E is compared with the absorption of X-rays. The y-rays of radium-E are absorbed somewhat similarly to characteristic secondary X-rays excited in silver. There is no discontinuity with respect to absorption between X- and y-rays.Tin absorbs the y-rays of radium-E to an abnormal extent but for iron and gold compared with aluminium the absorption is similar to that of the silver An investigation of the radiation reflected from radiators of various materials showed that the y-rays of radium-E excite the characteristic X-radiation in silver tin barium neodymium and praseodymium This furnishes the most definite proof possible that X-rays and y-rays are of the same nature. Litstly the scattering of y-rays of radium-E and of X-rays has been compzred and it is shown that the phenomena is similar both in magnitude and character for both radiations. Expansion Apparatus for Making Visible the Paths of Ionising Particles in Gases and the Results Obtained with this Apparatus.CHARLES T. K. WILSON (Jcchrb. Radioaktiv. h'lektronik 1913 10 34-35. Compare A 1911 ii 565).-The expansion apparatus and method of illuminating the condensed water droplets described i n the previous paper have been improved in several X-rWp. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 93 respects with the result that i t has been possible to obtain photo- graphs of the most rapidly moving P-rays which show the droplet8 due t o the individual ions. The greatly increased size of the cloud cbamber in the new apparatus not only enables the entire course of the longest-ranged a-particles to be registered but its depth is such that horizontal beams of X-rays may be examined without any danger of interference from the proximity of the roof or base of the chamber.The photographic records obtained iinder the new conditions are more- over much more distinct than those given by the earlier form of apparatus. I n regard to the a-particles the photographs show that these move along paths which are approximately rectilinear except for the last 2 mm. where there is a very marked change in direction. Apart from this sudden and pronounced change at the end of the range there is however in many cases a small and gradual change in direction over the greater part of the course and the photographs thus afford evidence of both single and compound scattering. The photographs of the P-rays indicate that the ions are formed in pairs over a considerable portion of the path but that a t certain pointe closely packed groups of twenty or thirty ions are produced.The occurrence of these groups of ions is regarded as evidence of the emission by the atoms of secondary corpuscles which possess sufficient energy to produce ionisation over a small range. I n opposition to the a-rays the @rays never exhibit sudden changes in direction although the slow change due to compound scattering is clearly shown pro- vided the velocity of the rays is not too large. The X-ray photographs show t h t t P-rays proceed from points in the paths of the X-rays beam. Apart from this production of /3-rays t h e X-rays appear to give rise t o no effect which is photographically regis- tered on the plates. Corresponding with the heterogeneity of the X-rays it is found that the paths of the individual P-particles vary considerably in length.The rays appear t o show both simple and compound scattering although the latter effect appears to be the much more frequent and characteristic type. The emission of the ,%rays appears to be uniformly distributed in all directions and no evidence of any dependence on the direction in which the X-ray beam is propagated has been obtained. I n the case of both the p-ray and X-ray photographs it has been possible to ascertain approximately by counting the droplets the number of ions which are produced per centimetre of path. H. M D. Ionisation Produced by p- and 7-Rays at High Pressures. D. C. H. FLORANCE (PhiE. Bug. 1913 [vi] 25 172-183).-The absorption and ionisation produced in air at high pressure with the P-rays of uranium-X and with the secondary /3-rays generated by the y-rays of radium-C have been studied by means of a special cylindrical ionisation vessel with pressures of air up to 80 atmospheres.Corn- plete saturation could not be obtained even with a field of 2800 volts per cm. the shape of the curves being similar to those obtained with a-rays. There is for constant voltage a constant ratio for the ioniss-ii. 94 ABSTRACTS OF CHEMICAL PAPERS. tion currents at any two pressures and although saturation is not attained the ionisation currents are proportional to the intensity of the radiation at different pressures. The experimental value found for p(cm.-1 of air a t atmospheric pressure) for the P-rays of uranium-X was for plates 7 cm. diameter and 1 cm. apart 0.04 but the true value for a parallel beam of P-rays was deduced t o be 0.007 in agree- ment with the value of p in solids.The values for the emergent and incident P-rays produced by y-rays of radium-C were 0.046 and 0.056 and they appear to be independent of the nature of the material in which they originate. With plates 1 cm. apart the part of the ionisation due to /3-rays originating in the gas is negligible st atmospheric pressure and 25% of the total ionisation at 80 atmospheres. F. S. Recombination of Ions Produced by Rontgen Rays S. J. PLIMPTON (Phil. Mug. 1913 [vi] 25 65-81 ; Anzer. J. Sci. 1913 [iv] 35 39-53).-The value of a the coefficient of recombination of the ions in the equation drL/dt = -. an2 mas determined by ionising the gas between two parallel plate electrodes by a single flash of X-rays restricted so as not to fall upon the plates allowing the ions produced to recombine in absence of any external field for small intervals of time regulated and determined mechanically and then by sudden application of a field driving the residual ions t o the electrodes and so evaluating their numbers. I n this way the effect of ionic diffusion can be greatly reduced corpuscular radiation from the metal plates eliminated uniformity of X-rays secured and the initial stages of recom- bination studied.The results revealed especially for carbon dioxide an initial value of a relatively large but decreasing and becoming constant after intervals usually of about one-third of a second. This is explained by initial recombination of the pair of ions formed before they have moved by diffusion out of their range of mutual influence and the high value in carbon dioxide and the slower rate at which the normal value is attained are ascribed to the slower diffusion in this gas than in air.If a field acts during the flash ceasing to act simul- taneously with the cessation of the flash the final value of a is not affected but the initial value is decreased. A table is given of the absolute values of a at various time-intervals from the cessation of ionisation for air carbon dioxide sulphur dioxide methyl iodide ethyl chloride ethyl bromide and ethyl ether at various pressures. For air the initial value of a/e when e is the atomic charge is 11,540 and the final value 3960. F. S. Further Experiments on the Mobility of the Positive Ions at Low Pressures.GEORGE W. TODD (Phil. Mag. 1913 [vi] 25 163-171. Compare A. 1912 ii 245 lOfiO).-The ex- periments have been repeated with a larger apparatus in order to obtain information at lower pressures at which it was formerly suggested sub-molecular particles might constitute the positive ions. The new experiments show nothing like the enormous increases in the mobilities previously observed but indicate that below theGENERAL AND PHYSICAL CHEMISTKY. ii. 95 pressure of 1 mm. the mobilities vary with the period of alternation of the field when the period is high (above 150-). F. S. Combination of Hydrogen and Oxygen in the Presence of Heated Platinum and Carbon. J. K. THOMPBON (Physrkccl. Zeitsch. 1913 14 1 l-l5).-Experiments have been made with the object of ascertaining whether there is any connexion between the temperature a t which hydrogen and oxygen begin to combine in contact with heated platinum or carbon and that a t which these begin to emit negatively charged particles.The platinum spiral or carbon filament was contained in a cylindrical glass tube which could either be exhausted or connected with a supply of the gas mixture. The temperature of the spiral could be gradually raised by means of a regulated current from an accumulator battery and a voltmeter placed across the ends of the wire enabled the resistance to be measured. An aluminium cylinder surrounding the heated wire was connected with one pair of quadrants of a Dolozalek electrometer and permitted the measure- ment of the electrical effect a t gradually increasing temperatures.From observations made when the tube was highly exhausted and when hydrogen and oxygen were admitted at different pressures meaaured by the manometer it has been found that in the case of platinum and of carbon the temperature a t which the emission of negative particles is first observed is within the limits of experimental error identical with the temperdture a t which combination occurs between the hydrogen and oxygen. I n all cases the explosive com- bination of the gases was found to be accompanied by large ionisation currents but these could not be measured. The actual temperatures a t which the two effects occur were not measured the temperature being measured in terms of the resistance of the wire as ascertained from the readings of the voltmeter and ammeter.The influence of the gas on the observed resistance was allowed for by means of a series of readings with the apparatus when the heated wire was in contact with air a t different pressures. Preliminary observations shorn also that combination of hydrogen and oxygen occurs if the platinum wire is subjected to the action of B beam ot X-rays. The combination occurs more readily if the percentage of hydrogen is less than 10. Investigation of the Spectrum of Ionium. ALEXANDER S. RUSSELL and R. ROSSI (Proc. Boy. Soc. 1912 A 87 478-484).- The ionium preparation employed (Boltwood A 1911 ii 359) from measurements of the number of a-particles emitted should contain 16% of ionium if the period of that substance is 100,000 years the remainder being thorium oxide.After chemical purification of the ionium-thorium preparation by various methods its arc spectrum between the wave-lengths 3800 to 5000 was photographed in juxta- position with that of a pure thorium oxide preparation in the first ordef by a Rowland’s grating of 21.5 feet radius giving a dispersion of 2.6 Angstrijm units per mm. The spectrum was identical with that of pure thorium save for the presence of five of the stronger lines of H. M. D.ii. 96 ABSTRACTS OF CHEMICAL PAPERS. scandium the amount of which in the purified preparation was esti- mated as three or four parts per thousand. It was found that an admixture in thorium oxide of 1% of cerium oxide could easily and 1% of uranium oxide could just be detected spectroscopically.The obvious conclusion is that ionium cannot be present in the preparation to the extent of more than 1 or 2% and that its period of average life cannot be more than 12,000 years. This result is consistent with the estimate given by Soddy of at least 100,000 years only if at least one unknown product of long life intervenes between uranium and radium. On the other hand the period deduced from the range of the a-rays 200,000 years is not consistent with the result obtained unless the a-rays of ionium are exceptional. It is possible that ionium has no arc spectrum in the region investigated although this is improbable or that ionium and thorium have identical spectra as they have identical chemical properties. In a note the paper on the same subject by Exner and Haschek (Sitxungsber.K. Akad. Wiss Wzen 1912 121 iia 1075) with the same result is referred to the ionium in the Austrian preparation being estimated as two-thirds of that in the one employed The Solid Radioactive Disintegration Products Suspended in the Atmosphere. K. W. FRITZ KOHLRAUSCH (Physikal. Zeitsch. 191 2 13 1193).-Certain corrections are discussed in the methods employed in the measurement of the solid radioactive products in the atmo- sphere and new expressions more in accord with recent work are deduced. For the determination of the amount of radium-A in the air by passing the air a t a suitable velocity for a known time through a tubular condenser with inner electrode negative and measuring the ionisation current a t the end due to the active deposit on the inner electrode tables are given showing the ratio of the effect for any time of aspiration to that for an indefinitely long time.I n the second place the effect of the thorium products in the air is taken into consideration. F. S. Electro-chemistry of Extremely Dilute Solutions in P a r t i - c u l a r of Radioactive Substances. KARL F. HERZFELD (Physikal. Zeitsch. 1913 14 29-32).-1f a metal plate is immersed in a solution of one of its salts which contains a mixture of two radioactive substances in a definite ratio then according to the experiments of Hevesy (A. 1912 ii 414) the ratio in which $he radioactive metals separate on the metal plate is dependent solely on the potential difference a t the contact surface of the metal and its salt solution.This observation is contrary to what would be expected on the basis of Nernst’s formula for the equilibrium a t the surface. The discrepancy may be explained if i t is assumed that the quantity of deposited radioactive metal in the equilibrium condition is not sufficient to form a complete moiscular layer. If P’ denotes the solution pressure of the radioactive metal p the osmotic pressure of the amount initially present in the solution and ‘IT the pressure correspond- ing with the metal deposited in the equilibrium condition then the cathode potential E will be related to these quantities by the equation F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 97 E’= RTlogP’r/( - T). The application of this equilibrium equation to two radioactive substances present in the solntion leads to results in agreement with the observed facts.I n regard to the variation of the ratio of the deposited metals with the magnitude of the potential at the metal surface the formula gives a curve which is also of the same type as that representing the experimental data. H. M. D. Electrical Excitation in the Splashing of Liquids (Ballo- Electricity). CHRISTIAN CHRISTIAKSEN (Ann. Yhysik 19 1.3 [iv] 40 107-137).-An account is given of experiments in which the electrical phenomena associated with the incidence of liquid spray on a solid surface have been investigated. By means of a current of air under constant pressure the liquid under examination is made to issue from a small aperture in the form of a fine spray which impinges on a plate or on the walls of a tube of the solid substance t o be investigated.I n most of the experiments a platinum disk or tube mas employed and this was connected by a wire with the liquid in the supply reservoir and also with one pair of quadrants of an electrometer the opposite pair being eai thed. The magnitude of the electrical effect obtained when distilled water is sprayed mas found to vary very considerably with the sample of water employed. I n searching for the cause of these irregularities it has been found that contact of the water with any substance such as glass paper wool silk o h etc. which has been exposed to the air for a considerable time gives rise to a greatJy increased electrometer deflection. The influence of electrolytes on the ballo-electric effect is relatively very small and the much greater influence of contact with the above-mentioned substances is supposed to be due to the condensa- tion of radioactive substances on the air-exposed surfaces.The deflections obtained with aqueous solutions of acids bases and salts and the influence of dilution have been examined with the result that the chemical nature of the electrolyte appears to be of little importance in connexion with the phenomenon. According to the magnitude of the electrical effect it is possible to divide aqueous solutions into two groups. When solutions belonging to these diflerent groups are mixed i t is found that the ballo-electric activity of the mixed solution is very much greater than that of the com- ponents. As an example it may be mentioned that if equal volumes of molar solutions of ethyl alcohol and potassium chloride are mixed together the effects obtained with the mixed solution was 7.0 whilst that given by the alcohol solution was 0.9 and by the potassium chloride 0.1.Several such mixtures have been investigated in such a way as to obtain comparative numbers for related substances belonging to the two above-mentioned ballo-electric groups. Other experiments show that the effect varies with the nature of the solid surface on zhich the liquid spray impinges. With a distilled water spray platinum glass and ivory become positively charged whilst paratlin becomes negative. I n the case of wax and shellac the solid is at first negatively charged but after prolonged action the sign of the charge becomes reversed.The most constant results are obtained with a platinum surface. H. M. I).ii. 98 ABSTRACTS OF CHEMICAL PAPERS. Dielectric C o n s t a n t s of Dissolved S a l t s . 11. PAUL WALDEN (Bull. Acccd. Xt. Yitersbowg 1912 [vi] 1055-10SG).-Iuvestigations similar to those previously made with chloroform solutions (compare A. 1912 ii 421) have been carried out with solutions in dichloro- methane (dielectric constant 8.3) and in ethyl formate (dielectric constant 8 9 ) which differ from chloroform in giving measurable ionic dissociation of the salts employed (Zoc. cit.). Further ethyl formate is a solvent of an entirely different type so that its use opens up the possibility of studying the chemical rBle of the atoms constituting the solvent.As with chloroform so also with dichloromethane the dissolution of the salts is accompanied by a considerable increase in the dielectric constant of the solvent. Further the dielectric constants of the salts calculated by means of Philip’s Bouty’s and Silberstein’s formula are mostly very bigh the greatest values being obtained with the first of these fcrmuh. I n dichloromethane the value of the dielectric constant of any salt is much higher than in chloroform This con- stant also increases with the complexity of the salt and according to Philip’s formula has the values NHEt,,HCl 58 ; NEt,,HCl 390 and NEt,Cl 1980 ; the numbers for the corresponding nitrates are 71 425 and 1365 respectively. For one and the same salt a t equal dilutions the molecular con- ductivity is from ten t o thirty times as great in dichloromethane as in chloroform and whilst in the latter solvent it diminishes rapidly and continuously as the dilution increases in the former a minimum is observed at a certain dilution.The conclusion is drawn that the ions formed from the salt are able to raise the dielectric constant of the solution and alco the dissociating power of the solvent. Ebullioscopic measurements show that the salts have different molecular magnitudes in these two solvents those being for N Et,CI M i n chloroform and M in dichloromethane and for NEt,,IICI 21 and M - M respectively. The increased values ot the dielectric constants in dichloromethane may bs due partly to this depolymerisation and partly t o 8 specific catalytic influence of the solvent.The chemical process of salt-formation by the conjunction of two neutral constituents (NEt + EtBr etc.) is expressed physically in a reconstruction of the dielectric properties of these con~titueiit s in such a may that the new product shows a dielectric constnrjt which is about six t h i r t e e ~ or eighteen times t h a t calculated additively for secondary amine tertiary amine and tetralkylammonium salts respectively. Calculation by means of the Clausias-Rlosotti equation x = ( K - 1)/ ( K + 2) where x represents the fraction of the total volume actually occupied by the molecules shows that those salts are the best electrolytes for which x approaches the value 1. Not only is the general behaviour of ethyl formate as regards the alteration of the dielectric constants of dissolved alkylamino-salts similar to t h a t of dicbloromethane but the actual values of these constants are very nearly equal with the two solvents.Sodium iodide and lithium bromide are characterised by extremely high dielectricGENERAL AND PHYSICAL CHEMISTRY. ii. 99 constants in ethyl forniate the values obt,ained being 5595-6820 and 4760-5300 respectively according to Philip's formula ; calcium iodide shows a much smaller value (1540) and mercuric chloride one still snialler (490); thus the dielectric constant of these salts diminishes with their capacity t o dissociate. The results obtained with solutions of salts in the stxongly-ionking solvents acetone acety lacetone acetonitrile and propionitrile confirm the conclusion that if the dielectric constant of the medium remains constant the formation of ions increases the ionising tendency and the degree of electrolytic dissociation of the salt.Certain anomalies exhibited by solutions are discussed in connexion with the increases produced in the dielectric constants and hence in the ionising power of solvents by the dissolution of electrolytes. It is pointed out that this phenomenon must be taken into account in considering deviations from t h e law of mass action (Ostwald's dilution law) the r61e of neutral salts the disagreement of salts dissolved in media havicg feeble ionising actions with the requirements of the theory of Arrheniuy etc. since by it as well as by the other well- known factors the degree of electrolytic dissociation is appreciably altered.T. H. P. Behaviour of Carbon on Electrical Pulverisation. CARL TKOMAE (Zeitsclh. C I L ~ ~ . I2zd. Kolloicle 19 12 11 268-269).-1f a continuous current of 3-4 amperes a t 220 volts is passed between retort-graphite electrodes immersed in pure water the liquid remains quite transparent but if a very small quantity of sodium hydroxide is added a dark brown colloidal solution is obtained. The solution is stable and may be boiled withput change but the addition of hydrochloric acid or sodium chloride gives rise to a black precipitate. Similar resuIts were obtained with arc-lamp-carbon electrodes. H. $1. D. Theory of the Electrical Synthesis of Colloids. CARL BENEDICKs (zeitsch. Chem. Ind. Kolloide 1912 11 263-268).-A criticism of the views expressed by Kutscherov (A 1912 ii 1148) in connexion with the interpretation of the phenomena of electrical pulverisation.I n opposition to the theory that the process is partly electrochemical in nature the author maintains that the observations can be adequately explained on the assumption t h a t the action is entirely thermal in character. H. 31. D. The Mobility of the Bromide Ion in Water. CABL DRUCKER M. TARLE and L. GOMEZ. (Zeilsch. Elektrochsm. 1913 19 8-1 l).-The transport numbers of tribenzylmethylammonium bromide were deter- mined at 20' by the usual method employing a zinc anode and a platinum cathode. As a mean of many experiments the value n = 0.775 was obtained. To calculate the mobility of the bromine ion from this figure the conductivity values at 18' were used (Drucker A.1912 ii 732). The tempersture-coefficient of the conductivity was determined and found to be 0.022 between l S o and 25' and from these data the mobility of the bromine ion is 65.5. This value is muchii. IOO ABSTRACTS OF CHEMICAL PAPERS. lower than that obtained by Kohlrausch (67*0) and affects the con- ductivity at infinite dilution of potassium bromide making i t 129.8 instead of 132.6 as extrapolated by Kohlrausch. Possible sources of error in the Kohlrausch value are discussed. It is shown on calcu- lating the degree of dissociation of potassium bromide from the new value that it obeys the Ostwald dilution law up to 0.01 ?a. The authors assert that very probably all strong electrolytes obey the dilution law up to this concentration. J.F. S. Investigation of the Chemical Reactions Taking Place at the Cathode and Anode During the Electrolysis of Simple Salt Solutions. J. HAMILTON PATERSON (Proc. Univ. Du~ham Phil. Soc. 1912 4 187-220).-The author describes a small electrolytic cell which allo6a of the microscopic examination of the deposits formed on the electrodes during electrolysis Experiments made with simple salts (chlorides nitratep or sulphates) of a number of metals have shown that it is possible to obtain from cobalt nickel iron zinc cadmium manganese and possibly lead salts either the pure metal or the hydroxide deposited on the cathode. In the case of cobalt the film of hydroxide has a deep blue colour but the moment the current stops i t turns green; the composition of the green com- pound corresponds with the formula Co(OH),,H,O.The conditions of concentration and current density affecting the production of these substances has been noted and it has been found that the dilution necessary to produce the hydroxide increases and the limit of current strength decreases as we proceed along the list of metals in the order given. The hydroxide of the metal is not produced as a secondary reaction of the metal deposited on the cathode but is a precipitate from the electrolyte in the cathode area. F. B. The Constitution of Water and the Thermal Variation of its Magnetisation. AUGUSTE PICCARD (Compt. rend. 1912 155 1497-1499. Compare this vol. ii 17)-From a study of the change in the coefficient of magnetisation of water on solidification at 0" and a comparison of the curves representing respectively the variation i n density and magnetisation coeficient with respect to temperature the author draws the conclusion that in water at the ordinary tempera- ture there a r e two different substances in equilibrium.W. G. New Thermo-regulator for Instantaneous Adjustment to any Given Temperature. R. FANDER (Chem. Zeit. 1913 37 40j.-The regulator bears much resemblance to that of Reichardt but differs in having the adjusting screw on the lower half of the capillary tube the upper half of the tube being graduated from 30°to 1.00'. The regulator is set by immersing it in a water-bath at any tem- perature and adjusting the mercury column so that the readings on t h e capillary tube correspond with those of a thermometer in the bath €or about a minute.The mercury is then raised or lowered to the graduations corresponding with the desired temperature and the regulator is ready for use. H. B. H.GENERAL AND PHYSICAL CHEMISTRY. ii. PO1 The Expansion Coefficient of Graphite. ARTHUR L. DAY and ROBERT B. SOSMAN (J. Ind. Eng. Chern. 1912 4 490-492).- Contains sketches of the apparatuq employed by the authors for measuring the expansion coefficient of graphites whilst the resiilts obtained are demonstrated in tables and curves. From the wide divergence in expansion coefficients obtained the concluqion is drawn contrary t o the views of Le Chnteliur and Wologcline ( A . 1908 ii 177) aud in harmouy with tho.;e of Arsem (A 1912 ii 5 0 ) that there must be some fundamental difference between the vhrious forms of graphite.F. M. G. M. Volume Changes of Amalgams. J. W URSCHMIDT ( B v . Deut. physzkal. Ges. 19 12 14 1065-1087).-The influvnce of temperature on the thermal expansion of a number of amalgams has been examined with the aid of a special type of dilatorneter. The curves obtzined by plotting tho coefficient of expansion as n function of the temperature exhibit very sharp msxima at definite temperatures. I n the caye of the tin lead and cadmium amalgams which according to Puschin (A 1903 ii 212) consist of solid solutions these teriiperntures are identical with the melting points of the alloys. On the other hand the zinc amalgams which consist of mechanical mixtures of the components exhibit the maxiruum expansion a t temperatures bet ween 50' and 70° which are very much lower than the melting points of the alloys.I n regard to the nature of the expansion temperature curve sodium amalgam resembles the corresponding tin lead and cadmium alloys but differs from these in t h a t the volume changes with time when the temperature is kept constant. H. M. D. Thermal Conductivity of the Metals and its Relation to Their Other Properties. STEFANO PAGLIANI (i'vuovo C m . 191 2 [vi] 4 ii 48'2-497).-'l!he author gives a table showing the coetfi- cients of thermal conductivity the specitic heats and the densities of a number of metale the material being derived from published reTults of various workers. By-a comparisou of other published data he shows that the metals can be arranged in a series in which increased con- ductivity and reflecting power are associated with decrease of emis4ve power and that these properties also fall within the regulmty of the periodic law.R. V. S. Theory of Specific Heats. MAX BORN and TH. VON K ~ R M ~ N (Physikul. Zeitsch. 19 13 14 15-19).-Reference is made to a previ\)us payer (ibid. 1912 13 297) in which the discrepancy between the observed specific heats of solid substances at low temperatures and the values calculated from Einstein's formula has been eliminated to a large extent by means of a modified specific heat formula. The t8heory on which this is based is compared with the theory advanced by Debye (A. 1912,ii 1134) and it is shown tnat the approximation formula proposed by Debye for the calculation of the atomic heats of solid non-atomic substances can be deduced from the geueral formula given by the authors.In the case of anisotropic substances the approxima- VOL. CIV. ii. 8ii. 102 ABSTRACTS OF CHEMICAL PAPERS. tion formula is inapplicable and the general formula referred to must. be employed in the calculation of the specific heat,s. H. M. D. Specific Heat of Certain Elements at Low Temperatures. TADEUSZ ESTREICHER and M. STANIEWSKI (Bull. h a d . Sci. Cy*acow 1912 S34-S41. Compare A. 1911 ii 16).