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J O U R N A L OF THE GHEMICBL SOCIETY. ABSTRACTS OF PAPERS ON ORGANIC PHYSIOLOGICAL AND AGRICULTURAL CHEMISTRY. &omtnittet of A. CHASTON CHAPMAN. A. W. CROSSLEY D.Sc. Yh.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. BERNARDYER D.Sc. 11. 0. FORSTER D.Sc. Ph.D. F.R.S. A. HARDEN D.Sc. Ph.D. E.R.R. T. 11. LOWRY D.Sc. F.R.S. @ ttbXicrrtio1r J. C. PHILIP D.Sc. P1i.D. F. L. PYMAN D.Sc. Ph.D. A. Scom M.A. D.Sc. F.K.R. G. SENTER D.Sc. Ph.D. S. SMILES D.Sc. J. F. THORPE D.Sc. Pli.D. F.R.S. mitor Snb- @bitor J. C. GAIN D.Sc. Ph.D. A. J. GREENAWAY. G. BARGER M.A. D.Sc. F. BARROW M.Sc. Ph.D. H. W. BYWATERS D.Sc. Ph.D. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Pl1.D. W. GODDEN B.Sc. E. GOULDING D.Sc. W. D. HALLIBURTON M.D. F.R.S. H. R. HUTCHINSON Ph.D. L. DE KONINGH. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. (4. F. MORRELL Ph.D. D.Sc. T. S. PATrEmoN D.Sc. Ph.D. T. H. POPE KSc. T. SLATER PRICE D.Sc. 1’11.D. E. H. RODD D.Sc. S. B. SCHRYVER D.Sc. 1%. I). W. P. SICERTCIILY. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHEKS Ph.D. H. WREN M. A. D.Sc. Pl1.D. R. v. STANFORD M.Sc. Ph. n. 1916. Vol. CX. Part I. LONDON GURNEY S J-ACKSON 33 PATERNOSTER ROW E.C. 1916.PRISTYD IS GREAT BHITAIS BY RICHARD CLAY k SOW LIMITED BUI'KSWICY ST. STAMFORD RT. I.K. ASD BUSGAT SVFFOLli.

ISSN:0368-1769    

DOI:10.1039/CA91610FP001

出版商:RSC    

年代:1916

数据来源: RSC

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J O U R N A L A. CHASTON CHAPMAN. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. RI. 0. FORSTER D.sc. Ph.D. F.R.S. A. HARDEN D.Sc. Ph.D. F.R.S. T. M. LOWRY D.Sc. F.R.S. BERNARDYER D.Sc. OF J. C. PHILIP D.Sc. Ph.D. F. L. PYMAK D.Sc. Ph.D. A. SCOTT M.A. D.Sc. F.R.S. S. SMILES D.Sc. J. F. THOILPE D.Sc. Ph.D. F.R.S. G. SENTER D.Sc. Ph.D. THE CHEMICAL SOCIETY. G. BArbGER M.A. D.Sc. F. BARROW M.Sc. P1i.D. H. W. BYWATERS D.Sc. Ph.D. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. W. GODDEN B.Sc. E. GOULDING D.Sc. W. D. HALLIBURTOX M.D. F.R.S. H. B. HUTCHINSON Ph.D. L. nE IiONINGH. F. hf. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. G . F. MORRELL Pli.D. D.Sc. T. 8. PATTERSON DSc. Ph.D. ABSTRACTS O F PAPERS T’. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. E. H. RODD D.Sc. 8. 13. SCHRYVER D.Sc. P1i.D. W. P. SKERTCHLY. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. 1‘. STANFORD M.Sc. 1’h.D. I>. F. TTVISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS P1i.D. 13. W m N M. A. D.Sc. P11.D. LONDON GURNEY AT JACKSON 33 PATERNOSTER ROW E.C. 1916.PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMITED BRUNSWICK ST. STAMFORD ST. S.E. AND BUNGAY SUFFO1.K.

ISSN:0368-1769    

DOI:10.1039/CA91610FP003

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 27 Chlorous Acid and Chlorites. G. BRUNI and G I,E;VI (Gctxicttcr 1915 45 ii 161-179).-The authors have prepared various clilorites and investigated certain of their physical properties. The analogy between chlorites and nitrites is shown by the methods of preparation and by the existence of the compounds AgClO,,NH AgC10,,2NH3 and AgC102,3NH3 which are similar to those formed from silver nitrite and ammonia. Barium chlorite may be obtained absolutely free from chloride by the action of a mixture of chlorine dioxide and carbon dioxide free from chlorine on barium peroxide suspended in hydrogen peroxide solution. The sodium salt may be obtained from barium chlorite and sodium sulphate the liquid being evaporated in a vacuum a t the ordinary temperature ; the ammonium and hydroxyl- amine salts are not obtainable in this way.The basic mercuric chlorite 3Hg(C102),,Hg0 ( ?) obtained from barium or potassium chlorite and mercuric nitrate forms a bright red crystalline pre- cipitate and explodes when dried ; the yellow mercurous salt reddens in the air and decomposes spontaneously on drying. A number of the known reactions for soluble chlorites have been confirmed and the following new o n a added. No precipitate with mercuric chIoride ; red precipitate with mercuric nitrate in neutral and not too dilute solution; with mercurous nitrate a yellow pre- cipitat’e becoming white with excess of the reagent ; with neutraI ferrous sulphate solution a brownish-yellow coloration and in the hot an ochre-yellow deposit and liberation of chlorous vapours ; oxidation of potassium ferrocyanide t o ferricyanide in acid solution ; brucine and diphenylamine show the same behaviour with chlorites as with chlorates ; with reagents for nit’rous acid chlorites slowly give colorations analogous t o those given by nitrites prob- ably owing t o the oxidising action exerted.With concentrated sulphuric acid solid chlorites deflagrate more energetically than the chlorates. Electrical conductivity measurements of potassium silver and barium chlorites give for the mobilitlv of the ion C10,’ a t 2 5 O the values 50*6-51.7 the mean being 51.0 which is less than that for the ion C10,’ and less still than that for C10,’. Similar measurements with sodium potassium and silver nitrites give the mean value 75.4 f o r the mobility of the ion NO,’ a t 25O this being greatelr than that for the ion NO,’.Cryoscopic investigation of potassium chlorite in aqueous solutioas gives the respective values 0.930 0.920 0.935 and 0.959 f o r a with solutions containing 1.0656 grams of the salt in 10 15 20 or 40 grams of water. The decomposition of barium chlorite was studied in the bomb calorimeter and found to take place according to the equation Ba(ClO,),=BaCl + 20,+ 48.6 Cal. From this follows the equa- tIons Ba -I- C3 + 20 =Ba(ClO,),(soIid) + 148.4 Cal. and BaClz +ii. 28 ABSTRACTS OF CHEMICAL PAPERS. 2O,= Ba(C10,) - 48.6 Cal. Ba(ClO,) + 02=Ba(C103) 4 22.8 Cal. and Ba(C10& + 0 = Ba(C10,) + 30.2 Cal. Consequently in com- pounds containing chlorine in different degrees of oxidation the formation is the less endothermic or the more exothermic the higher the degree of oxidation.This apparently paradoxical intro- duction of successive atoms of oxygen with continually increasing energy is in agreement with Angeli’s observations on oxygenated nitrogen compounds (Rend. Accnd. Lincei 1894 [v] 3 i 510). T H. P. Rhythmic Cry stallisation of Sulphur. FRITZ KOHLER (Kolloid Zeitsch. 191 5 17 10-1 I).-Micro-structures of rhythmic character are formed when thin layers of liquid sulphur are allowed t o crystaJlise. These are illustrated by photographs. The author does not agree with the explanation given f o r the formation of these structures by von Fischer-Treuenfeld (A. 1915 ii 553). I n his opinion the rhythmic character of the crystallisation process is due to the rate of crystallisation exceeding the rate of diffusion. This is consistent with the fact that the phenomenon is readily shown in the crystallisation of viscous liquids.H. M. D. Internal Temperature of Sulphur Furnaces. STEFANO PBGLIANI (Ann. chi??^. Applicata 191 5 4 268-270).-Reply to criticism appearing in L’Inrlitstriu (1915 No. 42 Milan) on the author’s work (A. 1915 ii 766). Preparation of Thionyl Chloride and Sulphur Tetrachloride. CHEMISCHE FABRIK BUCKAIJ (D R.-P. 284935 ; froni J Soc. Clzem. Id. 1915 34 1092).-Carbonyl chloride! reacts with sulphur dioxide a t temperatures above ZOOo with the formation of thionyl chloride and sulphur tetrachloride acccrding to the equations SO + COC1 = SOCI + CO and SO + 2COC1,= SCl + 2C0,.The first reaction predominates a t lower temperatlures and with excess of sulphur dioxide and by suitable adjustment of conditions one o r other of the reactions may be almost entirely excluded. The reactions are carried out by passing the gasea over a heated contact substance such as wood charcoal and the carbonyl chloride may bO partly or entirely replaced by a mixture of carbon monoxide and chlorine o r carbon monoxide and sulphuryl chloride may be employed. G. F. M. H. B. NORTH and C. B. CONOVER ( J . Anzw. Chenz. Soc. 1915 37 2486-2490).-The action of thionyl chloride on the sulphides of zinc cadmium silver arsenic antimony iron copper tin (stannic) and mercury has been studied. It is shown that a reaction occurs when the two substames are heated in a sealed tube a t 150-200° for several days.I n general the reaction may be represented by the equation MS + 2SOC1 =MCl -+ SO + S,Cl,. The case of ferrous sulphide presents a slight difference f o r here an oxidation occurs and ferric chloride is formed according t o the equation 6FeS + 16SOCl,= 6FeCls + $SO + 7$2c&. T. H. P. Action of Thionyl Chloride on Sulphides. J. F. S.lNORGANIC CHEMISTRY. ii. 29 Vapour-pressure Investigations of the Fusion Products of Iodine with Sulphur Silenium and Tellurium. ROBERT WRIGHT (T. 1915 107 1527-1531).-A simple method is described f o r the measurement of the pressure of tile iodine vapour in equilibrium with the solid products which result from the fusion of iodine with sulphur selenium and tellurium.Products which contain a large excess of iodine have in all three cases the same vapoar pressure as pure iodine a t the same temperature. With excess of sulphur and selenium the same result was obtained but with excess of tellurium the iodine vapour pressure is very small up t o 1 5 0 O . The results show that in no case are solid solut.ions formed that sulphur and selenium do not combine with iodine on fusion but that tellurium forms a compound TeI,. H. M. D. Metallographic Study of the System Tellurium-Selenium YASUKIYO KIMATA (Mew. CoZZ. Sci. Kyoto 1916 1 119-121).- Tellurium and selenium form two series of solid solutions. These meet a t 95% Se and 130° a t which temperature the liquid and solid phases have the same composition. The two branches of the liquidus and solidus curves intersect a t a sharp angle suggesting a eutectic but all the alloys are microscopically homogeneous.Whether a compound is fosmed a t this point is undetermined. C. H. D. The Imide Character of Hydronicric Acid (Azoimide). I. Synthesis of Lizidoaithiocarbooic Acid. FRITZ SOAIMER (Ber. 1915 48 1833-1841).-1n accordance with its usual formulation as an imino-compound azoimide behaves in the same manner as a secondary amine towards carbon disulphide; analogous t o the formation of the compound NE&*CS*SH,NHEt from diethylamine and carbon disulphide sodium azoimide and carbon disulphide react with formation of the sodium salt of azidodithio- carbonic acid N,*CS*SNa. Sodium azidoclithiocarbonate N,*CS2Na,4H,0 is obtained by the interaction of carbon disulphide and an aqueous solution of sodium azoiinide a t 40-50° a pale yellow solution being obtained which yields colourless prisms on evaporation; the salt is fairly pernian- ent if kept below loo in a closed vessel.It explodes when heated being more explosive in the anhydrous condition. The corresponding potassium salt obtained in a similar manner is a crystalline solid which explodes violently when pressed. The barium salt was also prepared forming hexagonal tablets (N3CS,),Ba,513,0 which were comparable with the sodium salt in explosive nature the anhydrous ,salt being somewhat more explosive. Salts of certain of the heavy metals were prepared by precipita- tion from solutions of the sodium salt. The fact that the colour of the products in some cases deviated from the usual colour of the salts of the metal and their occasional solubility in organic solvents indicate t h a t in common with the xanthic acids azidodithio- carbonic acid bends to form complex salts of abnormal dissocia-ii.30 ABSTRACTS OF CHEMICAL PAPERS. tion. Most of these salts of the heavy metals were exceedingly explosive. SZZ u e ~ salt amorphous; cupric salt yellow ; mercuric salt colourless crystals soh ble in ether carbon disulphide and ethyl acetate ; mercurous salt colourless ; lead salt yellowish-white ; tlwdlium salt yellowish-white ; cadmium salt colourless needles ; bismuth salt yellow ; zinc salt colourless. The addition of ferric chloride to the solution of the sodium salt instead of effecting the precipitlation of the ferric salt of the acid caused oxidation to the disulphide S2(CS*N& which separated in needles; a similar result was obtained with other oxidising agents.This compound is so explosive that even on warming in aqueous suspension a violent explosion may ensue. By treating the concentrated solution of sodium azidodithio- carbonate with hydrochloric acid i t is possible to obtain free azido- dithiocarbonic a c i d ; this by oxidation can be converted into the corresponding disulphide. Details of these compounds will be published later. D. F. T. Explosive Mixture of Phosphorus and Liquid Air. ARNALDO PIUTTI (Atti. R. Accad. Lincei 1915 [v] 24 ii 25%-2.53).-Yellow phosphorus does not comb'ine with liquid oxygen but after removal from the liquid explodes with extreme violence if struck t'ouched with hot iron or subjected t o the action of an electric spark.This property is conferred on the phosphorus only by actual contact with the liquid oxygen. With highly compressed red phosphorus o r with ordinary sulphur no explosion occurs under the above condi- tions but the substance burns vigorously. T. H. P. Fibrox. E. WEINTRAUB (Trans. Amer. Electrocliem. SOC. 1915 27 267-284).-When silicon is heated in a graphite crucible a t 1400-1500° in a gas furnace a small quantity of calcium fluoride being present the crucible becomes filled in a few hours with a fibrous mass of silicon oxycarbide. After breaking away the slag and re-heating a further quantity may be obtained. This material known as fibrox is made up of very fine amorphous threads some- times carrying minute beads of vitreous silica.It is formed by reactions in the s t a b of vapour and experimelnts in an electric furnace show that the presence of carbon dioxide is necessary. The density varies from 1-84 t o 2.2 increasing with the percentage of silicon. The apparent density of the fibrous mass is only 0*0025-0.0030 or 2.5-3-0 grams per litre. Ths thermal resist- ance in the loosely packed condition is very high but diminishes with rising temperature. C. H. D. The Temperature of Reaction between Acheson Graphite and Magnesia. 0. L. KOWALKE and D. S. GRENFELL (Trans. Amer. Electrochem. Soc. 1915 27 221-239. Compare Slade T. 1908 93 327; Lebesu A. 1907 ii 460).-When electrically fused mag- nesium oxide is powdered and heated in a granular carbon resist- ance furnace in contact with graphite the temperat8ure being measured by an optical pyrometar sighted on a hollow graphiteINORGANIC CHEMISTRY. ii.31 ‘‘ black-body,” the reaction MgO + C = Mg + CO begins slowly a t 1950° and becomes very violent a t 2030O. This temperature is sufficiently constant to serve as a fixed point for the calibration of optical pyrometers. When a vacuum furnace is used observa- tions are difficult on account of the fumes produced in the reaction. L. BALBIANO (AWL. Chim. Applicatn 1915 4 231-245) .-Investigation of preparations of graphitic acid and graphitic oxide obtained from three different samples of graphite shows that the compositions of these products vary with the method of preparation and with the quality of the graphite employed.Brodie’s method (Phil. Trans. 1859 149 249) gives a graphitic acid which contains C = 57.35 H = 1-47 and 0 = 41.17 these figures corresponding with the formula C13H407; for the product obtained by Sbaudenmaier’s method (A. 1898 ii 472 ; 1899 ii 481) the composition is C=59.2 H=1*4 and 0=39.4 and the formula CI4H40,. With graphitic oxide the analytical numbers also correspond with the1 formula C,,H40 o r C14H407. Them graphitic products which deflagrate when rapidly heated and vary in colour with the nature of the original graphite and t’he method of preparation are found however to be merely adsorption products of graphite water carbon monoxide and dioxide varying in composition between narrow limits. They have no acidic o r quinonic functions and it is suggested that they be termed yellow green or black hydrocarboxygraphites instead of graphitic acid and oxide.The System Sodium Sulphate-Sodium Chromate-Water. ISAKICHI TAKEUCHI (Mem. CoZZ. Scz. Kyoto 1915 1 249-255).-The equilibrium of this system has been determined a t 1 5 O and 25O. The decahydrates of sodium sulphate and chromate are miscible in all proportions at 15O. A t 25O the solubility curve consists of three branches corresponding with decahydrate solid solution from 0 to 34 mol.% of chromate anhydrous sulphate and sodium chromate hexahydrate respectively. The limit of miscibility of the decahydrate crystals coincides approximately with but the existence of a double salt has not been definitely proved. C. H. D. C. H. D.Graphitic Acid. T. H. P. 2Na2S0,,Na2Cr 0,,30H20 Allotropy of the Ammonium Haloids. I. F. E. C. XCHEFFER (Proc. K. Akad. Wetensch. Amsterdam 1915 18 446--458).- According t o Wallace (A. 1910 ii 208) ammonium chloride and ammonium bromide are enantiotropic having transition tempera- tures a t 159O and 109O respectively. Further experiments with ammonium chloride have shown that the cooling-curve method which was used in the determinations referred to gives a much lower temperature than the true transition temperature in conse- quence of the retarded transformation. I n presence of glycerol o r mannitol which act as catalysts the thermal method yields much better results in that the temperatures indicated by cooling andii. 32 ABSTRACTS OF CHEMICAL PAPERS. heating curves are in fairly close agreement.The value thus obtained f o r the transition t’emperature is 184.5O. The same result has been arrived a t on the basis of measurements of the solubility of ammonium chloride in water between 160° and 205O. If x represents the number of mols. of salt in one mol. of saturated solution then it is found on plotting logz against 1/T that two straight lines are obtained which intersect at 184*5O. The equation for the solubility of the modification which is stable a t the lower temperatures is - logx = 464.5 / T - 0’5400 and for that stable a t higher temperatures - logx = 3 2 7 q T - 0*2412. I n a discussion of the nomenclature of isomerism the author considers that. allotropy may be1 conveniently used to include all cases of isomerism and polymorphism.Where two or more solid modifications occur the allotropy would be distinguished as phase allotropy t o distinguish it from molecular allotropy. H. M. D. Solubility of Calcite in Water in Contact with the Atmos- phere and its Variation with Temperature. ROGER C. WELLS (J. Washington Acad. Sci. 1915 5 617-622).-The solubility of calcite in water exposed t o the air has been determined a t a series of temperatures. The method consisted in placing powdered calcite in water in Jena flasks and bubbling air of average content 3-18 parts of carbon dioxide per 10,000 through it until saturation occurred. The content of calcium carbonate was then estimated by titration with 0*02N-sodium hydrogen sulphate. Saturation required usually about eighty days.The following results expressed in parts of calcium carbonate per million were obtained a t lo 82; 21° 60; 22” 57; 2 3 O 57; 30° 55. The rate a t which saturated solutions deposit calcite on keeping was also determined. The results of the decreased solubility with increase in temperature are discussed from a geo-chemical point of view in connexion with the deposits of the Mississippi and the presence of marble in certain coral islands in the Philippines. J. F. S. The Reactions between Several of tne Salts contained in [Natural] Wa~ers at the Soiling Point. P. PETIT (iVon. Sci. 1914 [v] 4 537-541).-Whilst the precipitation of calcium carbonate from dilute solutions of the hydrogen carbonate is but little influenced by external conditions t’he similar precipitation of magnesium is greatly dependent on the method of heating and the size of the vessel and the condition of its walls.After one hour’s boiling the quantity of calcium carbonate remaining in solution is about 17 mg. per litre and is independent of the initial concentration. With magnesium carbonate on the other hand the percentage precipitated decreases with decrease in initial concen- tration and for concentrations of about 110 mg. per litre 50% a t most is eliminated by an hour’s boiling in clean vessels. Water containing both calcium and magnesium hydsogen carbonates loses nearly all its calcareous matter when the calcium considerably predominates; the magnesium is precipitated as if it were alone. Sodium chloride diminishes the precipitation of calcium carbonate,INORGANIC CHEMISTRY.ii. 33 and also of magnesium carbonate except in minute quantities in which case the precipitation of magnesium carbonate is increased by about 10%. From a water containing calcium hydrogen carbonate and magnesium sulphate with a preponderance of calcium the precipitation of calcium carbonate is almost unaffected by the presence of the magnesium salt but with a preponderance of magnesium precipitation of calcium carbonate is diminished and in neither case is much magnaium carbonate eliminated. Calcium sulphate in excess facilitates the precipitation of mag- nesium carbonate and with a pmponderance of 21 1 92% of the lather is eliminated. With increasing 0xcess of magnesium hydro- gen carbonate increasing quantities of calcium carbonate are precipitated from a sulphate solution G.F M. Formation of Magnesium Suboxide in the Electrolytic Preparation of Magnesium. FRANCIS C FRARY ahd HARRY C. BERMAN (Trans. Amer. Electrochem. Soc. 1915 27 209-219).- When magnesium and potassium chlorides ar0 electrolysed in a graphite crucible small mame5 of a dark substance which evolves hydrogen with water are found in the mass after cooling. The gas so obtained contains 95% of hydrogen the remainder being nitro- gen. The dark solid oxidises so rapidly that it has not been found possible t o make an analysis. It is without action on a solution of anhydrous nickel chloride in absolute alcohol whilst metallic magnesium powder rapidly precipitates nickel. The dark sub- stance is not formed when oxygen is completely excluded from the electrolyte by melting in a stream of hydrogen chloride and con- tinuing the passage of the gas during electrolysis.Adding a little magnBium oxide to this electrolyte results in the formation of suboxide. C. H. D. Atomic Weight of Cadmium. W CECESNER DE CONINCK and G&RARD (Compt. rend. 19 15 16 1. 676- 677).-The substance used was cadmium carbonate which was prepared by dissolving metallic cadmium in sulphuric acid and passing a current of hydrogen sulphide for several hours; the precipitata after washing was dissolved in concentrated hydrochloric acid the excess of acid evaporated off and a large excess of a concentrated solution of ammonium carbonate added cadmium carbonate alone being pre- cipitated. This process was repeated three times. A definite weight of the dried cadmium carbonate was ignited in a special crucible in a current of pure hydrogen and from the ratio CdC03:Cd the atomic weight of cadmium was calculated.The mean of five determinations was 112.32. W. G. Red Lead. JAROSLAV MILBAUER (Chenz. Zezt. 1915 39 858-859). -The presence of silver in lead oxide has a Tavournble eff ecb on thO formation of red lead a t low temperatures; a t 300° 27% of Pb304 was obtained against 9% in the absence of silver. At higher temperatures no effect was observed on the formation of red lead. Bismuth is also indifferent but zinc and antimony cause an appre- VOL. CX. ii. 2ii. 34 ABSTRACTS OF CHEMICAL PAPERS. ciable reduction in the amount of the higher oxide formed. Iron and copper likewise have no accelerating effect and they tend t o influenm the colour unfavourably.The formation of red lead is accelerated by using amorphous preparations of lead oxide and by employing air or oxygen under pressure (Austrian Pat. 58167). The equilibrium conditions semain thereby unaltered. The prepara- tion of pure red lead by fusion of lead oxide with potassium nitrate (A. 1914 ii 464) is not possible owing to the reversibility of the reaction. A new wet method f o r the preparation is suggeded namely by boiling lead peroxide (3 mols.) and lead oxide (2 mols.) with concentrated aqueous potassium hydroxide. The product is 100% pure and its colour varies from purplish-red t o bright red with increasing concentration of the alkali. G. F. M. MASAO KINURA (Mem.CoZZ. Sci. Kyoto 1915 8 149-152. Compare Fay and Gillson A 1902 ii 260).-This system is of a simple type the only compound melting a t 904O with one eutectic point a t 412O and 24% Pb the other eutectic practically coinciding with pure lead. Solid solutions are not formed to any appreciable extent. The micro-structure is simple and accords with the thermal diagram. C. H. D. Alloys of Tellurium with Lead. Metallography of the System Thallium-Selenium. TAKEJIRO MURAKAMI (Mem. CoZZ. Sci. Kyoto 1915 1 153-159).-The equili- brium diagram of this system is complex. There are three com- pounds of which two present themselves as maxima on the freez- ing-point curve whilst the third decomposes below its melting point. There are three eutectic points a t 281° 283O and 150° respectively.These correspond with alloys containing 1% 21% and 52% of selenium respectively. Tl,Se decomposes a t 265O and undergoes a transformation a t 165O. There are two gaps of miscibility in the liquid state extending from 4 to 14.5% Se and from 55 to 97.5% Se. All the compounds are brittle and the micro-structure is in accordance with the thermal diagram. T1,Se melts a t 368O and TlSe a t 310O. C. H. D. The Structure of Electrolytic Copper. M. VON SCHWARZ (Intern. Zeitsch. Metallographie 1915 7 124-173. Compare Faust A. 1912 ii 1173).-Very large crystals 5 cm. or more in length may be obtained from an ordinary sulphate bath for the electrolytic deposition of copper the temperature being 1-7O and all agitation being avoided. The crystals are repeatedly twinned octahedra and their orientation is confirmed by etching.The growth of crystal grains in massive electrolytic copper on annealing is also described. The larger grains absorb the smaller excep't where the metal has been locally strained. The very small grains produced by straining grow much more rapidly than the others a t first but this difference only persists for a short time of annealing. Electrolytically deposited crystals grow parallel to the surfaceINORGANIC CHEMISTRY. ii. 35 of the cathode oiie octahedral face being in contact with the cathode and elongation taking place along a trigonal axis. Twin- ning occurs when these crystals are annealed but again disappears after prolonged annealing. The effect of pressure on isolated crystals in causing the forma- tion of new crystal centres is also shown by the experiments and the observations are utilised for a discussion of the hypothesis of an a,morphous modification produced by flow and also present a t the crystal boundaries in cast metals.Micro-structural Changes accompanying the Annealing of Bronze. HENRY S. RAWDON (J. Washiizgtoii. Acud. Sci. 1915 5 589-591).-Specirnens of bronze containing 88% of copper 10% of tin and 2.4 of zinc have been annealed a t various temperatures. The cast a.lloys lose their dendritic structure a t 800° but without any change in the form of the crystal grains. Bronze which has been deformed in the cold recrystallises completely the depth of the layw affected by the deformation remaining constant as the crystals increase in size.Cerium Alloys. I. The Constitution of Cerium-Copper Alloys. FRANZ HANANAN (I?zter?z. Zeitsch. AletaZlogruphie 1915 7 174- -212).-Tlie metallic cerium used contains cerium 96.71% iron O.SO% the remainder being cerite metals. It melts a t 715O and as a small quantity of an iron eutectic is undoubtedly present the true melting point of cerium must be close to 720O. The metals are melted in unglazed porcelain crucibles under a layer of sodiurn chloride or mixed potassium and sodium chlorides. The cerium is best added t o molten copper except for alloys containing morethan 80% Ce for which the reverse process is used. The thermo-couple is pro8tected by a very thin tube of unglazed porcelain and the cooling curves are determined by the inverse-rate method. The freezing-point curve has two well-marked maxima corre- sponding with a compound Cu6Ce which melts a t 935O and Cu2Ce melting a t 820O.There are also two compounds which are formed by reactions between solid and liquid thus giving rise to breaks in the freezing-point curve; Cu,Ce a t 780° and CuCe a t 514O. There are three eutectic points a t 875O 757O and 415O occurring at 1776 44% and 84% of cerium respect'ively. Solid solutions are not formed. The alloys richest in cerium contain traces of a ternary eutectic of copper cerium and iron. The hardness curve of the alloys determined by Brinell's method has two pronounced maxima corresponding with the compounds Cu&e and Cu,Ce the former being nearly four times as hard as copper. The micro-structure of the alloys is described in detail and illustrated.The colour of the alloys resembles that of copper as far as the first eutectic; from that point t o the third eutectic i t resembles that of bronze and then becomes steel-grey. Only those which lie between 55% and 85% Ce are pyrophoric. Those containing less than 30% Ce are stable and retain their colour in air ; richer alloys soon disintegrate. C. H. D. C. H. D. C. H. D. 2-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. Calorising Metals. W. E. RUDER (I'ra7z.s. Amer. Electrochem Soc. 19 15 2 7 253- 266) .-The process of '' calorising " consists in heating the metal a t 700-950° in a mixture of powdered alumia- iuin and alumina with the addit'ion of about 1% of ammonium chloride Copper and brass are heated a t 700-BOOo iron and steel at 9QQ-950° a larger proportion of metallic aluminium in the mixture being required by the latter metals.The time is usually two t o three hours. Aluminium alloys supesficially with the metal and gradually diffuses inwards. When heated for a long time a t or above 1000° the greater part of the layer of alloy disappears owing to diffusion and a thin layer of oxide. remains on the surface. Nickel wire or ribbon may be coated with a layer sufficiently thick t o resist oxid& tion without injuring its flexibility. The stages in the diffusion are illustrated by photo-micrcgraphs. C. IX. D. Manganese-Bismuth Alloye. E. BEKIER ( I a t e m Zeitsch. ~Ietullogrc~phie 1914 7 83 -92 Compare Parravano and Perret A. 1915 ii 565).-Powdered manganese may be dissolved in molten bismuth by heating very cautiously in unglazed porcelain tubes around which a reducing atmosphere is maintained.There is a eutectic point very close t o pure bismuth. Only a single com- pound is formed the composition of which lies between MnBi and Mn,Bi. Partial miscibility in the liquid state extends from 39% t o practically 100% of manganese the horizontal part of the curve being a t 1240O. C. H. D. The Iron-Carbon Equilibrium Diagram. OTTO RUFF (Ferrunz 1915 12 121-123. Compare A. 1913 ii 56).-The cementite which is decomposed wibh formation of graphite during the cool- ing of liquid iron-carbon alloys is that which is in excess of the equilibrium concentration but below the saturation concentration. Any excess above this latter concentration separates as free cementite.The true eutectic temperature is 1125O or possibly nearly 1 I3O0 ; the pseudo-eutectic te'mperature is higher about 1138O. C. H. D. The Pseudo-eutectic Temperature of the Iron-Carbon Alloys. OTTO RUFF and WALTER BORMANN (Ferrzmz 1915 12 124-126. Compare preceding abstract).-The true eutectic tem- perature is that a t which the iron solid solution and cementite solidify in the same ratio as that in which they are present in the liquid. The pseudo-eut'ectic temperature is that a t which the liquid is simultaneously saturated for cementite and graphite. Experiments t o determine thel latter temperature must be made with hypereiltectic alloys ; otherwise the absence of graphite nuclei causes great undercooling. An iron containing carbon 4.13 silicon 0.074 sulphur 0.006 manganese 0.15 phosphorus 0.02 and copper 0.005% is melted in a graphite crucible the atmosphere of the electric carbon furnaceINORGANIC CHEMISTRY. ii.37 containing about 30% of carbon monoxide. The pseudo-eutectic temperature is found quite sharply 1138.8O +_ lo. It is slightly raised by addition of silicon and lcwered by that of manganese. C. H. D. Can the Dissociation Theory be Applied to Solid Solutio s in Steels 3 EDWARD D. CAMPBELL (J. Anze?.. Chem Soc. 1915 37 2522).-Owing to an ammeter used in the experiments described previously reading too high (A. 1915 ii 779) a correction of from 0.42 to 0.48 microhms is to be applied to the figures there given. This correction does not effect the significance of the figures o r the deductions drawn from them. J.F. S. The Behaviour of Slag Enclosures in Acid Steel. F. GIormn and S. ZURLENA (Ifbtem. Zeitsch. Illetallogrnphie 191 4 7 35 - S3. Compare Giolitti and Tavanti A. 1915 ii 57).-Specimens are cut from the sound central portion of an ingot of acid open-hearth steel containing carbon 0*38% manganese 0*60% silicon 0*22% sulphur O*OOS% phosphorus 0.02% and nickel 2.02%. I n all cases the enclosures of grey sulphide slag are found in the central part of the ferrite masses completely separated from the pearlih. When heat'ed for four hours a t a constant temperature of 1060O in carbon dioxide slight decarburisation takes place and the slag enclosures are now frequently in contact with pearlite. The effect is more marked a t llOOo. In carbon monoxide a t l l O O o the carburised portion shows the1 ferrite and slag completely independent.This occurs whenever carburisation takes place whilst ferrite formed during an oxidising process encloses the slag. The results are attributed to the influence of the slag on the oxidation of the carbide and consequent liberation of ferrite. Repeating the experiments with a steel containing carbon 0*40% manganese 0*58% silicon 0*20c;/ sulphur 0*006% phosphorus 0.03"/ and nickel 1*98% also of acid open-hearth origin the same changes are found t o take place still more readily. The only slag enclosures which exert an influence on the distri- bution of ferrite are those of light grey colour usually regarded as manganese sulphide. LESLIE AITCHISON (T. 191 5 107 1531-1538).-The influence of molybdenum on the corrodi- bility of '' high-speed " steels has been investigated by comparative experiments with a standard pure carbon steel and a series of steels containing approxiniately the same percentage of carbon and quantities of molybdenum varying from 2.5 t o 20%.The results obtained with 3% sodium chloride and 1 t o 10% sulphuric acid sohitions show that the addition of small quantities of molybdenum i3 accompanied by a considerable increase in the corrodibility ol' the steel. I n the salt solution the corrosion increases somewhat with further increase in the molybdenum content but in the acid solutions this is accompanied by a diminution in the corrodibility. I n tap-water molybdenum first produces a slight diminution and then a slight increase.C. H. D. Corrosion of Molvbdenum Salts.ii. 38 ABSTRACTS OF CHEMTCAL PAPERS. The results obtained in the investigation of the action of 10%) sulphuric acid on the steels shows that no trace of molybdenum dissolves until the proportion of molybdenum exceeds t h a t required’ for the formation of carbide (19-20%). This is in agreement with the micro-structure of the samples. H. M. D. An Acid-resisting Alloy to Replace Platinum in the Con- struction of a Bomb Calorimeter. S. W. PARR ( J . Amer. Chenz. SOC. 1915 37 2515-3522).-After a large number of experiments an alloy has been obtained which on account of its high tensile strength resistance to acids and closely-grained structure has been used for making calorimetric bombs. This alloy which melts a t 1600° renders the use of a platinum lining quite unnecessary.It. has the following composition; 6.42% Cu 0.98% Mn 1*04% Si 3.13% W 60.65% Ni 1.09% Al 0.76% Fe 21.07% Cr and 4.67% No. J. F. S. The Monoclinic Double Sulphates containing Ammonium. Completion of the Double Sulphate SQries. *4. E. H. TUTTOR (Phil. Tm?zs. 191 5 A. 216 1-62) -The crystallographic and optical properties of the double sulphates of the series R,M( S0,),,6H20 i n which R is ammonium and M represents magnesium zinc and iron have been described in previous papers (compare T. 1905 87 1123; A. 1913 ii 603). The present paper gives an account of the properties of the five remaining double salts in which M represents nickel cobalt manganese copper and cadmium. The densities of the corresponding potassium rubidium and msium double sulphates have been redetermined by the immersion method the values previously obtained by the pyknometer method being rather low.The chief experimental data of interest t o the chemist are given in the following summary Ammonium nickel sulphate-monoclinic [a b c = 0.7373 1 0.5000 p= 106’57’1 ; Di’ 1.923. 2.586 czsium 2.872. For corresponding potassium salt D;’’ = 2.237 rubidium Ammonium cobalt sulphate-monoclinic [a b c = 0.7386 1 0.4975 ; p = 107’2’1 ; r)? 1.901. Potassium salt DF =2*219 rubidium 2.567 caesiuni 2.844. Ammonium manganese sulphate-monoclinic [a b c = 0.7400 1 0.4931 ; 0 = 106’51’] ; UiO 1.831. Rubidium salt DT’ =2*461 caesium 2.740. [a b c = 0.7463 1 5066 ; /3 = 106’9’1 ; DT 1.926. Potassium salt D:” =2.233 rubidium 2.574 caiuni 2.858.Ammonium copper sulphate-monoclinic Ammonium cadmium sulphate-monoclinic [a 71 c = 0.7364 1 0.4931 ; /3 = 106°41’] ; Uy) 12.061. Rubidium salt DY 2.695 cxsium salt 2.957. The results obtained for the above five amnioniuni salts are per- fectly in line with those yield-ed by the three! salts examined.INORGANIC CHEMISTRY. ii. 39 previously. The close similarity of the crystal angles the axial ratios the volume constants and the optical constants indicates that the ammonium salts of the double sulphate series are fully entitled t o be considered as truly isomorphous with the correspond- ing potassium rubidium and caGum salts. The ammonium salts do not however exhibit the eutropic relations which are found to exist between the salts of the three alkali metals.I n spite of the departure of the ammonium and also the thallium salts from the law which in the eutropic series expresses the connexion between the crystallographic properties and the atomic weight of the alkali metal i t has been clearly established that non-eutropic replacement may occur with extremely small alterations in the crystalline structure. These changes are almost vanishingly small when rubidium is replaced by either ammonium or thallium. H. M. D. Metallographic Study of the System Antimony-Tellurium. YASUKIYO KIMATA (Mem. CoZZ. Sci. Kyoto 1915 1 115-128. Compare Fay and Ashley A. 1902 ii 266).-The freezing- point curve of this system has a maximum a t 620° correspond- ing with the compound Sb,Te,.There are two eutectic points a t 540° and 28% Te and a t 420° and 89% Te respectively. There is no indication of the formation of solid solutions. The flatness of the curve in the neighbourhood of the eutectic point on the bismuth side led Fay and Ashley to assume that solid solutions were formed on this side the curve passing through a minimum. Microscopical examination confirms the' existence of the two eutectics. C. H. D. Nitrogen Compounds of Gold. ERNST WEITZ (AnnuZen 1915 410 117-222).-Explosive nitrogenous compounds of gold are obtained not only from the salts or oxides of gold and aqueous ammonia or ammonium carbonate but also from auric hydroxide and the ammonium salts of strong acids. I n 1840 Dumas assigned t o the substance obtained from chloro- auric acid and ammonia the formula 4 ( AuN ,NH,) ,2 (A u C1,2 N H,) ,9H,O and to another prepared from auric hydroxide and ammonia the formula 2(AuN,NH3),3H,0.Raschig in 1886 regarded the latter as goldamidine NH:Au-NH ; another compound obtained from ammonia and an excess of chloroauric acid was defined as gold- iminochloride NH :AuCI whilst the former of Dumas' compounds was stated t o be a mixture of these two. These formulz have been generally accepted without further evidence of constitution and no attempt has hitherto been made t o formulate the nitrogen compounds of gold in accordance with the co-ordination theory. The compounds described by the author &re generally obtained only under definite conditions of concentration of the reagents and most of them have been analysed in the wet state on account of their explosiveness and decomposition by washing ; the names are The paper deals with these two points,ii.40 ABSTRACTS OF CHEMICAL PAPERS. determined by the ratio Au:N. From the numerous data re- corded in the paper the following summary may be made By treating an aqueous solution of chloroauric acid with ammonia (5 mols. o r more) precipitates are obtained containing gold nitrogen and chlorine; as the amount of ammonia is increased the quantity of chlorine in the precipitate diminishes the ratio Au:N however remaining constant a t 1 1.5. These precipitates which are called by the general name " explosive gold-chloride," are mix- tures of two substances t o which after drying the compositions Au203,,3NH3 (.sespz~iammipzect.lIric oxide) and NH(AuCI*NH& (diamznoiminodiauric clhloride) are given.The chlorine-free con- stituent has been isolated. When air-dried it has the composition 2Au(OH),,3NH3 and is relatively harmless but after drying a t 105-110° or in a vacuum over phosphoric oxide it loses water and then explodes very violently by mere rubbing or pressure with a spatula . Other mixtures (explosive gold-nitrate -bromide etc.) have been prepared by another method; the ratio Au N is still 1 1.5. When N / 5-chloroauric acid containing ammonium chloride is added t o a cold saturated solution of ammonium chloride saturated wit 11 ammonia an individual compound diaminoauric chloride Au(NH,),Cl is obtained which contains 1H,O. This is a dense yellow powder which is not explosive and is decomposed by washing with water yielding ultimately a substance ( ? Au3N2,zH,0 or 3Au0,2NH3,yH20) which is explosive.Explosive gold-chloride and diaminoauric chloride are each con- verted by continued treatment with aaueous ammonia into seaqui- ammineauric hydroxide. This is changed t o diamminetriaurozis oxide ;-Au2Q,2NH3 a very explosive black substance by heating a t 115-120° and into a more explosive monoammineauric oxide Au203,2NH3 by hot water. Sesquiammineauric hydroxide is con- verted by warm dilute hydrochloric acid into chloroauric acid explosive gold-chloride being an intermediate product. The hydr- oxide is scarcely attacked by dilute sulphuric o r nitric acid in the cold but by warming ammonia is eliminated and explosive pro- ducts (Au N = 1 1) are obtained. Cold conesntrated nitric or sulphuric acid does n o t decoinposd the sesquiammineauric liydr- oxide a salt only being formed.Te tru-n m mineauric nitrate [Au (NH,),](NO,) colourless needles is obtained when about N/5-chloroauric acid saturated with ammonium nitrate is added t o a cold saturated solution of ammonium nitrate the mixture treated with gaseous ammonia a t the ordinary temperature and the precipitate washed with water. The salt can be crystallised from warm water. I n not too dilute solution itl is precipitated unchanged by almost all nitrates but with potassium sodium or ammonium nitrate in sufficiently con- centrated solution it yields double nitrates [Au(NH,),](N03),,MN0 crystallising in needles. By double decomposition tetra-ammine- ainric nitrate has been converted into other salts containing theINORGANIC CHEMISTRY.ii. 41 cation [AU(NH~)~] (represented by R in the formulze; the phos- phate RPO,,H,O fkely crystalline colourless precipitate; oxalate nitmte NO,*R(C,O,) ; .perchlorate R(ClO,) stout prisms (specially suited by reaction with potassium salts for the preparation of other soluble tetra-ammineauric salts) ; oxalate perchlorate C10,*R(C20,) very small leaflets; chlorate R(C10,),,2H20 tufts of very thin leafy needles; iodate; two sulphate nitrates NO,*R*SO,,H,O and R4( S0,),(N0,)2,2H,0 ; a complex hydrogeu sulphate R,H,(SO,) ; sulphate perchlorate ; and chromate R,(CrO,) have been prepared. These salts are very stable in the solid state and retain their ammonia even against the attack of concentrated acids. The salts of the strongest acids have a neutral reaction.Tetra-ammineauric hydroxide has not been isolated but its existence is indicated by the facts that the nitrate is distinctly more soluble in aqueous alkali hydroxides or ammonia than in water and that from these alkaline solutions the nitrate is again precipitated by the rapid addition of nitric acid; when the alkaline solutions are kept they become brownish-yellow and yield yellow explosive precipitates which appear to be mixtures (explosive gold- nitrate etc.) constituted similarly to explosive gold-chloride or such mixtures containing also monoammineauric oxide. Tetra-ammineauric salts of the halogen acids cannot be obtained a t all events in solution; when the colourless solutJon of tetra- ammineauric nitrate is treated with f o r example aqueous potassium chloride a yellow colour is produced and a yellow ex- plosive precipitate (explosive gold-chloride nitrate) is obtained..Bromides iodides cyanides and thiocyanates produce similar changes; potassium fluoride does not produce any coloration o r precipitate. Constitutional formulz of the preceding nitrogen compounds of gold are discussed and attempts are made t o extend the formula to the explosive nitrogen compounds of other noble metals and of mercury. c. s. Organosols of Metals and Metallic Hydroxides of the Platinum Group. 111. CONRAD AMBERGER (Kolloicl Zeztsch. 1915 17 47-51. Compare A. 1912 ii 1053 1059; 1914 ii 60). -Colloidal osmium dioxide may be obtained by the method which has been used previously f o r the preparation of organosols of platinum and palladium.Lanolin is impregnated with a solution of potassium osmate and the mixture relduced by the addition of hydrazine hydrate The product is dissolved in light petroleum and can be precipitated by the addition of alcohol. It consists of colloidal osmium dioxide in admixture with lanolin as protective colloid. I f the precipitated organosol is heated in a current of hydrogen a t 50° to 60° the oxide is reduced to metal and the metallic organosol dissolves readily in ethyl ether benzene light petroleum and other organic solvents. An organosol containing 21% of metallic osmium has been obtained in this way. H. M. D. 2*ii. 42 ABSTRACTS OF CHEMICAL PAPERS.The Hydroxylammonia Complexes of Bivalent Platinum. L. TSCEIUGAEV and I. TSCIIERNJAEV (Compt. rend. 1915 161 637-639).-The authors have succeeded in preparing all the members of the series of compounds [Pt(NH2*OH).(NH,) - n]C12 namely [ P t (NH,. OH) 4] C1 [Pt (NH,*OH),(NH,)ICI (1.1 (11.) [OH*NH,>pt<NH NHJ c1 2 [ OH*NH N H ~ > P t < ~ ~ ~ * O l I ] C 1 2 OH-NH (IIIA ) (IIIB.) [P t (NH,* OH) (NH3)31 c1 [Pt(NH3)&1 (IV. 1 (V. ) Of these only I and V were previously known and IIIB very imperfectly. Starting with Yeyrone’s chloride this when digested with hydroxylamine in aqueous solution gives the compound IIIA which yields the mixed complex N ~ > P t < ~ ~ ~ . o 1 4 on treatment with hydrochloric acid at the temperature of a water-bath. This complex easily fixes two molecules of hydroxylamine t o give the compound 11 o r two molecules of ammonia t o give the compound IV. The compound IIIB is readily prepared by the action of hydroxylamine in aqueous solution on the chloride of Reiset’s basel 11 the1 latter chloride being regenerated by the action of hydrochloric acid. All the members of this series of compounds are colourless and more or less soluble in water being ionised. The molecular con-. ductivities lie between 240 and 260 which corresponds exactly with electrolytes of the type (Pt,4A)X2. They yield platinochlorides palladochlorides and picrates. Of these the platinochlorides pre- pared by precipitation with potassium platinochloride are the most characteristic those of the compounds I 11 and IIIA being rose- violet in colour and those of IIIB IV and V being green. This reaction readily distinguishes between the isomerides IIIA and IIIB. The chloride [Pt(NH,),NH,*OH]CI gives when heated with hydrochloric acid Clew’s salt (Yt,SNH,,Cl)Cl. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9161005027