-The authors have deter- mined the mean specific heats of bromine iodine sodium potassium and manganese over the temperature intervals -190' to 1s" and - 18" t o 18'. The mixture method was employed with water or toluene as calorimetric liquid. The specific heat of toluene a t the ordinary t,emperature was found to be 0.4015 f 0.0003 cal.From the observations the following average specific heat values are deduced bromine 0.07016 ( - 1'30' t o - 1s') ; iodine 0.0454 ( - 191' t o - SOo) 0.04852 ( - SO" to 1'7') ; sodium 0.2478 ( - 191" to - SO') 0.2714 (-SO' t o 17'); potassium 0.1551 (-191' t o -SO') 0,1677 ( - SO' to 18"); manganese 0.08203 (-18s' to - 79*2O) 0*10906 ( - 79.2" to 15'). These values agree in general very well with the numbers obtained by Koref (A. 1911 ii 964). H. M. D. Measurement of the Specific Heat of Solid Substances at High Temperatures. MARCELLO VON PIRANI (Ber. Deut. physika2. Ges. 1912 14 1037-1054).-Three methods are described by means of which the true specific heats of different metals have been determined at high temperatures.I n the first methcd the apparatus consists of a n insulated electrically heated tube furnace the temperature of which is adjusted to that at which the specific heat measurement is to be made. Inside this is a much smaller tube furnace the temperature of which is measured by means of a thermo-couple. If a quantity of electrical energy measured by a watt-meter is passed through the coils of the inner tube during time t its temperature will be raised by a small amount AO which is measured by the couple. Under exactly eimiiar conditions the energy required to produce the same rise of temperature when the inner tube is filled with the sub- stance under examination is determined. From the data thus obtained the specific heat of the substance may be calculated The two other methods are somewhat similar and depend on the fact t h a t when a conducting substance is heated electrically to a bigh temperature in a vacuum the electrical energy communicated is lost almost entirely in the form of radiant energy.If the supply of electrical energy is increased for a short interval of time the tempera- ture mill increase to an extent determined by the specific heat of the substance and by the increased amount of radiation. Since the latter case can be determined by experiments in the stationary con- dition it is obvious that the measurement of the extra electrical energy and of the consequent rise in temperature will afford a means of obtain- ing the specific heats of the metals at very high temperatures.The specific heats of tantalum and tuugsten have been measured in this way at temperatures between about 350" and 1400'. Data are also recorded for iron between 110' and 9'70". The curve showing the relationship between the specific heat of iron and the temperature isGENERAL AND PHYSICAL CHEhIlSTRY. ii. 103 very irregular showing a very decided maximum a t about 7 Oo and a sharp minimum at about 790'. No evidence of this minimum has been obtained in previous high- temperature measurements. H. M. D. Measurement of Specific Heats of Solid Substances at High Temperatures. ALFRED MAGNUS (Physikd. Zeitsch. 19 13 14 5-lO).-The measurements were made with a form of calorimeter similar to t h a t used by Nernst Koref and Lindemann (A. 1910 ii 263) but in order t o diminish the influence of the heat losses incurred in the introduction of the heated substances into the calorimeter its capacity was increased about fifty times.The block of copper weighing 22 kilograms was provided with a conical shaped central cavity for the reception of the heated substance which was contained in A conical silver tube fitted with a stopper. The rise in temperature of the copper calorimeter was measured by means of a battery of 50 iron constantan thermocouples half the junctions being situated in deep holes in the block of copper and the other half in the water-bath surrounding the D e w n vessel containing the copper block. Data representing the mean specific heats between the room tempera- ture and looo 270° 550° and 750' have been obtained the substances examined being quartz amorphous silica magnesium oxide calcium oxide zinc oxide lead oxide sodium and potassium chlorides sodium and potassium bromides and calcium carbonate.The molecular heats apperr t o be in satisfactory agreement with those arrived at by recent workers at lower temperatures continuous curves being obtained when the available molecular heats are plotted a s a function of the temperature. The values for sodium chloride potassium chloride and potassium bromide are also in agreement with those calculated from t h e equation Cp = C + ACp2T in which A = 8.7 2.7 and 3.3 x for the three salts respectively. H. A l . D. Investigations on Specific Heat. VI. Calculation of Atomic Heats. WALTHER NERNST and F. A. LINDEMANN (Sitzungsber.K. Akad. Wiss. Berlin 1912 1160-1171. Compare A. 1911 ii 464 964 1059).-On the assumption t h a t a vibrating atom gives rise to a continuous spectrum corresponding with a continuous series of component vibrations Debye (A. 1912 ii 1134) has obtained a modified Einstein formula for the specific heat of a monatomic element. This has been applied in the calculation of the atomic heats of aluminium copper silver diamond potassium and sodium chloride at different temperatures and the results are compared with the experimental data. This comparison shows t h a t the new formula agrees better with experiment than either of the older formulae of Einstein and of Nernst and Lindemann. The available specific heat data indicate that two groups of elements may be distinguished.In t h e one group the variation of the specific heat with the temperature can be satisfactorily represented by means of Debye's formula whilst the substances in the other group are characterised by a n appreciably less rapid fall in the specific heat with falling temperature than is required by the formula. Crystalline 8-2ii. 104 ABSTRACTS OF CHEMICAL PAPERS. elements belonging to the fir& group are probably monatomic whilst those of the second group are probabIy polyatomic. The fact that potassium and sodium chloride behave like monatomic substances is attributed t o the approximate equality of the vibration frequencies of the component atoms. H. M. D. Investigations on Speciflc Heat. VII. Calculation of Chemical Affinities. WALTHER NERNST (Sitzungsber.R. Akud. IT'iss. Berlin 19 12 11 72-1 176).-The effect of the substitution of Debye's formula for the specific heat in place of that used by Nernst and Lindemann is considered in reference to the application of the author's heat theorem to the calculation of chemical affinities. Tables are given which indicate the magnitude of the correction factors for a series of vi bratiori frequencies. H. M. D. The Polymerisation of Substances at Low Temperatures. JACQUES DUCLAUX (Compt. Tend. 1912 155 1509-1511. Compare this vol. ii 18).-A mathematical paper in which the author shows that the value of -- where dQ is the quantity of heat necessary at each temperature Y' to produce the modification studied To the absolute zero and 5'; is the absolute boiling point of the substance is a constant for all substances and equal to 42 or twice the value of the constant in the Pictet-Trouton law obtained by dividing the mole- cular beat of vaporisation by the temperature of vaporisation.The values are given as calculated for ten substances the specific heat of which has been completely studied. E d W. G. The Liquid Condition (Correction). WILLTAM C. McC. LEWIS (Z~itsch. phyeikal. Chem. 1913 81 626-628. Compare A. 1911 ii 855).-The author shows that the expression L= - Ta/& has only an emrirical meaning and he develops from thermodynamical principles the expression I = - 2h//3 in which I is the latent heat of expansion that is the amount of heat which must be added to a system t o cause an increase in volume of one unit whilst tho temperatureis kept constant a is the coefficient of expansion and p the compressibility.The expression only holds for homogeneous systems that is either entirely liquid or entirely gaseous. The author has calculated the values of 2 for a number of liquids and finds that its value is of the same order as the latent heat of vaporisation from which he draws the conclusion that the region of molecular attraction must be of the same order as the mean distance of the molecules from one another that is about cm. J. F. S. Simple Method for Determining the Melting Point of the Less Fusible Substances. XRN. HAVAS (Chem. Zeit. 1912 36 1438).-The author recommends a modification of the mercury method in which the substance of which the melting point is to be determined is placed in small quantity on the surface of mercury,GENERAL AND PHYSICAL CHEMISTRY.ii. 105 which is gradually heated. The mercury is replaced by an alloy of 2 parts of t i n and 1 of lead (ordinary soft solder) and melting points up t o 450" can readily be determined. T. S. P. Melting Point of Fire Bricks. C. W. KANOLT (Tech. Papers Bur. Stands. 1912 No. 10 I-l'I).-The melting point was taken as the lowest temperature at which a small piece of the brick could be distinctly seen to flow. An electric vacuum furnace was used and the melting points of fifty-four samples of fire brick including fire-clay bauxite silica magnesia and chromite bricks were determined as well as t h e melting points of the following materials important in the manufac- ture of fire brick kaolin 1740'; pure alumina 201bO; bauxite 1820" ; bauxite clay 1795 ; chromite 2180O.T. S. P. Pressure-temperature Diagrams for p - Azoxyanisole and a-Naphthylamine. NICOLAI A. PIJSCHIN and I. V. GREBENSCHTSCHIKOV (J. Rugs. Phys. Chem. Soc. 19 12 44 17%- 1736).-These diagrams have been investigated by the manometric method. TJp to pressures of 1088 kilograms per sq. cm. the melting point of p-azoxyanisole is a linear function of the pressure and is expressed by the formula tp = 135*9O+ 0.03949~. Hulett whose measurements were confined to the region 1-300 atmospheres found the value 0,0486 for the pressure-coefficient of the melting point (A. 1899 ii 468). this differing considerably from the authors' value 0.U395. A possible bending of the melting-point curve a t higher pressures such as occurs with the great majority of other substances has n o t been investigated.The transition point from the crystalline state t o the liquid-crystalline condition varies linearly with the pressure as far as 3000 kilograms per q. cm. and is expressed by tp = 11 7.3" + 0.02560p (Hulett Zoc. cit. foutid dT21dp=0*0320). Increase of the pressure from 2000 to 2645 kilograms per sq. em. is accompanied by increasing divergence of the transition point from the rectilinear curve this behaviour being similar to that of the melting points of substances crystallising with diminution of volume. The considerable difference between the pressuve-coefficients of the melting and transition points of p-azoxyanisole and the rectilinear character of the curve connecting melting point and pressure up to 1088 kilograms per sq.em. are regarded as contradictory to O~twald's assertion (Lehrbuch der allyemeinan Chemie 2nd Edition 11 2 392) tbat with liquid-crystalline substances small values tor the change of volume on melting and for the heat of crystallisation readily become zero a t pressures slightly in excess of t h a t of the atmosphere; or i n other words that with liquid crystals the critical point for liquid-to-crystals can be realised experimeutally. For pressures up t o 3000 kilograms per sq. cm. the melting point of a-naphthylamine is nearly a linear function of the pressure and is given by tp= 48-5O-t 0~01723p-0~000000555p2. The value 0.0168 for dT/tlp from 1 t o 500 kilograms per sq. cm.differs considerably from the value 0*0%10 found by Hulett (Zoc. cit.). The authors' results do not agree with those of Damien (Compt. Tend. 1891 112 785) which would indicate a maximum for the temperature-pressureii. 106 ABSTRACTS OF CHEMICAL PAPERS. curve of a-naphthylamine a t a pressure of 83 atmospheres The equation given above shows that a maximum may be expected at about 182’ (15500 kilograms per sq. cm.) so that a t higher tempera- tures and pressures crystalline a-naphtbylamine would be incapable of exietence. T. H. P. Thermal Analysis. T. VAN DER LINDEN (J. Chim. phys. 1912,10 454-466).-The paper gives an account of the theory of the method largely used by Holleman and his pupils of estimating the com- position of mixtures from freezing-point data alone.I n a homogeneous liquid with n components,. which form no com- pounds or mixed crystals a t atmospheric pressure the totlal weight of the system being 100 the degrees of freedom = n of which (n - 1) are variable concentrations and the remaining one is the temperature. On cooling the system one of the 12 constituents crystallises out at the first freezing point and as there are now two phases the degrees of freedom are reduced to (n - 1). The first solidifying temperature is therefore fixed by the proportions of the (n - 1) constituents remain- ing in the melt. Similarly the second solidifying point is a function of the ( n - 2 ) constituents remaining and so o n ; thus the (n-1)th freezing point is independent of the proportions of the (n - 2) con- stituents already solidified but dependent on the fatio a of the two constituents remaining in the melt that is the (9% - 1)th freezing point = f ( a ) .This function is represented by a curve similar to the ordinary binary freezing-point curve given by the two constituents in question. Hence the observation of the (n- 1)th freezing point enables the ratio cb of the remaining constituents to be estimated. Any pair of constituents can be arranged to crystallise out last by the addition of suitable amounts of certain of them and thus by the observation of the (n - 1)th freezing points of (n-1) solutions the composition of the original mixture of n substances is arrived at. Binary mixtures (9% = 2) are therefore analysed by one freezing-point measurement. Ternary mixtures require two estimations of second freezing points quaternary mixtures three estimations of third freez- ing points and so on.The observation of third and higher freezing points is very difficult. owing to the large amount of solid matter already present. With ternary mixtures it is necessary to obtain two complete second freezing-point curves with mixtures of known composition. Each of these curves ropresents the binary freezing- point diagram of t w o constituents saturated with the third. For instance when the freezing-point diagram of a ternary mixture has the “ideal ” form the three binary curves are superposable. The influeme of a quantity of 0 on the solidifying point of P being the same as the influence of an equimolecular quantity of M is also the same as that of an equivalent quantity of a mixture of 0 and icf mixed.In this ideal case the first freezing points of two solutions depositing P and 0 respectively say are sufficient to establish the compositions of t h e two solutions. This is tantamount to reducing a ternary mixture to a binary one. The method most used is to combine the two principles and establish I n some cases simplified methods are possible.GENERAL AND PHYSlCAL CHEMISTRY. ii. 107 the composition of the solution by one first and one second freezing point measured successively. Similar simplifications are sometimes possible in the case of quaternary mixtures particularly where some of the four constituents are isomeric substauces. R. J. C. Relations of Isomorphism in Organometallic Compounds.111. Derivatives of Bivalent Metalloids. PAUL PASCAL (Bull. SOC. chim. 1912 [iv] 11 1030-1037. Compare A. 1913 i 739).-The author has determined the freezing-point curves of binary mixtures of phenyl ether pfienyl sulphide phenyl selenide and phenyl telluride. These substances we1 e each purified by fractional crystallisntion and were found to have the following melting points 26" - 21.5' 2*5' and 4.2' respectively. Phenyl sulphide and phenyl selenide give a continuous series of mixed crystals the freezing-point curve passing through a minimum at -26*7" corresponding with the mixture containing 5% of the selsnide. Similar results are obtained with mixtures of the selenide and the telluride the minimum point being - 4*2" corresponding with the mixture containing S0.4% of the selenide and with mixtures of the sulphide and telluride the mixture containing 83.42% of the sulphide having tbe minimum freezing point - 30.7'.Phenyl ether and phenyl sulphide do not form a continuous series of mixed crystals the freezing-point curve exhibiting a eutectic point at - 27*7O corresponding with a mixture cont.3ining 13.3% of the ether. The two series of mixed crystals in equilibrium a t the eutectic point contain respectively 4.5 and 53% of phenyl ether. The above results agree with the classification of sulphur selenium and tellurium apart from oxygen. T. s. P. Internal P r e s s u r e and L a t e n t Heat of Liquids. WILLIAM C. McC. LEWIS (Pld. Mug. 1913 [vi] 25,61-65. Compare A. 1912 ii 136).-For the internal pressure of a liquid the author has obtained previously the expression K - 1 = I'dK/dl' where R is the internal pressure and I the latent heat of vaporisation OF 1 C.C.According to Davies (A. 1912 ii 903) the temperature-coefficient oE the internal pressure dKjKdT is equal to the coefficient of expan- sion a and by substituting in the above equation i t is found that K = Z / ( l + uT) which is identical with one of the results 'obtained by Davies. If I is considered to represent the latent heat of expansion of the liquid (the heat absorption corresponding with isotherinal expansion equal to 1 c.c.) it is deduced that 1 = - Ta//3 where a is the coefficient of thermal expansion and the compressibility of the liquid. For non-associated liquids the latent heat of expansion calculated from this equation is of the same order of magnitude as the latent heat of vaporisation.For associated liquids the differences are much greater. Values representing the internal pressure are calculated for a number of liquids from the equation K=Z/(l + a T ) on the assumption that I is the latent heat of expansion. The numbers so obtained are approximately double those recorded previously. H. 11. D.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. Guldberg’s Law and the Corresponding States. ANATOLE LEDUC (Compt. rend. 1913. 156 65-66).-8 criticism of Boutaric’s deductions (this vol. ii 21) in which the author suggests a modification of Guldberg’s lam to read the boiling points of substances under equally reduced pressures are corresponding temperatures. Composition and Pressure of the Vapour of Solutions.31. S. VHEWKI ( J . IZuss. Phys. Chem. Soc. 1912 44 1739-1747).- The re-ults previously obtained (A. 1912 ii 1139) with aqueous solutions of methyl ethyl and proppl alcohols containing from 20-30% to 100% of alcohol are in complete accord with the relation e*tablibhed by Duhem and Mnrgules between the partial pressures of the vaponrs arid the compohitions of the solutions d In p,/d Zn x = d 2rL p 2 / d En( 1 -x). The applicttbility of this relation t o the solutions coritnir~irig less than 20-30% of alcohol remains undecided owing to t h e lack of det,ailed experimental data. The author discusses the numerical results from which he draws the following conclusions (1) The displacement produced i n the equi- librium between solutions of two liquids and their saturated vapours with constant volume of the system by change of temperature is siillject to Le Chatelier and van’t HOB’S law which may be formulated :IS f’ollows I n all cases of equilibrium between phirses of variable compouitiou heating of the system under constant volume leads in the phase formed with absorption of heat to increase of that component ttle transformation of which absorbs the greatest quantity of heat.(2) On the basis of Kirchhoff’s theory the change in the composition of tht vapour under the influence of temperature m4y be regarded as the result of the corn bined action of two Factors the physico-mechanical arid the phybico-chemical. I n every sysrem foi med with either development or absorption of heat there exists a region of parallel anti one of opposed action of the two factors.The limits of these regions ate the solutions corresponding with the maximum or minimum heat of formation. (3) The direction in which the change in composi- tion of the vapour proceeds under the influence of temperature remains the same for all concentrations of the solution if in the region where the actions of the two factors are opposed the magnitude of the physico-rYieehanica1 factor always predominates. (4) On change of texriperatu~ e of solutions formed without heat-effect the variation in the coniposition of the vapour takes place under the influence of a sirlgle physico-met hanical factor and follows the same law as does change in the cumposition of the vapour of mechanical mixtures ; (5) with change of temperature of a solution which possesses a vapour- prSesbu1.e curve showing a maximum the composition of the vapour and thxt of the mixture with constact boiling point change in one and the S;IWO direct:on.(6) If however the vapour-pressure curve shows :L r n i ~ i m ~ r i i the compositioris of the vapour and that of the mixture W. G. with constant boiiing point charrge in opposite directions. T. H. P. Association of Ethyl Ether and Chloroform in the Gaseous State. k’ni~~nrcrr DOLEZALEK and ALFHED SCHULZE ( B e y . Deut.yhys?kd. GBM. 1912 14 1~9l-lW6).-.tt is shown that the mixing of theGENERAL AND PHYSICAL CHEMISTRY ii. 109 vapours of ethyl ether and chloroform at 80” and atmospheric pressure is accompanied by contraction. When the volumes of the two vapours are equal the data obtained correspond with a reduction of pressure of 4.8 mm.of mercury when the volume is kept constant. I t is shown that the observed contraction is not due t o deviations of the vapours from the gas laws and the change in volume is consequently attributed t o the formation of a compound. The magnitude of the volume change indicates that an equimolar mixture of ethyl ether and chloro- form at SOo and atmospheric pressure contains 0.64 mol. % of the compound. By applying the lam of mass action it is seen t h a t the molecular proportion of the compound in thevapour mixture will increase almost; in the same ratio as the total pressure. Similarly it is shown t h a t the saturated vapour in equilibrium with an equiruolar liquid mixture of the two substances at 80” should contain 1.4 mol.% of the compound. Since the liquid phase contains 14.6 1x01s. % of the compound it follows from the vapour pressure law for binary mixtures that the vapour pressure of the compound at 80” should be about 0.26 atmosphere. H. M. D. Isotherms of Diatomic Gases and of their Binary Mixtures. XI. Determinations with the Volumenometer of the Com- pressibility of G a s e s under Small Pressures and at Low Temperatures. W. J. DE HAAS (Proc. K. Akad. Vetensch. Amsterdum 1912 15 299-306. Compare A 1912 ii 1138)-The question of the distribution of pressure between the volumenometer and the piezometer used in the mclawrements of the compressibility of gases at low temperatures is discussed and a formula is deduced for calculating the change in the difference of pressure between the two communicatitlg vessels as a function of the time.This formula involves the dimensions of the apparatris and the distribution of temperature along the connecting capillary. The curve corresponding with the formula is in sat ihfactory agreement with the actual observations of the change in the pressure difference with time. H. M. D. The C r i t i c a l Point. ETTORE CABDOSO (J. Chinz. pAys. 1912 10 4’70-496. Compare A. 1911 ii Sb4).-1n order t o evaluate the compression coeficients of gases to 1 part in 10,000 for atomic-weight caltwlations the critical tamperir tures and pressures must be known wihhin the limits 0.1’ and 0.1 atm. respectively. The temperature and pressure ought t o be observed a t the same time with the same specimen of gas so that any error due to impurity may affect both values equally. Although various investigators have given critical pressures to within 0.01 atm.tbe author considers that they were not justified since in general a variation of O * O 0 l o in the temperature corresponds with 0.01 atm. in the pressure. At the same time i t is admitted t h a t observations of pressure or temperature made separately a s by the Natterer tube may be more accurate than the author’s as far as the actual specimen handled is concerned. The paper dexribes the methods employed at Geneva in critical constant investigations. The gases were purified by fractional dis- tillation under vwuum (compare Briaer and Cardoso A. 1909 ii,ii.110 ABSTRACTS OF CHEMICAL PAPERS. 124) alternating with passage through suitable absorbents maintained slightly above the boiling .qoint of the gas. A sample of gas was not considered sufficiently purified until it could be liquefied at pressures constant to within 0.05 atm. a t two different temperatures one of which was near the critical point. A manometer of the barometer type was used consisting of a 1 mm. capillary tube with suitable bulbs in the upper and lower parts surrounded with a glycerol-water jacket maintained at a constant temperature. It was filled with atmospheric nitrogen the corn- pressibility of which is known froin Amagat's accurate data. The manometer was read to 0.1 mm. corresponding with not more than 0.02 atm. pressure. Owing to the uncertainty of the capiliary cor- rection in a 1 mm.tube cloher reading would have been useless and the use of a finer capillary would have introduced unknown errors due to diffraction and the retention of small gas bubbles below the meniscus. The different manometers agreed to within 0.1 a t m . at least and the accuracy of the methods was confirmed by the fact t h a t concordant critical data were obtained with different mano- meters and different samples of gas often at considerable intervals of time. The working tube was provided with a small piece of soft iron wire constituting the armature of an electromagnetic agitator of the Kuenen type. On approaching the critical temperature the meniscus disappears and the so-called " critical opalescence " is seen.The point of maximum opalescence is held by some to be the critical temperature (compare Nernst " Theoretical Chemistry "). The opalescence usually exteuds over a range of 0*03O but by means of the Kuenen agitator the range could be extended to 0.3Oto 0.4". The opalescence is therefore due to the formation of a n emulsion of gas and liquid which being of nearly equal density do not separ- ate. The true critical point is taken as the point a t which the opalescence disappears. This could be estimated t o within +_ 0.05" and is about 0.15' higher than the point of maximum opalescence. 16 is possible that an invisible opalescence persists at an even higher temperature since i n experiments made without the stirrer a slight diffraction could still be observed a t the spot where the meniscus had been.Critical data to the nearest 0.05 atm. and 0.05' are tabulated for hydrogen chloride ammonia carbon dioxide sulphur dioxide nitrous oxide hydrogen sulphide acetylene ethylene ethane and cyanogen. R. J. C. Critical Constants of Ethane Carbon Dioxide and Sulphur Dioxide. ETTORE CARDOSO and It. BELL (J. China. phys. 1912 10 497-503).-Xthane prepared from ethyl iodide by the Grignard reaction contained a i r and ethyl iodide and ether vapours as well as other impurities which were removed by suitable absorbents followed by fractional distillation. Ethane prepared by Frankland arid Kolbe's method by cautious addition of propionitrile to metallic sodium in :I vacuum was readily purified by absorbents only. The purified ethane having m.p. - 172.5" and b. p. -S4.l0 possessed a n agreeableGENERAL AND PHYSICAL CHEMISTRY. ii. 111 ethereal odour. I t s critical constants mere tc = + 32*10°F O * l O o and pc = 48.85 f. 0.10 atm. Carbon dioxide prepared by heaticg sodium hydrogen carbonate was washed and fractionated ten times. Its critical constants were t - + 31.00" +_ 0*103 and p c = 72-83 t- 0.10 atm. The critical opalescence mas observed as low as 30*60° but the point of maximum opalescence could not be decided. Commercial sulphur dioxide was washed and purified by ten distillations. I t s critical constants were t = + 157.15" t 0.10" and p = 77.65 0.10 atm. The point of maximum opalescence could n o t be observed owing to an opzlescent deposit on the glass tube. This appeared to result from the action of light and heat on the sulphur dioxide but i t was ascertained t h a t even 300 hours' heating did not alter the critical constants of the gas.R. J. C. Critical C o n s t a n t s of Ethylene N i t r o u s Oxide and Hydrogen Sulphide. XTTORE CARDOSO and E. ARNI (J. C h k . phys. 1912 10 504-508).-Ethylene prepared by the action of sulphuric acid on ethyl alcohol and purified by washing and fractional distillation had m. p. - 169.00' and b. p. - 104.3'. The critical constants were found to be t = +9*50'+_0*10' and pc=50*65 +_ 0.10 a t m . The critical opalescence extended from + 9.05" t o 9-50'. Nitrous oxide was prepared by the action of saturated aqueous sodium nitrite on hydroxylamine hydrochloride in a vacuum. When washed and fractionated ten times i t gave a perfectly colourless solid.The critical constants were tc = + 36-50'? O.lOo and pc = 71.65 & 0.10 atm. The critical opalescence extended from 36.0"to 36*5O and had its maximum a t about 36.3'. Hydrogen sulphide prepared by the action of hydrochloric acid on purified precipitated iron sulphide in a vacuum was mashed in water containing iron sulphide in suspension and then dried and fractionated fourteen times in a vacuum. The purified gas of f. p. - 83' and b. p. - 60.2' was without action on clean mercury and was perfectly stable at the critical point. The critical constants were tc = + 100.40" +_ O * l O o and pc = 89-05 5 0.10 atm. R. J. C. Critical Constants of Ammonia. ETTORE CARDOSO and (&file.) A. GILTAY (J. Chim. phps. 1912 10~514-516).