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 42 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. The Occurrence of Nodules of Manganese in Mesozoic Deep-sea Deposits from Borneo Timor and Rotti; their Significance and Mode of Formation. G. A. F. MOLENGRAAFF (Proc. K. Akad. Wetensch. Amsterdam 1915 18 415-430).- Analyses &re given of nodules obtained from the island of Rotti,M INERA LOG1 CAT CHEMISTRY. ii. 43 where they occur in siliceous limestones marls and clay shales. I refers to a nodule from Sua Lain and I1 to a iiociule found in the neighbourhood of Bebalain. SiO,. Fe,O,+Al,C),. H,O,. MnO,. COO. BaO. CaO. Na,O. H,O. COT I. 2.9 2.3 57.7 10.5 0.3 11.7 5.6 1.1 - trace I n the case of 11 calcium oxide1 and alkalis were not estimated. 11. 3.44 1.45 62.06 6.03 - 9-15 - - 8.86 - H. M. D. Iron Ore on Calambaganga Island Philippine Islands.The small island of Calambayanga in the ba.y of Mambulao south- eastern Luzon contains a deposit of iron ore in metamorphosed sedimentary rocks probably of Miocene age which are intruded by andesites and overlie granite and diorite. The ore consists of almost pure haematite with only traces of magnetite and is associated with some pyrites and quartz. Analysis I is of an average sample and I1 of a hand-specimen. SiO,. Al,O,. Fe,O,. FeO. CaO. MgO. Mn02 P. S. TotalFe. \VALLACE E. PRATT (Phdippiite J. S C ~ . 1915 10 A 323-331).- I . . . . 1.02 1.31 97.35 - - - 0.11 0.001 - 64.14 I1 .... 1.29 6.52 68-28 9.22 2-77 0.29 0.09 0.10 0.12 54-94 L. J. S. Iron Ore in Surigao Province Philippine Islands. WALLACE E. PRATT and VICTOR E.LEDNICKY (Philippine J. Sci. 1915 10 A 335-346).-The iron ores of the (' Red Hills," on the north-eastern coast consist of ferruginous (limonitic) clay covering the surface with a maximum thickness of about 20 metres. They are residual weathering products of igneous rocks (apparently peridotites) being of lateritic origin and they resemble the clayey iron ores of Cuba. An analysis gave SO,. A1,0,. Fe,O,. FeO. Cr,O,. S. P. combined. scopic. Total. 1-04 10.56 66-SO 0.36 1.15 trace trace 6.60 13.50 100.01 The average of numerous samples from bore-holes gives 47.40% Fe in the dehydrated ore. Ilvaite and other Minerals from Perda Niedda Oriddese (Sardinia). ERNESTO MANAYSE (Atti R. Accad. Lincei 1915 [v] 24 ii 285-289).-The ferriferous deposits of Perda Niedda contain a number of minerals of which the following are1 described (1) Ilvaite which occurs in pit'ch-black compact o r radiating fibrous masses usually coated with ferric hydroxide hardness about 6 D 3.95 composition as follows H,O H,O hyg1-0 - L. J. S. H,O. SiO,. Al,O,. Fe,O,. FeO. 2.66 29.37 0.67 19.47 27.74 (2) Garnet usually dark gre.en but hardness 6-7 D 3.83 composition SiO,. Al,O,. Fe,O,. MnO. 35.09 2.01 29-82 0.53 3lnO. CaO. MgO. Total. 6.48 13.25 0.51 100.15 sometimes colophony-coloured CaO. MgO. Total. 33.10 0.48 101.03 2*-2ii. 44 ABSTRACTS OF CHEMICAL PAPERS. (3) Wollastonite white radiating fibrous masses hardness 4-5 D 2.86 composition H,O. SiO,. A1,0,. Fe,O,. CaO. MgO. Total. 0.85 50.49 Trace 0.54 47-72 0.51 100.1 1 T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9161005042

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 44 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Purification of Filter Paper by Hydrofluoric Acid. A. GAWALOWSKI (Zcitsch. nizcll. Chew. 1915 54 5OS).-Treatment of filter-paper with hydrofluoric acid results in the removal of silica but any calcium and iron salts which may be present are converted into their respective fluorides ; calcium fluoride is insoluble and ferric fluoside is very slightly soluble in water and although the latter may be removed by prolonged washing of the paper care must be taken that the wash-water is free from even traces of ammonium potassium or sodium salts since these convert the ferric fluoxide into a still less soluble double salt. The hydro- fluoric acid solution used t o remove the silica from the paper should be very dilute and the paper should then be washed thor- oughly; otherwise the paper becomes “hardened.” W.P. S. Use of the Colouring Substance of Red Cabbage as a n Indicator. ECKERLIN (Chem. Zentr. 1916 ii 489-490 ; from Mztt. I<. Lumkmnst. Wcuserhygienc 1915 58- 69).-A solution of the indicator is obtained by boiling red cabbage leaves for thirty minutes with three times their weight of water filtering the extract and after cooling neutralisiiig i t with N / 100-potassium hydroxide solution. The indicator is green in alkaline solution and red in acid solution; a t the neutral point in the presence of alkali salts the colour is bright blue although the neutral indicator itself is violet. The indicator solution may be preserved by the addition of 0.2% of chloroform o r 0.9% of phenol and should be stored in the dark (compare A.1913 ii 237 522). w. P. s. Some New Indicators for the Colorimetric Determination of Hydrogen Ion Concentration. HERBERT A. LUBS and WILLIAM MANSFIELD CLARK ( J . Wc~shiizgton Acnd. Sci. 1915 5 609-617).- The authors have pxepared and investigated a number of substances of the methyl-red type with the object of ascertaining their use for the estimation of the hydrogen-ion concentration in bacterial media. Among those newIy prepared were monoethycred [ethyl- amino b enze?ze-o-a.zob e?izoic acid] which gives colour changes over the range P’r 4*25-Pf 6.00; diethyl-red (diethylaminobenzene- o-azobmzoic acid) colour changes over the range Pf 4.50-Pb 6 - 5 0 ; monopropyl-red f o r the range Pf 4.25-Pk 6.25; and dipro&-ANALYTICAL CHEMISTRY.ii. 45 red f o r the range Pf 4*50-P+ 6.50. Of indicators already known the following have been investigated t o ascertain tlie range of concentration over which they may be used monomethyl-red (Pi 4-2-Pi 6.3); a-naphthylamine-red (Pz values of little use f o r the present purpose) ; dimethyl - a - iiaphtliylamine -red (P; 4-50-P$ 6.50) ; and diphenylarnine-red (P ;I 4.25-Pfi 5.50). the symbol PS is defined as log. 1 /CIT w1iei.e C is the concentra- tion of the hydrogen ion. A number of indicators of the sulphone-phtlialein type have been prepared by a new method and investigated. The method consists in tlie action of the phenol in question on the acid chloride of o-sulphobenzoic acid in the presence of zinc chloride. The follow- ing substances were prepared and the range of usefulness deter- mined phenolsulphonephthalein (P$ 6.50-PL 8.50) ; o-cresol- sulphonephthalein (P!r values similar t o those of the phenol com- pound) ; thymolsulphonephthalein (P$ S.O-Pf 9.75) ; a-naphthol- sulphonephthalein (P$ 7.50-Pz 9-00> ; tetrabromophenolsul- phonephthalein (P; 3.50-P f 4.50) ; and bromothymolsul- phonephthalein (Pi 6.00-P-f; 7.25). Full details of the method of application of all the indicators mentioned are given in the paper.J. I?. S. Qualitative Micro-analysis. E. EMICH (Zeitsch. ctizcil. Chevz. 1915 54 489-502).-Directions and methods are given for the preparation of reagents used in micro-chemical tests and for the manipulation of precipitates etc. in capillaries. The presence of nitrogen in 0.002 mg.of urea may be detected by heating this quantlity of the substance with calcium carbonate and allowing the ammonia formed to come into contact with a minute fragment of red litmus paper contained in the capillary in which the mixture is heated; the ammonia may also be identified by means of its reaction with platinum chloride. A quantity of 0.0002 mc. of mercury can be detected by heating a drop of the solution containing the mercury with a piece of copper wire a few mm. in length and 0.1 mm. in diameter then transferring the wire t o a capillary and subliming the mercury ; the sublimed mercury may also be identified by converting it into the iodide. W. P. S. Activation of Chlorate Solutions by Osmium. 111. Separa- tion of Rydrogen and Methane Catalysis of Mixtures of Hydrogen and Oxygen.K. A. HOFMANN and OTTO SCHNEIDER (Ber. 1915 48 1585-1593. Compare A. 1913 ii 62 609).-The behaviour of various noble metals towards oxidisable gases in the presence of chlorate solutions has been studied. Preparations were made by evaporating the salts of the metlals in quantities equiva- lent t o 1 gram of potassium osmate to dryness with formic acid and then adding a solution containing 15 grams of sodium chlorate and 2 grams of sodium hydrogen carbonate to 100 C.C. These mixtures were tested against the gases in a Hempel pipett'e. Towards hydrogen the activity decreased in the order P t Rh Ru Pd Au Os Ir Ag the higheik absorption being only 18 C.C. inii. 46 ABSTRACTS OF CHEMICAL PAPERS. twenty-four hours.Carbon monoxide was even less absorbed the highest rate being 11 C.C. per day and the order Os Rh Au Pt Ru Pd Ir Ag. Methane and ethylene were scarcely absorbed a t all. The addition of an equimolecular quantity of osmium dioxide to these catalysts frequently gave a mixture that was much more active towards hydrogen or carbon monoxide than the two catalysts separately this being particularly so in the case of palladium. It has been the aim of the authors t o improve the rate of absorption of hydrogen so as to apply an activated chlorate solution in the estimation of hydrogen and they have devised an absorbent which is prepared as follows Tubes o r rods of porous earthenware are steepe-d in 5% platinic chloride solution then ignited in a flame so that they are covered with thin films of platinum and packed into a Hempel pipette with the platinised ends uppermost.The pipethe is then filled with a solution containing 35 grams of sodium chlorate 5 grams of sodium hydrogen carbonate 0.05 gram of palladous chloride and 0.02 gram of osmium dioxide in 250 C.C. Such a mixture becomes more active after using it a time or two and can easily be arranged to absorb about 100 C.C. of hydrogen per hour without shaking whilst thel one quantity will oxidise slightly more than 22 litres. The cost of the soluble catalysts is only a few pence. The contact “poisons” are usually removed before i t is neces- sary t o estimate hydrogen in a gaseous mixture but having done this the above absorbent gives excellent results with pure hydro- gen and mixtures of hydrocen and methane with or without nitrogen. Although oxygen alone is not absorbed yet when mixed with hydrogen some of it takes part in the oxidation.This has led t o a study of the catalysis of mixtures of hydrogen and oxygen that is the oxidation of hydrogen under the influence of the above absorbent with the difference that the chlorate was left out’. Hydrogen alone is scarcely absorbed a t all. The speed of the oxidation is influenced by the composition of the gaseous mixture and is greatest not with electrolytic gas but with a mixture containing more hydrogen. Higher concentrations of oxywn have a bad retarding effect’ owinp. no doubt t o an action ~n the catalyst’ but this is overcome by dilutinq with nitrogen o r nitrown and methane. That is mixtures of hydrogen and air soon give the correct absorption calculated f o r the gas which happens not to be in excess.Carbon monoxide is much more slowly oxidised by the above combination of catalvsts than hydrogen but strange t o say i t does not “coison” the mixture for this is just as useful for hvdrogen after being treated with carbon monoxide as before. Neither does a change in the reaction of the solution affect the catalyst much for phosphoric acid may replace the sodium hydrogen carbonate without changing the activity. J. C. W. Estimat;on of Hvgroscopic Moisture in Soils. W. 1). HAIGH (Sci. Proc. Roy. Dublin Soc. 1915 [S.S.] 14 5%-534).-The soilAKALY TICAL CHEMISTRY. ii. 47 is mixed with about three times its weight of calcium carbide and the acetylene evolved measured after a few minutes.The apparatus employed is similar to that described by Masson (T. 1910 97 851). The results obtained by this method were slightly lower than those obtained by heating the soil in zn oven for sixteen hours. M7hen much organic matter is present as in peat for instance the difference between the two methods is greater which seems to be due to the loss of volat,ile substances other than water when the soils are heated. Soil which was heated for several hours a t 180° and then exposed t o the air for several days gave results by the two methods zgreeing within 0.04%. It was found that 0.018 gram of water gives 10.5 C.C. of acetylene; the theoretical amount is 11.2 C.C. N. H. J. M. Estimation of Total Chlorine in Caoutchouc Substitutes.A. HUTIN (Aim. Chim. cmal. 1915 20 241- 242). - From 0.2 to 0.5 gram of the substance is placed in a crucible the latter is about one-half filled with a mixture of sodium carbonate and potassium nitrate and then heated until gases burning with a luminous flame are no longer evolved and the mixture is melted. After cooling the contents of the crucible are dissolved in dilute nitric acid and the chlorine is estimated volumetxically. w. P. s. Estimation of Fluorine. WILLIAM H. A 4 ~ ~ ~ ( J . Anzer. Chem. SOC. 19 15 37 2500-2515).-Practicall;y the whole of the methods hitherto proposed for the estimation of fluorine have been subjected to a critical experimental examination. As the result of a large number of experiments it is shown that the Berzelius-Rose method of fusion of insoluble fluorides will give good results and account for the whole of the fluorine in the mineral if the residue insoluble in water after the first fusion is submitted to a second fusion.I n studying the Offermann method by which the fluoride mixed with silica is converted into silicon tetrafluoride which is decom- posed by water and the solution titrated with alkali it is shown that although the results are always low the best results are to be obtained by using 98.6% sulphuric acid a t 200-220° and employ- in5 powdered quartz. The estimation of soluble fluorides is best effected by precipitation as lesd chlorofluoride. The precipitate in this case is washed by means of a saturated solution of lead chlorofluoride. The only satisfactory method of detecting and estimating fluorine in small quantities is the colorimetric method of Steiger-Merwin.J. F. S. Estimation of Oxygen by Winkler’s Method. G. BRUHNS (Chenz. Zeit. 1915 39 845-848).-Tlie author discusses Winkler’s modified method f o r the estimation of oxygen in waters (A. 1915 ii 277) and suggests further manipulative simplification such as keeping the potassium iodide in the solid form and adding a small crystal immediately before’ acidification and conducting the titra-ti. 48 ABSTRACTS OF CHEMICAL PAPERS. tion in the original bottles after withdrawing a small measured volume t o make room for the thiosulphate solution required for the absorption of the iodine. Also in cases where nitrites o r organic matter is present instead of using carbon dioxide gas f o r converting the manganous hydro'xide into carbonate the addition of about 1.5 grams of solid potassium hydrogen carbonate is recom- mended. The precipitate rapidly settles and the supernatant liquid can be removed and the precipitate washed without removal from the bodtle by decantation followed by upward filtration through a plug of cotton-wool placed in a fairly wide glass tube a t the upper end of which suction can be applied.Three rinsings with wash water are sufficient. G. F. M. Determination of Gases Dissolved in Waters and Effluents. A. A. SWANSON and G. ,4. HULETT (J. Anzc~.. Chcnz. Soc. 1915 37 2490-2500).-A method of determining the amount of gases dissolved in waters is described. This method is applicable in all cases whether the water contains oxidisable material which would effect all tiiximetric methods o r for gases to which chemical methods are not applicable for example nitrogen.The method consists in principle in shaking a known volume of the water in a vacuum until the gas has distributed itself between the vacuum and the liquid and set up an equilibrium. This gas is then withdrawn t o a gas analysis apparatus and analysed in the usual way. From the volumes of t h e water and vacuum and the1 partial pressures of the gas in equilibrium in the vacuum with that in the water the total coiicentration of the gas originally present is calculated. I n the case of oxygen a modification is introduced. A volume of water is shaken with a known volume of hydrogen and the oxygen in the gas phase determined by passing the mixture over heated copper.Apparatus suitable for carrying out the above operations is described in detail in the1 paper. J. F. S. Method for the Estimation of Inorganic Phosphorus in Body Tissues and Fluids. A. COSTANTINO (Chem. Zentr. 1915 ii 287 ; from Arch. Farmacol. sperim. 1915 19 307-316).-The substance or fluid is treated with acid mercuric chloride solution (see this vol. ii 62) excess of mercury is removed as sulphidel the' solution is neutralised and treated with 25 C.C. of 10% barium nitrate solution and 1 2 C.C. of 10% ammonia. After twelve hours the pre- cipit'ate is collected washed with a solution containing 0.1% of barium nitrate and 0.1% of ammonia then dissolved in dilute nitric acid and the phosphoric acid estimated by the molybdic acid method.w. P. s. Estimation of the Citric Acid Soluble Phosphates by the Ferric Citrate Method. N. ZACHARIADES and J. CZAK (Chenz. Zentr. 191 5 ii 724 ; from Zeitsch. landzc. Versiich.c.- Wesen Oes ferr. 1915 18 472-475).-The authors consider Popp's method for the estimation of phosphates in Thomas slag t o be preferable t o the Darmstadb hydrochloric acid method and to give more accurateANALYTICAL CHEMISTRY. ii. 49 results. They point out that addition of hydrogen peroxide for the oxidation of any hydrogen sulphide compounds is usually superfluous and secondly that i t is quite unnecessary to filter off the precipitate a t once; it may without prejudice remain over- night. G. F. M. Purification and Physiological Action of Animal Charcoal.A. G. BARLADEAN (Pharm. Zentr.-h. 1915 5 6 683-687).-Animal charcoal usually contains impurities some of which are soluble in water and some in alkali or acid. Non-carbonised organic material is also frequently present. After recarbonisation and repeated extraction with alkali acid and water animal charcoal still retains salts which are sufficient to double1 o r hreble the growth of the rootlets of germinating wheat corns (Triticum sa"tivum) immersed in distilled water and animal charcoal as compared with those immersed in distilled water alone. H. W. B. Detection of Carbon Monoxide in Blood. KNUD SAND ( J . Pharm. Cham. 1915 [vii] 12 366-368; from Am,. hyg. pub. vied. Zkgnle 19 15 222).-The suspected specimen of blood is compared spectroscopically with normal blood and with blood saturated with carbon monoxide.I n each case 10 C.C. of a 3% dilution of the blood is taken and treated with about fifteen drops of a solution of iodine in potassium iodide which transforms the hzemoglobin into methzemoglobin whilst the carbon monoxide-hzemoglobin remains unchanged. The solutions are then filtered and examined by the spectroscope. The author states that in this way 5% of carbon monoxide in blood can be detected. H. W. B. Apparatus for the Transference of Gases used in Hesse's Method for the Estimation of Atmospheric Carbon Dioxide. EMIL GROZEA (Chenz. Zentr. 1915 ii 297-298; from Bzd. Snc. Ftiinte BzLcurestz 1914 16 156-159).-The air is originally contained in :I holder supplied with a tap above and one below.The gas is displaced from this holder by water entering a t the lower tap and passes through the upper tap into a Hesse flask. This flask is originally filled with water but as the air enters a corresponding amount of water flows out the cork being doubly bored and fitted with tubes f o r this purpose. The carbon dioxide in the transferred air is then estimated by titration with barium hydroxide solution. D. F. T. Estimation of Carbon Dioxide in Carbonates Decomposed by Ammonium Chloride Solutions. A. CAVAZZI (Ann. Chinz. Applicata 191 5 4 137-144).--The carbonates of calcium barium strontium magnesium zinc lead cadmium bismuth copper lithium sodium potassium and probably other metals ar0 gradu- ally decomposed and dissolved by boiling ammonium chloride solution chlorides of the metals being formed and the carbon dioxide liberated as ammonium carbonate (compare A.1915 ii 795). The latter may then be passed into an ammoniacal calciumii. 50 ABSTRACTS OF CHEMICAL PAPERS. chloride solution and the carbon dioxide estimated as calcium carbonate by titration with acid. This method is not affected by the presence in the carbonate of organic matter and avoids the inconveniences caused by such impurities as hydrogen sulphide sulphur dioxide etc. sometinies contained in the gas liberated by acid from complex mixtures like cements. When the carbonate is insoluble in water the mixture containing i t must be very finely powdered in an agate mortar; even with precipitated carbonates this treatment is recommended. The method has been applied t o argillaceous limestone cement soil ash alkali carbonate mixture of the latter with alkali hydroxide white lead bismuth carbonate malachite azurite siderite etc.T. H. P. The Interaction of Perchloric Acid and Potassium Sulphate a8 an Example of Reversible Change. WILLIAM ALFRED DAVIS (T. 1916 107 1678-1681).-Tt is shown t h a t potassium may be accurately estimated by the perchlorate method even in presence of sulphates if the residual solution contains a sufficient excess of perchloric acid. I f the evaporation is continued so as t o expel the greater portion of the perchloric acid the precipitate is con- taminated with hydrated potassium hydrogen sulphate which increases the weight of the precipitate and thus leads to high results. In general practice i t is advisable however t o eliminate the sulphate by evaporating with the addition of baryta igniting very gently and using the aqueous extract for evaposation with per- chloric acid.The treatment with baryta removes not only sulphate but also silica magnesium and phosphates. (KH SO,,H,O) H. M. D. The Estimatinn of Small Quantities of Po+a,ssinrn. A. J. HAMBURGER (Riochem. Zeitach. 1915 71 415-463).-The principle of the method consists in the precipitation of the potassium in the form of the pota-ssiliw sodium colnaltinitrite. C'o(NO2),*3(K / NaNO,),.nH,O which is then centrifuged and the volume of the preciDitate is measured. The cobalt> reagent is prepared by dissolving 50 grams of cobalt nitrite in 100 C.C. of water to which solution 50 C.C. of glacial acetic acid is added.A second solution is made by dis- solving 50 grams of sodium nitrite in 100 c . ~ . of water. Six parts by volume of the solution of the cobalt salt are mixed with ten parts hv volume of the solution of sodium nitrite shortly before use. Five C.C. of the solution containing the Dotassium salt are mixed with 1.5 C.C. of the cobalt solution and the mixture is kept f o r sixteen hours at 3 7 O . It is then introduced into a special form of funnel (of which an ihstration is given) which ends in a Cali- brated capillary tube of 0.04 C.C. capacity etched in 300 parts. each of which corresponds with 0*001 gram of potassium. The precipitate is separated by centrifugalisation into this tube and the volume is then determined. It is necessary t o keep t o the snecified con- ditions of experiment t o obtain satisfactory results which are notANALYTICAL CHEMISTRY.ii. 51 influenced by the presence of relatively large amounts of sodium nor by the presence of calcium magnesium or sulphates. Phos- phoric acid must however be removed and for this purpose a mixture of calcium chloride and hydroxide or magnesia mixture can be best employed. Attention is called to the advantages of this method as compared with others that have been used for the estimation of potassium. S. B. S. Estimation of Potassium in Fertilisers. FERDINAND PILZ (Chem. Zentr. 1915 ii 365 ; from Zeitsch. laizdw. Vers.-Wesen Osterr. 1915 18 77-108).-The author has investigated the per- chlorate method and recommends the following procedure for the estimation of potassium in fertilisers (A) In potaslh fertzlisers (potassium chloride Icainite etc.).-Ten grams of the sample are heated with 200 C.C.of water and 10 C.C. of concentrated hydro- chloric acid ; barium chloride solution is added in quantity sufficient t o precipitate all the sulphate present the mixture is cooled diluted to 500 c.c. and filtered. Twenty-five C.C. of the filtrate are transferred to a glass basin 10 C.C. of perchloric acid (D 1.125) are added and the mixture is heated until hydrochloric acid vapours are no longer given off; after cooling the contents of the basin are treated with 25 C.C. of alcohol containing 0.2% of perchloric acid the precipitate is rubbed down to a fine powder then collected in a Gooch crucible washed with the acid alcohol and dried at 120-130° for thirty minutes.The process must be carried out in an atmosphere free from ammonia vapours. (B) I n mixed f ertilisers (superpihosphates wood-ash etc.).-Ten grams of the sample are dissolved and the sulphate precipitated as described under (A); the solution is then rendered ammoniacal heated treated with ammonium carbonate cooled diluted t o 500 c.c. and filtered. Fifty C.C. of the filtrate are evaporated in a platinum basin the residue is dried and heated to expel ammonium salts then dissolved in water the solution filtered and the potassium precipitated with perchloric acid as described (compare Davis T. 1915 107 678). w. P. s. Determination of the Speciflc Electrical Conductivity in the Testing of Potable Watera.M. FORXAINI (Ann. Chim. Applicnta 1915 4 150-183).-According to Kohlrausch the amount of dissolved salts in an ordinary potable water is given in mg. per litre approximately by the expression 0.75 . x . 106 where x is the specific electrical conductivity of the water (compare Doroschevski and Dvorshantschik A. 1913 ii 1071). The author's investigations in this direction show that the water should be freed from gas by thorough shaking prior to the measure- ment of the conductivity and that care should be taken to avoid the formation on the electrode of gas bubbles which may alter the capacity and thus lead t o appreciable error. I n order to avoid the use of a thermostat the conductivity may be measured a t any temperature between Oo and 25O and the value corresponding with 1 8 O calculated from the formula xls=)it/[1 + 0*023(t - lS)]=xt.w t ;ii. 52 ABSTRACTS OF CHEMICAL PAPERS. a table is given showing the value of mt for each tenth of a degree between Oo and 25.9O. The proportions of organic matter normally present in natural waters have little influence on the conductivity and the silicic acid which varies from 0 to 0.1 gram per litre and may exist in the colloidal condition usually introduces an error of from 0% to 4-5% although in rare cases it may amount to 10%. A number of waters from different parts of Italy have been examined and the results indicate that 0.71 represents more nearly the average value of the coefficient of the above expression than Kohlrausch's value 0.75. Wit'h the former number the approxi- mation of the calculated t o the actual amount of salt present varies between -4.2% and 3.1%.Further it is found that if the saline residue calculated in mg. per litre according to Kohlrausch's ex- pression (factor 0.75) is diminished by the number of mg. corre- sponding with the total hardness determined by Clark's method and expressed in French degrees the resultant number differs from the actual salt content by from - 3.9% to + 2.1%. When the value of xis. 106 is less than 200 calculation of the saline residue from the conductivity gives somewhat untrustworthy results since observational errors become appreciable a t such dilu- tions unless indeed special precautions are taken. Further when xis. lo6 exceeds 700 anomalies become to increase in frequency and magnitude owing to the diminished dissociation of the dissolved salts and the greater complexity of the salt solution; in these cases it is advisable t o dilute the water with doubly distilled or con- ductivity water before measuring the conductivity.A bibliography is appended. Separation and Estimation of Aluminium and Glucinum by the use of Acetyl Chloride in Acetone. H. D. MINNIG (Amer. J. Sci. 1915 [ivl 40. 482-485).-The method of procedure is the same as that described for the separation of aluminium and iron (A. 1915 ii 107) aluminium being precipitated from concentrated solution as the hydrated chloride and weighed as oxide whilst glucinum remains in solution and is precipitated by ammonium hydroxide after diluting with water and warming on a steam-bath to volatilise the acetone.It is essential that the acetyl chloride be free from phosphorus compounds and it is accordingly best prepared from acetic anhydride by saturating with hydrogen chloride and distilling a t looo in a rapid current of the same gas. The insolu- bility of glucinurn chloride in the acetone-acetyl chloride mixture limits the process to the separation of quantities of the two elements which do not exceed the equivalent of 0.15 gram of the oxides and of this amount glucinum should not greatly exceed one- third otherwise there is a danger of inclusion of glucinum chloride in the aluminium precipitate. T. H. P. G. F. M. The Development of Electro-Analysis in America. EDGAR F. SMITH (T~nizs. Amer. Electrochem Soc. 1915 27 23-34).- Historical. A new method for the estimation of cobalt is described.The metal is converted into cobalt ammonium fluoride and electro-ANALYTICAL CHEMISTRY ii. 53 lysed in a platinum dish with 0.8 ampere and 2 volts. The cobalt is precipitated completely on the anode as the dioxide in a hydrated form which is weighed as Co30,. The separation from nickel is complete. The addition of ammonium fluoride is equally successful. C. H. D. The Quantitative Estimation of Nickel with Dimethyl- glyoxims. KARL WAGENMANN (Fermm 1915 12 126-129).- I n place of weighing the dried precipitate of nickel dimethyl- gfyoxime the metal may be deposited electrolytically. The dimethylglyoxime may be added in hot aqueous solution and the cold solution allowed t o remain twenty-four hours before filtration. It is then washed with hot water dissolved in dilute sulphuric acid boiled with a few drops of hydrochloric acid and hydrogen peroxide to destroy the oxinie and neutralised with ammonia.After the addition of an excess of concent’rated ammonia the nickel is deposited on a gauze electrode a t 70-80° in the usual manner for rapid analysis. Manganese if present as in the analysis of special steels may be kept in solution by addition of ammonium chloride. C. H. D. Action of Metallic Magnesium on Tin Antimony and Arsenic Sulphides. C. PERTUSI (Ann. Chinz. aisal. 1915 20 229-233).-When stannic sulphide is suspended in water and mixed with five times its weight of powdered magnesium it is reduced to1 stannous sulphide or metallic tin and hydrogen sulphide is evolved. Arsenic sulphide treated in a similar manner gives a t first a yellow solution from which hydrochloric acid precipitates arsenious sulphide; if the reaction is prolonged the whole of the arsenic may be removed from the solution.The addition of methyl alcohol tends to keep the arsenious sulphide in solution. Antimony sulphide reacts with magnesium in a similar way. The three elements in admixture as their sulphides may be detected as follows. A portion of the mixed sulphides is treated with mag- nesium powder and the mixture filtered as soon as the yellow colour changes to brown; the brown residue is dissolved in hydro- chloric acid and the heated solution treated with mercuric chloride when a grey precipitate indicates the presence of tin. Another portion of the sulphides is shaken for a few minutes with mag- nesium powder and 5 C.C.of methyl alcohol then heated slightly and filtered. The filtrate is acidified with hydrochloric acid; if arsenic is absent a slight precipitate of sulphur is obtained but if arsenic is present a yellow precipitate of arsenious sulphide is formed. A third portion of the precipitate is dissolved in con- centrated hydrochloric acid and a drop of 1% mercuric chloride solution and an excess of potassium hydroxide solution are added; a black turbidity indicates the presence of antimony. WELTON J. CROOK (Chem. LVezus 1915 112 237-238 ; from Chem. Eiujineer 1915 21).-To estimate the soluble acidity of ores a portion of the W. P. S. Testing of Ores for the Cyanide Process.ii. 54 ABSTRACTS OF CHEMICAL PAPERS. finely-ground sample is shaken for one hour with water the mix- ture then filtered and a portion of the filtrate titrated with standard sodium hydroxide solution using phenolphthalein as indicator.The total acidity is estimated by shaking a definite quantity of the sample for six hours with 100 C.C. of the sodium hydroxide solution filtering the mixture and titrating the residual alkalinity with oxalic acid solution. The difference between the total acidity and the soluble acidity gives the “ latent ” acidity of the ore that is the acidity due t o salts sulphides insoluble sub- stances etc. The quantities of the ore taken for the estimations and the strength of the alkali and acid solutions used are such that the results obtained expressed in C.C.of the alkali solution give directly the number of pounds of lime t o be added t o 1 ton of the ore to neutralise its acidity. w. P. s. Differentiation of ‘‘ Benzine ” [Light Petroleum] and Benz- ene. HERM. MIX (KoZZoZd Zeitsch. 1915 17 7-9).-A resin extracted from dragon’s-blood obtained from Sumatra is recom- mended for the differentiation of “ benzine ” and benzene. The resin has a deep red colour and after treatment with hot petroleum (heavy and light) it is inactive towards “benzine ” in the cold but gives a deep coloration when acted on by benzene. The resin has been named dracorubin and in the form of coloured test-papers it may be used for the approximate estimation of benzene in com- mercial samples of “ benzine.” The behaviour of dracorubin tesb papers on treatment with various organic liquids (pure and com- mercial) has been examined in detail.H. M. D. Physico-chemical Studies on Wines Electrolytic Dissocia- tion Constant of Wines. (MLLE.) CLELIA DI MAIO (Ann. Chiin,. AppZzcata 1915 4 245-2265~.-Measurements made on a series of ten wines give the following results I n genuine wines the process of electrolytic dissociation follows with good approximation the law of dilution. The dissociation constant K varies with different wines but the variations lie within narrow limits; a means is thus furnished of determining adulteration with strong mineral acids. With nine wines the mean value of K was found t o bO 0.0184 +0*0016 with a probable error of 9.1%. Besides modifying considerably the value of the dissociation constant the addition to wine of strong mineral acids in greater proportion than 0.05% effects an appreciable alteratio’n in its degree of constancy owing t o the prevalence of strong electrolytes which do not conform to the laws of dilution.Lack of constancy of K may also be observed in wines of low natural acidity which have been treated with meta- bisulpliib. T. H. P. Jaundice Produced by the Absorption of Picric Acid. Analysis of the Blood and Urine under this Condition. POGNAN and B. SAUTON (J. Phawiz. Chim. 1915 [vii] 12 360-352).-The picric acid is first extracted by ether or benzene from the urine or blood and is then recognised by the usual tests. The resultsANALYTICAL CREMISTRY. ii. 55 show that tliere is not the slightest difficulty in distinguishing between pathological jaundice and the condition produced by the absorption of picric acid.Recognition of Picric Acid in Urine in the Presence o r Absence of Biliary Pigments. VILLEDIEU and MANCEAU ( J . Pharm. Chim. 1915 [vii] 12 366 ; from Arch. med. pharm. nzilzt. 1915 64 255).-The method depends on the solubility of barium picrate and the insolubility of biliary pigments in the presence of salts of the alkaline1 earths. To 100 C.C. of urine are added about 20 C.C. of a saturated solution of barium chloride. The mixture is shaken filtered and the precipitate washed with 10-15 C.C. of boiling water. The filtrate and washings are treated with excess of sulphuric acid (about 5 c.c.) and after removal of the precipi- tate extracted twice with 20 C.C.of ether. After evaporation of the ether the residue is dissolved in 2 C.C. of boiling water filtered and tested for picric acid in the following ways (1) 2 drops of the liquid on a microscopic slide1 are mixed with 2 drops of a 10% solution of cocaina hydrochloride; tufts of silken crystals of cocaine picrate are observed under the microscope; (2) 10 drops of the liquid are mixed with 2 o r 3 drops of alkaline potassium cyanide; a dark red colour appears on heating; (3) a piece of wool is dipped into 10 drops of the liquid diluted with water and heated on the water-bath; the wool is dyed yellow and the colour is not removed by washing in water. H. W. B. LEOPOLD KADL- UERGER (Chem. Zeiztr. 1915 ii 493 ; from Oster?-.-ung. Zeztsch Lz~cker-z7zd. 1915 44 261-26.1.Compare A. 1912 i 1020; 1913 I 1386).-'1he author considers that the diphenylamine reaction of l m d o s e takes place in two stages; the diphenylamine is first con- verted by the concentrated sulphuric acid into diphenylbenzidine and this is then oxidised by the laevulose into A'-phenyldi-imine- p-diphenoquinone an indamine. The blue colour reaction of carbohydrates described by Ihl (Chem. Zezt. 1885 9 451) with diphenylamine is probably due to1 the fact that carbohydrates yield laevulose and dextrose when heated a t 68O and that both the H. W. B. The Diphenylamine Reaction of Lze vulose. latter act as oxidising substances. w. P. s. Action of Copper Solutions in Sucrose. Estimation 01 Invert-sugar in the Presence of Sucrose. MILE SAILLARD (C'ompt. rend. 191 5 16 1 59 1-593).-1n estimating invert-sugar in the presence of sucrose by the reduction of alkaline copper solu- tions the results obtained are always too high owing to a portion of the sucrose being attacked and then exerting a reducing action.This attack is more marked the more alkaline is the copper solution and i t varies with the amount of invert-sugar present. The author advises the use of a solution containing 69.26 grams of copper sulpliate per litre and a solution containing 346 grams of Rochelle salt and 130 grams of sodium hydroxide per litre. Ten C.C. of each of these solutions are mixed and heated for twenty-two minutesii. 56 ABSTRACTS OF CHEMICAL PAPERS. with 50 C.C. of the prepared sugar solution a t 62-64O. The blue filtrate from this estimation is similarly heated for a further twenty-two1 minutes and if this second heating precipitates less cuprous oxide than the first the sugar solution contains reducing sugars.Action of Sucroae on the Alkaline Copper Solution. L. MAQUENNE (Cow@. rend. 1915 161 61'7- 623. Compare Saillard preceding abstract).-Working with Barreswill's alkaline copper tartrate solution the author finds that with sucrose the amount of reduction increases rapidly with the1 concentration of the copper and the time of heating for a given concentration of sucrose. The reduction is apparently not due to a preliminary inversion of the sugar but to a direct oxidation of the sugar accompanied or followed possibly by hydrolysis. As the concentration of the suga.r solution increases the amount of cuprous oxide produced a t first increases rapidly to a maximum and then slowly decreases.This maximum effect is reached when the concentration of t4h0 sucrose with respect -to the total volume of solution is about 11%. It is probable that complex copper and potassium sucrates are formed the dissociation of which diminishes in the presence of the excess of sucrose thus seducing the alkalinity and active copper content of the liquid. The presence of inverbsugar acts in the same way as an excess of sucrose causing a diminution in the reduction due t o the sucrose. W. G. A table is given f o r calculating the results. W. G. New Method for the Estimation of Fatty Acids in Soaps. H. F. SLACK (Pharnz. J. 1915 95 696-697).-Fivegrams of the soap are heated with 10 C.C.of glycerol'until the soap has dis- solved; the mixture is theln acidified with 4 c . ~ . of hydrochloric acid (1 3) and the liberated fatty acids are drawn up into a graduated 5 C.C. pipette; hot water is added if necessary to bring the whole of the fatty acid into the pipette. The top of the latter is now closed and the pipette suspended in a water-bath a t 55O. The volume of the fat'ty acids is read a t this temperature; the volume multiplied by the sp. gr. gives the weight. It is necessary for this purpose to know the sp. gr. of the fatty acids of the more common classes of soaps and these numbers should be determined a t 5 5 O . The use of glycerol for dissolving the soap has the advantage that the liberated fatty acids form a perfectly clear layer above the Detection of Lactic Acid in Leathers and aleo in Tanning Lyes and Other Liquids.R. LAUFFMANX (Chem. Zentr. 1915 ii 763- 764 ; from Ledertech. Rzmdschau 1915 14 264-268 287-292).-Lactic acid may be detected by conversion into acet- aldehyde by distillation with le'ad peroxide. I f the solution under examination is very dilute it must first be concentrated by evapora- tion with the addition if sulphate or chloride be present of 10 C.C. of 10% sodium carbonate solution the equivalent quantity of sulphuric acid being again added before the distillation. Twenty- layer of glycerol etc. w. P. s.ANALYTICAL CHEMISTRY. ii. 57 five C.C. of t'he prepared solution are distilled in a 500 C.C. flask with 3 grams of lead peroxide a t such a rate that about 40 drops are collected per minute. I n the distillate which is collected in 5 C.C.fractions the acetaldehyde is detected by adding 10-12 drops of an aqueous diethylamine solution (2 drops in 25 drops of water) and 5-6 drops of a 0.08% solution of sodium nitroprusside. I n presence o l acetaldehyde the blue colour which appears in one t o two minutes persists according t o the amount present for from one to fifteen minutes after the distillation is complete; otherwise it rapidly fades during the distillation. The presence of aceb aldehyde may also be detected by the iodoform reaction. About 8 drops of 10% solut.ion of iodine in potassium iodide and sufficient sodium hydroxide to decolorise is added to the distillate and a distinct cloudiness after some minutes is conclusive of the presence of acetaldehyde ,which may be further confirmed by warming the alkaline solution with a little resorcinol when a carmine-red colora- tion is produced and the odour of iodoform becomes still more apparent.G. F. M. Detection of Free Mineral Acids and Lactic Acid in Leather. R. LAUFFMANN (Chem. Zentr. 1915 ii 765; from Ledertech. Rundschau 191 5 8 292-301).--Dried and undried portions of the leather are dialysed; if the former dialysate is acid mineral acids or oxalic or lactic acids may be present. I f only the latter dialysate is acid the acidity is due to volatile organic acids. I n the former eventuality an extract of 20-30 grams of the leather in 200 C.C. of hot water is tested for sulphate chloride and oxalic acid ions. I f the latter is present the question as t o whether the leather contained free mineral acid cannot be decided.I f absent lactic acid is tested for in an extract of the finely divided leather prepared by prolonged digestion at 60-65O by the author's melthod (preceding abstract). If both oxalic and lactic acid are thus proved absent the sulphate and chlorine ions must have been present as free acid. I n this case the dialysing process can be utilised for their quantitative estimation the aqueous dialysate being titrated with N / 10-alkali hydroxide using Congo-red as indicator. Estimation of ToBal Tartaric Acid Ca,laium Tartrate Potassium Hydrogen Tartrate and Free Tartaric Acid in Wine. RUDOLF KUNZ (Chem. Zenti-. 1915 ii 287-288; from Arch. Chem Mikroscopie 1916 No. 3).