-Arnmonia was prepared by heating purified ammonium chloride with excess of calcined marble.It was dried by barium oxide and sodium wire and distilled four times through the same reagents. Four further fractional distillations served to remove traces of air and hydrogen. tc = + 132.90" 2 O.lOo and pc = 112.30 maximum at about 132.75'. The critical constants were 0.10 atm. The critical opalescence was observed from 132.6" to 1 3 2 . 9 O with a R. J. C. C r i t i c a l Constants of Hydrogen Chloride. ETTORE CARDOSO and A. F. 0. GERMANN (J. Chiin. phys. 1912 10 517-519).- Purified sodium chloride was decomposed with pure concentrated sulphuric acid in a vacuum the 'apparatus being constructed with fused joints throughout. The hydrogen chloride was dried with sulphuricii.112 ABSTRACTS OF CHEMICAL PAPERS. acid and phosphoric oxide and fractionally distilled twelve times in all first through phosphoric oxide and afterwards without it. The solidi- fied hydrogen chloride was absolutely free from the pink t i n t usually attributed to a compound of phosphorus or t o nitric oxide. It had m. p. - 111-4° and b. p. - 83.1'. The critical constants were t,= +51-40° +_O.lOo andp,.=81*55+0.15 ntm. R J. C. Free Energy of Chemical Substances. Introduction. GILBERT N. LEWIS (J. Amer. Chem. Soc. 1913 35 1-30).-This paper is introductory to a series in which the free energy of chemical substances will be systematically studied. A detailed account i s given of the general methods used in free energy calculations including the con- sideration of the notation and fundamental units the laws of energy the change of energy with pressure the relation between activity and fugacity and the free energy free energy and the equilibrium constant free energy and E.M.F.and the influence of temperature on the free energy change. E. G. Tempering [of Metals] without Deformation. MAURICE HANKIOT (Compt. rend. 1912 155 1502-1504. Compare A. 1912 ii 1137).-Cubes of a number of metals and alloys were submitted to high pressure when immersed in vaseliu and i t was found that whilst the cubes were not deformed and the internal structure as examined microgrsphically for brass was iinaltered the substances had under- gone considerable tempering as was shown by measuring their hardness elongation and breaking strain before and after the compression.W. G. The R e c t i l i n e a r Diameter for Argon. EMILE MATHIAS H. KAMERLINGH ONXES and C. A. CROMMELIN (Proc. K. Akad. Netensch. 19 12 15 667-673).-8 preliminary account is given of the apparatus and mode of procedure adopted in the determination of the densities of liquid and saturated vapour at a series of different temperatures. The mode of calculating the requisite data from the experimental observations is described but no results are corn mun ica ted. H. 11. D. Specific Gravities of Saturated Aqueous Solutions of Various Salts at Different Temperatures. N. A. TSCHERNAJ (J. Buss. Phys. Chem.. Soc. 19 12 44 1565-1576).-The author has determined the specific gravities (weights of 1 c.c.) of saturated solutions of a number of salts at intervals of 10' from 0' to 70" (or 90'). These salts may be divided into two groups (1) those forming saturated solutions which increase i n specific gravity with rise of temperature and with in- crease in the salt-content potassium chloride nitrate and sulphate sodium and barium nitrates; ( 2 ) those with which the reverse takes place sodium chloride. These salts also show different behaviour with reference to the variation with temperature of' the quotient dP/d V where d P represents the increase per 10' of the amount of salt (grams) dissolved by 100 grams of water and d V the corresponding increase in volume (c.c.) ofGENERAL AND PHYSICAL CHEMISTRY. ii.113 the solution. With rise of temperature from 0’ to 70° this quotient shows a continuous increase from 0.12 t o 0.5 with sodium chloride remains almost constant with potassium chloride (1.69) sodium nitrate (1.9) potassium nitrate (2-1) and potassium sulphate (2*2) and con- tinually diminishes from about 5 to 1.6 with barium nitrate.T. H. P. Compressibility of Gases. GEORGES BAUME and E. WOURTZEL (J. Chirn. phys. 1912 lo,’ 520-522).-’rhe relation of pressure to volume in sulphur dioxide methyl ether and chloroform vapour has been represented by the equation pv= 1 +a(l - L/L,) where L is the density at pressure p and L the weight of a normal litre of the gas considered (compare Baume A. 1908 ii 372). The deviation co- efficient a is numerically the same as Berthelot’s deviation coefficient Al iu the case of permanent gases but with easily liquefkble gases A = u/(1 +a).This equation may be reduced to A = a - a2 when cc3 is negligible. R. J. C. Adsorption and Saturated Surfaces. ROBERT MARC (Zeitsch. pliysikul Cf~em. 1913 81 641-694 Compare Schmidt A. 1910 ii 1041 ; 1911 ii 969).-L’he adsorption of a large number of substances on the cryst-tl surfaces of barium sulphate bdrium carbonate rhombo- hedral calcium carbonate strontium carbonate ledd carbonate and lead sulphate was investigated by measuring the change in the refractive indices of the solution of many substances by means of a n interferomet w. I t was shown that colloidal substances are easily adsorbed on crystal surfaces whereas crystalline substances are only adsorbed t o a very slight extent. Crystalline substances adsorb more if they are capable of forming isomorphous or mixed crystals with the adsorbing substances ; thus potassium nitrate is adsorbed by barium carbonate whil-t sodium nitrate is not ; on the other hand sodium nitrate is adsorbed by rhombohedra1 calcium carbonate whilst potassium nitrate is not.The adsorption Lothermals can be divided into three types (1) Those in which a stronger bend is present than is demanded by the exponential formula and which reach the satura- tion value continuously. (2) Those which agree at all points with the exponential formula. I n this case even though the measurements were made very close together it was impossible t o determine whether there was a break in the curve or not. (3) Those curves of substances which at low concentrations have a great tendency to be adsorbed and give a very steep curve and reach the saturation point at very low concentrations.The adsorbed substance is the factor which conditions the type of curve in any case. It is shown that when the saturation values for a series of substances with one given adsorb- ing medium have a given ratio then the ratio of the saturation values for those substances with another adsorbing medium will be the same. The formulae of Schmidt and Arrhenius are discussed and it is shown that the Arrhenius formula holds well for Substances giving curves of the first type but for curves of the second type it holds only over a portion of the curve and ceases t o hold some distance before the saturation value is reached whilst for curves of the third type itii.114 ABSTRACTS OF CHEMICAL PAPERS. does not hold at all. It is however shown that; the Arrhenius formula probably represents ideal conditions which axe only existent when molecular compounds are not formed in the adsorption layer. J. F. S. Adsorption. VII. Chemical Hysteresis of Starches. ADAM V. RAKOVSKI (J. Russ. Yhys. Chem. Soc. 1912 44 1722-172S),- The investigations here described are a continuation of those published in papers I. and 11. (A. 1911 ii 470) and deal with curves inter- mediate t o those of hydration and dehydration of Bermuda arrowroot and rice starches. These intermediate curves are found to be virtually reversible but not throughout their whole length. Detailed study of such curves would however be possible only with colloids showing a considerably greater separation of the curves of hydration and dehydration than is the case with starches. The presence of about 1% of mercuric chloride in potato starch exerta no appreciable influence on the course of either hydration or dehydration.T. H. P. Relation between the Conductivity of Acids and their Absorption by Hide. ANDRB BROCHET (Compt. rend. 1912 155 1614-1617).-Measurements have been made of the amount of acid absorbed by shaking 10 grams of hide powder for four hours with 200 C.C. of a n N/lO-solntion of the acid concerned containing 100 grams of sodium chloride per litre. lVleasurements have been made with three classes of acids varying in conductivity namely (1) good conductors (2) moderate conductors (3) poor conductors. In class (1) inorganic acids and organic acids of the type of trichloroacetic acid were examined.The absorption of acids by the hide is a general phenomenon and is the result of a chemical combination the amount of acid absorbed being proportional to the chemicai equivalent of the acid. The fraction of the gram-equivalent of acid absorbed by one kilo. of dry hide whilst constant for each class does show a slight diminution with diminution in conductivity ; but while the absorption diminishes only in the ratio 3 2 the conductivity diminishes as 100 1. W. G. Some Properties of the Tbiocyanate Ion. HERBERT FREUND- LICH and A. N. SEAL (Zeitsch. C’ham. lnd. Kolloide 1912 11 257-263).-The lyotropic properties of solutions of potassium chloride and potassium thiocyanate have been compared in a quantita- tive manner with the object of determining the position of the thio- cyanate ion in the lyotropic series.The properties examined were the following the influence of the electrolyte on the solubility of benzoic acid the effect on the surface tension the absorbability by animal charcoal the retarding influence on the rate of ester saponification and the elfect on the rate of increase of the viscosity of gelatin solutions. The observations show that the lyotropic influence of the thiocyanate ion is distinctly smaller than that of the chloride ion and that its position in the series of anions is close to the iodide end in theGENERAL AND PHYSICAL CHEMISTRY. ii. 115 series fluoride sul phate,. phosphate chloride nitrate bromide iodide. In this series the ljotropic influence diminishes from left t o right.H. ItT. D. Surface Tension of P r o t e i n Solutions. 11. FILIPYO BoTTAZZr and E. D’AGOSTIKO ( A t t i 12. Accad. Lincei 1912 [v] 21 ii 561-572. Compare Bottazzi A. 1912 ii 1043).-The paper records in tables and curves the results of further experiments with Traube’s stalag- mometer on solutions of serum-albumin t o which various quantities of hydrochloric acid sodium hydroxide or sodium chloride were added. From the experiments i t appears that the value n (number OF drops) depends entirely on the undissocieted molecules of the protein or of its salts for a n increase in the concentration of these molecules increases n (that is the surface tension is lowered). I n order t o obtain the maximum diesociation of the albuminate it is necessary to add more acid or alkali in weak solutions than in stronger ones.This indicates the presence of salts of a weak base (or acid) and for the same reason the maximum dissociation will be reached only when more than the equivalent amount of sodium hydroxide or of hydrochloric acid is added. From the amounts thus added i t appears that the molecular weight of the albumin ehould be somewhat above 1000. From the curves it also appears t h a t the albumin chloride is much less disso- ciated than the sodium albuminate a t the same dilution. The addition of sodium chloride diminishes the dissociation of both the albumin salts but its influence is much greater on the chloride than on the albuminate. The addition of sodium chloride also diminishes the dissociation of the free albumin probably owing to the formation of undissociated secondary products.WILLIAM E. S. TURNER (J. Chim. phys. 1912 10 467-469. Compare Guye A . 1911 ii 1067).-The author agrees with Guye that liquids which give a high value of Ramsay and Shields’ constant are not necessarily dissociated since error may arise from abnormality in the surface film of the liquid but cannot agree that in his experiments criticised by Guye the surface films of diphenylamine and phenylurethane were oxidised. The value obtained with diphenylamine was in accord with t h a t obtained by Dutoit and Friedrich (A. 1900 ii 194). Mode of I o n i s a t i o n of Sulphuric Acid i n Dilute Aqueous Solutions. JOSEPH A. MULLER (Comnpt. rend. 1912 155,1499-1502).-From a series of determinations of the coefficients of ionisation and heat of dilution of aqueous solutions of sulphuric acid the author deduces that in di1ut.e aqueous solutions sulphuric acid is ionised i n t o the two ions S0,H’ and H’ and that this ionisation is accompanied by development of heat within the limits of the experimental temperatures Applicat.ion of the Theory of Chemical Potential t o the Thermodynamical Theory of Solutions. 111. Action of G r a v i t y on a Solution. The Solute Potential. E x t e n s i o n of the Theory. SYDNEY A. SHORTER (Phil. Mag. 1913 [vi] 25 31-42. Compare A. 1912 ii 24 437)-From a general theorem R. V. S. Molecular Complexity in the Liquid State. R. J. C. (1 4-38’) w. G.ii. 116 ABSTRACTS OF CHEMICAL PAPERS.enunciated by Gibbg the author deduces a formula for the influence of gravity on a binary ruixture. This formula is found to be in accordaoce with the equation obtained directly by Dtihern. Formtile are also given for the practical calculation of the gravity effect from osmotic pressure vapour pressure and freezing-point data. I n the second part of the paper the theory given in Parts I and TI. (Zoc. c i ~ ) is extended to solutions containing any number of non-volatile solutes. Exact formulae are deduced connecting the osmotic pres,sure vapour pressure and freezing poiot with the lowering effect exerted by the solutes on the chemical potential of the solvent. Thermo- dynamically the solutes may be regarded as a single substznce,and hence the formulae relating t o a binary solution may be generalked i n a very simple manner.H. M. D. Studies of the Processes Operative in Solutions. XX. The Conversion of Ammonium Cyanate into Carbamide Especially as Influenced by Alcohols. ERIC WALKER (Proc. Roy. Soc. 1913 A 8'7 539-554. Compare J. Walker and Kay T. 1897 489).-Experiments have been made t o determine the influence of ethyl propyl and isobutyl alcohol on the rate of trans- formation of ammonium cyanate into carbamide when the ratio of cyanate t o water in the solution 1s kept constant. The measurements were made at 40" and the rate of change at any moment way obtained by determining the tangent t o the smooth curve drawn through the points representing the cyanate concentrations after a series of time intervals. I n aqueous solution the rate of change varies approximately as the square of the concentration of the cyanate as found by Waiker and Hambly ( r.1895,?'1,746) but the carbamide and ammonium carbonate which are formed have some influence on the velocity. Sirice the carbonate is formed very rapidly a t the beginning of the experiment the velocity coefficient is abnormally high at first and during the later stages of the change the coefficient is again too large because of the accelerating effect of the ammonium carbonate. The addition of carbamide t o t.he original solution has also the effect of increasing the mean velocity coefficient a result which is probably due to its influence on the side-reaction by which ammonium carbonate is produced. The data obtained in a series of experiments in which the molar ratio of ammonium cyanate to water was 0.15 100 and iu which tho number of mols.of ethyl alcohol was increased from 0 to 180 per 100 of water show t h a t the rate of change is increased in proportion to the amount of alcohol present. When the alcohol and water are presert in equimolar proportions the rate of change is however only about five times as large as the rate in the absence of alcohol (compare Walker and Kay From comparative experiments in which ethyl propyl and isobutyl alcohols were added to the aqueous solution of the cyanate it appears that the activity increases considerably with the molecular weight of the alcohol. The percentage increase in velocity per mol. of added alcohol was found t o be 3-30% 4-92% and 7.3% respectively for a solu- loc.cit.).GENERAL AND PHYSICAL CHEMISTRY. ii. 117 tion containing 0.15 mol. of cyanate per 100 mole. of water. The order in which the alcohols are arranged is the same as that obtained on contrasting their activities as precipitants of salts from aqueous solutions and their physiological activity as hormoneq. It is supposed t h a t the action of the alcohols is largely mechanical the larger molecules having the greater effect both on account of their size and their greater mobylity by reason of their smaller affinity for water. H. M. I?. Studies of the Processes Operative in Solutions. XXI. Hydrolysis of Sucrose by Dilute Acids. FREDERICK P. WORLEY (Proc. Roy. SOC. 1912 A 87 555-563).-The conclusion drawn by Armstrong and Caldwell (A.1904 i 1070) t h a t the hydrolytic action of dilute acids on sucrose is closely analogouq to that of enzymes has been subjected t o examination in a further series of experiments with dilute sulphuric acid at 25". I n three comparative observations the solutions contzined 0-01 mol. acid 200 mols. of water and 1 2 and 4 mols. of sucrose respectively. From the measured time changes in the rotation of the solutions i t is evident t h a t the rate of hydrolysis diminishes as the reaction proceeds in accordance with the requirements of the mass law. The view that the hydrolysis in dilute acid solution is characterised by a n initial period in which the sucrose is hydrolysed at a constant rate finds no support from the data which have now been obtained. Thero is therefore a considerable difference between the sucroclastic action of dilute acids and small quantities of enzymes.It is pointed out that this conclusion has already been drawn by Rosanoff Clark and Sibley (A. 1912 ii 34) but t h a t the arguments put forward by these authors are unsound. Studies of the Processes Operative in Solutions. XXII. Hydrolysis of Sucrose by Sulphuric Acid ; Improvements in Polarimetric Apparatus. FREDERICK P. WORLEY (Pvoc. Roy. Xoc. 19 12 A 8'7 563-581).-Similar experimeuts to those described i n previous papers have been made with sulphuric acid as a catalyst in order to ascertain the influence of dilution on the hydrolytic activity i n the case of a dibasic acid. The various substances were used in the proportion of 1 mol. of sulphuric acid 30 to 200 mols.of water and either 0.125 or 0-25 mol. of sucrose. From the velocity coefficients at the different dilutions the value of the apparent molecular hydration has been calculated. This increases from 12.2 t o 15.8 when the molar ratio of water t o acid increases from 30 to 80 remaining practically constant on further dilution. By comparing the results with those obtained for hydrochloric nitric and p-dichloro- and p-di- iodobenzenesulphonic acids it is found t h a t the maximum apparent hydration is reached at a n earlier stage in the case of sulphuric acid than when the monobasic acids are employed as catalysts. Prom the final and initial rotations of the differently concentrated solutions it ap ears t h a t the degree of optical inversion varies with of the rotations was found to be 0.342 whereas 0.298 was obtained for the most dilute solution.This variation is attributed t o the influence H. hl. D. the dilution. P n the case OF the most concentrated solution the ratio VOL. CIV. ii. 9ii. 118 ABSTRACTS OF CHEMICAL PAPERS. of the acid on the rotatory power of the sugars present the lzevulose being responsible in all probability for the major part of the effect. I n view of this phenomenon and of the influence of the mutarotation of the dextrose and laevulose it might be doubted whether the polarimetric method affords a satisfactory measure of the rate of hydrolysis of sucrose. A theoretical examination of the subject from this point of view shows however that the velocity coefficient is not affected either by an alteration in the rotatory power of the invert sugar as a consequence of the presence of the acid or by the muta- rotation of the monoses.Considerable improvements have been made in the apparatus employed for the polarimetric study of chemical changes and these together with the precautions which must be observed in accurate work are described in detail. H. M. D. Studies of the Processes Operative in Solutions. XXIII. Hydrolysis of Metbyl Acetate by Acids. FREDERICK P. WORLEY (Proc. Boy. Xoc. 1912 A 87 582-603. Compare Armstrong and Watson A. 1907 ii 149).-With the object of determining the apparent molecular hydration of the acid by the method employed in connexion with the hydrolysis of sucrose (P. 1910 26 298) measurements have been made of the rate of hydrolysis of methyl acetate under the influence of hydrochloric acid.The experiments were carried out a t 25" the molecular proportions of the substances employed being 1 cf methyl acetate 120 of water and from 0.6 to 4 of hydrochloric acid. Under these conditions the proportion of methyl acetate ultimately hydrolysed is never greater than 95% and in consequence it is necessary to take the reverse chango into account in calculating the velocity coefficient of the hydrolysis the reaction taking place in accordance with the equation dx/dt = k(a - z) - k1x2 in which a is the initial concentration of the ester and x the amount transformed after time t. For a given ratio of water and methyl acetate the proportion of the latter which is hydrolysed when equilibrium is attained decreases slightly as the concentration of the catalyst increases.In view of this it is suggested that the usual interpretation of the equation k[CH,*C02CH3][H20] = k1[CH3*C0,H][CH,0H] is incorrect and that since hydrolysis is probably effected by the direct interaction of hydrated hydrolyte and hydrated catalyst the factor [H,O] does not necessarily represent the active mass of one of the substances taking part in the reaction but probably expresses the degree of dilution. From the velocity coefficients values representing the apparent molecular hydration of the hydrochloric acid have been obtained. Corresponding values have also been calculated for sodium potassium and ammonium chlorides from the increase which these salts produce in the velocity coefficient.These molecular hydration values are much smaller than the Corresponding numbers obtained when sucrose and raffinose are used as hydrolytes. Whereas with methyl acetate the apparent hydration value increases from 2.5 to 5 when the molecularGENERAL AND PHYSICAL CHEMISTRY. ii. 219 ratio of water to acid increases from 30 to 80 the corresponding series of numbers from the data for the hydrolysis of sucrose increases from 12 4 to 18.7. It is considered probable that the differences involved repre$ent actual differences in t’he condition of the acid in presence of such different hydrolytes as methyl acetate and sucrose. H. M. D. Studies of the Processes Operative in Solutions. XXIV. Nature of the Hydrolytic Process. HENRY E. ARMSTRONG and FREDERICK P.WORLEY (PTOC. Roy. SOC. 1912 A 87 604-623).- The authors discuss the general character of the results obtained in this series of papers and their theoretical interpretation. As indicated in previous communications tha view is put forward that hydrolysis is essentially an associative process which involves the association and direct interaction of two complexes one of which consists of the hydrated hydrolgte and the other of the hydrated catalyst. Such associated systems are being constantly produced broken down and reformed in such a manner thttt while some give rise to the original components others are resolved into the products of change. According to this view hydrolysis is a bimolecular change the second factor being the active mass of the hydrated catalyst and not as is generally supposed the active mass or concentration of the water.The similarity of the results arrived a t by the study of different properties such as electrical conductivity f;;ydrolytic activity and osmotic effects is quite consistent with this view the similarity being due to the fact that the determining factor in all these cases is the interaction involved in the production of the electrolyte from water and the solute. The increase of molecular Conductivity t o a maximum on dilution is attributed partly to a gradual increase in the extent of the interaction between the solute and water and partly to the gradual simplification of the complexes formed by the dissolved substance. On the other hand the decrease of electrical activity as exemplified by the hydro- lytic activity of the acids to a minimum on dilution is considered to be the necessary result of a gradual weakening of the acid by further combination with water.Ths greater the extent to which the activity of the acid is used up in combining with water the less must be the residual activity available for hydrolytic processes. Stress is laid on the fact that this associative theory is directly opposed to the generally accepted dissociative hypothesis and i t is claimed that the facts disclosed in the investigation of the processes operative in solution go far to show that this hypothesis is no longer tenable. H. M. D. Intercrystalline Cohesion in Metals and the Formation of Twinned Crystals in Silver. WALTER ROSENHAIP; and DONALD EWEN (J.Inst. Metals 1912 8 149-185).-Many of the properties of metals especially at high temperatures may be accounted for by assuming the presence of an amorphous film between the crystals. Tho hypothesis hits been tested in the following manner. The amorphous modification being unstable should have a higher vapour- 9-2ii. 120 ABSTRACTS OF CHEMICAL PAPERS. pressure than the crystalline. Two specimens of silver are taken one having coarse and the other fine crystals. The latter which has a larger area of intercrystalline boundaries in unit volume than the former always loses weight more rapidly when heated in a vacuum. Similar results are obtained with zinc and copper. Microscopical examination shows t h a t the intercrystalline boundaries are developed as if by etching by such treatment.Boundaries between twin crystals are not thus affected. Cast silver even without any mechanical treatment shows numerous twinned crystals which are revealed by heating in a vacuum. 0. H. D. Formation of Twin C r y s t a l s by Quenching and its Influence on the Hardness of Metals. CHARLES A. EDWARDS (Internat. Zeitsch. Metallopaphie 191 2 3 179-194).-The light and dark acicular structure observed in quenched alloys of copper and aluminium containing 9-16% Al is not due to the presence of two constituents but to repeated twinning brought about by the mechanical pressure due to quenching. The vitreous modification of the metal is formed at the surfaces of slip thus increasing the hard- ness of the alloys. This explanation is extended to the general case of hardening of alloys by quenching.C. H. D. E t c h i n g at E i g h Temperatures. H. HANNEMANN (Ifiternat. Zeitsch. Mctallogrupivie 1912 3 l76-178).-The method of investi- gating the crystalline structure of alloys at a high temperature by exposure to etching vapours is faulty because the surface etched is not a section through a crystal but the surface of a crystal and segregation is not thereby reveded. Further recrystallisation may take place during the action of the reagent thus producing a false structure. C. H. D. Colloids. PAUL B ~ R Y (J. Chin&. phys. 1912 10 437-453. Corn- pa.re A. 191 1 ii 702).-Colloidal solutions comprise three classes namely (1) Jellies which are solutions of liquids in solids of great cohesive power.(2) Electrical colloids which are suspensions of very fine insoluble powders without solvent power which acquire a n electrical charge in contact with the liquid. Colloids of this class exhibit Brownian motions and are coagulated by reducing their electro- static charges. (3) Mixed colloids consisting OF micella formed from irregular particles of jelly by the action of excess of liquid. These micella exhibit Brownian motions and may acquire an electrostatic charge. They can therefore be coagulated by altering the external osmotic conditions or by electrical methods or by both combined according t o circumstances. The micella in class (3) are to be regarded as minute osmotic cells into which the surrounding liquid diffuses until its pressure is balanced by the surface tension or cohesion of the small particles. The surface tension of the colloidal substance is negative to start with and tends t o approach zero as the jelly becomes saturated.Caoutchouc (Red Tonkin unvulcanised) absorbs approximately the same volumesGENERAL AND PHYSICAL CHEMISTRY. ii. 121 of chloroform benzene carbon disulphide and tetrachloroethane to form saturated jellies before breaking up into micella. I n some cases the surface tension does not attain zero so t h a t the limit of osmosis inwards is reached in the jelly stage and the true solution of class (1) does not pass into a pseudo-solution of class (3) on further addition of liquid. Examples of this are the swelling of gelatin in cold water and of cellulose tetra-acetate in cold tetra- chloroethane.I n such cases micella can usually be obtained from the jellies by heating or even by violent agitation. The jelly separates out again on cooling as with cellulose tetra-acetate unless Brdwnian motion and electrification of the micella supervene as in the cdse of gelatin. R. J. C. Determinations of the Volume of Voids in Silicic Acid Gels. WILHELM BACHMANN (Zeitsch. anorg. Chem. 19 12 79 202-208).