-Fifty C.C.of the wine are treated with exactly 3 C.C. of N/2-hydrochloric acid and 2 C.C. of 20% potassium chloride solution and evaporated to 10 C.C. Another portion of 50 C.C. of the wine is evapor- ated a t the same time( without any addition until the residual solution weighs 10 grams. To each of the residual solu- tions are now added 100 C.C. of 96% (by vol.) alcohol; after twelve hours the precipitates are collected washed with alcohol the11 dissolved in hot water and the .solutions titrated with AT/ 10-alkali solution. The quantity of tlie total tartaric acid and of the potassium hydrogen tartrate in the wine is thus G. P. M.ii. 58 ABSTRACTS OF CHEMICAL PAPERS. obtained. The filtrate fromm the potassium hydrogen t a r t r a h estimation (the precipitate also contains the calcium tartrate) is now treated with 2 C.C.of 20% potassium chloride solution; after twelve hours 2 C.C. of iV/lO-hydrochloric acid are added the pre- cipitate is collected washed with alcohol dissolved in hot water and the solution titrated. This result gives the amount of free tartaric acid present and the difference between the quantity of total tartaric acid and the sum of the quantities of free tartaric acid and that present as potassium hydrogen tartrate gives the amount present as calcium tartrate. w. P. s. Source of Error in the Estimation of Tartaric Acid in Wine Lees and Tartars. P. CARLES (Ann. Chim. anal. 1915 22 240- 241).-When the Goldenberg method (A. 1908 ii 237) is employed f o r the estimation of tartaric acid in tartars etc containing calcium carbonate the weighed portion of the substance should be mixed with twice its weight of water and then treated with hydrochloric acid in small quantities a t a time until the mixture no longer evolves carbon dioxide when the acid is added.Eighteen C.C. of hydrochloric acid (D 1-10> are now added and the process carried out as described. Unless the calcium carbonate is first decomposed the ,quantity of hydrochloric acid added subsequently may not be sufficient to dissolve the tartrates. w. P. s. Estimation of Acidity in Potatoes. J. F. HOFFMANN and FR. PRECKEL (Landto. Versmhs-Stat. 191 5 87 237-239).-The expressed potato sap (50 c.c.) is diluted t o 250 C.C. with 95% alcohol frequently sha,ken during an hour and filtered. Of the filtrate 100 C.C.are diluted with 100 C.C. of water vigorously shaken t o expel carbon dioxide and titrated in presence of 1 C.C. of rosolic acid. A titration is also made in a similar vessel in a mixture of alcohol (80 c.c.) and water (120 c.c.) and the result deducted from that obtained with the potato sap. It is of importance t o employ solutions containing the same relative amounts of water and alcohol ; with greater proportions of alcohol the change of colour is retarded. The Salicylates. 11. Methode for the Quantitative Recovery of Salicyl from Urine and other Body Fluids. T. ‘MT. THOBURN and PAUL J. HANZLIK ( J . Biol. Chem. 191.5 23 163-180).-The term “salicyl” is employed to indicate the salicyl group in what- ever form it occurs. To recover salicyl from urine the fluid is distilled in the presence of syrupy phosphoric acid (20 C.C.of 80% acid solution t o 100 C.C. of urine). By this means the conjugated salicylates such as salicyluric acid are hydrolysed and the salicylic acid distils over with the steam. The amount is then estimated colorimetrically in an aliquot part of the distillate by the addition of 2% ferrous ammonium sulphate the colour produced being estimatgd by comparison .with solutions containing varying amounts o f a standard solution o f which 1 C.C. contains 0*0001 gram of salicylic acid. To estimate salicyl in blood tlhe free salicylic acid N. H. J. M.ANALYTICAL CHEMISTRY. ii. 59 is extracted with ether and the amount estimated colorirnetrically. To estimate the conjugated salicyl the proteins are first removed by addition of ten times the volume of alcohol; to an aliquot past of this liquid a few drops of saturated zinc chloride solution are added and the mixture is boiled.The filtrate is then freed from alcohol by boiling and the aqueous solution is hydrolysed by phos- phoric acid and the estJmation completed by the method described above in the case of urine. A method is also suggested for the estimation of salicyl in faxes. S. B. S. Biochemical Reaction of Rancid Fata. J. VINTILESCO and Arm POPESCO. ( J . Phnrnz. Chim. 1915 [viij 12 318-323).-The rancidity of fats and oils is due t o the fixation of oxygen and the authors show that this oxygen may be liberated by the action of peroxydase and detected by the guaiacum reaction. Ten grams of the fat are just melted in a test-tube 5 drops of diluted blood or of 3% haemoglobin solution are added followed by 10 drops of guaiacum tincture and 10 C.C.of water and the mixture is shaken for one minute. I f the fat is rancid the emulsion is coloured blue the intensity of the coloration depending on the degree of rancidity whilst in the case of non-rancid fats o r oils the mixture remains colourless. The blue coloration may be rendered more distinct when deafing with fats which are only slightly rancid by adding an equal volume of 95% alcohol to the mixture after the latter has been shaken. That the acidity of a fat is not a function of the sancidity is shown by the fact that a rancid acid fat after being neutralisea and washed with water and alcohol gives a reaction equal in intensity to that yielded by the fat before neutral- isation.Rancid fats still give the reaction after being heated a t 120° for a few'minutes but not after being heated a t 2 0 0 O . w. P. s. Applied Plant Microchemistry. XI. Microchemical Detec- tion of Baptisin in Baptisia Tinctoria (Roots). 0. TUNMANN (Chem. Zentr. 1915 ii 288-289; from Apoth. Zeit. 1915 30. 272-274).-Pyridine is a better solvent than dilute alcohol f o r the extraction of hapfisin from the powdered soots of Baptisia tinctoria (wild indigo) ; after repeated crystallisations from dilute alcohol the glucoside is obtained as a white crystalline powder m. p. 2 4 4 O . It is soluble in aniline pyridine amyl alcohol and potassium hydroxide solution insoluble in ethyl acetate and tur- pentine and slowly soluble in chloral hydrate solution and acetic acid Baptisin may be detected in sections of tlie r o o t by treating the section with vanadium sulphate; the edge of the section exhibits a violet colorakion which changes t o light blue; cerium sulphate and tungsten sulphate yield reddish-violet colorations.Baptisin sublimes for the greater part without decomposition. I f 5 mg. of the powdered root are heated the first sublimate o'btained consists of colourless o r light yellow needles of the glucoside; the sinhseqnent sublimate consists of white prisms of baptigenin. The glucoside and its derivative give a red coloration with vanadiumii. 60 ABSTRACTS OF CHEMICAL PAPERS. sulphate the colour changing gradually t o violet and brownish- blue. When the sublimate is treated with a drop of sulphuric acid and a crystal of tungstic acid is added the edges of the crystal show a deep violet coloration.If the sublimate is mixed with iodic acid solution dried the residue washed with water and then treate’d with sulphuric acid the crystals become red then violet or black and dissolve whilst the edge of the sulphuric acid exhibits a bluishlgrey colour. . Baptisin is 1;calised in tfie parenchyma. w. P. s. A Frangula Substitute the Barks of Rhamnus Carniolica and Alnus Glutinosa. 0. TUNNANN (Chew. Zentr. 1915 674; from Schweix. Apoth. Zeit. 1915 53 313-318 ; 325-332).-A proposed subst’itute for frangula consists of a mixture of 15% of the bark of Rhamnus c n r n i o l i c a and 75% of the bark of Alnus ylzctinosn. The former bark contains both free and combined hydroxymethylanthraquinonee and might serve as a substitute for frangula but the bark of L4hus glutinosa is worthless.The three Rhccmrms drugs may be distinguisheld by the rays in the cambium layer; in the case of frangula they form one or two very seldom three layers; in R. purshinrLzis they appear in one t o three seldom four layers; in R. cariziolica they are in four six o r even eight layers. A?. car7~ioZica contains 1.84% of free and 3.78 of combined hydroxymethylanthraquinones ; frangula-emodin is also present but not chrysophanic acid. The total anthraquinonw in R. c a r n i o l i c a may be1 estimated as follows Five grams of the dry powder are boiled with 100 grams of dilute sulphuric acid f o r thirty minutes under a reflux apparatus the mixture then filtered and the filtrate extracted twice with chloroform (50 and 20 grams).The cliloro- form solution is shaken for fifteen minutes with two quantities of 50 grams of 5% sodium hydroxide solution the alkaline extract is acidified with hydrochloric acid the precipitated hydroxymethyl- anthra.quinones collected dried a t looo and welighed. IV. P. S. Identification and Estimation of (‘ Saccharin ” [o-Beazoic- sulphinide] in Foodst,uffs. FEDERICO CECCHERELLI (BoZZ. chim. farm. 191 5 54 641-648).-Before a foodstuff is treated with ether in order t o extract any “saccharin” present i t is necessary that alcohol should be completely removed since even a small residuum of alcohol may result in the extraction of other sweet substances such as glycerol lzvulose various glucosides etc.I n some cases tho whole of the alcohol is not expelled by a single evaporation and it is advisable repeatedly t o take up the residue in distilled water and evaporate. The residue obtained after extraction with ether and expulsion of the latter should be purified by treatment with permanganate and should then (1) be pronouncedly sweet ; (2) give the reaction f o r salicylic acid only after fusion with sodium hydroxide a t 2 5 0 O ; (3) contain sulphur in the theoretical proportion; (4) yield 9 silver derivative containing 37% of the metal; (5) give Tarugi and Lenci’s reaction (compare A. 1912 ii 397) after hydrolysis by means of sulphurio acid. T. B. P.ANALYTICAL CHEMISTRY. ii 61 The Microchemical Method for Gasometric Determination of Aliphatic Amino-nitrogen. DONALD D.VAN SLYliE ( J . Biol. Chem. 1915 23 407-409. Compare A. 1910 ii 751; 1911 ii 164 ; 1916 ii 1008 ; 1913 ii lO84).-A niodification of the gas-burette employed for measurement of the nitrogen is described. This is of 3 C.C. capacity graduated into divisions of 0.01 C.C. placed 1 mm. apart. The zero point is placed a few millimetres below the stop- cock. A modification in the manipulation of the author’s micro-method is also described. Readings to 0.001 C.C. are possible. S. B. S. The ‘‘ Ninhydrin ” Reaction. VICTOR JOHN HARUING (Tram. BOY. XOC. Canada 19 15 9 33 -42).-A critical examination of the conditions governing Ruhemann’s test for amino-acids with triketo- hydrindene hydrate (T. 1910 97 2025).The author finds that under accurately defined conditions of concentration and tempera- ture the test can become specific for amino-acids these being the only substances which give the test readily and clearly in very dilute solution. He recommends that in testing for amino-acids not more than 0.1 mg. of nitrogen be present in each C.C. of the liquid to be tested and that 1 C.C. of it should be heated in a boiling water-bath with 1 C.C. of a 1% solution of “ninhydrin” for fifteen minutes. Evaporating the liquid t o be tested t o dryness in a dish with the reagent is unsatisfactory. I n the presence of pyridine ammonium salts and primary amines as well as amino-acids react strongly with triketohydrindene hydrate and theref ore the colori- metric method of Harding and MacLean for estimating the nitro- gen in a-amino-acids present is inapplicable to the analysis of physiological fluids (compare A.1915 ii 382). The blue colora- tion obtained by Halle Loewenstein and Pribram with this reagent and glycerol and allied substances (compare A. 1913 ii 922) is shown to be due t o the presence of traces of nitrogenous impurity. The blue colour obtained with amino-acids is character- ised in three ways namely (1) It gives a broad absorption band in the visible spectrum extending from the red into the green part of the spectrum when viewed in dilute solution; (2) the blue colour changes t o purple when viewed in artificial light; (3) the colour is resistant to mild oxidation the passage of a rapid current of air for five minutes through a standard colour having no effect on the quantity present.The blue colour given by hydrindantin and potassium o r sodium hydroxide differs from this very markedly in that i t gives no absorption band in the visible spectrum; it remains blue when viewed by artificial light and i t is very readily oxidised t o a colourless solution when shaken with air. W. G . New Reaction of isoThiocyanates. G. DEXIGBS ( B d l . SOC. chz7t~. 1915 [iv] 17 380-381).-To a few C.C. of the solution to be tested twice its volume 09 a solution of mercuric sulph‘ate (28 grams per litre) is added the mixture shaken filtered if necewary and heated in a boiling water-bath for one to five minutes according t o the dilution. isoThiocyanates if present to the extent of 0.25 gram per litre will give a crystalline precipitate of dithio-ii.62 ABSTRACTS OF CHEMICAL PAPERS. trimercuric sulphate (compare A. 1915 ii 835 839) which can be examined under a microsco,pe and characterised. W. G. Mercury Ureometer of Simple Gonstruction. HENI~I MARTIN (J. Pharm. Chim. 1915 [vii] 12 352-354).-9 modification of Esbach's ureometer is described f o r the estimation of urea in the blood. The blood is treated with an equal volume of a 20% solution of trichloroacetic acid and the urea in a measured volume of the filtrate decomposed by sodium hypobromib. The nitrogen gas evolved is collected in the modified Esbach's ureometer over mercury. H. W. B. Method for the Extraction of Greatine and Creatinine from Body-tissues and Fluids. A. COSTANTINO (Chem. Zentr.1915 ii. 287 ; from Arch. Farmacol. sperim. 1915 19 254-258),- The fluid or the finely-divided organ is shaken for two hours with 200-250 C.C. of 2% mercuric chloride solution containing 1% of hydrochloric acid; the mixture is then filtered and the excess of mercury is removed as sulphide. An aliquot portion of the solution is heated to expel hydrogen sulphide neutralised with sodium hydroxide and concentrated to about 10 C.C. The solution thus obtained is colourless and free from proteins and serves for the colorimetric estimation of the creatine. w. P. s. The Use of Trichloroacetic Acid as a Protein Precipitant. I. GREENWALD (J. Amer. Chem. Soc. 1915 37 2604-2605).-The author disclaims any right to the discovery of the general use of trichloroacetic acid as a reagent f o r prot'eins (compare Graves and Kober ibicl.2445). D. F. T. Analysis of Proteins by Determination of the Chemical Groups Characteristic of the Different Amino-Acide. A Cor- rection. DONALD D. VAN SLYKE ( J . Bid. Chenz. 1915 23 411)- The formula for determination of histidine and arginine given in the original paper (A. 1911 ii 944) should read Histidine= 1-6670 - 1-225 Arg. as there given. 0 = diamino-acid nitrogen Arg. = arginine nitrogen. - i(0 - 2Arg) = 1.50 - 1-125 Arg instead of 'Histidine N = S. B. S. The Proteins in Caoutchouc and in Caoutchouc Latex. FR. FRANK (Chenz. Zentr. 1915 i 1345 ; from Gummi-Zeit. 1914 29 196-198).-The following method is recommended for the separa- tion of the nilxogenous substances in crude caoutchouc. From 1 to 2 grams of the sample are mixed in a test-tnbe with 30 C.C.of cumene limonene; o r dipentene and the mixture is boiled under a reflux apparatus until a homogeneous solution is obtained. The tube and its contents are then submitted tot centrifugal action (2500-3000 revs. per minute) for one tloc one and a-half hours the clear liquid is decanted the sediment next boiled with xylene and again submitted to centrifugal action and these operations are repeated using light petroleum and ether respectively as theANALYTICAL CHEMISTRY. ii. 63 solvents. The residue is then dried weighed and further ex- amined. It yields distinct reactions with the biuret and xantho- protein tests with Millon's reagent and in most' cases the presence of tyrosine can bel detected. The substance responds to' all the precipitation tests f o r proteins.The cleavage products obtained when the substance is hydrolysed completely are the same as those obtained from the latex and from the serum after coagulation. The presence of the following products may be detected mono- aminomonocarboxylic acids aromatic amino-acids (phenylalanine tyrosine) heterocyclic amino-acids (tryptophan) diarninomono- carboxylic acids monoaminodicarboxylic acids and cystine. It follows that in working up latex the proteins should be separated simultaneously with the caoutchouc in such a way that they do not undergo further decomposition. w. P. s. Estimation of the Ammonia from the Amino-acids and Proteins of Urine by Means of Formaldehyde. M. W. SCHELTEMA (Plaarrn. Weekblad 1915 52 1549-1555).-A historical survey of the application of formaldehyde t o the estima- tion of combined ammonia in urine and an account of the results obtained by the author by this method. A.J. W. Acid Ratio A New Method for Estimating the Proteolytic Strength of Germinated Grain in Technical Analysia. CARL A. NOWAK ( J . Iitd. Eng Chem. 1915 7 858-859).-The method is based on the formaldehyde titration of the amino-groups. Bifty grams of finely-ground malt are shaken for thirty minutes with 150 C.C. of cold water and the mixture then filtered the first por- tions of the filtrate being returned t o the filter. Exactly forty- five minutes after starting the extraction o r fifteen minutes after removing the mixture from the shaking machine 20 C.C. of the filtrate are transferred to a beaker 20 C.C.of water and 0.5 C.C. of 0.5% phenolphthalein solution (in 50% alcohol) are added and the solution is titrated with N / 10 sodium hydroxide solution. This titration gives the natural acidity. To the mixture are now added 10 C.C. of 40% formaldehyde solution (previously mixed with 5% of its volume of 0.5% phenolphthalein solution and then neutralised) and the titration is continued until a distinct pink coloration is obtained. This second titration is a measure of the amino-groups present. The ratio between the amino-acidity and the natural acidity obtained by dividing the number of C.C. of alkali solution representing the amino-acids by the number of C.C. representing the natural acidity is as 1 :1 or greater. This ratio is termed the acid ratio of malt.A really good malt should be high in natural acidity and should show an acid ratio of 1 1.10 which may be expressed as 110; in some malts it may be as high as 130. To obtain comparative figures as t o the proteolytic strength of different malts the remainder of the filtrate is main- tained a t the ordinary temperature for sixteen hours and a second estimation of the acid ratio is then made. Malts showing the greatest increase in the acid ratio are those having the greatestii. 64 ABSTRACTS OF CHEMICAL PAPERS. peptic strength; the increase may timount t o ff0.m 5 to more than 30 units. w. P. s. Analysis of Soils with Strong Hot Hydrochloric Acid. D. J. HISSINK (Bied. Zentr. 1915 44 367-369 ; from liztermt. Mitt. Bode& 1915 5 l).-Whilst the amount of acid per gram of soil and the duratioa of the boiling do not vary much in the method usually employed there seems t o be less uhiformity as regards the strength of the acid and hence the temperature which depends on the density of the acid.The following method is pro- posed. The soil (10 grams) is first treated with water or dilute acetic acid to remove any acid or carbonates. It is then boiled for a few minutes in an open flask with hydrochlotic acid (about 25%) until the temperature l l O o is reached after which it is boiled for two hours in a reflux flask. N. H. J. 31. Method for the Estimation of the Immediate Lime Requirements of Soils. W. H. MACINTYRE (J. Ind. Eng. Chem. 1915 7 864-867).-There is a considerable difference between a soil’s ability to decompose immediately calcium carbonate and its power of continuing the decomposition when the soil and an excess of calcium carbonate remain in moist contact. I n certain lime-treated plots 35% of the accumulated lime after thirty-two years’ treatment was found to be present as silicate. The method described deals with the immediate lime requirement. From 5 t o 10 grams of the soil are mixed with 150 C.C. of calcium carbonate solution (see below) and evaporated to a paste; the latter is then washed into a flask with 60 C.C. of water free from carbon dioxide the carbon dioxide is liberated with phosphoric acid and absorbed in a definite volume of N / 2 sodium hydroxide solution. The amount of sodium carbonate formed is estimated either by the double titration method or by adding barium chloride and titrating the alkali hydroxide after the barium carbonate has settled. The calcium carbonate solution employed is prepared by passing carbon dioxide for four hours into 4 litres of water containing 20 grams of calcium carbonate in suspension then filtering the solution and storing it under pressure of carbon dioxide. The difference between the calcium carbonate content of the 150 C.C. of this solution employed and the residual calcium carbonate found in the actual estimation is a measure of the calcium carbonate decomposed by the soil. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9161005044

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