- The transierit opacity of silica gels during dehydration has been considered by Tschermak and also by Tarnmann to indicate the appear- ance of a new hydrated phase. On the other hand the fact that the same change is observed when such different liquids as cedar oil or a mixture of olive oil and chloroform are used indicates that the process is one of mechanical imbibition.The view of Zsigmondy (A. 1911 ii 880 ; Bachmann A. 1912 ii 145) that the gel is traversed by minute capillaries accords best with the facts. It is now shown that the weight of different liquids taken up by a gel is proportional t o their density. The gel is prepared by exposing glassy silicic acid to steam and then washing with water and drying over sulphuric acid. T h e e gels are examined the liquid being generally introduced by exposure to its vapour. Measurements with water benzene cbloroform ethyl iodide and acetylene tetrabromide the last being used in the liquid form only give concordant results. c. H. D. Theory of Emulsification. IV. WILDER ID. BANCROFT (J. Physical Chem. 1912 16 739-758. Compare A. 1912 ii 834). -Robertson’s paper on emulsions of oil aud water (A.1910 ii 697) and the article on emulsions in Remington’s ‘‘ Practice of Pharmacy ” (1907) are reproduced in full. Robertson’s work is valuable because he was able to prepare emulsious of water in oil as well as of oil in water. Moreover by means of a n especially efficient shaker he emulsified the whole of his ingredients iu one operation instead of working in the dispersed phase gradually. The author holds t h a t this succeshf ti1 preparation of emulsions of water in oil was due t o the fact that the olive oil used has some solvent power for the emulsifier sodium oleate whereds kerosene and benzene in which the soap is insoluble give no such emulsions. The author does not accept the conclusion drawn by Robertson that one type of emulsion passes into the other at a definite concentration but argues that there may be a range of concentrations within which no emulsion whatever is produced or the emulsions may overlap.The emulsions known t o Pharmacy which contain upwards of 95% of oil are all of the oil in water type with gum acacia egg-albumin orii. 122 ABSTRACTS OF CHEMICAL PAPERS. casein as emulsifying agents. The object of the pharmacist is to divide the oil into minute globules and surround each one with a n adhesive envelope. The exact proportions of oil water and gum are probably not so important as is generally supposed. Composition of the Disperse Phase in Emulsoids. EMIL HILTSCHEK (Zeitsch. Chem. Ind. Kolloide 1912 11 284-286).-0n the assumption that the velocity of displacement of the juxtaposed layers exceeds a certain critical value it has been shown (A.1911 ii 9s) that the viscosity v’ of a n emulsoid is given by the equation 7’ = y~ u2/(uA - l) in which 77 is the viscosity of the dispersive medium and A is the ratio of the volume of the emulsoid to that of the disperse phase. If the viscosity of the pure dispersive medium is taken as unity this equatlion gives A = (q’/(v‘ - l)13. From the viscosity data for a series of glycogen and sodium casein hydrosols the author has calculated the values of A given by this formula. When these values are compared with the values of A’ representing the ratio of the volume of the ernulsoid t o the weight of disperse phase present it is found that the ratio of A’ to A remains very nearly constant if the less concentrated hydrosols are left out of account.The constancy of this ratio indicates that the disperse phase consists at a given temperature of the dissolved substance together with a definite and constant quantity of the dispersive medium. The Existence and Probable Thickness of Adsorption Envelopes on Suspensoid Particles. EMIL HATSCHEK (Zeitsch. Chem. Ind. Kolloide 1912 11 280-284).-The properties of suspensoid systems which depend on the movements of the particles indicate that the volume of the disperse phase is not independent of t h e degree of dispersity. On the assumption t h a t this is due t o the formation of an envelope of the dispersive medium round each suspensoid particle and that the thickness of the covering film is constant for varying degrees of dispersity i t can be shown that the effective volume V’ and the actual volume V of the disperse phase are connected with one another by tho equation Y’/Y= (1 + 3t/r) where 1.is the radius of the nucleus of disperse phase and t is the thickness of the envelope of dispersive medium. From this i t is evident that the effective volume of the disperse phase will increase continuously as the degree of dispersity increases. Experimental measurements have shown that the viscosity of highly disperse systems increases with the degree of dispersity when the proportion of disperse phase is kept constant and this is probably due t o the incr.e:tsing importance of the surrounding envelope of dispersive medium. From OdBu’s measurements of the viscosity of colloidal sulphur solutions of different degrees of dispersity (A.1911 ii 971 ; 1912 ii 240) the arithor has calculated by means of the above formula the thickness of the surrounding envelope t o be 0.87pp. Accepting this value it follows that for colloidal particles of diameter lOpp the volume of the envelope amounts to 62% of the volume of the colloidal sulphur. H. M. D. R. J. C. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 123 The Equilibrium of a Gas in a State of Binary Dissociation. J. DE BOISSOUDY (Compt. rend. 1913 156 61-64).-A mathematical discussion of the equilibrium of a gas such as nitrogen peroxide acetic acid vapour etc. when partly dissociated into two identical constituents. The equilibrium is expressed by the equation X x2]v( 1 - x) = MT3e-= where x is the degree of dissociation w the volume containing one gram-molecule 5" the temperature .X the energy necessary to dis- sociate the normal molecules into their constituents and M a constant coefficient.W. G. Action of Temperature on the Equilibrium of Nitrous and Nitric Acids Formed from the Oxides of Nitrogen and Water. EMIL BRINER and E. L. DURAND (Compt. rend. 1912- 165 1495-149T).-In a previous paper (A. 1912 ii 1045) the authors studied the effect of pressure and concentration on various systems of oxides of nitrogen and water the temperature remaining constant. They have now estimated. the relative molecular amounts of nitrous and nitric acids formed in the solutions a t varying temperatures and find that increase in pressure of the nitric oxide and diminution of temperature favour the formation of nitrous acid.W. G. The Equilibrium in Acid Solutions of Potassium Salts. 11. ALBERT J. J. VANDEVELDE (Bull. SOC. chirn. Belg. 1912 2G 513-532. Compare A 1912 ii 30).-A continuation of the study of the constitution of the solid phase obtained from acid solutions of potassium salts. I n the former communication the salt chosen was pottssium sulphate and the three acids hydrochloric nitric and sulphuric. To complete this study the equilibrium has been deter- mined (1) for solutions of potassium chloride (2) for solutions of potassium nitrate mixed in turn with one of the three above- mentioned acids in such proportions as to produce a solid phase. I n the systems studied the same results are obtained by having present the same ions in equal quantities independently of the manner of their original combination ; thus from solutions containing 20KCl; 10H2S04 or 10K2S04 20HC1 the solid phase in each case had the composition 8KCI 4KHS0,.I n the system potassium chloride sulphuric acid and water the blid portion was only a single phase consisting of potassium chloride when the sulphuric acid was in the proportion 40KC1 5H,SO or less the solubility of the chloride diminishing as the concentration of the acid diminished. On replacing the sulphuric acid in the system by hydrochloric acid the solid phase was a1 ways potas4um chloride the solubility increasing with diminution in concentration of the acid. In the system potassium chloride nitric acid water the solid phase in all cases contained both potassium chloride and nitrate the amount of the former diminishing and of the latter increasing with rise in concentration of the acid.In the case of potassium nitrate sulphuric acid and water theii. 124 ABSTRACTS OF CHEMICAL PAPERS. solid phase consisted solely of potassium nitrate and its solubility seemed but very slightly affected by the concentration of the acid. On replacing the sulphuric acid with nitric acid the nitrate was found to be less soluble but to an extent independent of the acid concentra- tion. I n the system potassium nitrate hydrochloric acid water the solid portion was a single phase potassium nitrate until the acid reached the concentration 20KN0 20HC1. W. G. Heterogeneous Equilibria between Aqueous and Metallic Solutions.11. Interaction of Mixed Salt Solutions and Liquid Amalgams. GEORGE MCPHAIL SMITH (J. Amer. Chem. Soq. 1913 35 39-49. Compare A. 1910 ii 401).-This work was under- taken for the purpose of studying by an independent method the ionisation relations existing in mixtures of salts. By agitating dilute sodium or potassium amalgam with successive portions of a solution of sodium and potassium chlorides or sulphates a mixture is soon obtained i n which a t equilibrium the concentrations of the salts in the mixed solution are identical with those in the original saIt solution; the amalgams are then analysed. The ion fractions of sodium and potassium in experiments in which the salts were present in equivalent quantities have been calculated on t,he assumptions that (1) the reaction takes place according to the equation KHg,+ Na' S NaHgn+ K' + (m - n)Hg and (2) that in the solutions containing a common ion and having a total salt concen- tration 0*2N the relation Na salt/K salt = Na'/K' is approximately true.The results show that the sodium ion fraction increases with the total salt concentration of a solution. In order to explain this phenomenon it is suggested that sodium and potassium chlorides in mixed aqueous solution form the complexes Na(CI-K*Cl) and K(C1.Na-Cl). The formation of the latter complex would lower the value of the sodium ion fractioqand the conclusion is therefore drawn that the preponderating complex is Na(Cl*K*Cl) and t h a t this ionises into Na' and (CI*K*Cl)' ions. E. G. Influence of Temperature on the Velocity of Chemical Reactions.B. SCHVECOV (J. Russ. Phys. Chem. Soc. 1912 44 Yhya. Part 470-474).-Owing to the inconstancy of the ordinary temperature-coeficient of chemical .reactions which is represented by the expression y = (R,/K,)lO/(t - t l ) where Kl and K are the velocity constants a t the temperatures 8,' and t,' respectively Plotnikov (A. 1905 ii 376) suggested the use of the so-called logarithmic tempera- ture-constant given by a = (logK - logK,)/(t - t,). Comparison of these two equations shows that a would be constant only over intervals of temperature for which y gives constant values. Auerbach (A. 1905 ii 57 1) has indeed shown that Plotnikov's logarithmic temperature- constant is a variable magnitude. From theoretical considerations the author regards i t as more likely that constant values will be obtained for the ratio between the velocities of reaction if these are calculated for absolute temperatures having a constant ratio (p).The logarithmic temperature-coefficient 11 would then be given by the equations 7 = KpT/KT 7 = Kp271'/KpT I.GENERAL AND PHYSICAL CHEMISTRY. ii. 125 . . . . q=KpnP/Kpn-lT. The product of all these equations gives qn= KpnTlKI' or if KpnT= Kz KT= Kl pnT- T2 and 5!'= Tl pn= T2/Tl or n = (log T2 - log T,)/log p. The relation between this logarithmic coefficient cofficient y is expressed by the equation Hence 7 = yKKp"T/KT= (K2/Kl) log ppog T - log TI. and the ordinary logq = w . - T,-*1- . log y. 10 log TI2 - Jog T'l Taking p to be 1.1 that is an increase of 10% in the abcolute temperature the values yI 2 and y2 = 3 for the ordinary coefficient at ordinary temperatures give yl = 7 *23 and qz = 23.02 respectively. On the assumption that the latter magnitudes remain constant the corresponding values for y a t different absolute temperatures will be as follows T.q1 7.23. qa 23.02. 100 y,=8'00 y2 = 27 *02 150 3 '98 8.93 200 2 -84 5.22 300 2.00 3 .oo 1000 1-23 1 *38 These numbers are in agreement with the general variation of the ordinary temperature-coefficient which diminishes with rise and rapidly increases with fall of the temperature. I n the particular case of the decomposition of hydrogen iodide the values of y calculated by means of the above equation agree within the limits of experimental error with the observed values ; thus for the temperature-intervals 300-400° 400-500° and 500-600" Bodenstein (A.1899 ii 637) found 1.89 1-64 and 1.53 respectively the calculated values being 1.94 1.64 and 1.49. The Relation between Oxidation Potential and Oxidation Velocity JULIUS G R ~ H (Zditsch. physikal. Chem. 1913 81,695-712. Compare Bodenstein A 1904 ii 717 ; Bogrim A. 1910 ii 282).- The oxidation of acetaldehyde and formic acid was effected by means of chlorine and the velocity constants determined. Considerable diffi- culty was experienced owing t o the reactions being complicated through the action of the chlorine on water ; however by effecting the changes in t h e presence of a known concentration of nitric acid it became possible to bring the secondary reaction into the calculation and obtain a moderately good velocity constant.Other experiments namely the action of iodine on acetaldehyde the oxidation of aldebyde by cerium ammonium nitrate and the oxidation of chloral and bromal with bromine were tried but were found t o be too complicated to furnish results. The velocity of oxidation by T. H. P. chlorine i n the two cases investigated when results for bromine (Zoc. cit.) show that they oxidation potentials of chlorine and bromine Acetaldehyde. Er. c1 Velocity constants ...... 1'205 0'648 Oxidation potelltial ... 1.334 1-639 compared with Bognaris are j u s t opposite to the thus Formic acid. - Br. el. 3280 431 1-334 1.639ii. 126 ABSTRACTS OF CHEMICAL PAPERS. This anomaly can be explained in two ways (1) The chemical resistance is greater in the case of chlorine than in that of bromine.(2) That the course of the reaction is different in the two cases. The first reason is held by the author to be unlikely the second case becomes likely if it is supposed that the halogen forms a n inter- mediate compound with the reducing substance which breaks iip with greater or lesser velocity to form the end products of the reaction. Attempts were made by spectrophotometric measurements t o confirm the second conclusion but they led to no definite results. J. F. S. Velocity of Reaction of Different Bases with Halogen- substituted Acids. 11. HJ. JOHANSSON (Zeitsch. physikal. Chm. 1913 81 573-589. Compare A. 1912,ii 544; Holmberg A. 1912 ii 443; Senter T. 1912 91 460).-The velocity of reaction of the decomposition of monobromosuccinic acid is investigated in neutral and alkaline solution and aloo in the presence of neutral salts.It is shown that two reactions take place t h e first unimolecular in which the hydroxyl ion reacts with the ion of monobromosuccinic acid with the production of the ion of fumaric acid and bromine ion thus ‘O*CO*CHBr*CH,*CO*O’ + OH’= ’O*CO*CH:CH-CO.0‘ + Br’ + H,O and the second a bimolecular reaction in which the ion of monobrowo- succinic acid forms first the ion of propiolactonecarboxylic acid and bromine ion thus ’O*CO*CHBr*CH,-CO*O‘ = ’O*CO-$!H-YH + Br’ and the lactone ion then reacts with the hydroxyl ion giving the ion of malic acid thus 0-co 0--co ’O*CO.VH.YH + OH’ = ‘O*CO*CH(OH)*CH,*CO*O’. The reaction constants of both reactions are determined the former being determined in neutral solution using the sodium potassium barium and strontium salts of the acid.The reaction constant is found to be k=0*002403 and is independent of the nature of the metal ion. The addition of neutral salts causes the constant to increase slightly but this is held t o be due to the superimposing effect of the second reaction. The second reaction constant wits determined in alkaline solution using the hydroxides of sodium potassium barium strontium both with arid without the addition of the nitrate corre- sponding with the hydroxide. This reaction is shown to depend on the nature and concentration of the cation and follows the empirical rule of Holmberg (Zoc. c i t . ) C,=C[M.]a. I t is found that d=&C,= 0.095 C = 0.093 ; Cha = 0,197 and C = 0.196.J. F. S. Theory of EfBorescence. Influence of the Size of the Crystal. CH. BOULANOER and GEOEGES URBAIN (Compt. rend. 1912 155 1612-1 6 14. Compare this vol. ii 34).-Starting from their law log (m - mt) = logcc + A log (0 - t ) the authors deduce the equa- tion log a’ = log a + (1 - A/3) log p‘/p for the relationship between the efflorescence of two crystals of weights p’ and p respectively.GENERAL AND PEYSICAL CHEMISTRY. ii. 127 They have applied this to two crysta.ls of sodium sulphate and consider that the values found and calculated are in agreement within the limits of experimental error. W. G. Kinetics of Chemical Reactions of Combination Deoxida- tion and Oxidation. 11. E. I. ORLOV (J.Rzcss. Phys. Chem. Soc. 19 12 44 1576-1597).-Exarnination of Spitalsky’s results dealing with thz catalytic decomposition of bydrogen peroxide (A 19 11 ii 36) in the light of the considerations previously advanced by the author (A. 1912 ii 243) leads to the following conclusions. The cat,alytic decomposition of hydrogen peroxide by chromic acid furnishes an example of the transformation of a unimoleculnr reaction of the first order into a unimolecular one of the second order. This transformation is conditioned by the action of an intermediate form of the oxide formed during the reaction and entering the sphere of the catalysis only after the peroxide is docomposed to a certain extent. The influence of this intermediate form is complicated by the fact that one form of catalysis is converted into the other not suddenly but gradually; when the intermediate form comes into action the coefficient f appears in the differential equation dx/dt = k( B -fx)(B +fx).This appearance o f f is dependent on the consumption of a certain proportion (one-fifth to one-eighth part of the original amount remains) of the hydrogen peroxide and the consequent difficulty of oxidation of Cr’” to C”; a more rapid process of oxidising Cr20,(0,H,) to Cr,07H is then initiated Cr(OH) being formed as an intermediate product in the change. I t is hence necessary to assume in t h e kinetics of chemical processes the principle of least loss of time; chemical processes strive to take place in such a way that there occurs the least waste of time. The reducing properties of hydrogen peroxide are explained as due to the quadrivalency of oxygen in the molecules of the peroxide and of water.The oxidation of the hydrogen ions is regarded as a com- bination with the molecule H-OiO-H thus H*OiO*H + 2H’ = H . H,:o:O:H - 2 >Oc::.:.. The first stage of this reaction requires 2 - H time but the second proceeds instantaneously. This hypothesis of the quadrivalency of oxygen necessitates the O:H awumptions that aqueous solutions contain the complex H,:O< O:H possessing reducing properties and that the ions Cr,O,” and the molecules H,O give an intermediate oxide of the type - Cr,O,[_~~>OH,] 4 or This oxide is the oxygen-carrier and takes part in the conversion of CrV1 into CrI’I and of the latter into Crvl again. After combina- tion of the hydrogen ions with hydrogen peroxide the remaining groups (Cr,07)d:: with free affinities also combine with H*O:O*H,ii.128 ABSTRACTS OF CHEMICAT PAPERS. giving H*O=O*H which is highly unstable under the conditions of Spitalski’s experiments (Eoc. cit.) and decomposes into Cr2y 2H’ and 0 but is ~omparat~ively stable under the ordinary conditions of room-temperature and absence of vigorous shaking. I f the catalytic decomposition of hydrogen peroxide by means of potassium dichromate proceeds under ordinary conditions the stable compounds \,/ ant3 I are obtained and the decomposition follows the differential equation dx/dt = k(A - x ) ( B + x). This equation is applicable t o reactions of combination. The form dx/dt = Ic(A - z) represents a particular case.K i n e t i c s of Chemical Reactions of Combination Deoxida- tion and Oxidation. E. I. ORLOV (J. RUS. Phys. Chem. SOC. 1912 44 1598-1623 1633-1658).-The considerations advanced in .previous papers (see preceding abstract) are applied t o other reactions. The decomposition of hydrogen peroxide by an iodide in aqueous solution is shown t o be a unimolecular reaction of the second order decomposition by means of potassium dichromate or molecular platinum proceeding siniilarly. ‘V Cr,O H*0=0- H H.O-- O*H 1i CrO H d r 0 ’ ( 3 - 2 0 7 T. H. P. 111 and IV. The mechanism of these changes is discussed. T. H. P. Universal Significance of the EleDi entary Quantum. OTTO SACRUR ( A m . Physik 1913 [iv] 40 67-86. Compare A 1912 ii 145 1151).-By a process of reasoning similar to that adopted in the previous papers equations have been deduced for the energy and entropy of ideal monatomic solid substances and of monatomic gases The reasoning is based on a more precise definition of the (physical) conception of probability and not on the usual assumption of elemen- tary energy quanta.The only quantities occurring in the equations are certtain general constant8 and also the atomic vibration frequency in the case of the solids and the molecular weight in the case of the gases. The values of the “chemical constants,” which determine the chemical behaviour of the gases and the vapour pressures of their condensation products are calculated for helium neon argon krypton xenon aod mercury I n atmospheres this constant C is given by the equation C = - 2.055 + 1.5 log M where M is the molecular weight of tbe gas.It is shown that the calculated vapour pressures of mercury between 0” and 360’ are in fairly good agreement with the observed values when the “constant” for mercury given by this equation is applied in the calculation of the vapour pressure curve. The calculat,ed and observed vapour pressures of argon a t 84’ nbs. are also concordant H. M. D. The ‘‘ Chemical C o n s t a n t s ” of Di- and Tri-atomic Gases. OTTO SACKUR (Ann. PI~ysik 1913 [iv] 40 87-106. Compare preceding nbstract),-On the assumption that the di- and tri-atomic gases haveGENERAL AND PHYSICAL CHEhlIS’L‘RY. ii. 129 the structure assigned to them by Boltzmann formuh are deduced from which the entropy and the ‘‘ chemical constants ” of these gases may be calculated.The values obtained for hydrogen oxygen nitrogen the halogen and halogen acids carbon monoxide nitric oxide water hydrogen sulphide carbon dioxide and sulphur dioxide are recorded. The “ chemical constants ” are applied in the calculation of the vapour-pressure curves of iodine and ice and of the dissociation constants corresponding with the equilibria 2HCl ZZ H + CI 2HBr Hz+Br 2HI Z H,+I BH,O ZZ 2H,+0 2CO,= 2UO + 0 and 2NO From a comparison of the calculated vapour pressures and dissociation constants with experimental data i t is found that the values obtained for the “ chemical constants ” may be regarded in most cases as approximately .correct. The existence of considerable discrepancies between theory and experiment which is found in certain cases for example the dissociation of carbon dioxide and nitric oxide indicates however that the values of the ‘‘ constants ” cannot be regarded as final and that i t will probably be necessary to modify the theory of poiyatornic molecules before the true values can be derived.H. 11. D. N + 0,. Volume and Valency. 31. SEBALDT (Zeiisch. ph ysikal. Clmtz. 1 9 1 3 81 749-753).-8 theoretical paper in which the relationship between valency arid atomic volume and also other properties of the elements is shown to be periodic. In one diagram the logarithms of the atomic volumes are plotted as ordinates the elements being placed on lines parallel to the ordinate axis which represent the eight groups of the periodic system.This arrangement shows clearly the relationship between the electroaffinity and the volume ; atomic magnetism and compressibility are also shown to be functions of the atomic volume. I n another arrangement the elements are placed round a polar co-ordinate ring in order of atomic weight those o€ even valency to the left of the ordinate axis and those of odd valency to the right ; the logarithm of the atomic volume is plotted on the ordinate. This arrangement brings out most of the relationships betweeu the elements very clearly. J. F. S. The Nature of A u x i l i a r y Valencies. 11. Metal Ammonias. FRITZ EPHRAIX (Zeitsch. physikcd. Chern. 1913,19,513-538. Compare A. 1912 ii 546).-The present paper contains further details on ammonia derivatives of the metal salts.It is shown that errors are likely to come into the prevsure measurements of ammine derivatives owing to incomplete drying and absorption of air by the finely divided compounds. Precautions for avoiding these errors are indicatad. The gaseous pressure at a series of temperatures is determined for the hexammine derivatives of the halogen salts of cadmium zinc man- ganese nickel cobalt iron copper calcium and magnesium. It i s found that the ratio lLl/T1 is a constant for a given pair of salts at all pressures where 5” is t h e temperature a t which the two compounds have the same gaseous pressure. Compounds of this type therefore obey the kamsay-Young rule. The value of the factor varies from 0.9138 for Zn12/ZnBr2 to 1.232 for MnI,/AlnCl,. The temperature a tii.130 ABSTRACTS OF CHEMICAL PAPERS. which the dissociation pressure of the various salts is 500 mm. is given and i t is seen t h a t t h e pressure generally decreases as the atomic volume of the central atom increases. The hexammines of zinc iodide cupric bromide and those of the chloride bromide and iodide of cadmium being exceptional. The value 3E is shown to be constant for all the hexammines except those mentioned above and in this con- nexion i t is shown that taking the mean value of JpT= 14.0 it is possible to calculate the atomic volume of the central atom with fair approximation when T is the absolute temperature a t which the dis- sociation pressure is 500 mui. It is found that when the absolute temperatures for pressures of 700 mm. and 200 mm. are taken the ratio is approximately constant (1.085-1.073). Moduli are calculated for the pressure-temperature relationship of I C1 I Br Br C1 and from these it is seen that generally a t a given temperature the tension is greatest for the chlorides and least for the iodides. From calculations from the Nernst equation logp = - Q/(4,571Y’) + 1.75 log T’+ 3.3 i t is shown that the dissociation of the hexammines of the bivalent metals occurs by first splitting off one molecule of ammonia R(X),GNH R(X),5NH3 + NH,. The heats of formation of the various ammines are calculated both from the Nernst formula and the van’t Hoff formula. A series of notes on the preparation of the ammines used in the investigation is given. J. F. S. The Nature of Auxiliary Valencies. 111. The Region of the Existence of Auxiliary Valency Compounds. FRITZ EPHRAIM (Zeitsch. physikul Chenz. 1913 81 539-542. Compare preceding abstract).-The dissociation of the hydrates and ammines is theoretically considered. It is shown that whilst the ammines dissociate by success- ively aplitting off one molecule of ammonia this is not analogous to the hydrates. The reason is the formation of bolutions in the case of the hydrates. I t is concluded that all the possible hydrates exist if only in a labile condition and in solution. It is also shown why the dissociation curves of the ammines show no transition points whilst those of the hydrate do. What are Bases and Acids? DAKIEL VORLBNDER (J. p r . Chem. 19 13 [ii] 8’7 84-91).-Theoretical. New Shaking Apparatus. WILHELM STEINKOPF and HANS WINTERNITZ (Chem. Zeit. 19 13 3’7 4O).-The apparatus resembles a retort stand where the upright is fitted by means of ball-bearings into a heavy cast-iron base. A short horizontal arm is attached to the upright and connected with the ecceotric of a small motor. The usual retort stand clamps may be used for holding water- and hot-air baths and flasks for the distillation of viscous llquids which other- wise have a tendency to bump. The apparatus may also be used for holding burettes for the titration of boiling liquids. On account of the gentle rotating movement imparted t o the contents of the vessels it is not necessary to use stoppers and hence any risk of introducing impurities is avoided. J. F. S. F. B. H. EL H.INORGANIC CHEMISTRY. ii. 131 Shaking Apparatus which can be Exhausted Fitted with an Inner Temperature Regulator. RICHARD KEMPF (Chem. Zeit. 19 13 37 58-59).-A modification of the apparatus previously described (A 1906 ii 433) the principle remaining the same. The method by which the apparatus may be used in invest,igating catalytic reductions with colloidal or finely divided platinum is described. T. S. P. A Simple Experiment Illustrating the Luminosity of Phos- phorus. DOUGLAS F. Twrss (Chem. Jaws 1913 107 16).-A vertical glass tube 2-2& cm. internal diameter and about 120 em. long. is fitted at the lower end with an indiarubber bung carrying a glass tube which is bent upwards so as to be parallel to and of approxi- mately the same height as the wider tube. A solution of phosphorus in olive oil is introduced into the wider tube so as to reach about 6 inches from the top and steady suction is applied at the mouth of this tube by means of a water pump. Air enters through the narrow tube and a beautiful series of bell-shaped phosphorescent air ttubl)les rises through the column of oil. T. s. P.