ii. 65 General and Physical Chemistry. The Double Refraction of Vanadium Pentoxide Solution. H. DIESSELHORST and H. FREUNDLICH (Physikal. Zeitsch. 1915 16 419425).-The anisotropy exhibited under certain conditions by a colloidal solution of vanadium pentoxide has been further investigated. I f the sol is allowed to flow through a tube the axis of which is parallel to the line connecting crossed Nicols placed at opposite ends of tLhe tube the field of view is illuminated in convergent light and shows the cross and concentric rings which are observed when the light passes through a plate of a uniaxial crystal cut perpendicularly to the axis. By the use of a quarter- wave mica plate it is found that the streaming sol behaved like a positive uniaxial crystal. If a coiicentrated colloidal solution is made to flow through a tube of triangular cross-section which is used as a prism it is found that the red line of hydrogen is resolved into two oppositely polarised lines.The more strongly refracted ray has its vibrations parallel to the direction of flow and therefore parallel t o the major axes of the colloidal particles and in accordance with Babinet’s rule this extraordinary ray is more strongly absorbed than the other. Some of these effects have also been observed although less clearly with an old ferric hydroxide solution. The properties of such sols are obviously similar to those shown by crystalline liquids and in this connexion the general question of the anisotropy of the amorphous state is discussed. H. M. D. The Arc- and Spark-spectrum of Silver in International Normals.JOSEPH FRINGS (Zeitsch. wiss. Photochern. 1915 15 165-182).-Accurate measurements of the wave-lengths of lines i n the arc and speck spectra of silver have been made by the use of a large concave grating. The data are compared with the results of previous observers and the series relations exhibited by certain pairs of lines are discussed. H. M. D. Changeable Lines in the Arc Spectrum of Iron. JOSEPH LANG (Zeitsch. wiss. Photochem. 1915 15 223-252).-According to the measurements of Goos (A. 1912 ii 404 1016) the wave- lengths of certain lines in the arc spectrum of iron vary to an appreciable extent with the length of the arc which is employed as the source of the. radiation. I n view of the importance of this result in connexion with the determination of the wave-lengths of secondary and tertiary normal lines in the iron arc spectrum further experiments have been made in order to ascertain more exactly the relation between the wave-length and the conditions of the arc discharge.Observations were made with short (2-4 mm.) and long (9-16 VOL. CX. ii. 3ii. 66 ABSTRACTS OF CHEMICAL PAPERS. mm.) arc; the strength of the current was varied from 3 t o 15 amperes and the applied potential from GO t o 440 volts. I n the case of the long arc series of ineasurenients were also made with the light emitted in the neiglibourhood of the anode and of the cathode. The data obtained from observations in the greenish-yellow region ( ~ 5 3 6 0 to h5660) show clearly t h a t the wave-length of a large number of lines varies with the length of the arc the strength of the current and according to whether the light is emitted by the anodic or cathodic portion of the arc.These changeable lines are all more or less diffuse and this is more particularly the case for the short arc spectrum when a strong current is passed between the poles. This circumstance suggests t h a t the observed displace- ments are not real and are attribut'able to unsymmetrical broaden- ing of the lines but tlie author maintains that many of the observed changes in wave-length are greater than can be accounted for on this assumption. Although no explanation of the effects can be given it is quite improbable t h a t they are of the same nature as the displacements which are observed when the pressure is varied.The view t h a t they are pressure effects would neces- sitate the assumption of variations of pressure' within the1 arc of such magnitude as to preclude the possibility of this affording a reasonable basis of interpretation. Similar measurements were also made in the ultra-violet region ( ~ 2 4 0 0 to h3330) and variations in wave-length with the con- ditions of the arc discharge of the same kind were found. The results obtained in this region are however n o t nearly so' definite as those f o r the greenish-yellow and the author considers t h a t it is possible t h a t the apparent displacements may be due to un- symmetrical broadening of the lines. I n favour of this view attention is drawn t o the fact t h a t many diffuse lines in the ultra- violet are not displaced a t all whereas all the diffuse lines in the greenish-yellow region are found t o undergo a shift of measurable amount.The fact that all the diffuse iron lines in the greenish-yellow region are variable in wave-length leads to the conclusion that the spectrum of some other element should be employed in the determination of tlie secondary and tertiary normals in this region. I n regard to the region (X2400-/\3330) only certain lines are suitable and a table is given in which unsuitable lines are indi- cated. 13. M. D. Absorption Spectra of Aqueous Solutions of Poly- and Simple Hydrated Salts by Means of a Radiometer. E J. SCHAEFFER M. G. PAULUS and HARRY C. JONES ( Z e i t s c h . physl'kn7. Chenz. 1915 90 561-593).-The influence of a number of salts on the' int'ensity of the infra-red absorption bands of water has been yarefully studied and measurements of the intensity of the bands have been made by means of a radiomicrometer used in connexion with a Hilger spectrometer.The saltc; used were1 such as possessed no absorption of their own and included potassiumGENERAL AND PHYSICAL CHEMISTRY. ii. 67 chloride sodium chloride iiiagiiesiuin chloride magnesiuln bromide magnesium sulphate zinc sulphate calcium chloride zinc nitrate magnesium nitrate ainmoiiiuni bromide a i d sodium nitrate. The results are expressed by means of a large number of tables arid curves. It is showri that lion-hydrated salts which have no absorp- tion of their owii cause aii increase in the intensity or' the middle of the water bands.It is suggested that this may be due to a slight shift of the baiids toward the red end of the spectrunl. Hydrated salts cause a decrease in tlie absorption of tlie middle of the water baiids. 'To this observation nitrates form an excep- tion. I n general it can be stated that all aqueous solutions of noii-hydra ted and noii-absorbing salts are inore transparent than water f o r all the wave-lengths made use of in the present investigation ( A = 706-1426). This is particularly the case for the band 1 . 2 5 ~ . Magnesiunl nitrate presents a number of irregularities which could be due conceivably to an absorption by tlie salt. To settle this point the absorption of magnesium nitrate in both acetone and .ethyl alcohol was measured with tlie result t h a t this salt is shown t o have no absorptioii a t any point.Tlie general result of the work is to show t h a t combined water has a smaller absorptive power than free water and this is regarded as an additional piece of evidence in favour of the solvate theory. Absorption Spectra of a Series of Aniline Dyes and the Separation of Certain Portions of the Spectrum by Means of Gelatin Filters. ADOLF HNATEK (Zeitsclz. zuiss. Photochenz. 1915 15 133-148).-The absorption spectra of some sixty aniline dyes have been examined and of these twenty-four have been found suitable for use in the preparatjoii of gelatinised filters. The filters are arranged into three groups for which the range of transmitted light is ahout I000 A 5 0 O 4 0 0 A and 200-500 A respectively.In most cases the filters contain a single dye but in others tlie absorptioii is produced by suitable admixture of two cr inore dyes. Further reduction in the widtli of the transmitted bands can be obtained by contbination of two or more filters. 3. F. S. H. M. D. Colorations Produced by Some Organic Nitro-compounds with Special Reference to Tetranitomethane. 11. ALEXANDER KILLEN MACBETH (T. 1915 107 1824-1827. Compare T. 1915 107 87).-Some points of interest which arose in tlie earlier study on tlie coloratioiis produced by treating tetranitromethane with uiisaturatetl substances are discussed. 111 the first place a rough examination suggested that the deptli of colour oktaiiied might he ail iiidicatioii of tlie relztivef reactivity or of the amount of residual affinity of a snbstance.A quantita- tive spectrographic study of the colours produced by tetrahydro- I 4-thiopyran 1 4-dithian and 1 4-thioxan has shown t h a t the reactivities of these compouiids are of the same order a;> Clarke determined in the case of their combination with bromoaceto- phenone (T. 1912 101 1788). 3-2ii. 68 ABSTRACTS OF CHEMICAT PAPERS. The existence of inhibitory factors is also revealed. The pre- sense of electronegative atoms (such as Cl) in ethylenic com- pounds for example is one factor and no colours are obtained also in the case of unsaturated compounds containing conjugated double linkings (ethylene with carbonyl or nitrogen with carbonyl) except in the aromatic series which exhibits many anomalies. The effect of the nature of the solvent medium has alyo been examined.Light petroleum and chloroform appear t o hinder the development of colour but water accelerates it. It seems that certain solvents have the power of preventing the ‘‘nitrite isomer- isation ” of the tetranitromethane. J. C. W. Phosphorescence. K. SCHERINGA (Chens. TVeekbZad 19 15 12 1106-1109).-An account of the close relationship between phos- phorescencel and fluorescence. A. J. W. The Photobromination of Toluene. K. ASDRICII and M. LE BLANC (Zeitsch. wiss. Photochem. 1916 15 148-164 183-223).-The bromination of toluene has been examined with special reference to the influence of light of varying wave-length on the yield of benzyl bromide. I n a preliminary series of experi- ments the influence of various solvents on the absorption spec- trum of bromine was examined.The curve of absorption for a solution of bromine in carbon tetrachloride shows a maximum in the blue (400-450pp) and a minimum in the neighbourhood of A =313 pp. Similar selective absorption is also exhibited by solutions of bromine in hexane. On the other hand the curves for ethyl acetate benzene and toluene solutions show gradually increasing absorption with diminishing wave-length. The absorption spectra of solutions in hexane and carbon tetrachloride resemble that of bromine vapour and the authors draw the conclusion that the bromine in these solutions is largely. present in the free condition whereas in ethyl acetate benzene and toluene solutions it is present in the form of complex molecules resulting from the combination of the bromine with the solvent.Comparative bromination experiments in presence of hexane and ethyl acetate indicate that the free bromine molecules are photo- sensitive whereas thei solvated molecules are not. This relation affords an explanation of the fact that the photo-sensitiveness of the reaction between bromine and toluene diminishes rapidly as the wavelength of the incident radiation decreases. The yield of benzyl chloride is found to depend on the presence of oxygen in the reaction mixture the yield increasing with the amount of oxygen. This has been traced to the oxidation of the hydrogen bromide whereby bromine is regenerated. Phenolic substances are also formed in these circumstances and there is some evidence of the formation of intermediate peroxides.Both toluene and hexane which have been brominated in presence of pure oxygen exhibit oxidising properties. The yield of benzyl bromide is nearly independent of the wave-length of the incidentGENERAL AND PHYSICAL CHEMISTRY. ii. 69 light between h 579 and A 325 pp; the reaction velocity decreases rapidly below 40Opp and is not affected by light of wave-length ~300-1202. The addition of water t o the reaction mixture reduces the velocity considerably in presence of pure oxygen but the effect is small in presence of air. Some convenient light filters and an arrangement for producing spark discharges of high intensity are described. Reference is also made to the action of anhydrous phosphoric acid on potassium bromide as affording a simple method for the production of hydrogen bromide.H. M. D. Attem ptcJ made t o Influence the Velocity of Radioactive Transformations by Means of a-Rays. JEAN DANYSZ and LOUIS WERTENSTEIN (Compt. rend. 1915 161 784-787).-The authors have endeavoured to increase the velocity of transformation of uranium-Z t'g uranium-X and of mesothorium-l t o mesotliorium-11 by means of a-rays but without success. I n the first case a tube containing a t the commencement 18 millicuries of emanation was allowed t o act f o r six days on 3 layer of ura.nium oxide TT308 just sufficiently thick t o absorb the a-rays. I n the second case an ampoule. containing 30 millicuries of emanation was allowed t o act for thirteen hours on 3 mg. of mesothorium-radium con- tained in a capsule covered with mica 0.005 mm.thick. I n neither case could the slightest i r crewe in the velocity of transformation be detected and the authors consider from a calculation of the1 possible collisions that even the most intimate contacts of the a-rays with the atoms are unable t o provoke an artificial radio- activity o r a premature transformation of the atom struck. W. G. The Charge of Radioactive Recoil. LOUIS WERTENSTEIN (Compt. rend. 1915 161 696-699).-The author has studied the charge of recoil in the case of radium-D projected during the transforma- tion of radium-C. Measurements were made of the charge received by a cylinder receptor the source being a deposit of radium-C (1) when the rays had no obstacle t o traverse; (2) when they were filtered through a screen of aluminium foil 0.7 p thick; (3) when they had to traverse a sheet of aluminium foil 0.05 mm.thick which arrested all the a-rays. The whole apparatus was contained in a vessel having a high vacuum maintained by a Gaede molecular pump giving 0.6 dyne/cm.2 as measured on a Knudsen's absolute manometer. All the three measurements were made in one experi- ment the screens being moved by an electromagnetic control out- side. The difference between the values from (1) and (2) gave the charge of the a-rays and that between (2) and (3) the charge of the a-rays. In the high vacuum 0.6 dyne/cm.2 the atoms of radium-D when projected do not carry an electric charge but as the pressure rises they acquire a gradually increasing positive charge which may equal or even exceed that of the a-rays. This positive charge is a consequence of the collisions of the atoms of radium-D with the molecules of the surrounding gas one or more electrons beingil. 70 ABSTRACTS OF CHEMICAL PAPERS.sq.arated from the radioactive atom. The pressure under which the recoil attains a charge equal to half of that of the a-rays corresponds with a free path of the atoms projected equal t o tile distance of the source from the receptor. The experimental results give the value of the iiieaii free path a t a pressure of 1 dyne/cm.2 as 100 nim. whilst tlie value calculated from the ionisation pro- d u c d is 90 nim. The free path of a particle of radium-C calcu- lated in the same way f o r the initial portion of its path is 440 mm.and the n-rays ioiiise a t their commencement five times better than the a-particles. A t the atmospheric pressure the atoms of recoil behave as univalent ions and the dissociatioiis of the radioactive atoms resulting from the collisions with the molecules inust therefore be followed by recombiiiations as the velocity of the atoms diminish this behaviour showing the close analogy existing between the n-rays and the canal rays. W. G. Influence of Foreign Substances on the Adsorption of Uranium-X by Charcoal. H. FRBXJNDLICH and H. KAEMPFKE (Zeitsclh. p h y s i l d . CJietu. 1915 90 681-’716).-A large number of experiments have been carried out 011 tlie influence of thorium salts and many other substances on the reversal of the adsorption of uranium-X1 by charcoal.These experiments are in part a repeti- tion of those of Ritzel (A. 1909 ii 851) and partly an extension of Ritzel’s work. It is shown t h a t the presence of small concen- trations of thorium salts causes a reversal of tlie adsorption of uranium-X1 by clmrcoai. Thus the presence of 0.0004 millimol. of thorium nitrate increases tlie amount of uranium-X which remains in solution after shaking with charcoal by about 20%. The action however is not specific f o r thorium or the radioelements for a large number of substances such as zirconium salts benzoic acid strychnine nitrate and basic dyes have a similar action. A number of points of difference between the action of thorium iiitza te and the other substances was noticed. The adsorption of benzoic acid strychnine nitrate and zirconium oxychloride was measured by means of th% radioactivity of uranium-X,.The method adopted consisted in determining the end concentration iii solutions of these substances of the uraiiium-LX which had been shaken together with these substances and charcoal and from the amount of reversal of the adsorption of the uranium-X the adsorption of the other substance was deduced. In the case of benzoic acid and zirconium oxychloride the usual adsorption isotherms were obtained by this method but in the case of strych- nine nitrate there was a tendency to reach a saturation value. In all three cases an elid condition was reached which was independent of time. When an attempt was made t o determine the ailsorption of thorium nitrate by the same niethod a difference was noticed in the beliaviour from that observed with the other substances in the sense that the end concentration appeared t o decrease with time.This decrease could not be confirmed by iiephelometric measurements on the oxalate and was explained by the fact thatGENERAL AND PHYSICAL CHEMISTRY ii. 71 a solution of thorium nitrate wliicli has been shaken with charcoal afterwards produces a niuch smaller reversal of the adsorption of uranium-S,. This corresponds with the observation of Ritzel which was confirmed that freshly produced uranium-X in uranium nitrate solution which has been shaken with charcoal is more strongly adsorbed by charcoal than uranium-Xl of long standing. The authors explain the above phenomena by the assumption that in thorium and uraiiyl nitrate solutions small quantities of still iindiscovered radio-elements exist) and t h a t these exert a sirong reversing action on the adsorption of uranium-S but t h a t they are completely adsorbed by charcoal when shaken with it.Thorium nitrate differs from the other substances which reverse the adsorption of uranium-S in the fact t h a t it not only diminishes the adsorption of uranium-S when it is adsorbed a t the same time as tlie uraniurii-S but it also causes a reversal of the adsorption if i t is added to the charcoal after the uranium-S has been adsorbed. Tlie latter effect is not observed with the other sub- stances. The difference is probably to be explained in the follow- ing way uraniurn-S is not only concentrated on the surface of tlic cliarcoal but also penetrates into tlie interior; the same is ])robably also true for thorium nitrate mid the unknowii sub- Ftances mentioned above.These substances can therefore exercise their reversing action on tlie nraiiium-,Y when they are added after it has been adsorbed whereas the other substances such as btliizoic acid by adsorpticn are only colicelitrated on the surface and cannot therefore exercise this action. The foregoing observa- tions lead to the conclusion that- the statement of Soddy (T. 1911 99 72) to the effect that the reversal of the adsorption of uranium-3 by thorium is due t o the isotropy of the two sub- stances is not in accordance with experimental facts. On the other hand the fact t h a t other substances have the same action as thorium does not disprove in any way the isotropy of these two substances.The coefficient of the absorption factor of the adsorp- tion isothermal for both thorium nitrate and uranium-3 was found t o be very nearly unity. The reversal of the adsorption of uraiiium-91 by other foreign substances does not depend wholly on the adsorption of these substances and is not purely a decreas- ing of the power of the charcoal t o adsorb uranium-X but rather a hindrance by the foreign substance to the penetration of uranium-X into the interior of the charcoal much in the same way t h a t adsorbed substances hinder the crystallisation of super- saturated solutions. Ritzel (Zoc. c i t . ) found that thorium emana- tion also caused a reversal of the adsorption of uranium-X,; this the authors find does not occur if the emanation is filtered through wool before it is led into the solution.The reversal observed by Ritzel is therefore t o be attributed to dust of thorium nitrate carried over by the emanation. J. F. S. Transmutation of Chemical Elements. IT. W. P. JORISSEN and J. A. VOLLGRAFF (Zeitsch. physikc11. CI~enz. 1915 90 557-560. Compare A. 1915 ii 134).-The authors have sub-ii 72 ABSTRACTS OF CHEMICAL PAPERS. jected bismuth to a stream of cathode rays with the object of ascertaining whether by this action bismuth beconies radioactive o r is converted into thallium. The experiments show that bis- muth which has been treated in this way has no action on the leaves of a charged electrc4scope and has also no action on a photographic plate.On testing the metal for thallium it is shown that in the untreated metal there is a small quantity of thallium which although not sufficient t o give the usual micro- chemical reactions can be detected spectroscopically. The amount of thallium is not increased by the treatment with cathode rays. J. F. S. Dielectric Constants of Some Compounds of Vanadium. ALBERT G. LOOMIS and HERMAN SCHLUNDT ( J . Physical Chem. 1915 19 734-738).-The dielectric constants of vanadium oxy- chloride vanadium oxybromide and vanadium tetrachloride have been determined by the Drude-Schmidt method a t a series of temperatures. The compounds examined were prepared by the Roscoe methods and full details of the preparation are given in the paper. The following values were obtained for the dielectric constant vanadium oxychloride 3.42 a t 21° 3.38 a t -7OO; vanadium oxybromide 3.62 a t 25O 3.93 a t -2O and 4.38 a t - 70°; vanadium tetrachloride 3.05 a t 25O.J. F. S. Electrical Conductivity and Luminosity of Flames Contain- ing Salt Vapours. H. A. WILSON (Phil. Truns. 1915 [ A ] 216 63-90).-The author has studied the influence of an electric field on the velocity of positive ions of salt vapours in flames together with the relationship of electric conductivity of flames contain'ing salt vapours to their luminosity. Further experiments have been made to show the variation of the conductivity with the con- centration of the salt vapour and to determine the relative con- ductivity due to salts of different metals. From the experimental results it is shown that the luminous vapours of salts in a Bunsen flame are not deflected appreciably by an electric field and that the positive ions present in the luminous vapour can be made to move out of it by an electric field.The positive ions are not luminous but can form luminous vapour after recombination. The velocity of the positive salt ions in flames is about 1 cm. per second for 1 volt per cm. and is the same for all salts. The con- ductivity and luminosity of sodium chloride both vary nearly as the square root of the concentration of the salt vapour in the flame. The conductivities and luminosities of chemically equiva- lent amounts of sodium chloride and sodium carbonate are equal. A considerable excess of hydrogen chloride does not change the luminosity due to sodium chloride but it slightly increases the conductivity of the flame.A large excess of hydrogen chloride obtained by the introduction of chloroform vapour diminishes the luminosity due to sodium chloride by about SO% and diminishes tihe conductivity about six times. The percentage changes in the liiminasity and Conductivity are independent of the concentrationGENERAL AND PHYSICAL CHEMISTRY. ii. 73 of the sodium chloride vapour. The chloroform increases the current due to large potential differences but diminishes the con- ductivity as measured by the ratio of the current t o the uniform potential gradient in the flame. When the drop of potential a t the negative electrode is got rid of by placing potassium carbonate on it the chloroform diminishes the current to about the same extent as the conductivity.The presence of a large amount of potassium carbonate does not change the luminosity due to sodium carbonate although the potassium carbonate greatly increases the total conductivity. The variation of the conductivity (c) with the concentration (k) f o r alkali salts can be represented by the equa- tion klO4= (c2- l ) / ~ . ( 6 + ac) using proper values for the constants n and b for each salt. This expression can be deduced from the ionic theory and the fraction of the salt molecules which are ionised is equal to b / ( b + ac). Alkali chlorides and carbonates impart equal conductivities to the flame for chemically equivalent concentrations. The percentage of the salt which is ionised when the concentration is small has the following values c s i u m salts 91%; rubidium salts 69%; potassium salts 58%; and sodium salts 1.6%.The constant b is proportional tp the molecular weight of the salt and according to the theory this shows that all salts give negative ions having the same velocity due to an electric field. The conductivity due to solutions containing a mixture of salts agrees with that to be expected on the ionic theory. J. F. S. The Influence of Some Hydroxy-acids on the Electrical Conductivity of Boric Acid. J. BOESEKEN [with R. DE BRAUW s. DE ~ ' A A R D and c. VAN LOON] (Rec. truu. chtim. 1915 35 211-224. Compare A. 1915 ii 136 667).-Measurements were made of the electrical conductivity of boric acid solutions con- taining varying molecular proportions of 8-hydroxybutyric acid a-hydroxyisobutyric acid benzilic acid and a-hydroxydiphenylene- acetic acid.The three last named all give a marked increase in the conductivity the results showing that the amount of the increase is not directly connected with the dissociation constant of the acid. Apparently the group adjacent to the a-hydroxy-group is of much greater importance in this connexion. With P-hydroxy- butyric acid there was a marked diminution in the conductivity the difference being however less than in the case of the other three acids. W. G. Conductivity and Dissociation of Some rather Unusual Salts in Aqueous Solution. CHARLES WATKINS and HARRY C. JONES (J. Amer. Chem. Soc. 1915 37 2626-2636).-The elec- trical conductivities of solutions of sodium bromate thiocyanate thiosulphate dithionate pyrophosphate tungstate f ormate chromate dichromate dihydrogen phosphate and phosphate ammonium iodate thiocyanate chromate and dihydrogen phos- phate rubidium iodide lithium chromate and potassium f erri- cyanide have been measured a t various concentrations and a t Oo 15* 25* and 3 5 O .From these data temperature-coefficients are 3*ii. 74 ABSTRACTS O F CHEMICAL PAPERS. calculated and the influence of t,emperat,ure on the ionisation is discussed. H. M. I). Electrical Conductivity of Certain Salts in Pyridine. EDWARD X. ANDERSON ( J . Physicrrl Chem. 1915 19 753-789).-The electrical conductivity of pyridine solutions of silver nitrate lithium chloride bromide and iodide sodium iodide potassium thiocyanate ammonium thiocyanate mercuric chloride bromide and iodide copper chloride and nitrate cadmium nitrate cobalt chloride and lead chloride have been determined a t Oo 25O and 50° for a series of concentrations in each case.These substances constitute two series of electrolytes the one consisting of salts the equivalent conductivity of which increases with increasing dilu- tion and the other consisting of salts the conductivity of which drops to a minimum. The temperature-coefficients have been calculated and it is shown that the coefficieiits between Oo and 25O are larger than those between 25O and 50°. Solutions of lithium bromide sodium iodide cobalt chloride and cadmium nitrate have negative temperature-coefficients. Explanations are given for the minimum conductivity and f o r the differences in the temperature-coefficients.It has been shown that the anomalous behaviour in equivalent conductivity is due entirely to the presence and properties of tlie ionisable polymerised solute which pre- dominates in concentrated solutions. J. F. S. The Conductivity and Viscosity of Solutions in Formamide. P. B. DAVIS W. S. PUTNAM and HARRY C. JONES (J. Frankliir Znst. 1915 180 567-601).-1n a further investigation of the properties of non-aqueous solutions of electrolytes measurements have been made of tlie electric conductivity and viscosity a t 15O 25O and 35O of salts dissolved in formamide. By repeated distilla- tion of formamide dried over anhydrous sodium sulpliate under reduced pressure in a current of dry air the1 conductivity of the solvent has been reduced t o a very much smaller value than that previously recorded by Walden (compare A.1912 ii 2G). The lowest value observed was K=2.8 x 10-6 mho. a t 25O. The salts for which data are recorded are sodium bromide iodide and chromate potassium chloride iodide and thiocyanate ammonium bromide and iodide tetramethylammonium chloride and iodide rubidium chloride bromide iodide and nitrate caesium chloride and nitrate lithium nitrate barium chloride mercuric chloride and cobalt bromide. The results afford further support for the view that the ionising power of a solvent increases with the dielectric constant and the association factor. Salts which form hydrates in aqueous solution afford evidence of combination with formamide. The solutions of these solvated salts show a larger percentage change in conductivity with change in temperature as compared with solutions of non- solvated salts.The percentage temperature-coefficient is found to be approximately proportional to the viscosity of the solutions. Formamide is the only solvent for which tlie viscosity of theGENERAT AND PHYSICAL C'HEMISTRY. ii. 75 solutioiis exainitied is less tltan tliat of tlie pure solvent. This is supposed t o be connected witli the large value of the association factor. Mercuric chloride is ioiiisecl to a greater exteiit in formamide than in water. H. RiI. D. Hydrates of Alcohols and Fatty Acids. Ballistic Electric Investigations. [Mrss] JOHAXNE CHRISTIANSEN (Ze itsch. physikal. Ckem. 1915 90 628-640).-Christiansen has shown (;1 I ? ? ? .PJrysiE 1913 [iv] 40 107) t h a t when aqueous solutions of salts. to which small quantities of non-electrolytes such as alcohol have been added are sprayed agaiiist a plate tliey give up considerable quantities of electricity. This electricity is termed 7)ollo-plpcfi.icity. The present paper deals witli the potential of the electricity given up when solutions o f calcium chloride or sodium chloride in water containing varying quantities of alcohols or fatty acids are sprayed against a platinum plate coniiected to a sensitive quadrant electro- meter. Measurements were made with methyl alcohol ethyl alcohol propyl alcohol butyl alcohol and amyl alcohol formic acid acetic acid propionic acid and butyric acid. I n the case of all the substances examined it is shown t h a t the voltage at first increases t o a maximum and then falls again to zero with increase in the percentage of the noii-electrolyte added.The voltage then changes sign and slowly increases numerically. The point of zero voltage is termed the ballo-electric neutral point. I n the case of the first three alcohols the mixtures a t which this point is reached are 1 mol. of methyl alcohol to 1.95 mols. of water 1 mdl. of ethyl alcohol t o 3.98 mols. of water and 1 mol. of propyl alcohol t o 8.38 mols. of water that is tlie number of moleculds of water have approximately the relationship 2 2? 23. In the case of tlie acids the ratio of tlie number of molecules of water is 3 :3?:33 etc. f o r tlie ascending members of the series. The action is held to be due t o a mechanical separation of neutral molecules into ions.J. F. S. A Hydrogen Electrode Vessel. WM. ~IANSFIELD CLARK (J. Bid. C ~ L A ~ . 1915 23 475-486).-After a description of a number of vessels wliicli liave been used for the cletermiiiation of hydrogen ioii potentials the author describes a piece of apparatus which is based on the principle of tliat devised by Hasselbach (A. 1911 ii 182). The object of the modification is to enable measure- ments of hydrogen ion concentration t o be made in bacterial and other liquids which are undergoing fairly rapid change. The apparatus consists of a length of fairly wide glass tube to one end of which a small bulb is attached which is fitted witli a neck a t the top t o take the platinum electrode and with a three-way tap immediately below the neck f o r the purpose of connecting witli the calomel electrode.The other eiicl of the tube is fitted with a three-way tap which is connected t o a siiiall reservoir containing the liquid under examination a i d to a hydrogen generator. The 3"-2ii. 76 ABSTRACTS OF CHEMICAL PAPERS. apparatus is used as follows thO apparatus containing only the platinum electrode is filled with hydrogen and then the solution is added until it is about one-third full. Then the apparatus which is mounted on a rocker is rapidly rocked for five to ten minutes so tha€ the electrode is alternately exposed to the gas and immersed in the solution. The measurement is then made and is found to be at once constant to about 1 millivolt. I n many cases a much more constant result is obtained.A series of measure- ments with milk gelatin cultures meat infusion and peptone solu- tion are given to illustrate the type and constancy of the results. J. F. X. The Anodic Solution of Lead. Nomm MURRAY BELL (Trans. Faraday SOC. 1915 11 79-90).-Experiments have been made to test the supposition that univalent lead ions exist in aqueous solu- tions (Denham and Allmand T. 1908 93 424). The anodic sclution of lead is determined by measurements in solutions of lead acetate sodium acetate potassium hydrogen tartrate hydro- fluosilicic acid potassium bromide and sodium thiosulphate a t various current densities. Bars of cleaned “pure” lead are used. The loss of weight of the anode is generally greater than is indicated for bivalent ions.With the above solutions except the two sodium salts the loss is shown to be due to mechanical and chemical removal of lead but sodium acetate and thiosulphate give results which appear to indicate the formation of univalent lead ions t o the extent of 2.8% and 5.6% respectively. The chemical character of the black deposit formed on lead anodes in thiosulphate solutions has not been determined. C. H. D. Electrical Transference in Amalgams. GILBERr N. LEWIS ELLIOT Q. ADAMS and EDITH H. LAMMAN ( J . Amer. Chem. SOC. 1915 37 2656-2662).-When sodium is dissolved in liquid ammonia a conducting solution is obtained and according t o Kraus the carriers of positive electricity in this solution are the sodium ions whilst the negative carriers are free electrons.I n the expectation that a solution of a strongly electro-positive metal in mercury would show similar behaviour on the passage of a current experiments have been made t o determine the effect of the current on dilute sodium and potassium amalgams. Sodium and potassium amalgams prepared by electrolysis were subjected to the action of a current of from four t o eight amperes for several days under conditions which eliminated as far as possible the effect of convection and the alkali in the anode and cathode compartments was then estimated. The results of these experiments show that the passage of the current through the amalgam was accompanied by the transfer of alkali metal from the cathode to the anode. The number of equivalents transferred per faraday was found to be 2.9 x 10-6 in a sodium amalgam contain- ing 3.24 atoms per cent.of sodium and 0.29 x 10-6 in an amalgam containing 0.57 atom per cent. I n a potassium amalgam contain-GENERAL AND PHYSICAL CHEMISTRY. ii. 77 ing 2.16 atoms per cent. of the alkali metal the transfer per faraday was 3-6 x 10-6 equivalent. The diminution in the electrical conductivity resulting from the addition of the alkali metal is attributed to a diminution in the average mobility of the electrons. I f the atoms of sodium are supposed to form nuclei of large aggregates of mercury atoms which aggregates are less easily penetrated by the electrons than are free mercury atoms the negative transfer of the sodium can be explained. The fact that potassium has a greater transference number is on this view consistent with the fact that potassium produces a greater lowering of the conductivity of mercury as com- pared with that produced by an equivalent quantity of sodium.H. M. D. Application of the Theory of Allotropy t o Electromotive Equilibria. 11. Passivity of Iron. A. SMITS and A. H. W. ATEN (Zeitsch. physikal. Chem. 1915,90 723-743).-A theoretical paper in which anodic polarisation and the passivity of iron as brought about either by chemical means or by anodic polarisation are discussed. A number of theories are discussed and i t is shown that the primary manifestation of passivity which consists in the fact that a t moderately low current densities the potential differ- ence between iron and electrolyte increases so that the liberation potential of oxygen is rapidly reached is not in accord with the oxide theory and cannot be explained by this theory.The charg- ing of iron with oxygen and the resulting oxide formation are secondary manifestations of passivity. It is emphasised that passivity has its situation on the surface of the metal and i t is shown that the appearance of passivity due to all causes the change from the passive form t o the active form and abnormal cathodic polarisation can all be explained from a common point of view on the basis of the theory of allotropy. Polarisation occurs not because the heterogeneous equilibrium between the metal and the solution is set up too slowly but because the metal is com- pelled to dissolve more rapidly than the inner equilibrium is abls to set itself up whereby the metal surface becomes more noble.A strong experimental confirmation of the new method of considera- tion is found in the results of Finkelstein (A. 1902 ii 81) who showed that iron in a solution of ferric sulphate has a more positive potential than iron in a solution of ferrous sulphate of the same concentration. The formula A = - RT/nF log,K/C is not obeyed and the formula A = - R T / F log,(R . C / [ / / C / / ) may not be applied because iron in a solution which contains ferric ions cannot be in equilibrium and cannot act as non-soluble electrode. The iron is strongly attacked by such a solution and the above-mentioned phenomena are the result of a disturbance of the internal equil- ibrium of the metal surface. It is also shown that the activation curve points to a discontinuity in the mixture series of the pseudo- components.The abnormal cathodic polarisation and the con- nexion between the allotropy of iron and its passivity are dis- cussed in connexion with the theory of allotropy. J. F. 8.ii. 78 ABSTRACTS OF CHEMICAL PAPERS. The Thermomagnetic Properties of Various Compounds and the Weiss Theory of Magnetons. K~TARG HONDA and TORAJIR~ ISHIWARA (Sci. Rep. Tohokzc Imp. Univ. 1915 [ii] 4 215-260). -The experiments of Ishiwara a t lcw temperatures (A. 1915 ii 141) have n3w been extended t o higher temperatures. The susceptibility of - paramagnetic ccmpourids is not derivable from t h a t of their ccinpcrents by the additive law. Curie’s law is only applicable t o a very limited number of ccmpounds but a hyper- bolic law such as that given by K.Oiines and Perrier is generally applicable over tlie whole range of temperature within which the same phase is present. Either an abrupt departure from this law or a gradual one extending over a range of temperature indicates a phase change. The susceptibility of all the diamag- netic substances examined is constant for all temperatures within the range of existence of a single nhase. The effect of water of crystallisation is different in different compounds. Phase changes are readily detected by means of t h e m omagnetic obyervations. Weiss’s theory of magnetons is criticised the evidence on which it is based being considered insufficient and the magnetic moments of elements and compounds are calculated from the data in this paper and this vol.ii 105 leading t o the conclusion that the oxygen atom has a greater magnetic moment than that of iron whilst niolecules of tlie compounds of iron nickel and cobalt have magnetic momelits wliich are f a r greater thaii those of the ferro- magnetic elements themselves. An Electromagnetic Vacuum Balance. JOHN 8. RNDEHSC~ (Trans. Faraday SOC. 1915 11 69-75).-The balance is intended for repeated weigliings of silica gels and similar substances with- out removing from the vacuum. One af the scale-pans of a balance is replaced by a coil of wire with its axis vertical. This moves between two larger coils conc3ntric with it so connected that the movable coil may be attracted or repslled. The force is varied by varying the current.The balance is enclosed in a bell-jar which may be evacuated. The beam is released and fixed magnetically by means of an iron core and two solenoids. An electrical arrange- ment with slide resistances allows the current passing through the weighing coils t o be measured. This is calibrated by means of known weights. C. H. D. Relation between the Thermal Conductivity and the Viscosity of Gases with Reference to Molecular Complexity. J. A. POLLOCK ( J . Roy. SOC. N e w Soicth TT’cc7es 1915 49 249-252).- The relation between the thermal ccnductivity I; the viscosity ?I and the specific heat cv of a gas is expressed by the equation k=fqcV in which the coefficient .f has the same value for gases which contain the same number af atcJms in the mclecule. By the use of Eucken’s data (A.1913 ii 474) it is shown t h a t the con- nexion between f and the specific heat ratio y=cC?,/cv may be writhen in the1 form f = 7 * 3 2 ( y - l ) / - y 1 . 3 . It is also shown that rn y k / 11 is approxiniately constant n/ denoting the molecular weight of the gas. C. H. D. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 79 The Thermal Conductivity of Neon. ERICH BANNAWITZ ( A m . Physik 1915 [iv] 48 577-592).-From observations made according t o Schleiermacher's method the thermal conductivity of neon a t Oo has been found t o be 1~,=0*0001091 gr./cal. sec./cm. The temperature-coefficient of the thermal conductivity is 0.00259 which agrees closely with the values for air (0.00253) and argon (0*00260) but is smaller than the value f o r helium (0*00318).According t c Chapman (I'lid. Trans. 1911 [ A ] 211 433) the1 thermal conductivity I; the coefficient of viscosity 11 and the specific heat' a t constant volume cL. are in the case of monatomic gases connected by the equation K / 11 . c,.= 2.5. By substituting in this equation the' values 11 =3*036 x 10-4 (at 10*lo) c,,,=O*1474 /~=0~00011195 ( a t l0.lo) the value of l;,/qcL is found t o be 2.501. H. M. D. Determination of the Velocity of Sound and of the Ratio of the Specific Heats of Gases by the Method of Rundt's Dust Figuree. G u s ~ a v SCHWEIKERT ( A m . Physik 1915 [iv] 48 593-667).-Measurements have been made of the velocity of sound in various gases a t the ordinary temperature using Kundt's method in combination with tubes of varying diameter and notes of different pitch.Data are recorded for air nitrogen oxygen hydrogen carbon monoxide hydrogen clilor ide carbon dioxide nitrous oxide sulphur dioxide ammonia ethylene and acetylene. The data are applied to the derivation of 'the specific heat ratio k = c y / c and of the molecular heats. The following recorded values of the molecular heats at constant pressure c j a t 20° show that for diatomic and still more for triatomic gases the molecular heat increases with the density carbon monoxide 6.900 ; nitrogen 6.905 ; oxygen 6.924 ; hydrogen chlcride 7.046 ; carbon dioxide 8.904 ; nitrous oxide 9.214 ; sulphur dioxide 10.059 ; ammonia 8.933 ; ethylene 9.773 ; acetylene 9.783. These values are com- pared with the results obtained in direct measurements of the specific heats of the various gases.H. M. D. The Speciflc Heat of Platinum and of Diamond at High Temperatures. A. MAGNUS ( A m . Physik 1916 [iv] 48 983-1004).-By means of a modified form of the calorimeter described in a previous paper (A.? 1913 ii 103) measurements have been made of the specific heat of platinum and its variation with temperatures up t o about 900°. The lieat (Q) liberated by 1 grain of platinum in cooling from t o to f,' can be expressed by the equation Q =0*031590(t - to) + 0.0%9234(t2 - to2)) and from this the specific heat a t any temperature t is given by c1,=0*031590 + 0-0558468t. I n Weber's well-known measurements of the specific heat of diamond and graphite at high temperatures the temperature of the heated substance was determined indirectly by measuring the heat' liberated by platinum which had been heated t o the same temperature.I n view of the greater accuracy of the new measure- ments of the specific heat of platinum Weber's data have beenii. 80 ABSTRACTS OF CHEMICAL PAPERS. made use of in a recalculation of the specific heat of diamond and of graphite. F o r diamond c p = 0.31456 + 0*033824(t - 282) - 0*063168(t - 282)z and for graphite c,=0*28815 + 0*0346348(t - 225.3) - 0*063642(t - 225-3)z. The equation for the specific heat of diamond is in very good agreement with Weber’s data over the entire range of temperature but in the case of graphite there are discrepancies a t temperatures below 500O. A New Method for Determining the Specific Heat of Liquids. E. J.HARTUNG (Trans. Faraday Xoc. 1915 11,64-68).- The method requires the use of about 60 C.C. of the liquid and gives a high accuracy. It consists in introducing a known weight of ice enclosed in a bulb and noting the fall of temperature pro- duced. A small cylindrical glass bulb contains 1 t o 3 C.C. of water and as large a roll of silver gauze as possible. This bulb is sealed and will sink in the liquid. A glass tube 15 cm. long and 4 cm. diameter contains 100 C.C. of mercury and is provided with a rubber stopper holding the thermometer and having a hole large enough t o admit the ice carrier. Dry air may be drawn through the apparatus. The calorimeter is a thin copper cylinder silvered internally and supported in a Dewar vessel. The mouth is closed by a rubber stopper t.hrough which a thin glass stirrer passes.After placing 60 C.C. of the liquid in the calorimeter and the weight having become constant the ice carrier is secured under the mercury in the freezing tube and dry air is drawn through t o prevent condensation of water. The tube is cooled to -5O and kept a t about -lo after freezing has taken place. The tempera- ture being noted the bulb is introduced into the calorimeter which is stirred until the temperature reaches a minimum. The usual corrections are made. The values obtained for mixtures of sulphuric acid and water are in good agreement with those of Thomsen. C. H. D. A Simple Method of Obtaining Melting Points of Fats etc. ARTHUR W. KNAPP (J. Soc. Chem. Znd. 1915 34 1121-1122).- Very thin shavings of the fat wax or fatty acid are spread over about one half of the bulb of a thermometer which is fixed in a corked test-tube immersed in a transparent bath.It is easy t o determine when the sharp edges of the scrapings soften and when the substance is quite) transparent. For crystalline compounds the bulb of the thermometer may be rolled in the powdered substance when sufficient will adhere. The Freezing Point of Benzene as a Fixed Point in Thermometry. JULIUS MEPER (Zeitsch. physikal. Chem. 1915 90 721-722).-Richards and Shipley (A 1914 ii 765) recommend the use of the freezing point of benzene as a fixed point f o r Cali- brating thermometers. The author holds that benzene purified by the method indicated will have an indefinite freezing point on account of the varying amount of air and other gases dissolved in it.He recommends that it would be preferable t o use the melting point of pure benzene crystals as a fixed point. H. M. D. J. C. W. J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 81 The Solidification Curve of the System Ammonium Nitrate- Lead Nitrate. €3. BOGITCH (Compt. rend. 1915 161 '790-'791).