ISSN:0368-1769    

DOI:10.1039/CA9130405085

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

PHYS IOLOUICAL CHEMISTRY. Phgsiologioal Chemistry i. 119 The Regulation of Neutrality by the Respiratory Centre and its Stimulability in Maintaining the Carbon Dioxide Tension of the Blood. KARL A. HASSELBALCH (Biochem. Zeitech. 19 12 46 403-439).-The conception underlying these investigations is the following The magnitude of the lung ventilation is regulated by the magnitude of the stimulus and the stirnulability of the breath- ing centre. The stimulus is the excess of the hydrogen-ion concentra- tion above normal of the blood. A given magnitude of stimulus will cause a greater ventilation of the lungs the greater the stirnulability of the centre and vice versa. The C of the blood will alter therefore in the inverse ratio to the stirnulability of the centre. This theory was tested in the following way Considerable changes in the C of the urine were brought about on normal individuals by changes in the diet.The magnitude of the changes thus caused were greater than deviations from the normal found in pathological urine. The eEect oE such a change was to cause a change in the tension of the alveolar carbon dioxide in an opposite direction. It was experimentally shown furthermore that the changes in diet did not affect the stimulability of the centre. This fact was ascertained by measuring the effect on the respiration of breathing increased quantities of carbon dioxide. It was further found that the C of the blood (measured under a constant carbon dioxide tension) altered under varying conditions of diet in thei. 120 ABSTRACTS OF CHEBIICAL PAPERS.same direction as the C of the urine. The alveolar carbon dioxide tension appears to alter in such a way that the actual C of arterial blood (measured under the same carbon dioxide tension as exists in the arteries) remains R constant under the varying conditions. The theory is supported by experiments in which the stimulability of the centre was artifically diminished (as for example by morphine) or increased. 8. B. S. Absence of Apncea After Forced Breathing WALTER I\I. BOOTHBY (J. Physiol. 1912 45 328-337).-In some persons forced breathing is not followed by apncea; the loss of carbon dioxide consequent on forced breathing is made up within a few minutes but not so rapidly as when apnaea occurs. This exceptional condition is probably due to a compensating diminution of the circulation through the respiratory centre in consequence of which the gas tensions in the centre are still capable of exciting it.TiT. D. H. The Differences in Composition between Arterial and Venous Blood. HUGO WIENER (Zeitsch. physiol. Chem. 19 12 82 243-265).-The total protein in the blood of the renal vein is less than in that of the carotid artery and femoral vein (dog). Venous blood is relatively rich in globulin but this is not so marked in the blood of the renal vein. In nephritis the reverse obtains. W. D. H. Distribution of Sodium and Potassium in the Animal Organism. P. J. G~RARD (Chem. Zentv. 1912 ii 846-847; from Bull. Sci. pharm. 1912 19 265-283).-1n three successive vene- sections the ratio K Na in rabbit’s blood varied between 0.68 and 0.61.The sodium in contrast to the potassium remained constant deficiences of the former being replaced by sodium withdrawn from the tissues. The ratio was also determined in various marine and land animals and in various secretions. The author when working with mice and frogs was unable to confirm the antagonistic action of sodium salts on the toxic action of potassium salts as demonstrated by Loeb in the case of Fundulus. The toxic action of potassium depends to a large extent on the concentration of the solution employed. S. B. S. The Influence of Nitrogenous Metabolism Products which Occur Naturally in Blood and Urine on the Blood Pressure. E. LOUIS BACKMAN (Chem. Zentr. 1912 ii 624; from Zentr. Physiol. 1912 26 166-169).-Urea in from 2-10% solutions in saline caused a rise of blood-pressure (maximum 26 mm.mercury) when injected into rabbits. Ammonium carbamate in 0.5% solution caused a lasting rise whereas in 0.1% solution it exerted no action. Ammouium carbonate in 0.6% solution caused a lowering of blood- pressure (maximum 38 mm.) but in 0.1% solution a lasting rise. Six % ammonium hippurate caused a transient rise (9 mm.) followed by a lowering. Three % solutions caused a slight rise. Creatine hypoxant hine and sodium urate caused lasting rises. Allantoin inPHYSIOLOGICAL CHEMISTRY. i. 121 2% solution caused a lasting rise (maximum 5 mm.) and in 1% also a rise after a considerable latent period. Urea also exerts an influence on the heart beats. A mixture of 2% urea 0.05% ammonium carb- amate 1% sodium hippurate 1% creatine 0.2% hypoxanthine 0.01% xanthine 0.03% sodium urate causes a large (maximum 46 mm.) and long lasting rise but has small influence on the frequency of the heart beat.The investigations indicate that nitrogenous metabolism products exert an autoregulatory function in the organism and their action explains certain pathological conditions in gout and nephritis. S. B. S . The Part Played by the Suprarenals in the Normal Vascular Reactions of the Body. G. VON ANREP (J. Physiol. 19 12 45 307-31 7).-Stimulation of the splancbnic nerves causes a rise of blood-pressure which occurs in two phases. The second phase is accompanied by constriction of peripheral blood-vessels (even after denervation) and by increased cardiac activity (also after denervation).This second rise is due to discharge of adrenaline into the circulation and is absent after extirpation of- the two suprarenal glands. W. D. H. Local Vascular Reactions and their Interpretation. G. VON ANREP (J. Physiol. 191 2 45 318-327).-The contraction of blood- vessels described by Bayliss as a local reaction of the vessel wall to increased internal pressure is due to the action of adrenaline the secretion of which is increased under the conditions of his experiments. The dilatation of blood-vessels ascribed by Bayliss to lowering of internal pressure is due to the direct action on the vessel walls of asphyxia1 products. W. D. H. Glycolysis. 111. The Influence of Glycine and Boric Acid Anions on the Oxidative Deatruction of Dextrose in the Presence of Phosphates.WALTHER LOB and S. GUTMANN (Biochem. Zeitsch. 1912 46 288-295. Compare A. 1911 ii 504)-It has been already shown that phosphate mixture accelerates the destruction of dextrose by hydrogen peroxide. This is not due to the neutrality of the medium but is specific for phosphates as no acceleration takes place when neutral borate or other mixtures of the same hydrogen-ion concentration are employed. The authors now show that the addition of such a borate mixture to the phosphate mixture exerts no very marked action whereas a similar glycine mixture (prepared according to Sorensen) exerts a marked inhibitory action on the glycolysis. S. B. S. The Significance of Proteolysis in Specific Hmmolysis. KOHBHI OHTA (Biochem. Zeitsch.1912 46 247-252).-An immune serum (sheep’s blood into rabbit) haernolyses the specific blood (of sheep) without any proteoly sis. The Influence of the Hydrogen-ion Concentration on Specific Precipitin Reactions. LEONOR MICHAELIS and HEIN- RICH DAVIDSOHN (Biochem. Zeitsch. 1912 4’7 59-72).-The forma- S. B. S.i. 122 ABSTRACTS OF CHEMICAL PAPERS. tion of specific precipitins and agglutins is within wide limits independent of the hydrogen-ion concentration. This factor only comes into play to any extent when the reacting substances are in very dilute solutions. I n this respect the precipitin reaction differs from the non-speci6c precipitation of colloids as no optimal conditions for precipitin reaction analogous to the isoelectric point could be discovered. These results indicate that there is some specific chemical affinity coming into play and the electric charge of the particles plays only a subordinate part.S. B. S. The Coagulation of Blood. ERNST FULD and ERICH SCHLESINGER (Chenx. Zentr. 1912 ii 1569; from &3&n klin. woc?~ 1912 49 1323-1 327).-Dialysis of the blood against an isosmotic salt solution deprives the plasma of its power of coagulating the crystalloid which is removed being the calcium salt of fibrin. The absence of this salt also hinders the formation of another necessary element i n coagula- tion namely the fibrin ferment for the development of which cytothrombin from the cells and plasmothrombin from the plasma are also necessary. The injection of cytothrombin into a vein a t once causes coagulation owing to the formation of this ferment neothrombin.The smallest amounts of enzymes would soon set up fermentation processes which would hinder the circulation were there not also present substances which prevent coagulation. Fibrin may be redissolved by fi brinolysis which is partly due to salt action and also to an enzymatic agent thrombase. J. C W. The Dissociation of Oxyhzemoglobin in Human Blood During Partial Carbon Monoxide Poisoning. J. B. S. HALDANE (Proc. physiol. Soc. 19 12 xxii-xxiv ; J. Physiol. 45).-The presence of carboxyhamoglobin in the blood delays the dissociation of the oxyhsmoglobin present so that even though the amount of oxy- hsmoglobin may be half the normal (a3 it may also be in a man with anaemia without grave results) the combination of the remaining half of the haemoglobin with carbon monoxide produces a serious state of affairs.W. D. H. Blood-relationships of Animals as Displayed in the Com- position of the Serum-proteins. I. A Comparison of the Serum of the Horse Rabbit Rat and Ox in the Normal and Fasting Condition. T. BRAILSFORD ROBERTSON (J. Biol. Chsm. 1912 13 325-340).-The amounts of insoluble globulin total globulin and total albumin in serum were determined by the author's refractomctric method. In the rabbit the results agree with those arrived at by others in other ways. Horse serum yields not more than 40% of the total albumin in crystalline form. I n fully fed animals the three groups of proteins vary greatly ; but the average values are charact,eristic of the species.I n fasting the total protein is also highly variable; in starvation it rises. I n rabbit ox and horse inanition increases the relative amount of albumin whereas in r a t and dog the reveree obtains. W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 123 The Diastatic Action of Human Saliva. GOXCHI HIRATA (Biochem. Zeitsch. 191 2 47 167-183).-The diastatic value of saliva (as determined by Wohlgemuth’s method) remains practically constant throughout the day arid is not influenced by the time of meals or the diet. The value is also independent of the amount of saliva secreted and of the age or sex of the individual. It has the same value in certain pathological cases investigated as in normal cases and appears to be uninfluenced by the hzemoglobin content of the blood. In the case OF the Japanese it varies between Dii 160 and 640 in different individuals.S. B. S. Formation of Hydrochloric Acid in the Stomach. J. L~PEZ- SU~REZ (Biochem. Zeitsch. 1912 46 490-499).-The author discusses the evidence as to the acid-secreting function of the oxyntic cells of the stomach and considers that this has not been demonstrated. By direct chemical analysis he shows that the mucous membrane of the fundus contains more chlorine than that of the pylorus. He. shows furthermore by Macallurn’s histological method that the ordinary cells contain more chlorine than the oxyntic cells. S. B. S. The Fat-hydrolysing Ferment in Gastric Juice and its Esti- mation. HEINRICH DAVIDSOHN (Chem. Zentr. 19 12 ii 1 378-1 379 ; from Bed. kZin. Woch. 1912 49 1132-1134).-Rona and Michaelis’s drop method for following the course of butyrin hydrolysis (A.1911 ii 303) has been applied to a large number of gastric juices and a widely varying enzyme action has been observed. Directions are given whereby the method may be applied to the estimation of this hydrolytic enzyme J. C. W. Tryptic Digestion of Cynoscion regalis. GEORGE F. WHITE and ADRIAN THOMAS (J. Biol. Chem. 1912 13 lll-l16).-The flesh of Cynoscion vegalis an American fish known commonly as the weak- fish or squeteague was subjected to tryptic digestion in vitro and the amino-acids in the digest were determined by Sorensen’s formaldehyde method. The results were regular and in accord with those obtained by van Slyke’s nitrous acid method for estimating amino-nitrogen. The relatively low rate at which the protein besomes soluble agrees with the results of metabolism experiments. Very low cleavage products are formed as soon as the protein passes into solution the average size of the peptides being 2-02 after half an hour’s digestion; but there is a very stable nitrogen complex which is not attacked by trypsin.W. D. H. Animal Calorimetry. V. The Influence of the Ingestion of Amino-acids on Metabolism. GRAHAM LUSK and J. A. RICHE (J. Biol. Chem. 1912 13 155-184. Compare A. 1912 ii 1189).- After giving meat the metabolism of the dog during the second hour rose almost to a maximum and the respiratory quotient was 0.9; it therefore appears that carbohydrate and not additional protein is oxidised during this period. After the ingestion of amino-acids and especially of glycine there is a similar increase in the metabolism ;i.124 ABSTRACTS OF CHEMICAL PAPERS. this can have nothing to do with deamidation or urea-formation but is attributed to a direct stimulating action of the amino-acids on the cells of the body. A mixture of five amino-acids produced a more rapid metabolism than when given singly and more than meat con- taining the same amount of nitrogen. Animal Calorimetry. VI. The Influence of Mixtures of Food-stuffs on MeOabolism. GRAHAM LUSH and J. A. RICHE (J. Bid. Chem. 1912 13 185-208).-Further details are given of the effect of diet on metabolism and the conception of the process put forward is that to a basal metabolism (at rest) there may be added meta- bolism due to plethora that is an increased supply of fats and carbo- hydrates or the superadded metabolism may be due to the stimulus of amino-acids.When these two are added to each other there is no summation of effects. W. D. H. W. D. H. Fatty Acid Metabolism in the Liver. 11. The Relation of the Fatty Acids in the Food of the Plaice to those in their Livers and Myotomes. V. H. MOTTRAH (J. Physiol. 1912 45 363-369).-The fatty acids of the mussel have a high iodine value which falls between that of the fatty acids of the liver and those of the lozyotomes of the plaice. Such fatty acids are therefore not character- istic of the vertebrates and they occur before the appearance of a true liver Their formation is not exclusively a liver function. The experiments on the feeding of plaice on mussels cannot however be considered a refutation of Leathes’ theory of the deaaturating influence of the liver in fatty acid metabolism.The BiochemicalSynthesisof Fatty AcidsfromCarbohydrates. IDA SMEDLEY (Proc. phyvsiol. Xoc. 191 2 xxv-xxvii’; J. Physiol. 45).-Various hypotheses to explain the conversion of carbohydrate into fat are discussed. Although pyruvic and other a-keto-acids have not yet been detected in the tissues the theory is favoured that pyruvic acid is an intermediate product. Maintenance Experiments with Isolated Proteins. THOMAS B. OSBORNE LAFAYETTE B. MENDEL and EDNA L. FERRY (J. Biol. Chem. 1912,13 233-276).-Details are given and general questions discussed on the nutrition of white rats for long periods on foods con- taining a single purified protein.With the precautions described this is possible and they can be so maintained for periods equal to their adult lives. This is true for gliadin edestin and casein which are proteins of very different composition. As glycine is absent from casein lysine and glycine from gliadin and phosphoproteins from gliadin and edestin and purines throughout are practically absent the synthetic activities of fhe animal body are clearly brought to mind. The possibilities of transmutation of amino-acids must be con sidered and the view that proteins as near as possible in constitution to those in an animal’s body are most nutritious must be regarded with caution Long-continued experiments are necessary in all such work. Changes in the nitrogen balance over short periods may be entirely deceptive.W. D. H. W. D. H. W. D. H.PHYSIOLOCIICAL CHEMISTRY. i. 125 The Influence of Lecithin on the Nitrogen and Phosphorus Balance. ALDO PATTA (Chem. Zentr. 1912 ii 939-940 ; from Arch. Parm. sperim. 1912 13 515-528).-Small quantities of lecithin (0.05 to 0.10 gram) administered subcutaneously to a dog scarcely altered the nitrogen and phosphorus metabolism when there was a small deficit in these substances. Larger doses (0-5 t o 0.75 gram) caused a sparing action which was small when the nitrogen and phosphorus ingested were insufficient but was marked when these elements were in excess of the body needs The sparing action of the phosphorus was larger than the amount injected as lecithin and the fdct that the injection caused an increase of the nitrogen in the urine at the expense of the fecal nitrogen indicates that the lecithin Retention of Nitrogen after Feeding on Ammonium Salts.E. GRAFE (Zeitsch. phyrrioz. Chem. 1912 82 347-376).-The present experiments on pigs confirm those previously recorded on dogs (A. 1912 ii 659). Administration of ammonium salts mixed with abundance of carbohydrate-leads to nitrogenous equilibrium or even a retention of nitrogen. The Creatine Metabolism of the Growing Pig. ELMER V. MCCOLLUM and H. STEENBOCK (J. Biol. Chem. 1912 13 209-218).- In some animals (for instance the rabbit) fasting causes the appear- ance of creatine in the urine. I n dogs depletion of the liver of glycogen leads to the same result and Mendel and Rose (A. 1911 ii 1002 1007) consider that there is a definite relationship between creatine and carbohydrate metabolism ; they further think that creatine is not a result of exogenous protein metabolism but only of endogenous metabolism.The present experiments on pigs were planned to investigate this question but it was found that in this animal fasting does not lead to the appearance of creatine in the urine; this is explained in differences of metabolic habit. When a rabbit fasts the total nitrogen excreted rises indicating an increase of protein katabolism. This does not happen in the dog or only slightly and not a t all in the pig. The pig is an efficient fat-storer RO he might be expected to use it readily for energy production. On an uniform diet considerable irregularities in the excretion of creatine occur and the idea that creatine is destroyed by enzymes is supported. Data are also given which leave but little doubt that creatine may arise from exogenous as well as from endogenous protein metabolism and that its source or one of its sources is arginine is regarded as probable.W. D. H. The Behaviour of Some Hydantoin Derivatives in Meta- bolism. I. Hydantoin and Ethyl Hydantoate. HOWARD €3. LEWIS (J. Biol. Chem. 1912 13 347-356).-After hydantoin is given an insoluble benzylidenehydantoin can be recovered from the urine which accounts for only part of the hydantoin administered. No toxic effects follow which is against Lusini's theory of the toxicity of -HN ,,>c:o groups. stimulates the degradation of the injested proteins. s. B. s. W. D. H.i.126 ABSTRACTS OF CHEMICAL PAPERS. Hydsntoic acid of which hydantoin is the cyclic anhydride is not The hydan- W. D. H. destroyed in metabolism wben given as the ethyl ester. toin nucleus is not destroyed in the body of cat rabbit or dog. Purine Metabolism. X. The Property of the Organism to Destroy or Form by Oxidative Processes Uric Acid in Animals Capable of P r o d u c i n g this Acid Synthetically. V~TTORIO SCAFFIDI (Biochem. Zeitsch 191 2 47 215-225).-1n experiments carried out with ducks it was found that animals which normally synthesise uric acid can also destroy this acid after ingestion when added to a normal diet to the extent of 33-59% of the total. They can also degrade guanine to xanthine and into still simpler complexes which no longer contain n purine group. From the xanthine thus formed a certain amount of uric acid can be formed by an oxidative process.Ingestion of nucleic acid also causes a slight increase in the amount of purine bases execreted and a considerable increEse in the uric acid the origin of which is ascribed t'o the protein groups. S. B. S. The Metabolism of Endogenous and Exogenous Purines in the Monkey. ANDREW HUNTER and MAURICE H. GIVENS (J. BioZ. Chem. 1913 13 371-388).-1n the urine of the guenon monkey (Cercopithecus) allantoin accounts for 75% of the nitrogen arising from the katabolism of endogenous purines The rest appears princi- pally as purine bases uric acid being practically absent on a purine- free diet. Allantoin is a true end-product. When purines are given allantoin is increased and uric acid appears as an intermediate product.Only 12-54% of total purine intake is accounted for. The deficit is probably due to decomposition prior to absorption. There is no approach in this monkey to the human type of nuclein metabolism W. D. H. OTTO FOLIN and HARRY LYMAN (J. BioZ. Chem. 1912 13 389-391).-A reply to London's recent criticisms (A 1912 ii 1189). Behaviour of I n t e s t i n a l Wall After a Prolonged Period of Functional Inactivity. PAOLO MARICONDA (Zeitsch. pliysiol. Chem. 1912 82 406-412).-After making a Vella fistula a dog was kept for several months so that no local stimulus had reached the intestine. The amount of fluid secreted by the intestinal wall was now very small and the amount of the various enzymes was also reduced although not to the same extent.The results are opposed to the theory that the secretory function of the intestine is due to chemical stimuli carried to it by the blood. Sucrose introduced into the fistula passes the wall without being changed ; the selective absorptive power of the intestinal wall has been destroyed. Absorption of Cholic Acid in the Dog's Intestine. BAREND C. P. JANSEN (Zeitsch. physiol. Chem. 1912 82 342-345).- Experiments with intestinal loops showed that in all probability cholic acid is absorbed unchanged by the intestinal wall. Absorption from the Stomach. W. D. H. E. F. A. W. D. H.PHYSIOLOGICAL CHEMISTRY i. 127 The Fate of Deeply-degraded Proteins in the Intestine. PETER RONA (Biochem. Zeitsch. 1912 46 307-316).-Experiments were carried out with the object of ascertaining whether any protein synthesis takes place in the small intestine.Pieces of surviving intestine were placed in Tyrode’s solution and various digestion pro- ducts or mixtures of amino-acids were placed either in the solution in which the intestine was kept or introduced directly into the lumen. The experiments were carried out a t 3 8 O and during this time the intestine maintained its peristaltic movements. The amino-nitrogen was estimated bot,h befoie and after the experiment. There was generally an increase in this nitrogen a t the end due probably t o amino-substances given up by the intestine itself. The amount of increase was of tho same order as that in which the experiments were carried out in Tyrode’s solution without any addition.No evidence was obtained therefore of any synthetical process affecting amino- derivatives in the intestine S. B. S. The Investigation of the Permeability and Antagonistic Action of Electrolytes by means of a New Method. JACQUES LOEB (Biochem. Zeitsch. 1912 47 127-166).-1t has been already repeatedly shown by the author in experiments on Eicndulus eggs that treatment with a solution of one salt alone (for example sodium chloride) alters the permeability of the membrane and that this alteration can be inhibited iny the addition of certain quantities of another salt (calcium chloride). Salt solutiong of such composition that the antagonistic action of the salts is at its maximum are designated equilibrated solutioas. If fertilised eggs of Pundulus be brought into a solution of 50 C.C.3M-sodium chloride + 2 C.C. 10/8M- calcium chloride they will remain on the surface for three days after which the membrane will be rendered permeable by the hypertonic solution; the eggs will then begin to shrink and owing to the passage outwards of water the specific gravity will increase and they will then siDk in the solution. If brought into a solution of 3M- sodium chloride alone without presence of calcium chloride they will sink within three to four hours and the membrane rapidly becomes permeable. Similar phenomena are observed when tho eggs are brought into other corresponding solutions containing only salts. By the method of experiment the various earlier investigations of the author have been confirmed. The changes in the permeability appear t o be due chiefly to the proteins and there is an antagonism between the action of acids and the corresponding salts which is characteristic of proteins as Pauli and his pupils have shown.Furhhermore the antagonism in the system H,SO,-Na2S0 is more complete than in the system HC1-NaCl. The antagonistic action of these acids and salts on the RunduEus egg as studied by the method described above confirms the theory as t o the alterations of the proteins by salts. The qunntitative study of the action of alcohols however indicates that these alter the permeability by the action on the fatty constituents of the membrane. Provided t h a t the action has not gone too far the change of permeability produced by salts is a reversible one and eggs which have been a short time in a toxici.128 ABSTRACTS OF CHEMICAL PAPERS. solution will recover their normal properties when brought into an equilibrated solution. Eggs will also remain alive in distilled water and fish will develop but they will not recover their impermeability. I f such eggs are brought into a solution of 50 C.C. 3M-calcium chloride + 2 cx. 10/8M-calcium chloride they sink in a few hours. 8. B. 5. The Influence of Neutral Salts on Ferment Action. 11. EMIL STABKENSTEIN ( Biochem. Zeitsch. 19 12 47 300-31 9. Compare A. 1910 i 449).-The number of salt molecules necessary to activate t o the maximum extetlt an inactive diastase preparation is pro- portional to the amount of ferment. This fact suggests a process for the determination of the quantity of ferment in a given organ.For this purpose the organ is dried a 5% suspension of the dried powder is made up and dialysod. The amount of salt which produces the maximum diastatic effect with this Auid can then be ascertained. By this means the diastase content in various animal organs was investigated. Organs of warm-blooded animals contain more ferment than those of the cold-blooded The ferments obtained from both kinds of animals work more rapidly at higher temperatures. 8. B. S. Lipoids. XVI. The Cholesterol Content of Different Parts of the Brain. SIEGMUND FRANKEL P. KIRSCHBAUM and KURT LINNERT (Biochem. Zeitsch. 1912 46 253-256).-The cholesterol was estimated as its digitonin derivative. I n a human brain 4.03% was found in the pons and medulla oblongata 2.47% in the white matter of the cerebrum and 1.31% in the cerebellum.S. B. S. The Colloidal Structure of Nerve Cells and the Changes which they Undergo. G. MARINESCO (Zeitsch. Chem. Ind. Rolloide 1912 11 209-225).-The ultra-microscopic structure of nerve cells is described and interpreted on the assumption that the cell constituents are of colloidal character. The structural changes which are observed when the nerve cells are subjected to the action of acids alkali salts and various other substances such as ethyl alcohol carbnmide glycerol sucrose chloral hydrate and antipyrine are also described in detail. The results of these ultra-microscopic observations seem to show that the particular structures] which are presented by the nerve cells after treatment by the usual fixing and colouring methods are essen- tially determined by the nature of the histological processes employed.The fixing reagents have in general a coagulating effect on the colloidal cell constituents and the observed facts agree with the view that the protoplasm is a negative colloid. Chemical and Biochemical Investigations on the Nervous System under Normal and Pathological Conditions. IV. The Chemical Composition of the Brain in Progressive Paralysis. DOMENICO CARBONE and GIACOMO PIGIHINI (Biochem. Zeitxh. 1912 46 450-469).-The analyses of brains taken from H. M. D.PHYSIOLOGICAL CHEMISTRY. n. 129 individuals who have suffered from progressive paralysis and Dementia praecox paraxoica were compared with those obtained from mentitlly normal individuals.Whereas normal brains contain about 23% of dry substance those from mentally afflicted (five cases) varied between 17 and 2loA. Against a normal value of 20% the acetone extracts of the abnormal brains varied between 22.87% and 31.327;. The light petroleum extracts varied between 11.23% and 23.14% as compared with the amount from normal brains of 27.84%. The cholesterol varied between 13.9 and 24*2% and the other extractives between 4.5 and 11.84% as compared with the normal values of 10.96 and 9.64%. Full details as to analytical methods are described by the authors. S. B. S. Broncho-dilator Nerves. WALTER E. DIXON and FRED RANSOM (J. Physiol. 1912 45 413-428).-The broncho-dilator nerves are of sympathetic origin. Adrenaline given to an animal showing bronchial tonus causes active temporary dilatation ; atropine causes passive permanent dilatation.W. D. H. The Influence of Inorganic Salts on the Perfused Heart. W. BURRIDUE (Quart. J. e z p t . Physiol. 1912 5 347-372).-Potass- ium salts give rise to two types of contracrion in cardiac muscle (frog) which are termed " tonic contraction " and " contraction effect.'' Some salts produce one others the other effect but all temporarily abolish rhythmical activity and may produce " heart block " if perfused at high pressure. The effects are mainly explained by considering that these salts displace calcium salts and the various calcium salts are displaced at varying rates. Seasonal variations noted are explained as due to changes in the balance between calcium and potassium salts in the heart muscle; temperature may also be a factor.W. D. H. Physiology and Pharmacology of the Cardiac Vagus. I. The Influence of Chloral Hydrate on the Result of Vagus Stimulation. OTTO LOEWI (Arch. expt. Path. Pharrn. 1923 70 323-342).-Intravenous injection of chloral hydrate in small doses has no effect on blood pressure and heart rate but almost completely annuls the return of the heart-beat during vagus stimulation. Large doses abolish vagus excitability. Camphor has also no effect on blood-pressure or pulse rate but influences vagus stimulation in a similar way. The action of pilocarpine and muscarine is similarly weakened. W. D. H. Physiology and Pathology of the Cardiac Vagus. 11. The Importance of Calcium for Vagus Action.OTTO LOEWI (Arch. ex$ Path. €'harm. 1912 70 343-350).-Partial removal of calcium by small amounts of oxslate increases the excitability towards electrical stimuli of various nerves; the least affected is the pelvic nerve but the chorda tympani and especially the vagus are pro- foundly affected. This is not inhibited by calcium. The action of musca,rine on the frog's heart occurs after it is rendered poor in calcium VOL. CIV. i. ki. 130 ABSTRACTS OF CHEMICAL PAPERS or free from calcium. muscarine in mammals and frogs is not influenced by calcium. The paralysis of the vagus by pilocarpine or W. D. H. Physiology and Pharmacology of the Cardiac Vagus. 111. Vagus Excitability and Vagus Poisons. OTTO LOEWI (Arch. expt. Path. Pharm. 1912 70 351-368).-1n very small doses muscarine (and pilocarpine) increases vagus excitability in the frog.I n vagus paralysis produced by these drugs there exists neither in frog nor rabbit any automatic ventricular action. The effect of prolonged electrical stimulation of the nerve is either increased by muscarine or unaffected by it according to the duration of the stimulation or the dose of the poison. Similarly the pilocarpine effect can be superposed on the muscarine effect or vice versa. Yhysostig- mine does not sensibilise the muscarine or pilocarpine action. The action of pilocarpine and muscarine is considered to be on the myoneural junction W. D. H. The Behaviour of Acetic Acid in the Artiflcial Perfusion of the Liver. ADAM LOEB (Biochem. Zeitsch. 1912 47 118-126). -Various results obtained by Embden and his school are recapitulated and reasons are given as to why acetic acid might be expected as a normal degradation product of fats carbohydrates and proteins especially through the intermediation of pyruvic acid.As no evidence could be obtained of the formation of acetic acid when pyruvic acid was added to blood in a perfusion experiment the effect of adding the former acid itself to the blood was investigated. It was found that during perfusion a very marked disappearance of this acid took place. It was also found without exception in ten experiments that the addition of acetic acid to the perfusion of blood caused a marked increase in the formation of acetoacetic acid. The mechanism of this reaction is discussed and it is provisionally suggested that the degrada- tion of acetoacetic into acetic acid is a reversible process CH,*CO*CH,*CO,H 2CH3-C0,H and for this reason the acetic acid may inhibit the degradation of the acetoacetic acid normally formed to simpler products.S. B. S. The Fate of Glgoxylic Acid in the Animal Body. GEORG HAAS (Biochem. Zeitsch. 1912 46 296-306).-On incubation of minced liver of various animals with glyoxylic acid this substance partly disappeared but no definite degradation products were isolated. Its perfusion through rabbit’s liver gave rise to formic acid and this acid could also be isolated in the urine of a dog which had received glyoxylic acid per 08. S. B. S. The Destruction of Alkaloids by the Body Tissuee. A. J. CLARK (Quart. J. expt. Physiol. 1912 5 385-398).-The liver of frog and rabbit possesses the power of destroying atropine ; this persists after the cells are destroyed and is due to a soluble subatance resembling an enzyme in its action.The heart and kidneys of the frog and thePHYSlOLOGICAL CHEMISTRY. i. 131 blood of the rabbit have the same power in a less degree but all the other tissues are destitute of the power. None of the tissues in cat rat and dog has the power and the minimal lethal dose of atropine is highest in those animals the livers of which can destroy it. W. D. H. The Distribution of Nitrogen in Autolysis with Special Reference to Deaminisations. GERTRUDE D. BOSTOCK (Bio-Chem. J. 191 2 6 388-415).-The following nitrogen fractions in the autolysis products of liver were determined ammonia amide nitrogen and amino-acid nitrogen.It was necessary to ascertain these factors in order to determine the fate of ammonium salts and amino-acids when digested with liver tissue. In fresh liver the soluble nitrogen fraction is characterised by its low ammonia and amino-nitrogen content. The latter however increases after forty-eight hours’ incubation at the expense of the undetermined nitrogen fraction. The rate of autolysis reaches its maximum within this period. Acids stimulate and alkalis depress the autolysis rate and the distribution of nitrogen differs under these two conditions. Acids cause a lower and alkalis a higher percentage of ammonia and undetermined nitrogen fractions than in the control autolyses without addition of either acid or alkali. The reverse is the case with regard to the amide or amino-acid nitrogen. Putrefactive organisms cause a higher percentage of ammonia and undetermined nitrogen. No evidence could be obtained of the formation of amide nitrogen from ammonium sulphate or lactate when digested with liver pulp.There is also no evidence of liberation OF ammonia from glycine. I n view of the formation of ammonia by putrefactive organisms any statements as to the liberation of this substance from amino-acids when digested with tissues must be received with caution S. B. S. The Permeability of the Kidneys to Sugar a f t e r Repeated Injections of Adrenaline. ARTUR VON KONSCHEGG (Arch. expt. Path. Pharm. 1912,70 31 1-332).-Diuresis which followa the injec- tion of adrenaline is independent of glycosuria.After salt diuresis is produced i t is not possible to produce glycosuria by such injections; the blood contains no excess of sugar but the kidneys themselves contain more than normal. Inhibition of glycosuria is not brought about by the kidneys being unable to take up sugar from the blood. W. D. H. The Amount of Silicic Acid in Human Thyroid Glands. HUGO SCHULZ (Biochern. Zeitsch. 1912 46 376-392).-The mean content of the normal glands from t h e neighbourhood of Greifswald was 0.0084% and that of pathological glands from the same district 0.0175%. The pathological glands from Zurich on the other hand contained as much as 0.0434%. The author nevertheless giyes reasons for not believing that goitre is due to water containing silicic acid and he failed to produce the disease experimentally in animals which had received over long periods water containing relatively large quantities of the acid.S. B. 8. k 2i. 132 ABSTRACTS OF CHEMICAL PAPERS. The Creatine-splitting Enzyme of the Parathyroid8 and the Suprarenals. ALBERT HOLMES ROWE (Arner. J. Physiol. 1912 31 169).-A creatine-splitting enzyme is present in the thyro- parathyroid tissue; this confirms the results of Gottlieb and Stau- gassinger. A similar enzyme is found i n suprarenal extract. There is no evidence that either the parathyroids or the suprarenals contain a creatine-splitting enzyme which can be activated by the other. W. D. H. The Chemistry of Normal and Eclamptic Placenta. L. MOHR and W. HEIMANN (Biochem. Zeitsch. 19 12 46 367-373).-Estima- tions were made of the water content total phosphoric acid and nitrogen ether soluble substances cholesterol ueutral fat and diastearyllecithin.The last-named was appreciably larger in normal placenta than in cases of eclampsia. There was no marked difference in the other factors. S. B. S. The Physico-chemical Basis of a Theory of Muscular Contraction (Zuntz’s Theory). WILLIAM N. BERG (Pjiiger’s Archie. 1912 149 195-220. Compare A. 1912 ii 1077).-A critical and antagonistic discussion of Zuntz’s theory; the main point is that lymph contains practically no carbon dioxide in the simple gaseous condition and that when gases are dissolved in water they behave differently from substances in true solution and with the exception of hydrogen chloride and ammonia exert no osmotic pressure. The carbon dioxide which is formed by muscular activity bas therefore no osmotic pressure.W. D. H. The Anaphylactic Reaction of Plain Muscle in the Guinea Pig. HENRY H. DALE (Proc. physioi. Soc. 1912 xxvii-xxix; J. Physiol. 45).-Experirnents on the plain muscle (uterus) of the guinea pig sensitised to horse-serum and other proteins ; it reacts in response to minute doses (one in a million) of the specific antigen ; after response it is completely desensitised ; it can be re-sensitised by soaking in the serum of sensitised guinea pigs. The time relations of the reaction exclude the production of a poison by parenteral digestion. The antigen acts on the sensitised muscle like a stimulant drug the pecaliar feature being that the ‘‘ receptive or anti-substance ” is de- tachable. There is much evidence in favour of the view that the anaphylactic anti-substance is identical with precipitin.Synthesis of Lecithin in the Hen and the Character of t h e Lecithins Produced. ELMERV. MCCOLLUM J. G. HALPIN and A. H. DRESCHER (J. Biol. Chem. 1912 13 219-224. Compare A 1912 ii 368).-Further experiments are given to show that hens fed on a diet free from lipoids produce eggs which contain lecithin or lecithins. These differ in the nature of their fattv acid radicles. and variation W. D. H. may be produced by the nature of thedlipoids of the diet. W. D. H. Red Golouring Matter of Boiled Grabs. EUG~NE GRANDNOUGIN iChm. Zeit. 1912 36 1377-1378).-The change of colour observedPHYSIOLOCIICAL CHEMISTRY. i 133 when crab-shells are boiled has been attributed by Kornfeld to the formation of alizarin-red which depends on the presence of alizarin and aluminium oxide in the unboiled shell.The author points out that the presence of anthraquinone in the normal organism bas not previously been observed He also finds tbat the colouring-matter of crab- and lobster-sbell unlike alizarin-red is soluble in alcohol or ether and is very sensitive to light. When dis- solved in alcohol it shows characteristic absorption bands in the green portion of the spectrum which differ completely from the bands given by alizarin. Finally the presence of compounds of aluminium in the shell could not be detected with certainty. The exact nature of the colouring matter has not been determined It possesses no dyeing power.but the presence of anthraquinone dirivatives is extremely improbable. H. W. The Bio-chemistry of Termites. The Chemical Composition of the Faecal Stalactites of Entermes monoceros. KONRAD SCHUBEL (Arch. expt. Path. Pharm. 1912,70,303-310).-The tree ant of Ceylon protects its nest by so-called stalactites and it has been surmised that these contain cantharidin or some similar poison. The present work shows that the material consists of an organic non-toxic substance with a small amount of inorganic salts. The ash has the following percentage composition SiO 45.2; P,O 1.09; Fe,O + Al,O 23.5 ; Mn304 1.05 ; CaO 14.25 ; MgO 1.5 and K,O +Na,O 13.3. By distillation in a vacuum it was proved that the faecal matter con- tains preformed an olefine probably C,,H70 m.p. 75". These animals live almost exclusively on flies and a l g a W. D. H. Metabolism Studies on the Cold-blooded Animals. I. The Urine of the Fish. W. DENIS (J. Biol. Chem. 1912 13 225-232). -The urine of the dog-fish is clear odourless and almost colourless ; i t is acid to litmus It darkens and becomes cloudy when kept. It gives the murexide reaction and contains creatinino but not creatine. The following is the average composition expressed in grams per litre total nitrogeq 4.2 ; urea nitrogen 3*4 ; ammonia nitrogen 0.3 ; chlorides (as NaCl) 12.8 ; phosphates (as P,O,) 4.5 ; total sulphur (as SO,) 7.1 and total sdphates (as SO,) 3.4. The goose' fish (Lophius piscatorius) is the only teleost so far investigated; in general appearance and reaction t'he urine resembles that of the dog- fish ; uric acid creatine and creatinine were absent.The one specimen examined contained in milligrams per litre total nitrogen 400 ; urea nitrogen 248 and ammonia nitrogen 2. W. D. H. Behaviour of Alicyclic Gompounds in Ooupling with Glycu- ronic Acid in the Organism. JUHO HXMALAINEN (Chem. Zentr. 1912 ii 854-856; from Sknnd. Amh. Physiol. 1912 27 141-226). -A number of terpenes and allied compounds dissolved in olive oil were fed to rabbits. The urine produced was collected and the coupled glycuronic acids formed were either isolated or the products of their hydrolysis by acids were examined.i. 134 ARSTRACTS OF CHEMICAL PAPERS. Menthene in this way gave rise to a product which on hydrolysis yielded a hydrocai*bon C1oHIG b.p. 178-180' that on hydration gave a dihydric alcohol C,,H,,O m. p. 55-59' which may be p-menthan- 3 4-diol. Dihydrocnrveol in the same way yielded a menthadiene CI0Hl6 b. p. 179-181' which on oxidation gave dihydrocarvone and ou hydration furnished p-menthan-2 8-diol. Terpin yielded a mentha- diene b. p. 178-181' which gave terpin hydrate and terpineol on hydration and terpenylic acid on oxidation with chromic acid. Menthone before coupling with glycuronic acid appears to be oxidised t o A4-menthen-3-one since the latter is produced on hydro- lysis of the coupled product. Thujone is apparently first converted in the organism into p-menthnn- 2-one-4-01 by addition of 1 mol. of water. On hydrolysis the coupled product yields carvenone whilst oxidhtion with sodium hypobromite gives o-dimethyllzeviilic acid.Thujyl alcohol under like conditions wems to be converted into p-menthan-2 4-dio1 since the latter is formed on hydrolysis of the coupled glycuronic acid produced in t b e organism Sabinol yields sabinolglycuronic acid C16H2,07 m. p. 82-S3' as a colourless glassy mass giving crystalline sodium and strychnine ealts. The latter has m. p. 196-197' [a] - 39.66' in alcohol and crystallises with 2H20 in needles from hot water. Sabinene yields a coupled product which on hydrolysis with 5% sulphuric acid gives a gelatinous substance that on hydrolysis with stronger acid yields Al-menthenone (1). Pinene and nopinene appear to undergo oxidation before coupling since the coupled product yields p-cymene on hydrolysis. Camphaoe i s also oxidised in the organism and yields a mixture of d- and 1- Dorneolglycuronic acids C,,H,,07 m.p. 163-1 65O [a] - 56.9 lo as a colourless crystalline mass. 1-Fenchyl alcohol furnishes fenchylylycuronic acid C1GH260,,H20 in. p. 1 24-1 26' [a] - 63-07' crystallising from acetone and yielding well crgstdlised salm. 1-is0 -3'c;nchylglycuronic acid m. p. 140-150' [a]$' - S1*02' is amorphous. Camphenilolylycuronic acid C,,H2,07 m. p. 150-153° is a colour- less mass obtained by the use of either camphenilol or cam- phenjlone the latter apparently undergoing initial reduction in the organism. a-Santenol gives rise to a-santenolglycuronic acid C1,H2,O7 H,O mi. p 160-161' [a32 - 56*6O a colourless mass which yields crystal- line salts. p-Santenol also couples unchanged f urnishing p-santenol- glycurooic acid which mas not isoIated but was found t o yield santene on acid hydrolysis.Santenone is first oxidised to santenonol C9H14O2 m. p. 92-93' crystallising in colourless leaflets giving a crystalline semicarbazone m. p. 222-223' and yielding srtntenic acid on oxidation. .)'ctrrterconolglycuro.nic acid C,,Hz20 yields a crystalline strychnine salt C,,~H440,0N,,2H,0 m. p. 171-1772" and gives santenonol on hydro- Camphene hydrate couples unchanged with glycuronic acid in the organism and the product on hydrolysis gives camphene by loss of water from the regenerated camphene hydrate. lys1s. T. A. H.PHYSIOLOGICAL CHEMISTRY i. 135 The Relationships between Tumour Cells and Blood-serum. ERNST FREUKD and GISA KAMINER (Biochem. Zeitsch.1912 46 470-482).-The property possessed by normal sera of destroying carcinoma cells is due to an ether-soluble nitrogen-free fatty acid. The property of carcinomatous serum of protecting carcinomatous cells from destruction and of giving specific turbidity with saline extracts of carcinomas is due to the euglobulin (nucleoglobulin) fraction of the serum which is soluble in sodium carbonate and is distinguished from normal nucleoglobulin by its high content of carbohydrate group. The property of carcinoma extracts of giving turbidities with carcinomatous sera is due to a nitrogen-free carbohydrate compound. The specific precipitates of carcinomatous and sarcomatous extracts with their respective sera are characterised in the former case by carbohydrate-rich substances and in the latter case by groups yielding the biuret reaction.The carcinomatous precipitates carry down from solution added carbohydrates whereas the sarcomatous precipitates carry down added peptone. The tumour cells themselves show a similar adsorptive capacity the carcinomatous cells binding sugar lecithin or nuclein whereas the sarcomatous cells bind peptones and nuclein. S. B. S. The Interstitial Granules (Liposomes) in Fatty Metamor- phosis of S t r i a t e d Muscle. E. T. BELL (J. Path. Bact. 1912 1’7 147-159).-Fatty metamorphosis may be produced in the leg muscles of a rat by applying a ligature round the thigh ; in the fibres of these muscles the liposomes stain with greater intensity and are much larger than normal ; this is especially the case in well nourished animals or if the rat is fed on fat.Pathological fatty metamorphosis is an exaggeration of a normal process and consists in an increase in the size staining capacity and often the number of liposomes. Part of the fat is already present when the process begins. ‘The increase of size is probably due to the accumulation of triolein. Nature of the So-called Rlausner Serum Reaction G. KLAUSNEB (Biochem. Zeitsch. 1912 4’7 36-58).-The author has already shown that sera from certain cases of syphilis yield a precipi- tate when diluted with three times the volume of water. This property is lost if the serum is previously extracted with ether ,and is restored by the addition to the serum of the lecithin-cuorin- cephalin fraction of brain lipoids.A serum can also be rendered non-precipitable by water if heated but in this case the precipitability (activation) is not restored by lipoids. A serum activated by brain lipoids can also be inactivated by heating. The property of restoring activity by lipoids is not destroyed by heating. An artificially activated serum (by lipoids) if inactivated by heat is not rendered active again by the addition of fresh serum; hence the activating property of lipoids is best if they are heated in the presence of serum. I n all cases both of artificial and natural precipitin reactions the optimal condition for precipitation is dilution with three times iihe volume of water. The natural precipitin reaction when destroyed by heat is not restored on the addition of fresh serum.A poaitive serum. inactivated by extraction with ether can be reactivated W. D. H.i. 136 ABSTRACTS OF CHEMICAL PAPERS. by the addition of the ethereal extract which can also activate a normal inactive serum. Strong concentrations of the ethereal extracts of normal serum dissolved in water can also activate a normal serum. These results indicate that the precipitation is not due t o globulins and that in syphilitic sera the abnormalities are due t o excess of lipoids. Bence-Jones Proteinuria. E. PROVAN CATHCART and J. HEN- DERSON (J. Path. Bact. 1912 17 238-248).-A detailed account of the examination of the urine in a case of this disease. The general result of an examination of the protein present is that the findiugs of Hopkins and Savory (A.1911 ii 417) are confirmed. W. D. H. The Action of Carbon Dioxide on the Vascular System. S. I T m r (J. Physiol. 1912 45 338-344).-Srna11 percentages of carbon dioxide produce a rise of arterial pressure mainly by increasing the force of the heart. Higher percentages (over 8%) produce increased constriction of the arterioles by stimulating the vaso-motor centre and probably from an increased activity of the suprarenal glands. W. D. H. D. FERRON (Chem. Zentr. 1912 ii 370; from Arch. Farm. spe&a. 1912 13 283-288). -Intravenous injection of doses of 0*000010 to 0*000025 gram- equivalents of mercuric chloride per kilo. of body-weight causes in rabbits an appreciable diuresis but in larger doses the effect is less than that of the saline injection alone owing to the toxic properties.A simultaneous injection of sodium chloride decreases the toxic effects and vice versa. mercuric chloride diminishes the toxic effects of hyper- tonic sodium chloride solution. Action of Mercury Preparations on Spirochaete Diseases. I. Chemical-therapeutic Action of' Mercury Compounds Eepecially of a New Mercury Preparation which Strongly Attacks Spirochaete but is only very Slightly Poisonous. WILHELM KOLLE M. ROTHERMUND and S. PESCHIE (Cheni. Zmtr. 1912 ii 1574-1575 ; from Deut. med. Woch. 1912 38 1482-1585).-The therapeutic action of many mercury preparations such as colloidal mercury mercury peptonate dinitromercuridibenzoic acid sulph- aminophenyldimeth ylpyrazolonemercury etc. has been examined. The aliphatic compounds do not differ very much in their action but the benzene and pyrazolone compounds show many differences in toxicity and in the relation of the curative to the toxic dose.Sulphamino- compounds show a great lowering of the poisonous nature of mercury preparations without a diminution in their spirillocidal properties and sulphaminophenyldimethylpyrazolonemercury is especially to be recommended. 3. C. W. Action of Mercury Preparations on Spirochaete Diseases. 11. The Toxicology and Pharmacology of Some Mercury Compounds. J. ABELIN (Chern. Zentr. 1912 ii 1575 ; from Deut. med. Foch. 1912 38 1822-1825. Compare preceding abstract).- The poisonous nature of mercury compounds is influenced by their S. B. S. Diuretic Action of Mercury Preparations. S. B. S.PHYSIOLOGICAL CHEMISTRY. i.137 chemical constitution ; the introduction of aulpho- or amino-groups or of doubly-linked carbon atoms diminishes their toxicity. The most poisonous compounds are those in which the mercury is easily ionised such as mercuric chloride. After injection of mercury preparations the metal is always found in the liver. J. C. W. The Sugar of the Blood and Urine under the Influence of Con- tinuous Adrenaline Infusion. M. J. GRAMENITZKI (Biochem. Zeitsch. 19 12 46 186-209).-Adrenaline was continuously administered to rabbit8 by Straub’s infusion apparatus and tho effect on the sugar content in the blood and urine with varying dilutions of the drug was ascertained. It was found that there is in general a proportionality between the strength of the adrenaline stimulus and both the result- ing bypergl ycaemia and glycosuria.Under urethane narcosis the amount of adrenaline necessary to produce glycosuria is below the normal. Under these conditions the strength of the adrenaline stimulus necessary to produce glycosuria is less than that required to raise the blood-pressure. The adrenaline administration increases the diuresis within a few minutes and this effect is often but not always accompanied by glycosuria. The diuretic effect of urethane is to be ascribed to its urea components whereas its glycosuric effects can only be partly ascribed to these. Under urethane narcosis artificially introduced sugar disappears more slowly than i n normal animals; it also disappears more slowly from bound animals than from animals which are free. Venesection causes a distinct but slight hyperglycaemia which is sometimes accom- panied by glycosuria.The effects of the narcotic etc. were investi- gated in some detail in view of criticisms on Ritzmann’s work which was also carried out in Straub’s laboratory. I n experiments on non-narcotised animals it was found that the proportionality between the adrenaline stimulus and the effects was more marked than in the narcotised animals. The primary effect is hyperglycaemia which can be quite marked (up to 0.2%) even when there is no glycosurin. The smallest stimulus necessary to produce glycosuria is higher in non- narcotised than in narcotised animals. The diuretic activn of adrena- line follows definite laws and is independent of the glycosuric effect. The general theory of the drug action is discussed.S. B. 8. Effect of Adrenaline on the Pulmonary Circulation. E. 31. TRIBE (Proc. phyeiol. SOC. 1912 xx-xxii ; J. Physiol. 45).-The conflicting results of previou8 workers on this question are probably due to the use OF different preparations. Adrenaline preparations free from preservative cause constrictions a t body temperatures. Prepara- tions of adrenaline chloride preserved with 0.5% chloretone cause distinct dilatation of the pulmonary vessels. The constriction obtained with pure adrenaline is however hardly comparable with that seen in organs supplied by vaso-motor nerves and the question of the existence of such nerves in the lung-vessels is left undecided. W. D. H.i. 138 ABSTRACTS OF CHEMICAL PAPERS. The Vascularity of the Liver.VIII. The Influence of Adrenaline on the Arterial Inflow. RUSSELL BURTON-OPZTZ (Quart. J . expt. Physiol. 1912 5 309-324).-The complex nature of the blood supply of the liver renders the interpretation of records a matter of difficulty and much of this and the following papers is devoted to a discussion of this question. There appears however no doubt that adrenaline constricts the arterioles of the liver and leads then to a rise of pressure in the hepatic artery and an increase in the arterial inflow the general blood-pressure being also raised. This is followed by a period of lessened inflow although the hepatic pressure is still high but the general pressure is only slightly elevated. Exceptions to this rule are explained by the fact that an injection of adrenaline does not necessarily imply that it enters the hepatic artery; i t might be swept past the orifice of the artery; a similar accident in the case of arteries supplying other organs might explain unexpected results there.The Vascularity of the Liver. IX. Influence of Amy1 Nitrite on the Arterial Inflow. RUSSELL BURTON-OPITZ (Quayt. J. expt. Physiol. 1912 5 325-328).-1nhalation of amyl nitrite causes a fall of general arterial pressure but also causes a local change in the liver circulation. The fall of pressure in the hepatic artery is pro- portional to the general fall. On discontinuing the inhalation the pressure returns very slowly to normal. The arterial inflow is directly proportional to the systemic pressure and the local changes are attributed wholly to the general effect.The Vascularity of the Liver. X. The Influence of Adrenaline on the Venous Inflow. RUSSELL BURTON-OPITZ (Quart. J. expt. Phpiol. 19 12 5 329-342).-Evidence is adduced that the liver possesses two separate motor mechanisms one in the terminals of the hepatic artery and the other in the radicles of the portal vein both of which are stimulated by adrenaline. Metabolism Experiments in the Administration of Atophan. WITOLD SK~RCZEWSKI and J. SOHN (Chem. Zentr. 1912 ii 1381; from Zeitsch. expt. Path. They. 191 3 11 254-263).-Experiments on normal persons and on sufferers from gout show that the adminis- tration of atophan causes an increase in the output of uric acid which however falls off with subsequent doses more purine bases being discharged.An alteration in the functions of the kidneys is presumed for a retention of chlorides immediately follows the administration. The atophan urine always gives the diazo-reaction which becomes weaker after several doses; i t also gives the phenol reaction with bromine water a dirty rose-coloured precipitate with Millon’s reagent a yellow precipitate with phosphotungstic acid and a green colour with a mixture of ammonium sulphate and ammonia. J. C. W. W. D. H. W. D. H. W. D. H. W h y Does Atophan Increase the Excretion of Uric Acid? WITOLD SK~RCZEWSKI (Chem. Zentr. 1912 ii 1679 ; from Zeitsch. sxpt. Path. Ther 1912,11,501-507. Compare preceding abstract).-PHYSIOLOGICAL CHEMISTRY. i. 139 The action o€ atophan is presumed to be an oxidation disturbance of which the interference in the degradation of uric acid is a special case.This affords an explanation of the variations in uric acid values the increase in neutral sulphur and the appearance of the diazo-reaction in atophan urine. J. C. W. The Formation of Phenol from p-Cresol in the Organism of the Dog. MAX SIEGFRIED an6 R. ZIMMERMANN (Biochem. Zeitsch.. 1912 46 220-224).-1n view of Baumann’s conceptions as to the degradation of tyrosine in the organism through p-ctesol and p-hydroxy- benzoic acid to phenol the effect o€ the administration of p-cresol W A S investigated and it was found to yield phenol; 32-48% of the phenolic substances administered were recovered in the urine of which 23-46% was in the form of phenol. Various modifications in the technique of phenol and cresol estimation are given chiefly with regayd to the method of brozuination and the addition of sufficient alkali before evaporating the urine to prevent loss of phenol.S. B. S . Formation of Glgcine in the Body. 11. ALBERT A. EPSTEIN and SAMUEL BOOKMAN ( J . Hiol. Chem. 1912 13 117-132).-Free leucine does not yield glpcine although it undergoes decomposition in the body. When benzoyl-leucine is given with benzoic acid the output of hippuric acid is much greater than the leucine alone allows. Phosphorus poisoning causes no increaced production of glycine or hippuric acid. Phosphorus plus benzoic acid has also no such effect unless the animal is fasting; then the increase must be due to massive disintegration of protein. Much of the glycine liberated on feeding with benzoic acid must be the result of a synthesis in the body.W. D. H. Tolerance to Nicotine. WALTER E. DrxoN and W. E. LEE(&UCW~. J. expt. Physiol. 1912 5 373-382).-A person tolerant to nicotine may be so because nicotine is not absorbed but this is unlikely. A second explanation may be that it is more readily destroyed by the tissues. The present experiments were made on rabbits and in thirteen out of sixteen experiments tolerance was established the drug being injected under the skin or into the blood-stream. The analyses of the tissues show that the second explanation given above is correct but that all the cells of the body do not possess the power of destroy- ing nicotine in equal measure the liver is the most effective.Evidence is adduced t h a t the destruction is probably oxidative and due to the action of an enzyme. W. D H. The Oxidation of p - Phenylenediamine by Animal Tissues. FR. BATTELLI and (Mlle.) LINA STERN (Uiochem. Zeitsch. 1912 46 317-342).-1t is shown in investigations of the oxidative fiinctions of tissues that the p-phenylenediamine reaction is better than the indo- phenol reaction. All tissues can oxidise this substance. The amount of oxygen consumed was in most cases measured and it was found that in the accessory respiration of the tissues the amount consumedi. 140 ABSTRACTS OF CHEMICAL PAPERS. was the sum of that used up by the tissues when without the reagent plus the amount necessary to oxidise the reagent. I n the primary respiration on the other hand the p-phenylenediamine oxidation partly replaced the tissue respiration. The oxidation is most intensive in the heart red muscles liver and kidney and much less in the pancreas spleen and lungs.With the exception of the pancreas the tissues maintain their oxidative capacity for a long time after death. Under similar conditions of experiment most tissues use up the same amount of oxygen for oxidising p-pheoylenediamine as they do For succinic acid ; the brain however uses u p more. I n muscles and liver no more oxygen is used up if both substances are present than if they are present alone. The blood is an energetic oxidiser but not the serum and the action appears to be due mostly to the bzemoglobin as in the blood of some animals the oxidative capacity remains after heating to 60" or treatment with pancreatin.This is not even lost after heating the blood with mineral acids. An aqueous extract of liver inhibits the oxidative capacity of the blood and the inhibitory action is not destroyed by warmiug to 60'. Blood bas no appreciable oxidative action on succinic acid. S. B. S. The Influence of Various Factors on the Oxidation of p-Phenylenediamine by Animal Tiesues. FR. BATTELLI and (Mlle.) LINA STERN (Biochem. Zeitsch. 19 12 46 343-366).-Small amounts of acid or alkali inhibit oxidation. There is no marked optimal temperature of reaction between 30' and 50° but the action is lost by heating tissues to 60' for ten minutes. I n medium concentra- tions salts accelerate the reaction exerting an inhibitory action at higher concentrations.Up to a certain limit the rate of oxidation increases with an increase of the concentration of the p-phenylene- diamine. The oxydase is not washed out from the tissues by water and the washed tissues still contain the oxydase. I n oxygen the reaction is more energetic than in air. The oxydase is destroyed by treating the tissues with alcohol or acetone or with weak solutions of mineral acid@. Aqueous extracts of tissues osidise in presence of hydrogen peroxide and this function is not lost on heating. The mashed residue of muscular tissue will not oxidise in the presence of the peroxide after heating t o 60'. Treatment of tissue with pancreatin diminishes t h e oxidative capacity. Both fresh and heated pancreatin increase the oxidative capacity of the vegetable pol7 phenoloxydaees.Catalysts accelerating the oxidation of p-phenylenediamine and succinic acid are distinguishable from other oxydases by the facts that they are not dissolved out by water and are destroyed by alcohol acetone or trypsin. With the exception of those of the brain the catalysts appear to be identical. s. €3. 8. Pharmacology of Picrotoxin Picrotin and Picrotoxinin. ALFREDO CHISTONI (Chem. Zentr. 1912 ii 371-372; from Arch. Parrnacol. sperim. 19 12 13 220-240).-Picrotoxin and picrotoxinin in concentration 1 in 2000 reduce tbe tone and the amplitude of the contractione of smooth muscle but in concentration 1 in 10,000 they increase the amplitude and diminish the number of contractions,PHYSIOLOGICAL CHEMISTRY. i. 141 and either do not influence or slightly increase the tone of smooth muscle ; picrotin is inactive.All three substances in a concentration of 1 in 2000 slightly increase the tone of striped muscle. The frequency and contraction of the amphibian heart are affected by picrotoxin and picrotoxinin due to their action on the muscle; picrotin is inactive. Picrotoxin and picrotoxinin intravenously injected in dogs reduce the pulse and increase the blood pressure due to stimulation of the pneumogastric and the vasomotor centres. All three substances (1 in 2000-4000) fitill the isolated hearts o l cats and rabbits but this elfect ceases when the poisons are removed. In a concentration of 1 in 80,000 picrotoxin at first quickens and then slows the heart’s action and these effects are not inhibited by the previous application of atropine. Picrotoxinin (1 in 80,000) at first strengthens and quickens the heart’s action by its effect on the vagus but finally stills the heart by direct action on the muscle fibres. Picrotin (1 in 40,000) accelerates the heart-beats and reduces the strength of the pulse. T. A. H. The Poisonous Nature of Methyl and Ethyl Alcchols. ALEXANDER LANGGAARD (Chenz. Zentr. 1912 ii 1382-1383 ; froin Bed. kZin. Woch. 1912 49 1704).-Methyl alcohol is more poisonow than ethyl alcohol when taken in repeated small quantities but ethyl alcohol is much more dangerous when taken in a single large dose. J. C. W. Hamolytic Substances obtained from Serum and the Vitellus of Egg Submitted to the Action of Venoms. C. DELEZENNE and (Mlle.) S. LEDEBT (Compt. rend. 1912 155 1101-1103. Compare ibid. 1911,152 790 ; 153 81).-Cobra venom acts on the serum of horse blood or the vitellus of egg giving rise by diastatic action of the venom on the lecithin to haemolysin which differs from lecithin in that it is soluble in water and insoluble i n ether and its molecule does not contain any unsaturated fatty acid& (oleic acids). Jn the case of the serum the venom-serum mixture attains a maximum hemolytic power which then decreases until the mixture is inactive. A t the same time a very fine precipitate of calcium soaps (palmitate and stearate) is produced. This diminution in activity which is peculiar to serum corresponds with further decomposition of the hzmolysin and if the serum is dialysed prior to addition of the venom the second stage iu the action does not occur and it behaves in the same manner as the vitellus of egg. The liquid resulting from the dialysis of the serum produces this secondary effect on addition to a venom-vitellus mixture W. G. It resembles lecithin in its solubility in alcohol.

ISSN:0368-1769    

DOI:10.1039/CA9130400119

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 131 Early Work on Hydrofluoric Acid and the Isolation of Fluorine. FREDERICK D. CHATTAWAY (Cliem. News 19 13 107 25-26).-Historical. Reactions of Ozone with Certain Inorganic Salts. YOSHITO YAMAUCHI (Amel.. Chem. J. 1913,49,55-6S).-A study has been made of the action of ozone on certain inorganic salts with the object of ascertaining whether the oxidation is effected by only one oxygen atom of the ozone molecule or whether all three atoms take part in the process. A method has been devised by which each sample of ozonised oxygen can be divided into two parts one for carrying out the experi- ment and the other for analysis. The salts employed included potassium arsenite stannous chloride sodium thiosulphate thallous nitrate mercurous nitrate and ferrous ammonium sulphate.I n the case of stannous chloride the oxidation takes place according to the equation 3SnCJ2 + 6HC1+ 0 = 3SnC1 + 3H,O but in all the other cases only one oxygen atom of the ozone molecule reacts with the salt the ozone decomposing thus 0 = 0 + 0. When sodium thiosulphate is treated with ozone two reactions occur one involving the catalytic decomposition of the salt 3Na,S,O = 3Na,SO + 3S and the other effecting a partial oxidation of the sulphite formed 2Na,SO + 30 = 2Na2S0 + 20,. Thallous salts are rapidly and corn pletely oxidised by ozone and the thallic oxide produced can be readilii. 132 ABSTRACTS OF' CHEMICAL PAPERS. collected and weighed; the reaction is therefore applicable to the estimation of ozone.E. G. The Dynamic Allotropy of Sulphur. IV. HUGO R. KRUYT (Zeitsch. physikal. Chern. 1913 81 726-748. Compare A. 1908 ii 1028; 1909 ii 228 802).-The paper is chiefly polemical. It is shown that mixed crystals are formed by Sp and SX and that the transition S -+ S,,,. takes place a t a higher temperature in the presence of Sp. The transition point of pure Srh. is 95-3' whereas the generally observed transition point is 95.5' and the triple point S)+, S,,,. and Sliq lies a t 95.9Ok 0.1'. Attempts are made to calculate the transition point of rhombic sulphur on the basis of Nernst's theorem but this led to results which are in no way like the experimentally- determined values. An answer is given to the paper8 of Wigand (A. 1910 ii 602 1055) Snits and Leeuw (A. 1912 ii 40) Leeuw (this vol.ii 40) Preuner and Schupp (A. 1909 ii YS7) and to Wo. Ostwald (Grundriss der Kolloidchemie p. 132). The following thermal constants of sulphur are collected in the paper; these are held to be trustworthy. If. p. monoclinic sulphur (free from Sp) 119.25'. M. p. monoclinic sulphur as usually prepared 114.5'. M. p. rhombic sulphur (free from Sp) 112.8'. M. p. rhombic sulphur as usually obtained 110.2'. M. p. of nacreous variety of sulphur (free from Sp) 106.8". AX. p. of nacreous variety of sulphur as generally obtained 103*4O. Transition point Srh. -+ S,,,,,. (free frolu Sp) 95.3'. Transition point usually obtained 95.5' (3.1% Sp present). J. F. S. The Chemistry of t h e Formation of Nitric Oxide in the High Tension Arc. FRANZ FISCHER and EMIL HENE (Uer.1912 45 3652-3658).-The purely thermal formation of nitric oxide from nitrogen and oxygen has been questioned by various investigators (cotn- pare Haber and Koenig A. 1908 ii 34 940 ; Grau and RUSS A. 1907 ii 753). Escales in a discussion before the German Bunsen Society (Zeitsch. Elektrochsm. 1906 12,%539) raised the question whether the formation of nitric oxide might not be preceded by the activation of the nitrogen but Strutt has since shown (A 1912 ii 153) that active nitrogen does not react with oxygen. The authors now show that the energy of the discharge is probably used up i u dissociating the oxygen molecules this being an endothermic process. Outside the arc the following processes which are exothermic then take place (1) re-formation of molecular oxygen (2) oxidation of molecular oxygen to ozone (3) formation of nitric oxide.The latter may be a direct reaction between the active oxygen atoms and the nitrogen or may be due to a reaction between the ozone and the nitrogen which reaction would be exothermic. The above conclusions are based on the following experiments. When pure oxygen is sparked as i t passes out of a quartz capillary and mixes with pure nitrogen in a closed apparatus six and a-half times more nitric oxide is produced than when the nitrogen is sparked and mixeswithINORGANIC CHEMISTRY. ii. 133 oxygen. Similarly when air is sparked and blown into oxygen four time+ as miich when blown into nitrogen twice as milch nitric oxide is produaed as when pure nitrogen is sparked and blown into pure umparked oxygen.A higti-tension arc was produced in a quartz apparatu! cooled with wat,er. When air was sent through the arc and then mixed imme- diately with oxygen air and nitrogen respectively the volume percentages of nitric oxide produced were respectively 7.8 7.4 and 5.9. When air is submitted to the silent discharge i n a quartz Siemens ozone tribe heated a t varying temperatmws (20-7@0°) the percentage of nitric oxide pnbduced incl eases with rise in temp.eritture owing to the increased velocity of reaction between any ozone produced and the nitrogen reaction taking place before the ozone is destroyed by the high temperature. The above results indicate that better results would be obtained on a manufacturing scale if oxygen were paqsed through the arc flame instead of air u-ing magnetite electrodes and then rapidly mixed with nitrogen and cooled.T. S. P. The Inner Cone of Hydrocarbon Flames. FRITZ HILLER (Zeitsch. ylrysihcd. Cham. 1913 81 591-625. Clomprre A. 1910 ii 122).-A further investigation of the inner cone of certain flames. The ethrr and coal-gas flames are chiefly investigated and the analyses of the products of combustion a t the poiit of the cone the bide of the cone and at different positions aoove the cone in the space between the inner and outer cone are made. Tem- perature determinations were made by means of an iridium iridium- rhodium couple and these valries were compared with the teruperatrires calculated from the compo-ition of the gas in the sp’ce betweeu the two cones and the known specific heats and heats of cornbuytion on the one hand and with those obtained from the equilibrium constant and it.; relation t o temperature on the other Considerable difficulty was experienced in the calculations owing t o the uncertainty of the therm-tl data required for obtaining the temper- ature.The constant K= (H,O/CO,)*(CO/H,) is given for all experi- ments the various values bring obtained by gas analyticdl processes. The eqriilibrium constant is found t o be about 3.4 when the gtses coming from the inner cone are cooled to a temperature which allows of no further change but when the cod gas has been previously mixed with carbon dioxide the equilibrium constant is considerahly lower than 3.4 I n the ctse of the ether flbrne this constant is often found t o be as low as 2.8 the higher value only being obtainable when a very small flame is employed.J. F. S. The Various Forms of Silica and their Mutual Relations. CLAHENCE N. FENNER (J. Washhgton Acad. Xci. 1912 2 471-480).- The velocity of transformation of one form of silica into another is extremely slow and the different forms may exist together over considerable ranges of temperature. The inversions may be hastened VOL. civ. ii. 10i. 134 ABSTRACTS OF CHEMICAL PAPERS. by employing a catalytic agent (sodium tungstste). inversion points were determined from t,he heating curves gonal) 555'. The following P-quartz (Izemihedral hexa- a- Quartz ( t etartohedral hexagonal) /3 Quartz 7 /3-tridymite (holohedral hexagonal) 870'k 10'. P-Tridymite P-cristobalite (cubic) 1470°k 10'.On cooling P-tridymite and P-cristobalite promptly pass a t the foll(iwing temperatures into metastable forms possessing lower optical symmetry P-TI idymite Z a-tridgmite (biaxial perhaps orthorhombic) 1 1 5 - 1 20'. /3-Cri~tobalite a-cristobalite (biaxial) 180-270'. Chalcedony possibly represents a seventh form of silica. L. J. S. The Transformations of Silica at High Temperatures. KURD ENDELL aud KEINHOLD RIEKE (Zeitsch. unory. Chem. 1912 79 239-259).-'l'he present investigation deals with pure temperature cbangev in the absence of mineralisers. The specimens of native silica in fragments of 1-3 C.C. and also in powder are heated in a n electric furnace and the direction of the tramformation determined by measurements of t h e density using the dataD (quartz) 2.65 (cristobalite) 2.33 (silica glass) 2.21.Quartz and chalcedony which have been heated at 1450' have often been described a8 optically isotropic owing to the microscopic cracks produced during the tranhformation which also give rise to an error in the determinations of density. Cristobalite is best recognisd by its change of volume at about 230' measured in a mercury dilato- meter. Quartz and amorphous silica are converted into cristobalite by heat- ing above 800' but an exact temperature of transformation has not beeu fouud. Tbe velocity of conversion increases wit'h the temperature. Between 1200' and 1600' the transformation of silica glass is propor- tional to the time. Twinned quartz is converted more rapidly than simple crystals and chalcedony still more rapidly.Using an iridium furnace P-cristobalite is fouud to have m. p. 1685' + 10'. The factor determining the rate of tramformation is the extent of surface a twinned crystal having a greater effective surface than a simple one and fibrous varieties such as chalcedony a still greater surface. The quartz of pegmatite and graphic granite is often repeatedly twinned. Chalcedony may be regarded as a n unstable transitional form of quartz. Massive rock crystal may probably be melted by rapid heating without previous conversion into cristobalite. The present data do not allow of the construction of an equilibrium diagram for silica but an attempt is made t o classify the various modifications in accordance with Tammann's hypothesis (A 1912 ii 149).C. H. D. This is the only means of distinguishing it from tridymite. Capacity of Potassium Haloids for F o r m i n g Solid Solutions at High Tumperatures. MARIO AMADORI ( A t t i K. Accad. Lzncei 1912 [v] 21 ii 606-610 Compare A 1912 ii 758).-The author has repeated some of his former experiments with results which con-INORGANIC CHEMISTRY. ii. 135 firm those obtained by him and Pampanini (A 1912 ii 48) and not agree with those of Vrshesnevsky (A. 1912 ii 137). The author's conclusions are further supported by recent work of Nacken and Schobert (Diss. Leipzig 1912) and Nacken and Elack (unpubliahed). R. V. S. Some P r o p e r t i e s of Alkali Nitrites. MARCEL OSWALD (Compt. rend. 1912 155 1504-1506).-The author has prepared sodium and potassium nitrites in a high state of purity and examined their pro- perties.Sodium nitrite when heated in a vacuum melts a t 217' (compare Divers T. 1899 75 86) and decomposes at 320' ; potassium nitrite melts at 29'7.5O and decomposes at 350'. After firsion and resolidification they have respectively Di 2.168 and 1.912. The densities of their solutions a t various concontratiom are given. W. G. The Silver-Zinc Equilibrium. HENRY C. H. CARPENTER and W. WRITELEY (Internat. Zeilsch. Metahgraphie 19 12 3 145-1 69). -The eqiiilibrium diagram given by Petrenko (A. 1906 ii 284) is incompatible with the phase rule. It I S shown that the errors in the diagram are due to the use of insufficient quantities of material t o want of uniformity and t o the absence of proper annealing.The system has now been reinvestigated using larger quantities and employing greater precautions. The actual diagram is of a much simpler character. The liquidus has been determined accurately by Heycock and Neville (T. 1897 '71 407). The limits of the a-solid solution a t 220' (determined on samples annealed for six weeks) a r e 100 and 62.7 atomic 7; of silver. The p-constituent is unstable below 264O at which temperature there is a eutectoid point -+ a+y. The y-constituent is the compound Ag2Zn3 ; i t is highly brithle and develops conspicuous cleavage cracks A t 260' the y-range is from 40 to 37.3 atomic % Ag. The 6 constituent (probably Ag2Zn5) which is also brittle has a range 29 to 14.3 atomic % Ag whilst the y-con- stituent is confined to the immediate neighbourhood of the zinc end of the series.There is thus a very close resemblance throughout the whole system between the copper-zinc and silver-zinc series. The Copper-Zinc Silver-Zinc and Silver-Cadmium E q u i l i b r i a HENRY C. H. CARPENTER (Irderncct. Zeitsch. illetaZlogrupl& 191 2 3 170- 175).-A remarkable similarity is observed bet ween the equilibria in the systems copper-zinc (A' 1912 ii 764) silver-zinc (preceding abstract) and silver-cadmium (Petrenko and Fedorov A. 1911 ii 281 800). The €-constituent does not exist below 3 1 0 O . C. H. D. In each case a compound of similar composition cu2zn3 Ag2Zn3 Ag,Cd determines the form of the diagram. The a-solid solutions have a similar range of stability and near to the compositions CuZn AgZn and AgCd /3-constituents occur having a comparatively wide range of composition at a high temperature narrowing with falling tempera- ture until a eutectoid point is reached at or about 50 atomic %. The y-constituent is in each case the pure compound.It is remarkable 10-2ii. 136 ABSTRACTS OF CHEMICAL PAPERS. t h a t the systems copper-tin and copper-aluminium also include a /3-constituent stahIe only above a certain t3emperature and then undergoing a eutectoid inversion. The copper-cadmium diagram does not shorn any close analogy with the above. C. H. D. The Preparation and Investigation of Silver Oxide. E. HOST MADSEN (Zeitsch. anorg. Chern. 1912 79,195-201).-Silver oxide has not hitherto been obtained in a pure condition. A concentrated solution of silver nitrate is precipitated with a dilute solution of sodium hydroxide and the precipitate is washed with water previously freed from carbon dioxide.It is then dried at 85-88' in a stream of air free from carbon dioxide. The product contains 1.75% of silver hydroxide (0.1 25% of water) and about 0.5% of silver carbonate. Some reduction takes place as whilst the moiht precipitate yields a white chloride with hydrochloric acid even after exposure to light the dry solid always yields n red chloride the colour af which is deeper the higher the temperature of drying. At 280' the water is almost completely expellcd but i t is not possible to obtain a product of constant weight as appreciable dissociation of the oxide takes place. C. H. D. The oxide dried at 8 5 O is dark brown with a violet s5ade.Cement Limestones of Santa Marinella. NICOLA PARRAVANO (Gazxetta 19 12 42 ii 6 10-6 17).-The paper records analyFes of a number of specimens from this district (which lies south of Civita- vecchia) carried out to determine the suitability of the stones for the manufacture of Portland cement and gives the results of tests applied t o the cements made from them. E. v. s. Gelatinous Cdcium Sulphate and the Setting of Plaster. CAVAZZI (Gazxetta 191 2 42 ii 626-632).-When calcined calcium sulyhate is treated with water a gelatinous calcium sulphate is first Formed which in a few minutes at low temperatures and more rapidly at higher temperatures turns into crystals of CaSU,,2H20. The gelatinous salt can be observed t o crystallise under the microscope and i t is identical with that produced by the addition of alcohol to a supersaturated solution of calcium sulphate.That the setting oE plaster is not due to the crystallisation of CaS0,,2H20 from a super- saturated solution is shown by the fact that the lncrease of volume on setting is very much less than t h a t which is found to occur when this salt is allowed to crystallise from a supersaturated solution. R. v. s. The R61e of Calcium Sulphate and Barium Sulphate in the Reduction of Zinc Minerals. EUG~NE PROST and MAURICE UBAGHS (Bull. SOC. chim. Belg. 1912 26 532-541. Compare A. 1911 ii 283).-1n the presence of silica the sulphates of calcium and barium have a marked influence on the reduction of zinc minerals. They consume a large amount of heat for their decomposition or reduction and in the presence of silica react with it generating sulphurousINORGANIC CHEMISTRY.ii. 137 vapours which in contact with the zinc vapour cause the formation of zinc sulphide which remains in the distillation residue thus increas- ing the loss of zinc the sulphide only being reduced a t a much higher temperature. The presence of silica is necessary for the formation of zinc sulphide as in its absence the calcium and barium sulphides formed by the reduction of the corresponding sulphates do not yield their sulphur t o the zinc oxide of the roasted blende at the experi- mental temperature of 1200' (compare Netalluygis 191 1 8 763). W. G . Glucinum Phosphates and Glucinum Phosphite and Hypophosphite. BENNO BLEYER and BR. MULLER (Zeitsch.anorg. Chem. 1912 79 263-276. Compare A. 1912 ii 644).-Mono- ylucinum orthpJLosphate GlH,(PO,) prepared from the hydroxide and oi*thophosplioric acid forms colourless hygroscopic leaflets. Diglucinuiii orthophosphate GlHPO,,SH,O,. has not beon obtained free from adhering phosphoric acid. l'raylucimun orthophosphate GI,P,O,,GH,O obtained from disodium phosphate acetic acid and glucinum sulphate forms a loose precipitate. 2G1,P,08,G10 13H,O is obtained when trisodium phobphate is used €or precipitation. Potassium plucinum orthophosphabe and also the correspor,ding sodium and ammonium salts have only been obtained as precipitates of variable composition. The gliicinum phosphates previously de- scribed in the literature are mixtures. Glucirtum pyrophosphate GI,P,07.9H,0 is precipitated by means of sodium pyrophosphate.Gl,P,O 2Na,P20,,5 H ,O is a soluble hygroscoiic salt. Glucirmm metaphosphate Gl(PO,) forms colourless crystals and must be prepared in absence of water otherwise a basic salt is obtained. 4G 1HPc),,G10,7H20 and hypophosphite GlH,P,O have also been prepared. A basic salt Sodium glucinum pyrophosphate Glucinum phosphite C. H. D. Magnesium Ions as Oxygen Carriers. OTTO HAUSER (Chem. Zeit. 1913 37 58).-l'he ruhting of iron is accelerated by the presence of nlagnesium ions. I n general reactions which take place with absorption or evolution of oxygen are similarly accelerated. The effect of magnesium ions is best shown in the oxidation of hydro- chloric acid or chlorides by permanganate. T. S. P. Thermal Analysis of Binary M i x t u r e s of Chlorides of Bivalent Elements.IV. CARLO SANDONNINI ( A t t i R. Accc6c.d. Lirtcei 1913 [v] 21 ii 634-640. Compare A. 1912 ii 1172).-The present paper deals with the thermal analysia of the system M gCI,-SrC'l MgC1,- BaCI and MgCl,-MuCI,. The magnesium chloride used contained 1.1 1% of oxide which was allowed for in calculating the compositions of the mixtures dealt with Magnesium chloride and strontium chloride do not seem to form solid solutions; there is a n eutectic corresponding with 535' and 50 mols. % of strontium chloride.ii. 138 ABSTRACTS OF CEIEMICAL PAPERS The system MgC1,-RaCI is analogous to the system MnCI,-BaCI already studied. There is an eutectic corresponding with 36 mols. % of barium chloride and about 556'.Mixtures containing more barium chloride show a pause at 590° as well a s that of the eutectic; if the amount of barium chloride is increased only this upper pause is observed but if the amount is still further raised the pause falls amgain until it coincides with the eutectic. These indications point to the production of a compound decomposing on fusion. Magnesium chloride and manganese chloride are completely soluble both in the solid and in the liquid state and mixtures of them melt at temperatures intermediate between those of the constituents The author discusses the regularities which may be perceived in the thermal behaviour of the biuary mixtures of chlorides of bivalent elements investigated by himself and others. R. V. 5. [Metastable Metals ] E. B.WOLFF (Zeitsch. Elekhochem. 19 13 19 19-23. Compare Cohen A 1909 ii 1008).-Polemical. The author shows that an etching solution does not convert a metal which has been rendered metastable by deformation into the stable condition. The action is shown to be the removal of the deformed and metastable surface layer with the exposure of the stable underneath layer. It is also stated in opposition t o Cohen (Zoc. cit.) that a metal which has been rendered stable by etching is unable to innoculate other metal which has been subjected to deformation. J. F. S. [Metastable Metals.1 ERKST COHEN (Zeitsch. Elektrochem. 191 3 19; 23).-Polemical. A< answer to Wolff (preceding abstract). J. F. S. Physico-chemical Studies on Red Lead. JAROSLAV MILBAUER (Chem. Zed. 1912 36 1436-1437 1484-1485).-By means of a specially designed apparatus the author has investigated the formation of red lead from lead oxide under oxygen pressures varying from 1 to 12 atmospheres and a t temperatures from 325' t o 520".The results show that the equilibrium is independent of the pressure but is attained more rapidly with increasing pressure One hundred yo of red lead is formed at 470-480' the percentages being less above and below this temperature the time of experiment being in all cases three hours. T. S. P. The Structural Resolution of the Pure Copper-Zinc p-Constituent into a+y. HENRY C. H. CARPENTER (J. I n s t . Metals 1912 8 51 -58).-The p-constituent of alloys of copper and zinc which undergoes transformation at 4.70' during cooling (A. 1912 ii 764) does not segregate even after annealing for several months at 4 4 5 O although the presence of minute quantities of either the a- or 7-constituent brings about segregation much more rapidly.Repeated quenching in liquid air brings about the traiisitory development of a duplex structure the nature of which is unknown. Resolution of the P-alloy at 445' is brought about by contact with an ay-alloy of copper and zinc containing 0.95% of vanadium. C. H. D.INORGANIC CHEMISTRY. ii. 139 The Effect of Other Metals on the Structure of the ,&Constituent in Copper-Zmc Alloys. HENRY U. H. CARPENTER (J. Irhst. Metccls 1912 8 59-85).-‘rhe resolution /3 - a + y. which takes place in alloys of copper and zinc at 470’ (A. 1912 ii 764) is afiected by the presence of other metals in the alloy.Met& which are insoluble in the solid alloy such as lead and chromium are witbout influence but bismuth has .been found in one case to accelerate the resolution Antimony tin aluminium silicon and vanadium which enter into solid solution displace the eutectoid composition to the y-side and assist the resolution. Iron has much less effect. Nickel and manganese have little effect. C. H. D. Copper-Zinc-Nickel Alloys. LBON GIULLET (Compt. rend. 19 12 155 1512-1514. Compare A. 1905 ii 168).-A study of the influence of nickel when added t o certain brasse.;. It is found that the additim of nickel considerably improves their mechanical proper- ties and gives them a “fictitious” proportion of zinc considerably higher than their real proportion (compare A 1906 ii 357).W. G. Constitution of Aluminates. EDWARD G. MAHIN D. C. INGRAHAM and 0. J. STEWART (J. Amer. Chem. Soc. 1913 35 30-39).-The solubility of aluminium hydroxide in alkali hydroxide solutions and t b e existence of minerals containing the oxides of aluminium and certain other metals in apparently coristant proportions have led to the hypothesis that aluminium hydroxide is amphoteric. &lust of the investigations on the aluminates have been directed to the determination of their formulse and have given varying results; they have also shown that the quantitative relations between the alkali metal and aluminium differ according to the method of preparing the solution. I n view of these facts the present work WAS undertaken in order t o ascertain whether the solubility of aluminium hydroxide in alkali hydroxides is not due rather t o its colloidal properties than t o its amphoi eric chnracter.Measurements of the heat of solution of aluminium hydroxide in solution of sodium hydroxide a quantitative study of the action of ammonium nitrate on a solution of sodium aluminate and observations on the behaviour of sodium aluminate on electrolysis have been made. The results iudicate that the solubility of aluminium hydroxide in alkali hydroxide solutions depends very largely on its colloidal proper- ties and that it is doubtful whether aluminates have any existence as definite salts. E. G. The Heusler Ferromagnetic Alloys of Manganese. FRIEDRICH HEUSLER (Zeitsch. anyew. Chem. 191 2 25 2651-2653).-A claim for priority against Wedekind (this vol.ii 55). C. H. D. The Formation of Nitrogen Oxides by Heating Manganese Dioxide in Air. PAUL ASKENASY aud E. L. RENYI (Zeitsch. Elektro- chvrn. 1913 19 23-32).-The statement made by Odier (J. phys. chim. 1798 464) t h a t oxides of nitrogen are produced when manganeseii. 140 ABSTRACTS OF CHEMICAL PAPERS. dioxide is heated in oxygen is investigated. The authors heated natural and artificial manganese dioxide in a current of air a t various temperatures. It was folind that very small quantities of oxides of nitrogen were evolved which never amounted to more than 0.2 mg. nitric oxide from 10 grams of manganese oxide. The oxides made their appearance a t 280° but on beating for several hours ceased to be formed. On raising the temperat.ure 4 fresh quantity was produced.Ahove 700" no oxide could be obtained. The authors draw the con- clusion t h a t the oxides of nitrogen are not formed from atmospheric nitrogen since the same results could be obtained by suhstituting a current of carbon dioxide for that of air. They are of the opinion that the nitrogen is furnished by the manganese dioxide which probably contains a nitrogen compound to the extent of 0.002%. J. F. S. The Passive State of Iron. JAMES MACLEOD-BROWN (Chem. News 1913 10'7 15).-It is fIequentlgasserted that if part of an iron nail or mire ib rendered passive the remainder of the nail or wite also asstimcs this state. That this is not SO may be shown as follows An iron nail three inches long is immersed t o a delltli of one inch in con- centratrd nitric acid.The nail is allowed to drain and the other end imruersed to a depth of one inch in dilute nitric acid when it will be found to be active; the passive end remains passive. If the nail is lowered into the dilute nitric acid passive end fir& the whole of it becomes passive after a short time. Other experiments are described in which it is shown that when a passive iron nail is connected by means of a platinum or copper wire to a nail of ordinary iron the two nails being immersed i n dilute nitric acid that part ot the ordinary iron which dips into the nitric acid becomes pashive after a short time the passivity being produced by anodic polarisation. The author considers that the passive state is conditioned by some definite arrangement of the particles at the surface of the ixon.T. S. P. Equilibria in Quaternary Systems. VI. Quaternary Alloys of Iron Nickel Manganese and Copper. NICOLA PAHEAVANO (Gazaetta 1912 42 ii 589-609. Compare A. 1912 ii 1175 ; this vol. ii 33 55 58).-In the present paper which dors uot letld itself to abstraction the author summarises the results which he haH already obtained (loc. cit.) in the thermal study of the binary and ternary systeuis included in the nhove quaternary bystem and referring to a former theoretical discussion or" quaternary sy*tems (this vol. ii 33) he establishes theoretically the charavteristics which bhould be displaj ed by this quateraary bystem. The experimental pibrt wt1it.h is accou yanird by numerous tables diagrams and photomic:rl,grapbs gives the resulLs of the experimental verification of these theorer ical previsions.R. V. S. Determination of the Atomic Weight of Uranium. WILLIAM (ECHSNER DE CONINCK (Co,mpt. rend. 1912 155 1511-1512).-AINORGANIC CHEMISTRP. ii. 141 determination of the atomic weight of uranium by ignition of anhydrous uranyl oxalate and weighing the residual uranium dioxide. The mean of seven determinations gives the value 238.4 for the atomic weight of uranium. W. G. The Oxides of Uranium. WILLIAM CECHSNER DE CONINCK and ALBERT RAYNAUD (BUZZ. SOC. chim. 1912 [iv] 11 1037-1038).- When uranium formate covered with a layer of methyl alcohol is exposed t o the action of diffused daylight f o r three months uranous oxide (UO,) is deposited and formic acid formed.When urnnous oxide is heated in the air.to a bright red heat the oxide U,Ol0 is produced. T. S. P. The Basicity of the Tungsto-acids. HIPPOLTTE COPAUX (Conrp!. reud. 1913 156 71-75.. Compare Ann. China. Phys. 1912 [viit] 25 22).-The author has determined the conductivity of acids of the type of phosphoturrgstic acid in very dilute solutions and from his results deduced the b:tsicity of the acids. Silicotungstic acid is tetrabasic and even a t high orders of dilution is practically unhydroly sed. I t s isomwide tiingsto~ilicic acid and its isomorph silicomolybdic acid are also tetrabasic and not hydrolysed on dilution. Bot*otungstic acid is pentabasic this being in agreement with its known sodium barium and cadmium salts Aletatungstic acid is hexitbasic but is appreciably hydrolysed i n very dilute solutions.Pbosphotungstic acid is freely hydrolysed on dilution and whilst the composition of i t s ordinary salts and its analogy to other acids point t o its being tribasic the conductivity seems to reach a limit for a basicity of five. Phosphomolyhdic acid is tribasic but in moderately dilute solutions gives values for a tetrabasic acid seemingly due t o hydrolysis of the acid yieldiag two dibasic acids which the author suggests is represented by the equation H3[ P( M~~207),j€14] + 2 H20 = H ,[P( MO,O,)~(OH),H,] + H,MO,O~. I n geueral the corriposition of the soluble salts of strong basss is a criterion of the basicity of tungsto- and molybdo-acids and the value so obtained is in accord with that obtained by conductivity methods.Disagreement is a sign of hydrolysis of the acid on dilution. W. G. The System Tin. ANDREAS SMITS and H. L. DE LEEUW (Proc. K. Aknd. Wetcnsch. Amsterdrcvn 19 12 15 676-68l).-'l'he prohable existence of a transition point for tin in the neighbourhood of 20U" is indicated by a number of observations and in particular by t h e experiments of Werigin Lewkojev and T;irrimanri (Ann. Physik 1903 [iv] 10 147) on the rate of flow of tin under preasure. The fact that Cohen aud Goldschmidt (A. 1905 ii 268) obtained no evidence of the existence of the tramition point in dilatornetric expeliruents is now showu to be due in all probability to tbe slowness with which the change in qliestion takes place and new observatioiis with a dilatometer axe recorded which indicate that the temperature of the reversible change tetragonal tin ZZ rhombic tin is 202.8".Smallii. 142 ABSTRACTS OF CHEMICAL PAPERS. quantities of mercury act as a catalyst but a t the same time the transition temperature is depressed In the presence of 0.12 and 0.22% of mercury the temperatures obtained by the dilatometric method mere 173' and 151' respectively The occurrence of this chitnge at 202%' accounts for the brittleness developed when tin is heated to about 2110° The transition temperature of 170' deduced by Cohen and Goldschmidt from the flow experiments referred to above is based on a n erroneous interpretation of the data in question there being no evidence whatever for the occurrence of any change a t this tempera- ture. H. M. D. The System Tin-Iodine.K. S. VAN KLOOSTER (Zeitsch. aizorg. Chem. 1912 '79 223-229. Compare Reinders and de Lange this vol. ii 60).-Stannous iodide SnI m. p. 321° is practically im- miscible with molten tin at 400'. Stannic iodide SoI m. p. 1 4 3 O mixes in all proportions with iodine the eutectic point being at 1 2 atomic % of t i n and 76'. Stannous iodide is only slowly formed from its components even at 440' in a sealed tube. Stannous iodide crystallises in ruby-red needles D: 5.21. Crystallo- graphic measurement* [by F. M. Jaeger] show that the crystals are monoclinic a c = 1 0.5911 /3 = 83'55''. C. H. D. Thorium Compounds. FRANZ HALLA (Zeitsch. anorg. Chem. 19 12 79 260-262).-8 mixture of anhydrous t.lioriurn sulphate and magnesium carbonate mir h a little water yields a sandy precipitate of basic thoyiurn sulphnte ThOS0,,5H20.The same salt is obtained as a flocculent precipitate by the action of magnesium sulphate on a boiling solution of thorium sulphate or nitrate. The titration of thorium nitrate with potassium hydroxide and phenolphthalein is complete when 3.5 mols. KOH are present for 1 atom Th. With the basic sulphate the hydroljsis proceeds to the same stage It is not possible to wash thorium hydroxide free from sulphate by means of dilute ammonia. The addition of ammonium carbonate to a mixed solution of magnesium chloride and thorium nitrate yields a transparent emulsion the globules of which change to a hard glans on drying. Magnesium hydroxide and thorium sulphate or magnesium sulphate and thorium hydroxide yield a n opalescent jelly.C. H. D. ThOSO KOH = 1 1.75. The Preparation of Metallic Vanadium. 111. WILHELM PRANDTL and HERMANN MANZ (Zeitsch. anorg. Chem. 1912 79 209-222. Compare A.. 1909 ii 1022; 1910 ii 1075)-The vanadium obtained by Ruff and Martin (A. 1912 ii 166) by heating the trioxide with carbon in an electric vacuum furnace is only apparently purer than that obtained by the aluminothermic process the slag which is always present having been deducted in the course of Ruff's analyses. The addition of calcium fluoride in the aluminothermic process is not essential. Vanadium pentoxide gives better results than theINORGANIC CHEMISTRY. ii. 143 trioxide the higher temperature obtained favouring the elimination o€ slag. The presence of alkali is harmful as alkali vanadltte passes into the slag and an excess of aluminium remains.The attempt has been made to remove oxygen from the product by the addition of vanadium hydride prepared by heating electrolytically disintegrated vanadirim in hydrogen at 1000' (Muthmann Weiss and liiedelbauch A. 1907 ii 781) but a liydride has not been obtained the increase i n weight being due merely t o combination with oxygen and nitrogen. The reduction of vanadium trichloride with sodium in slight excess also yields a product containing about 96% of metal. Alumioothermic vanadium (95%) has D 5,987 and 96% metal from the chloride and sodium has D 5.819. C. H. D. The Annealing of Coinage Alloys. THOMAS K. ROSE (J. Inst. Metals 19 12 8 86-1 25).-The softening of metals and alloys hardened by mechanical treatment takes place at any given tempera- ture at first rapidly and then more slowly but at temperatures approaching the melting point it is almost instantaneous.The change is accompanied by recrystallisation. The formation of new crystals at 200' in the case of gold is too rapid to b3 accounted for by diffusion. The softening is accompanied by expansion which is greater in alloys than in pure metals. C. H. D. Condition of Gold in Gold Quartz. P. P. VON WETMARN (Zeitsch. Chem. Irzd. Kolloide 1912 11 287-290).-1f 0.1 to 1% solutions of sodium auric chloride and sodium silicate are mixed a clear solution is obtained which gradually develops a reddish colour and this changes slowly and finally becomes blue. Coagulation commences after several months and the microscopic examination of the coagulum has shown a close similarity in structure with that presented by the gold in auriferous quartz.H. M. D. Some Anomalies Observed in the Assay of Platinum Ores from Ural. H. C. HOLTZ (Ann. Chim. Phys. 1912 2'7 559-566).-The process employed is briefly as follows the mineral is treated with aqucc regia which leaves a residue composed of sand and a compound of osmium and iridium The solution is evaporated t o dryness the residue treated with hydrochloric acid and again evaporated and dried at 130' to reduce the iridium chloride to the ous-state. After dissolving in water the platinum is precipitated quantitatively by addition of excess of ammonium chloride and from the filtrate the other metals (iron excepted) are then precipitated by adding a little hydrochloric acidand a sufficiency of pure zinc. After weighing the deposit ('' blacks ") is treated with dilute nitric acid (1 l) which dissolves the palladium and copper.From this solu- tion the palladium is precipitated by means of mercuric cyanide; the excess of mercury is got rid of by ignition preferably after evapora- tion with hydrochloric acid and the copper precipitated finally as copper thiocyanate. Now on applying the process t o a mixture of the chlorides of platinum iridium palladium rhodium and copper theii. 144 ABSTRACTS OF CHEMICAL PAPERS. results were quite satisfactory but when assaying the ‘‘ Ural ore ” the following anomalies were observed. (1) The “ b l ~ c k s ” are not totally dissolved by the nitric acid (2) The copper oxide (after expelling the excess of mercury) is not completely soluble in hydrochloric acid. (3) The filtrate from the copper thio- cyanate is yellow and gives a dark precipitate on addition of zinc. From further experiments it seems that ( a ) ‘l’he oxide of this mysterious substance is insoluble in hydrochloric nitric nitrohydrochloric and sulphuric acid. ( b ) The oxide dissolves in aqueous sodium hydroxide with a yellow colour. This solution remains bright yellow on adding hydrochloric acid and does not react with potassium iodide ; stannous chloride decolorises it. (c) When fused with oxidising mixture the oxide is not attacked and a colourless mass is obtained. ( d ) The dark product (3) is reduced t o metal by ignition in a current of hydrogen with slight loss in weight. (e) The metal is dissolved by melting with potassium hydrogen sulphate yielding a brownish-red mass which does not give a white turbidity with water (absence of rhodium). (f) It is soluble in nitric acid and its hydrochloric acid solution is not precipi- tated by amrxioniulu chloride. These properties taken in conjunction with similar experiences of other writers lead the author t o believe that another unidentified element is present iu the Ural ore. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9130405131

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

i. 142 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. A Hygienic Pipette for Bacteriological a n d Chemical Work. SERGEI TSCHACHOTIN (Centr. Bakt. Par. 1912 i 67 319-320).-The pipette is intended to facilitate the removal of liquid cultures of pathogenic organisms volatile poisonous compounds or liquids above flocculent precipitates. A double-bored rubber cork is cut transversely and between the two parts an ordinary rubber cap such as is used for closing bacterial tube-cultures is interposed and the three cemented together. Holes are made through the rubber cap with a hot needle and two tubes are introduced (a) a short straight one projecting slightly above and below the cork; ( b ) a siphon tube having the longer arm through the cork. A test-tube having a diameter slightly larger than that of the rubber cork is used as receiver and closed by means of the flange of the rubber cap.The short arm may then be placed in the liquid to be pipetted off and the cork of the pipette depressed slightly into the tube; the short glass tube is then closed by the fore-finger and the cork raised slightly. By this means a sufficient vacuum is created in the tube to cause the liauid to siphon over and the flow is stopped by raising the short arm O U ~ of the &id. H. B. H. Detection of Chitin in Bacteria. A. VIEHOEVER (Ber. Deut. botan. Ges. 1912 30 443-452).-Chitin was found to be present in a number of bacteria and the occurrence of glucosamine in bacterial material is attributed chiefly to the abundant presence of chitin rather than to glucoproteins.The results are of interest in removing a supposed difference between fungi and bacteria. That fungi contains chitin has been known for a long time N. H. J. M. Gas Metabolism of Bacteria. I. Fermentation of Dextrose by Bacillus coli B. typhosus and Bacterium welchii. FHEDERICK G. KEYES and LOUIS J. GILLESPIE (J. Biol. Chern. 1912,13 291-304). -The evolution of gas accompanying bacterial growth on media containing dextrose was studied by an exact method. Dextrose peptone media yield with B. coli more carbon dioxide than hydrogen on anagrohic fermentation; on a medium of ammonium lactate di- sodium phosphate and dextrose nearly equal volumes of the two gases are obtained the mean value of CO,:H being 1.06. This ratio is raised by the presence of oxygen and by increase of phosphate.With B. typhosus the ratio is never below 19; with Bacterium welchii it is 1-48. W. D. H. Gas Metabolism of Bacteria. 11. The Absorption of Oxygen by Growing Cultures of Bacillus coli and Bacterium welchii. FREDERICK G. KEYES and LOUIS J. GILLESPIE (J. Biol. Clrem. 1912 13 305-31 O).-For both micro-organisms the absorption of oxygenVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 143 simulates a unimolecular reaction but the respiratory quotients are widely different. With varying oxygen pressures the ratio CO H varies enormously for B. coli but only slightly for Bact. welchii. W. D. H. Activation of Certain Processes of Microbic Oxidation by Uranium Salts. HENRI AQULHON and R. SAZERAC (Compt. rend.1912 155 1186-1188).-A further study of the influence of uranyl acetate on Mycoderma aceti (compare A. 1912 ii 973) and a compara- tive trial of the influence of uranyl nitrate and uranyl acetate on the sorbose bacteria. I n the case of the acetic acid ferment 1 part of uranyl acetate per 1000 gives an increase of 57% in the acid production and even at a dilution of 1 in 100,000 an increase is shown at the end of seven days. With the sorbose bacteria uranyl nitrate increases the rate of oxidation up to concentrations of 1 in 5000 but stops all fermentation at 1 in 1000. A t all concentrations the acetate has a more favourable influence than the nitrate and 1 part of the acetate in 10,000 produces an increase yield of 76%. W. G. Action of Infinitesimal Doses of Different Alkaline Sub- stances Fixed or Volatile on the Vitality of Microbes.AUGUSTE TRILLAT and M. FOUAPSIER (Compt. rend. 1912 155 1184-1186).-8 study of the effect of adding minute quantities of various alkalis and organic bases to distilled water to which is then added a drop of dilute microbic aqueous emulsion containing no nutrient medium. The results expressed ir numbers of colonies formed are given for the organism M. prodigiosus. With pure water there is slight growth for twenty-four hours and then the organism dies. Death is immediate with sodium hydroxide until a dilution of 1 in 50,000 is reached and it is only in the case of ammonia at dilutions of 1 in 50,000 and higher that there is any marked increase in the number of colonies. With organic bases a t higher orders of dilution (1 in 250,000) the number of colonies formed is greater with fatty amines than ammonia and still greater with aromatic amines aithough even here death ensues after fifteen days.The addition of traces of putrefactive gases t o the distilled water allows cultivation to proceed even after three months. W. G. Putrefaction with Special Reference to the Proteus Group. LEO F. RETTGER and CLYDE R. NEWELL (J. Bio2. Chem. 1912 13 341-346).-Putrefaction is taken to mean decomposition of protein with the production of malodorous substances. The power to bring this about has been attributed to various members of the Proteus group acting anaerobically. The present experiments do not confirm this. W. D. H. The Influence of Organic Acids on the Fermentation by Yeast.FRITZ JOHANESSOHN (Biochem. Zeitsch. 1913,47 97-1 17).- Formic acid and its higher homologues accelerate in sufficiently dilute solutions the rate of fermentation by yeast. The optimal action for each acid lies at the same molecular concentration. The smallesti. 144 ABSTRACTS OF CHEMICAL PAPERS. quantities of the acids which stop fermentation do not kill the past. The stoppage of fermentation depends on the concentration of the acid and not on the absolute quantity present The relationship between this concentration and the quantity of yeast is not a simple propor- tional one but can be represented by the equation of a parabola. No appreciable adsorption of acids by yeast takes place. The essenti 11 action of acids is to be ascribed not to the ions but to the whole undissociated molecule. S.B. S. The Mechanism of Alcoholic Fermentation. ALEXANDER VON LEBEDEV (Biochsm. Zeitsch. 1912 46 483-489).-A reply to the criticisms of Harden and Young (A 1912 ii 670). S. B. S. The Mechanism of Alcoholic Fermentation. 11. ALEXANDER VON LEBEDEV and N. GRIAZNOV (Bey. 1912 45 3956-3272. Com- pare A. 1911 ii 816 1122).-Pure glyceraldehyde is fermented by extract of dried yeast directly to carbon dioxide and alcohol. Hexose- phosphoric ester is not formed as intermediate compound as in the case of the fermentation of dihydroxyacetone. It is further shown that during the fermentation of sugar by yeast extract acetaldehyde is not reduced to alcohol; on the other hand in the absence of sugar yeast extract is able to reduce acetaldehyde to alcohol.'Phis reduction is effected by an enzymatic procesq. It is considered that during fermentation hexove is hydrolysed to two trioses one of which glyceraldehyde loses hydrogeu forming pyruvic acid which undergoes rearrangement immediately and breaks down into acetaldehyde and carbon dioxide (compare Neuberg A. 1911 ii 976 1019 1020). Methylglyoxal hydrate is possibly an inter- mediate product (Neuberg and Kerb A. 1912 ii 973) ; preliminary experiments indicate that methylglyoxal is fermentable by yeast juice. The decomposition of hexose into two molecules of triose is regarded as a reversible reaction ; it will proceed when part of the triose is withdrawn as hexosephouphate so that this last compound acts a8 a regulating factor. The following complete scheme is suggested for fermentation 4C6Hl2O6 = 8C,H,O,.' Glyceraldehyde. Dihydroxyacetone. ' - 4C,H@,-4H,= 4cs[~,o3 4C,H60,+ 4RHPO,= 4C,H,O + 4H2= 4C,H,*OH 4C3H403= 4C',H40 f 4C0 4C,HbO,KPO4 + 4HQO = 2C,H,,O6 + 4RHP0 =BC6Hl,O4(RPO,),+ 4H,O 2C,H,,O = 4C,H60 etc. E. F. A. Influence of Pressure on Alcoholic Fermentation. L ~ O N LINDET and L. AMMANN (Bull. Soc. chim. 1912 [iv] 11 953-956).- Regnard has shown already that under a pressure of 600 atmospheres yeast still ferments sugar solutions. I n the present paper it is demonstrated that under such pressures as may occur in practice in fermenting liquids with yeast in closed vessels the reproduction ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 145 yeast and the fermentation go on at the same rate as under atmospheric pressure although when the experiments are conducted under such conditions that the air is not renewed fermentation and the multiplica- tion of the yeast-cells take place more slowly although the same production of carbon dioxide and alcohol is eventually reached.T. A. H. Is Ethyl Alcohol Produced by Yeast Fermentation in Absence of Sugar ? CARL NEUBERG and JOHANNES KERB (Chem. Zen&. 1g12 ii 1299-1300 ; from Zeitsch. GarungsphysioE. Mykologie 1912 1 114-120).-Since pyruvic acid is easily attacked by yeast with the formation of acetaldehyde (A 1911 ii 1019) it was expected that the ferment alone might be able to carry the reduction further. No alcohol could be found however but in the presence of sugar much less aldehyde was formed than the amount of pyruvic acid destroyed would warrant It seemed therefore that in normal alcoholic fermentation a substance is produced which can reduce pyruvic acid or acetaldehyde to alcohol.Formic acid suggested itself but was found to be without influence. Glycerol however had the effect of largely diminishing the output of acetaldehyde. J. C. W. The Primary Transformation of Hexoses by Alcoholic Fermentation. HANS VON EULER and TH. BEROGREN (Chem. Zentr. 1912 ii 1383-1384 ; from Zeitsch. Garungsphysiol. Afykologis 1912 1 203-218).-The addition of yeast extract to living yeast expedites fermentation by loo% and the difference AC between the change in optical rotatory power and the carbon dioxide developed (compare A 1912 ii 377) is increased by 20%. Assuming that fermentation proceeds in two stages hexose -+ intermediate product and inter- mediate product -+ alcohol and carbon dioxide it follows that if the extract contain8 only one co-enzyme the first stage will be accelerated but if there is a co-enzyme in the extract appropriate to each stage then the two reactions will be unequally accelerated according to the relative amounts cf the co-enzymes. Sodium nucleate also increases the activity of living yeast.J. C. W. The Effect of Phosphates on the Work of the Proteolytio Enzymes in Yeast. NICOLAUV IWANOV (Chenz. Zentr. 1912 ii 1384-1385 ; from Zeitsch. Gariingsphysiol. Mykologie 1912 1 230-252).-The action of antiproteolytic by-products in yeast fermen- tation may be overcome by the addition of acid phosphates.Experi- ments with dead yeast cells (hefanol) show that the decomposition of albumin increases with the concentration of potassium dihydrogen phosphate and that this increase i! independent of temperature. By decreasing the volume of liquid or by the addition of autolysis pro- ducts the action is still further increased whereas leucine and tyrosine do not influeace the process but dipotassium hydrogen phosphate hinders it. The proteolytic enzyme may be partly extracted from hefanol by means of water. When heated to SO' i t becomes inactive but the addition of potassium dihydrogen phosphate revives its activity. It VOL. CIV. i. Ii. 146 ABSTRACTS OF CHEMICAL PAPERS seems that this salt is able to regenerate the peptase and to promote its action. J. C. W. Comparative Influence of Potassiuni Rubidium and C e s i u m on the Development and Sporulation of Aspergillus niger.BENJAMIN SAUTON (Compt. rend. 1912,155,1181-1 183).-Aspergidlus niger was cultivated on Raulin’s liquid in the presence of equivalent amounts of potassium rubidium and casiurn as chlorides and the crops weighed after four days at 37’. Potassium causes an enormous increase in the crop which is diminished by 50% on replacing the potassium by rubidium whilst caesium is not a nutrient substance for the organism. I n a mixture of the chlorides Aspevyillus sziger fixes the potassium before the rubidium and czsium thus forming a means of freeing the two latter from the last traces of the former metal. Potassium plays an important part in the sporulation although in the abEence of zinc this could not be conclusively demonstrated.On substituting rubidium or caesium for potassium no spores are formed. W. G. The Scission of a- and P-Methylglucoside by Aspergillus niger. AKTHUR W. Dox and RAY E. NEIDIG (Biochem. Zeitsch. 1912 46 397-402).-AspergiZZw niger acts on the two glucosides in exactly the opposite way to that in which yeast acts for it readily hjdrolyses the p-form (100% within six days) whereas i t acts only slowly on the a-form hydrolysing only 8% in twenty days. No capacity of adaptation of the ferment to the a-form could be demonstrated. S. B. S. The Bebaviour of Moulds (Aspergillus niger and Penicillium crustaceum) towards Phytin. M. A. JEUOROV (Zeitsch. physiol. Chent. 1912 82 231-242).-The moulds mentioned grow well in a solution of phytin and assimilate its phosphorus especially in the presence of sucrose and peptone or glycerol.They split off phosphoric acid in high measure from the phytin. W. D. H. Decomposition of Carbamide Uric Acid Hippuric Acid and Glycine by Moulds. ALEXANDER KOSSOWICZ (l’ied. Zentr. 1912 41 79 1-792 ; from Zeitsch. Garungsphysiol. Mykologia 1912 1 60-60). -Pure cultures of the following moulds were found to assimilate urea uric acid hippuric acid and glycine under sterilised conditions Botrytis bassiani Aspergillus niger lsaria farinosn a Fusisporium Mucor Boidin and Phytophthora infestam. PGniC&%Um brevkaule and Y. crustaceunz utilise urea uric acid and glycine whilst Cladosporium herbarurn and Aspergillus glaucus only utilised urea and uric acid as sources of nitrogen. N.H. J. M. The Apparent Respiration of Dead Cells in the Reduction of Pigments. OTTO MEYERHOF (Pfliiger’s Archiv 191 2 140 250-274).-Neutral and weakly alkaline acetone yeast possesses a measurable power of taking up oxygen and this is increased in the presence of methylene-blue. I n the presence of dead cells reductionVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 147 of methylene-blue occurs also but it occurs also if the dead cells are absent. It is therefore not due to anything of the nature of vitality. I n one living animal cell the egg of the sea-urchin dissolved oxygen is present. W. D. H. The Action of Uranium on the Plant Cell. C . ACQUA (CIurn. Zentr. 1912 ii 1471 ; from Arch. Farmacot. sperim. 1912 14 81-84).-Dilute solutions of uranium salts (1 20,000 to 1 40,000) are absorbed by the cells of the roots of higher plants where they hinder the division of the nuclei and consequently the growth The cells of the green parts are less permeable to uranium salts and are therefore scarcely injured.Thorium and manganese salts have a similar but much smaller effect. Absorption of Aniline Dyes in Living Plant Cells. E. KUSTER (Bied. Zentr. 1912 41 763-764; from Jahr6. wiss. Bot. 1911 50 26l).-It is shown that a considerable number of dyes insoluble in fats are abundantly taken up by plant cells. Overton’s lipoid hypothesis regarding the nature of the outer layer of protoplasm is therefore insufficient whilst Ruhland’s opinion that there is no relation between the diffusibility of dyes and their penetration into plant cells is incorrect.The Physical Character of Bio-electrical Differences of Potential. REINHARD BEUTNER (Biochem. Zeitsch. 1912 47 73-93). -The difference of potential a t the contact surfaces-part of plant/aqueous solution of an electrolyte-can be altered in the sense that increasing dilution of the electrolyte makes the solution more positive. The change can be expressed by the following equation. J. C. W. N. H. J. M. -~~ _____ Pot. diff. 1 - Pot. diff. 2 = 58 log ‘1- -58 log J1 + 106m2c12. c2 1 + J1+ lO6rn%c,2 where 1 m 58 Limiting value of potential difference - Pot. diff. for c = rh/EiOO log -= The method of arriving at these equations is given and also an ex- perimental verification of the same. The biological significance is also discussed.S. B. S. Sterile Cultures of a Higher Plant. Assimilation of Nitrogen as Ammonia and as Nitrates. IVAN SCHULOV (J. exper. Landw. 1912 13 200-205 (in Russian) 205-206 (German Abstr.). Com- pare Hutchinson and Miller A. 1909 ii 923)-The results of sand culture experiments under sterilised conditions showed $hat nitrogen in the form of ammonium sulphate is assimilated by maize plants. It is also shown that the availability of phosphorite is considerably increased by the employment of ammonium nitrate and that ammonium nitrate overcomes the injurious action of ammonium sulphate. K. H. J. M. Localieation and Function of Potassium in Plants. TH. WEEVERS (Bied. Zent?.. 1912 41 764-765; from Rec. trccu. bot. NZerZand. 191 1 8 289-332).-By means of Macallurn’s reagenti.148 ABSTRACTS OF CHEMICAL PAPERS. (sodium cobaltinitrate with ammonium suIphide and glycerol) it was found that potassium is present in all parts of Thallophytes whilst negative results were obtained with the pollen grains of crocus and tulips. The greatest amount of potassium in Phanerogams was found in the young embryonal tissues rich in plasma and in the paren- chyma of leaves seeds roots and stems. The conclusion is drawn that potassium takes part in the produc- tion of proteins. I t s absence in the chlorophyll is opposed to the theory of Grafe and Stoklasa that it takes part in the process of assimilation. N. H. J. M. Chlorogenic and Saccharic Acids in Latex. K. GORTER (Rec. trav. chim. 1912 31 281-286).-The colour reactions with ferric chloride which de Jong and Tromp de Haas (A 1904 ii 762) have shown to be characteristic of the latex of certain plants resembie the reactions with the chlorogenic acid obtained from coffee (A 1908 i 186).It consists in boiling the suspected substance with dilute hydrochloric acid for an hour extracting with ether and shaking the washed and not too concentrated extract with very dilute ferric chloride when a violet coloration is produced. By this means it is shown that chlorogenic acid is present in the latex of Ficus elastica and of Cnstilloa elastica. I t has actually been isolated from the latter substance 300 grams of the latex yielding 0.3 gram chlorogenic acid m. p. 208" [a] - 35.2". The latex of Ficus elastica contains in addition an organic magnesium salt which has now been isolated and given the formula C,H808M,q,3H,0. The free acid bas [a] + 36*5O and gives a sparingly soluble potassium salt which closely resembles potassium disaccharate and a diphenylhydr- azone m.p. 210° which is identical with that derived from d-saccharic acid. This magnesium salt is the first indication of the occurrence of d-saccharic acid in nature. A delicate test for this acid is now described. J. U. W. The Carboxylase of Higher Plants. W. ZALESKI aud ELISABETH MABX (Biochern. Zeitsch. 1912 147 184-185).-Neuber.g has shown that yeast can ferment pyruvic acid with evolution of carbon dioxide. The authors now show that the addition of this acid to powdered pea-seeds causes an increase of the post-mortal production of carbon dioxide which takes place with equal energy in air and hydrogen.S. E. S. Basic Constituents of Fly Agaric. E. BUSCHMANN (Cham. Zelztr. 1912 ii 613; from Pharm. Post 1912 45 453-454).-A methyl alcohol extract of fly agaric (Amanita muscaria) by precipita- tion with phosphotungstic acid and silver nitrate yield.ed hypoxanthine and xanthine the former predominating (compare Zellner Chemie der haheren Pilxe 1 9 0 7). The Inulin Metabolism of Cichorium Intybus (Chicory). 11. The Formation and Storage of Inulin. VIKTOR GRAFE and V. VOUK (Biochem. Zeitsch. 1912 47 320-330. Compare A 1912 ii 977).-From estimations of reducing sugar and inulin in different T. A. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 149 parts of the plant collected a t different periods the following con- clusions mere drawn.The inulin is not merely a reserve material but is intimately connected with the general carbohydrate metabolism as it can be readily detected macrochemically in the parenchymatous cells of the leaves of young plants. No difference in the inulin and lzevulose content of leaves of plants collected in the morning and afternoon could be detected. From this fact the conclusion is drawn that new carbohydrate is formed during the day in such quantity that an equilibrium is maintained between the laevulose and inulin. As the development of the root progresses there is a constant increase in the inulin content accompanied at first by a diminution of the laevulose ; the latter increases in quantity again as the roots ripen. S. B. S. The Organic Phosphoric Acid of Cotton-seed Meal.R. J. ANDERSON (J. Biol. Chem. 19 12 13 31 1-324).-The organic phosphorised substance from cotton-seed meal is probably either phytin or an isomeride ; this is to be ascertained by further work. W. D. H. Pigments of the Fucoidae. HARALD KYLIN (Zeitsch. physiol. Chem. 19 12 82 221-230).-'3!he fucoidaee contain carrotene and a crystalline yellow pigment probably identical with xanthophyll. They further contain a yellow pigment phycoxanthin which differs from xanthophyll in being soluble in light petroleum. E. F. A. Presence of Gentiopicrin Gentianose and Sucrose in the Fresh Roots of Gentiana Asclepiadea. MARC BRIDEL (Compt. rend. 1912 155 1164-1 l66).-The author has isolated and charac- terised gentiopicrin gentianose and sucrose from the fresh roots of Gentiana Asclepiadea and has obtained indications of the presence of another carbohydrate hydrolysable by invertin.W. G. The Constituents of Ip6 tabaco Wood (Bignonia tecorna). OTTO A. OESTERLE (Chem. Zentr. 1912 ii 1666-1667; from Schweix. TVoclL Chem. Pharm. 1912 SO 529-532).-1n order to investigate the nature of Lee's tecomin (T. 1901 79 284) the alcoholic extract of B. tecoma wood has been freed from resinous matter by means of benzene and light petroleum leaving a mixture which was partly soluble in boiling sodium carbonate solution. The soluble substance crystallised in yellow needles or leaflets m. p. 142-143" soluble in alkalis and alkali carbonates with intense red colours which disappeared on reduction but soon reappeared in the air.Tecomin is possibly identical with lapachol. From the substance which remained undissolved by sodium carbonate light yellow needles m. p. 242O were obtained. J. C. W. Variations of the Fatty Matters Sugars and Saponin-during the Maturation of Seeds of Lychnis Githago. (Mlle.) MARIE KORSAKOV (Compt. rend. 1912 155 1162-1164).-The fatty matters sugars and saponin have been estimated in the seeds of Lychnis Githagoi. 150 ABSTRACTS OF CHEMICAL PAPERS. at three stages in their development (a) just after flowering when young and white; (b) further advanced but still white; ( c ) almost ripe and black The results show a marked decrease in the content of fatty matters and sugars reducing and non-reducing and an increase in the saponin content with advance in development.The young seeds only contain traces of saponin and the amoiint of saponin in the other organs of the plant being practically nil it seems that the glucoside must be formed in the seed itself. W. G. Presence of Gentiopicrin in Swertia perennis. MARC BRIDEL (Compt. rend. 1912 155 1029-1031 ; J. Pharrn. Chirn. 1912 [vii] 6 481-484).-Swc~.tia perennis contains the glucoside gentiopicrin which can be isolated in the pure state and hydrolysed by emulsin (compare Bourquelot and Bridel A. 1910 ii 234). There are also indications of the presence of a carbohydrate which is only very slowly hydrolysed by emulsin. W. G. Occurrence of Trehalose Vanillin and d-Sorbitol. EDMUND 0. VON LIPPYANN (Ber. 1912 45 3431-3434).-After exposure to a sudden sharp frost in July the flowers of some blooming rushes Carex brunescen8 growing in a sheltered spot were observed to be covered with minute hard white crusts which proved to be hydrated t re halose C ,H,,O 2 H,O. The flowers of an orchid Gymrtadenia albida growing last summer on the heights above Davos were observed by the author to have a strong odour of vanilla; vanillin was isolated from them.Under normal conditions of growth the flowers of this orchid contain little or no vanillin. During last year's wet summer many fungi in the fields near Kissingen grew in enormouB quantities and t o prodigious size in particular a variety of Boletus bovinus which reached the dimensions of a dinner plate. After fine weather had set in a number of the tops of these fungi which had been struck off by a passer-by and had partly dried were found to be covered with a network of a crystalline substance which on examination proved to be hydrated d-sorbitol.c. s. Chemical means of Protecting Plants from Frost. N. A. MAXIMOV (Rer. Deut. bot. Ges. 1913,30 504-416. Compare A. 1912 ii 476).-The supposition that the protective action of the substances employed depends on the eutectic point of the solution is confirmed by the results of further experiments in which ,,mixtures instead of single substances were used. A mixture of mannitol and potassium nitrate considerably increased the power of resisting cold whilst the two substances singly have very little effect. As regards the connexion between the protective action and the permeability of the plasma for the protective substance it is now shown that the action takes place immediately and that the result depends on the action of the solution on the surface of the plasma.From this it follows that the death of plants by freezing is due to injury to the surface of the plasma. N. H. J. M.VEGETABLE PEYSIOLOGY AND AGRICULTURE. i. 151 Alfalfa. IV. Enzymes Present in Alfalfa Seede. C. A. JACOBSON (J. Arnsr. Chm. Soc. 1912 34 1730-1 740). -In continua- tion oE the investigation of alfalfa (Medicago scttiva) (A 1912 ii 80 239 976) a study has been made of the enzymes contained in the seeds. The results show that the seeds contain enzymes which like amylase and emulsin are capable of hydrolysing starch and amygdalin respectively ; an enzyme which coagulates milk like rennin ; an enzyme which like the peroxydases precipitates purpurogallin from a pyrogallol solution containing hydrogen dioxide and an enzyme resembling proteases in being able to digest casein and Witte peptone.This protease is found to be a vegetable erepsin since it will not begin the digestion of egg-albumin blood-serum legumin or conglutin and its digestion of casein and Witte peptone is checked to some extent by the presence of egg-albumin or blood-serum. The seeds do not appear to contain invertase or lipase. E. G. Comparative Efficiency for Growth of the Total Nitrogen from Alfalfa Grass and Gorn Grain. EDWIN B. HART GEORGE C. HUMPHREY and F. B. MORRISON (J. Biol. Chem. 1912 13,133-154). -Experiments on heifers show that the utilisation of nitrogen for growth is as efficient when the source is alfalfa hay as when it is corn kernel.There was no sudden increase or decrease in the nitrogen of urine or faxes when the animals were suddenly changed from one ration to the other. The amide-nitrogen which is high in the grass is therefore not valueless. The effect on milk production will be treated later. I n growing heifers the creatinine output rises with increased storage of nitrogen W. D. H. Observations on the Action of Fluorine in Nature. Uao ALVISI (Gatxxetta 191 2 42 ii 450-452).--The author confirms the presence of fluorine in wheat (wben ripe) and in human teeth. He suggests the employment of calcium silicofluoride as a manure. R. V. S. Reducing Substances Present in Fresh Sugar Beets. Their Influence on the Direct Estimation of Sucrose in the Beet.HENRI PELLET (Bull. Assoc. chim. Sucr. Dist. 1912 30 239-253),- Freshly harvested sugar beets always contain a small quantity of reducing sugar amounting to 0.05-0.87 gram per 100 C.C. of the sap. Thia amount is independent of the initial richness of the beet in sucrose and does not vary in different parts of the same beet. The estimation is made in the sap clarified by treatment with neutral lead acetate ; basic lead acetate precipitates some of the rcducing sugar. Beets of inferior quality contain 2-2-5 grams of reducing sugar per 100 C.C. of sap. Beets stored in silos lose some of their sucrose but the amount of reducing sugar does not increase. Beets damaged during harvesting or transport contain 0.3-0.35 gram of reducing sugar; in sickly beets the quantity increases to 0.4-0.5 gram per 100 C.C.of sap. Reducing sugar is not formed during diffusion. The amount arisingi. 152 ABSTRACTS OF CHEMICAL PAPERS. during the processes of manufacture is very small when proper care is exercised. The presence of this reducing sugar renders the polarimetric esti- mation of the sucrose in the beet-juice inaccurate. Sesame Cake. ACH. GR~GOIRE and EM. CARPIAUX (Bull. SOC. chirn. Belg. 1912 26 479-485).-A number of samples of sesame cake have been examined with respect to the content of pure ash lime fat acidity of fat and oxalic acid. The results show great variations in the composition of the commercial products. The pure ash contains as a mean value 34.5% of lime the extreme values being 28.4% and 39.8% respectively.This determination may be employed for controlling the purity of sesame cake since the great majority of other seeds yield an ash relatively poor in lime. Sesame cake free from oil and earth contains an average of 1.99% anhydrous oxalic acid the individual determinations varying between 1 *44% and 2.96%. This value is not sensibly altered when the oil becomes rancid. Free oxalic acid could not be detected. E. F. A. H. W. The Black Earths of the Valley of l’oued R’Dom in Morocco. G. GIN (Commpt. rend. 19 12 155 1166-1 167).-An account of a black arable earth from a fertile valley traversed by l’oued R’Dom. A description of the earth and results of chemical analyses are given. It is found to support vegetation even in the warm dry moaths and this is supposed to be due to the presence of a trihydrated aluminium oxide in the clay which supplies the necessary water during the dry months and recoups itself a t the next wet season.The black colour is due to an amorphous humic substance which is partly soluble to a brown solution in potassium hydroxide. W. G. Agronomic Study of Manganese. 9. NOTTIN (Compt. rend. 1912 155 1167-1169).-A study of the behaviour of different soils towards soluble manganese salts. Soil has the power of rendering the manganese insoluble and fixing it the constituents of the soil however having different absorbent powers. Silica and humus play no part in the manganese fixation. Chalk produces fixation of the manganese by interchange of the calcium and manganese. Natural clay also has a marked absorbent power independent of the lime present. W. G. Nitrolim and its Decomposition in the Soil. 111. C. J. MILO (Chem. Zentr. 1912 ii 1393; from Med. Proefstut. Javu- Suikerind 1912 601-634. Compare A 1912 i 16).-Nitrolim is hygroscopic and absorbs water and carbon dioxide with liberation of nitrogen. The calcium cyanamide decomposes into cyanamide and carbamide which with the help of micro-organisms gives rise t o ammonium carbonate. I n soils which are only slightly absorptive the calcium cyanamide gives basic salts and cyanamide and further decomposition proceeds very slowly. J.’C. W.

ISSN:0368-1769    

DOI:10.1039/CA9130400142

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

ii. 144 ABSTRACTS OF CHEMICAL PAPERS. Miner a l o g i c a1 C h emi s t ryl The Native Elements of the Earth's Crust. VLADIMIR I. VERNADSKI (Certtr. Jlim 191 2 758-765).-The author reproduces with some modifications and extensi0ns.a table from his recent Russian treatise on mineralogy (Opuit Opisatelrtoi Mineralogii part I St. Peters- burg 1908). The main headings in this table are (I) Solid crystalline chemical elements A metals B metalloids ; (11) solid colloidal ele- ments ; (I1 1 ) fluid eleuents ; (IV) gaseous elewents. By including such modifications and combinations as a- p- and y-ferrite a- and P-ferroplatinum bismuth-gold etc. this list is exteuded t o 106 minerals found in the state of native elements. The following forty-wven chemical elements as such occur native Ag Ar As Au Bi Br C Cd C1 Co Cr Cu Pe H He Hg Ir I K? Kr Mn N Na'? Ne Ni Nt 0 Os P? P b Pd Pt Ra? Ru S Sb Se Si? Sn Ta Te TI Zn Xe thorium emanation and actinium emanation.L. J. S. Optical Investigation of Ural Naphtha. MICHAEL A. RAKUZIN (J. Buss. Phys. Chern. Soc. 1912 44 1737-1738).-A sample of naphtha from Dos-Sor D15 0,8754 showed distinct dichroism had a carbonisation constant (K) in benzene (200 mm.) of S.75-4% and yielded distillates which were in all cases inactive. The naphtha is regarded as a perfect natural filter-distillate and the lack of dis- tillate below 150° indicates communication with the atmosphere. T. H. P.MINERALOGICAL CHEMISTRY. ii. 145 W h i t e Sublimates of the Volcano Chinyero (Canaries). ANGEL DEL CAMPO (And. Pis. Quirn.191 2 10 43 1-449). -The sublimates ariqing from the eruption of November. 1909 are pale yellow or pure white crystalline masses interspersed with specks of lava and consist of ammonium chloride (96*2O%) ammonium fluoride (2.45%) ferrous chloride (0.25%) and chlorides of magnesium aluminium etc. (0.70%). Spectrographic examination revealed traces of tin lead silver titanium manganese sodium and perhaps tantalum. G. D. L. An Aluminium Arsenate from Utah. FRANK W. CLARKE (J. Washanyton Acad. Xci. 19 12 2 5 16-5 18).-A white amorphous mineral found with orpiment in the Sunshine mine Mercur district Utah gave (anal. by W. F. Hillebrand) SiO,. A1,0,. Fe,O,. CaO. SrO. MgO. (Ii,Na),O. As2C,. 7'08 26.46 0'64 10.29 2.10 trace 0 12 33.82 P20,. SO,. CO,. F. C1. H20. Total.0.94 0.27 0.88 0'21 trace 17 23 100'04 Of the water 3 22% is lost at l l O o and the remainder below redness. Deducting silica strontianite and gypsum these resiilts correspond with 3(A102H2),As0,,3H,0 + Cw,(AsO,) or with Ca,( A102H2 ),(Ab0,),,5H20. Whether the substance is to be regarded as a simple mineral or as a mixture of liskeardite [ (A102H2)3As0,,5H,0] and berzeliite [Ca3(hs04),] is left undecided. Preslite [ = Tsumebitel a New Mineral from Tsumeb German S o u t b - W e s t Africa. VOJTECH ROSICK~ (Zeitsch. Kryst. &in. l912,51,521-526).-T'he mineral was observed in bmall ernerald- green crystals associated with cbesrylite cerussite calaurine and dolomite. The crystals are imperfectly thveloped and appear t o be orthorhombic (a b c = 0.977 1 0.879) with complex twinning ; D 6.09 H = 3%.A partial analysis by J . Frejka gave PbO. CUO. p,o,. H20. 65.09 11-97 10.26 not det. I n a postscript i t is admitted that this mineral is identical with the L. J. S. recently-described tsumebite of K. Busz (this vol. ii 6 5 ) . L. J. S. Chemical Composition of the Hauynite of the Albanian Hills. NICOLA PARRAVANO (Atti R. Accccd. Lincei 1912 [v] 21 ii 631-633).-The mineral has t h e following composition SiO,. .A1,0,. CaO. Na,O. K20. SO,. C1. Total. 32.18 27'11 10'26 16.34 0.08 14-10 0.31 100.31 The total being arrived at by deducting 0.07 for oxygen replaced by chlorine. This analysis agrees with the formula suggested by Brogger and Backstrom (A 1891 25). K. v. s. Alunogen and Halotrichite. JOHANNES UHLIG (Cent?. Min.1912 723-731 766-776).-8 review is given of the literature of theseii. 146 ABSTRACTS OF CHEMICAL PAPERS. minerals and the following formuh are considered as the most probable alunogen A12!3012,1 6H,O ; halotrichite FeA12S,0,6,24H,0 A sample of "hair-salt from a cave in the Waitopu valley in the Rotorua volcanic district New Zealand is yellowish-white and finely fibrous. Under the microscope it is seen to consist of ' a mixture of fibres of halotrichite (with oblique extinction of 38" and n = 1.49) and scales of alunogen (n= 1.47). D 1-735-1.899. The following analysis corresponds with 48.30% alunogen 41.98 balotrichite with a little free sulphuric acid etc. The material is soluble in water and the insoluble residue consists of 0.70 sulphur 4-15 silicates.AI,O,. Fe,Os. FeO. Na,O. K,O. SO,. H,O. Insol. Total. 11'59 1'24 3'26 0.86 0.53 35.43 43'43 4-85 100.19 Microscopical examination of simiIar materials from other localities shows the frequent intermixture of alunogen and halotrichite together often with some gypsum. L. J. S. Analysis of Garnet f'rom Tavolato. G . SIROVICH ( A t t i R. Accnd. Lincei 19 12 [v] 21 ii 643-645 *').-Two garnets analysed had the following compositions respectively SiO,. TiO,. A1,0,. Fe,O,. FeO. CaO. MgO. Nn,O. H,O. Total. I. 36.74 1-04 5'23 21'10 2-21 31.65 0 96 0'38 0'10 99.41 11. 37.88 096 5'46 21-13 2.17 31'02 0-84 0'29 0.08 99.83 These correspond with the accepted formula for the corriposition of this mineral. R. v. s. Kragerite a Rutile-bearing Rock from Krageroe Norway. THOMAS L. WATSON (Amer. J. Sci. 1912 [iv] 34 50'3-514).-This is a medium-grained rock of light colour and granitic texture consisting mainly of felspar (albite-oligoclase with some microcIine and ortho- clase) much rutile some quartz and a little ilmenite. It is a rutile- bearing aplite and was named kragerite by W. C. Briigger i n 1904. Analysis I by J. W. Watson is of the rock and 11 by W. &I. Thornton of the rutile D 2.225 isolated from it 8. Total. I.* 50-52 25.00 13.98 0'49 0.16 0'34 1.05 6'18 1.00 0.50 trace 0.12 99.34 SiO,. TiO,. A1,0,. Fe,O,. FeO. MgO. CaO. Na,O. K,O. H,O. P,O,. II. 1'06 97.68 - - 0.81 - - - - - - - 100'49 * Also Cr,O 0.39 ; v20 0.55. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9130405144

出版商:RSC    

年代:1913

数据来源: RSC