- The author has determined the solidification points of mixtures of ammonium nitrate and lead nitrate containing from 0-55% of lead nitrate. The temperatures a t which solidification commenced and finished were determined in each case for the mixtures contain- ing from 33-45*5% of lead nitrate the differences between these two temperatures f o r each mixture increasing rapidly with increase in the lead nitrate content.The temperatures of commencement of solidification were plotted and by extrapolation the temperature at which lead nitrate should melt was found t o be 450-470O. The eutectic mixture contained 33% of lead nitrate. W. G. The Critical Constants of %-Butane isoButane and Propylene and their Vapour Pressures at Temperatures Between Oo and 120". F. M. SEIBERT and G. A. BURRELL (J. Amer. Ch,em. SOC. 1915 37 2683-2691).-The substances used were carefully. purified by fractionation a t low temperatures. The vapour pressures recorded were independent of the relative volumes of liquid and vapour and the critical phenomena were quite normal. The following values are recorded f o r the critical temperature ( O ) critical pressure (T) and the constants a and b calculated from the van der Waals's equation n-butane 8 = 153*2O r = 35-67 atm.a = 0.02883 b = 0.005470 ; isobutane 8 = 133'7O T = 36.54 atm. a= 0-02562 b = 0*005096 ; propylene 8 =92*6O r = 45-34 atm. a = 0.01668 b = 0.003692. H. M. D. The Vapour Pressures of Sulpbur Dioxide and Nitrous Oxide at Temperatures Below their Normal Boiling Points. G. A. BURRELL and I. W. ROBERTSON (J. Amer. Chem. Soc. 1915 37,2691-2694).-The observed vapour pressures of liquid sulphur dioxide between - 1l0 and - 64.5O can be represented by the equa- tion log p= - 1448*01/T+ 8.425 and the data for solid nitrous oxide between -90-6O and -144'1O by the equation The Clausius equation gives 6619 cal. for the mean heat of vaporisa- tion of liquid sulphur dioxide and 5632 cal. for the mean heat of sublimation of solid nitrous oxide.The observations give - l l . O o and - 88*7O for the normal boiling points of sulphur dioxide and nitrous oxide respectively. lOgp= - 1232'2/T + 9.579. H. M. D. The Vapour Pressures of Some Saturated Solutions. MALCOLM PERCIVAL APPLEBEY and WILLIAM HUGHES (T. 1915 107 1798-1814).-1f P is the osmotic pressure of a solution of concentration c then as a general rule P / c increases with the concentration of the dissolved substance. According t o the boiling- point determinations of Berkeley and Applebey (A. 1911 ii 1062) concentrated solutions of thallous nitrate appear to be exceptional in that the saturated solution gives a value for P / c which is less than that calculated from the gas equation on the assumption thatii. 82 ABSTRACTS OF CHEMICAL PAPERS.the salt is non-ionised. I n view of this anomaly measurements have been made of the vapour pressures of saturated solutions of sodium nitrate sodium sulphate and thallcus nitrate by a static method covering a range cf yeveral degrees in the neighbourhood oE the respective bciling points. The temperature-coefficients a t 760 nini. derived from the vapour- pressure curves are sodium nitrite 21.3 mni. per lo; sodium sulphate 29.2 mm.; and thallcus nitrate 22.3 mm. From the experimental data the osmotic pressures af the saturated solutions have been calculated and the results shcw t h a t for sodium nitrate and sulphate the value of P / c iiicreases continuously with the con- centration whilst for thallium nitrate Y/ e first increases reaches a maximum and then falls ccntinuously.It is supposed t h a t this anomalous behaviour is connected with the association of the dis- solved salt. Special experiments showed that' the low boiling point of the saturated thallous nitrate solutions is not due to volatility of the salt. A form of thermostat is described which gives constant tempera- tures between looo and 120° within 0.02O. H. M. D. Vapour Pressure of Liquid Substances at Low Tem- peratures. C. DRUCKER E. JIM~NO and W. KANGRO (Zeitsch. pTiysilaZ. CTiem. 1915 90 513-552).-The vapour pressure of hexane ethyl alcohol ethyl ether toluene chloroform acetone carbon tetrachloride and iodobenzene have been determined at temperatures from + 15O to - looo. The pressures were measured by either a McLeod manometer or a horizontal modification of the Huygens manometer.I n this way pressures from 40 nim. to 0-001 mm. were measured with an accuracy of 0.001 mm. The experimental results are given in tables and curves and are shown t o be in good agreement with the values previously obtained by Poung. Using the vapour-pressure formula of Kirchhoff-Dupre- Rankine with four terms it is shown t h a t the experimental results may be calculated with accuracy. This is attained when the four coefficients are derived from the curves and also when one of them is chosen arbitrarily. These constants are consequently t o be regarded as empirical since they may have different values without affecting the final results. This indicates that it is not possible from the vapour-pressure measurements alone to deduce the * ' Chemical Constants " which correspond with temperatures which are not far removed froin the absolute zero.To determine these values accurately it is necessary t o know the specific heat and its changes with temperature a t these temperatures. J. F. S. The Vapour Pressure of Concentrated Sugar Solutions. D. ORSON WOOD (Tra'ns. Faraday SOC. 1915 11 29-50).-New measurements have been made by a direct method the solutions being prepared in a glass vessel thoroughly freed from grease and provided with taps. Distilled water is freed from air by boiling in a similar vessel and introduced through one of the tails. Water is then removed by evaporation under reduced pressure and theGENERAL AND PHYSICAL CHEMISTRY. ii. 83 last traces of air removed by heating a t looo and pumping.The concentration is then determined by weighing. The bulb in which the measurements are made is sealed cn to this apparatus and is provided with a stirrer consisting of a sealed glass tube containing short soft iron rods packed in glass wool. This bulb and the first part of the manometer are enclosed in a water-bath. Experiments with pure water show t h a t the results are slightly too low. Solutions containing 48 61 and 69% of sucrose have been examined. The heat of dilution calculated by means of Kirchhoff’s equation is of the riglit sign arid order. When the results are tested by calculating tlie hydration Callendar’s factor is found t o be about 4 whilst the csinotic pressures are of tlie right order but diminish with rise of temperature.This may be due to increased association and tlie theoretical meaning of the change is discussed. C. H. D. The Vapour Pressures and Specific Volumes of Binary Mixtures of Volatile with Non-volatile Liquids. F. H. CAMPBELL ( l ’ m n s . Pccrcrrlny SOC. 1915 11 91-103).-The vapour pressures of the liquids are determined by measuring the rise of mercury in an open manometer caused by allcwing a mixture of known com- position to escape into a space previously filled with hydrogen. Mixtures of cleic acid with either ether or carbon disulphide give vapour-pressure curves which closely approach the diagonal whilst in the third pair of normal liquids aniline and ether the curve has a point of inflection and cuts the diagonal. It is possible t h a t in this case a measurably volatile solvate is formed.The oleic acid-acetone curve acetone being associated lies above the diagonal. Sulphuric acid and ether give a curve with a point’ of inflection probably due t o a compound (C2H,),0,H,S04 which may combine with a further mclecule of ether. Of pairs of associated liquids glycerol-methyl alcohol gives a curve like t h a t of oleic acid and acetone whilst the curve of glycerol and water lies below the diagonal. The specific volume curves are also given. Attempts to apply Dolezalek’s theory quantitatively fail even in the simplest cases. C. H. D. Some Difficulties in Van Laar’s Theory of the Vapour Pressures of Binary Mixtures. R. T. Lmrm (Traits. Faraday SOC. 1915 11 118-120).-Van Laar’s formula is shown t o be inconsistent with the effects of temperature on the vapour pressure of mixtures of partly miscible liquids and even with the experi- mental facts when the comparison is made a t constant tempera- ture.The data fcr methyl ethyl ketone and water mixtures are used for the purpose. C. H. D. Von Babo’s Law and Rirchoff’s Equation for the Latent Heat of Dilution. ALFRED W. PORTER (Tram. Farady SOC. 1915 11 19-28).-Two thermodynamical derivations of von Babo’s law are given in order t o bring out the assumptions on which it is based. An alternative method of finding the internal latent heakii. 84 ABSTRACTS OF CHEMICAL PAPERS. of dilution is also given. The hydration factor a used by Callendar is here employed as representing an effect of alteration of volume of the solvent molecules the volume of a hydrated salt being greater than that of the anhydrous salt.Callendar's interpreta- tion breaks down unless water be assumed not t o be associated. The value for the hydration is the same on either explanation. C. H. D. Heat of Neutralisation and the Quantum Theory. ADOLF HEYDWEILLER (Ann. Physik 1915 [iv] 48 681-692).-Accord- ing to the quantum theory the heat changes associated with chemical reactions ought to bear some definite relation to the changes which occur in the optical properties f o r these are deter- mined by the electron frequencies. On the assumption that the chemical changes are due to changes in the frequencies of the valency electrons the author has calculated the change in frequency characteristic of the formation of a molecule of water from the corresponding H' and OH' ions (1) from the heat of neutralisation and (2) from the change in the refractivity due to ionisation.The first method gives vm - vi = 0.2895 x 1015(sec. -1) and the second v,-vi=0*292 x 1015(sec.-l). The agreement is excellent and is considered to furnish evidence in favour of the correctness of the author's method. H. M. D. Contradictions between the Real and Calculated Solubility of Certain Sodium Salts. ALBERT COLSON (Compt. rend. 1915 161 787-790. Compare this vol. ii 15).-By careful experi- mental work the author finds that for sodium chloride the value of p a t Oo is 28 cal. this development of heat being quite opposed to the marked cooling effect found a t loo and above. I n conse- quence of this sodium chloride should have a maximum solubility a t lo which is contrary to fact.Similarly in the case of sodium carbonate whether anhydrous or hydrated its solubility increases steadily from Oo to 38O and in consequence p should be positive in both cases but it is not. A t the mean temperature 1 8 O the value of p for the anhydrous salt is 5500 cal. and for the decahydrate -13,776 cal. Thus then the ordinary law of solubility does not apply to either of these common salts. W. G. History of Specific Gravity Determination. HRRMANN SCHELENZ (Chem. Zeit. 1915 39 913-915).-A historical description of the methods and apparatus employed for specific gravity determinations from the earliest times to the seventeenth and eighteenth centuries. G. F. M.A Convenient Thermostat for Accurate Speciflc Gravity Determinations and a Gas Pressure Regulator. K. G. BROWNING and C. T. SYMONS (Trans. Faraday SOC. 1915 11 60-63).-A large copper tank is used as the thermostat provided with stirring paddles on a horizontal shaft. The shaft is driven by a chainGENERAL AND PHYSICAL CHEMISTRY. ii. 85 from a spindle driven through a spring coupling attached t o an electrically-driven worm reduction gear. The heating is eit'her electrical or by gas. For electrical heating a heavy platinum wire is fused into the bottom of a Lowry thermo-regulator where it is in contact with mercury. The other contact is a platinum wire mounted on a thin brass rod having a fine thread cut on it a $-volt accumulator being in series with the mercury thread the platinum point and a relay.When contact is made the relay turns on part of the heating current. By shunting the platinum- mercury cont'act with a pair of insulated aluminium plates each about 12 sq. in. immersed in water the sparking is so far decreased as not t o cause fouling of the mercury. A gas regulator is also described consisting of a brass cylinder with a. horizontal partition carrying the valve seating the valve stem being connected with a sheet of rubber insertion t o which it is attached by two concave-convex washers. The regulator is set by adjusting the weight on the valve. C. H. D. The Critical Point of Game Liquefied with Difficulty Nitrogen Carbon Monoxide Oxygen Methane. ETTORE CARDOSO (J. Chim. Phys. 1915 13 312-350).-A detailed account of work part of which has been previously published (compare A.1915 ii 411). By measurements of the densities of co-existing liquid and vapour a t various temperatures the critical density of carbon monoxide is found t o be 0.3110 and of methane 0.1623. The author considers that the precision with which the critical data are determinable is frequently over-estimated. The errors attaching t o the values obtained for the four gases by the author are probably less than +0.lo for the critical temperature and rt0.l atmosphere for the critical pressure. H. M. D. An Interpretation of Van der Waals's Equation from the Point of View of Volume Determined by Equilibrium of Pres- sures. W. V. METCALF (J. Physicai! Chem. 1915 19 705-719).-A theoretical paper in which reasoning from the point of view that the volume of a gas or liquid under given conditions is due t o an equilibrium of opposing pressures it is shown that this equilibrium is represented by the van der Waals equation thus p + a/u2= RT/ (v - b ) .The author names the various pressure quantities thus external pressure + cohesive pressure = elastic pressure. From kinetic considerations it is shown that in the case of a stable liquid the elastic pressure which tends to increase the volume increases with density more rapidly than does the cohesive pres- sure which tends to decrease the volume. The difference between the density coefficients of these two pressures decreases as the density of the liquid decreases. The above-mentioned propositions are used t o interpret the various parts of the van der Waals curves.Explanations are given for the metastable portions of both the PF' and TV curves. J. F. S.ii. 86 ABSTRACTS OF CHEMICAL PAPERS. [Compressibilities of the Elements and their Relations to Other Properties]. Correction. TH E O I ~ R E W. R,ICHARDS ( J . A mpr. Chfnt. Soc. 1915 37 2696-2697).-The substitntion of inore accurate values f o r tlie atomic volumes given in the previous paper (A. 1915 ii 518) does not in any way invalidate the coil- clusions which were drawn. In nearly every case the effect of the substitution is t o improve the ngreeinent between the calculated and observed values. H. &I. T). The Viscosity Coefficients of Mixtures of Helium and Hydrogen. ARTHUR GILLE ( A n n Physik 1915 [iv] 48 799-83’7).-The viscosities of mixtures of hydrogen and helium have been measured a t Oo 15O and looo by the transpiration method. Ex- periments with air which were made to test the apparatus gave q=1.819G x at 19.83O whence ~ / = 1 . 7 2 2 1 x a t 0 O . For helium tlie coefficieiits obtained were ’1 x l o ’ = 1.8925 at 0 ) 1-9Gll a t 15O and 2.3408 a t looo; and for liydrogeii 11 x 104=0.8772 a t 14.79O. The viscosity coefficients for iiiixtures are only approximately represented by Puluj’s formula; a much closer agreement is found when the results are applied t o Thiesen’s formula (T’~rh. J ) P u t . w h . Phys. Ges. 1902 4 357). The influence of temperature on the viscosity of the mixtures is satisfactorily expressed by Sutherland’s formula but there is some1 evidelnce that mixtures falling near the middle of the series would begin to deviate from the requirements of this formula a t temperatures below Oo.13. M. D. The Study of the Density and Viscosity of Aqueous Solu- tions with Special Reference to Nitric Acid. IT. Viscositiee. WILLIAM ROBERT BOUSFIELD (T. 1915 107 1781-1797. Compare ibid. 1407; A. 1915 ii 744).-An improved form of viscometer of the gravity flow type is described for which it is claimed that an accuracy of 1 in 1000 is readily obtainable. Water is the oiily liquid which is adrnissible for the calibration of viscometers which are t o be used in the investigation of aqueous solutions and con- trary to previous statements the. author has found it quite suit- able as a calibrating fluid although i t is admitted t h a t sinall variations in tlie time of flow do occur f o r whicli no explanation can be given. In coiinexioii with the use of water as a calibrating liquid in viscosity work it has been found that the expoiiential formuke giveii by Thorpe arid Rodger to represent the influelice of temperature on the viscosity do not represent their experimental results so closely as the formula 11 =O*OI0514 { 1 + 0.025l(Q - 18) + 0*000115(0 - 18)2) -l.J / 4 - s / 2 - and iT-solu- tions of nitric acid were measured a t 4O 1l0 18O and 25O. The influence of temperature on the variation of the viscosity with the temperature is shown by a comparison of tlie values of the equi- valent viscosity increment as measured by ( 1 1 ~ . - 1)/ t i t where ?lw is the viscosity relative to that” of pure water a t the same temper- The viscosities of Ar/ 32- Nil&,GENERAL AND PHYSICAL CHEMISTRY.ii. 87 ature and ni is tlie number of equivalents of acid per litre. A t 4 O the recorded values are all negative a t lS0 and 2 5 O all positive whilst at I lo the iiicreinent shows a change of sign. By means o€ curves i t is shown that the several values of the increments lie on smooth curves the interpretation of wliicli is discussed in terms of tlie theory that tlie viscosity of a solution is approximately a simple function of the relative sizes of tlie different groups of molecules in the solution. 111 tlie particular case under investiga- tion the three groups concerned are tlie nitric acid molecules t’he dihydrol aiid the triliydrol molecules and account’ is taken of these in tlie author’s iiiterpretation of his observations.H. 31. D. The Viscosities of Solutions of Caesium Salts in Mixed Solvents. I?. B. DAVIS and HARRY C. JONES (J. Anzer. Cliem. SOC. 1915 37 2636-2G42).-Measuremeiits have been made of tlie viscosities of solutions of caesium chloride and caesium nitrabe in binary mixtures of water with methyl alcohol ethyl alcohol and acetone a t 1 5 O 2 5 O and 35O. Similar measurements have already been made for solutions of rubidium and potassium salts. The interest attaching to the salts of these three metals lies in the fact t h a t their atomic volumes are greater than those of all other metals. The atomic volume decreases in the order-czsium rubidium potassium and any peculiarities shown by solutions of rubidium and potassium salts may therefore be expected to be shown by czesium salt solutioiis in greater degree.Generally speaking the salts of these t h e e metals are the only ones whicli loner the viscosity of water. Tliis has been explained by reference t o tlie large volume of tlie cations resulting in a reduction of the frictional surface in comparison with that of pure water . As in the case of rubidium and potassium salts the transition from negative to positive viscosity as the proportion of non-aqueous solvent in the mixture increases is shifted towards the non-aqueous end of tlie series of mixtures aiid this effect is more marked with caesium than with rubidium. H. M. D. Willard Gibbs’s Adsorption Coefficient. ALFRED J\-. PORTER (Trrrns.Farcrdcry Soc. 1915 11 51-52).-A simple proof of Gibbs’s adsorption theorem obtained by taking the solut,iou in con- tact with its vapour aiid considering a trausf ormatioii in whicli an infinitesimal evaporation takes place so that tlie vapour pres- sure which is better known takes the place of the osmotic pres- sure. The formula is extended to the case of strong solutions for whicli it still holds good although tlie correcting term becomes relatively large. C. H. D. A Simple Method of Deriving the Gibbs Adsorption Formula. F. J. HARLOW and R. S. WILLOWS (Trans. Faraday SOC. 1915 11 53-54).-A simple thermodynamical proof of Gibbs’s adsorption formula is given avoiding the use of the chemical potential andii. 88 ABSTRACTS OF CHEMICAL PAPERS. obtaining the result in terms of osmotic pressure (compare pre- ceding abstract).(1. H. D. Determination of the Coefficient of Diffusion of Potassium Chloride by an Analytical Method. A. GRIFFITHS J. M. DICKSON and C. H. GRIFFITHS (Proc. Physical SOC. London 1916 28 73-80) .-The diff usometer described consists essentially of a series of parallel vertical tubes the lower ends of which communi- cate directly with a reservoir of large capacity containing the salt solution. The greater part of the reservoir is above the lower ends of the diffusion tubes and by the action of gravity the con- centration of the solution in this region is kept approximately constant. The upper ends of the diffusion tubes open into' a small chamber provided with inlet and outlet tubes. Pure water enters through the inlet tube and the dilute salt solution leaving by the outlet tube is collected and analysed.I n carrying out an experi- ment time is allowed for the attainment of- the steady state. This requires several days and the complete determination may take six weeks. The results obtained give 1.703 x 10-6 f o r the mean value of the diffusivity of potassium chloride a t 1 8 * 5 O in a solution of 3N con- centration. H. M. D. Velocity of Diffusion and Hydration in Solution. M. PADOA and PERNANDA CORSINI ( A t t i R. Accad. Lincei 1915 [v] 24 ii 461-467).-By means of an apparatus differing slightly from those employed by previous investigators the authors have studied the diffusion in aqueous solution of various non-electrolytes with the object of determining their molecular weights and consequently the extent to which they are hydrated (compare Herzog A.1911 ii 23). The measurements were made a t constant temperatures ranging from 20° to 2 4 O in the different cases alid the viscosity constants [ are calculated from Bingham and White's results (A. 1912 ii 1144). The results obtained are summarised in the follow- ing table II being the diffusion coefficient and the specific volume and the hydration being expressed in mols. of water per mol. of the compound /-<- Hydra- Mol. wt. k. V. & Calc. Found. tion. Methyl alcohol ............ 0.739 1-262 0.009172 32 66.6 1.9 Ethyl alcohol ............... 0.396 1.246 0.01006 46 319.0 15-0 Glycerol ..................... 0.555 0.793 0.009172 92 250.0 8.9 Phenol ........................ 0-525 0.932 0.009116 94 214.0 6.7 Sucrose ..................... 0.442 0.630 0.009616 342 530.0 10.5 Acetamide ..................0-709 0.870 0.009172 59 109.0 2.8 Hexamethylenetetramine 0.543 0.753 0-009838 140 221.0 4.4 Although these results are slightly incorrect owing t o the fact that ths calculated values of v do not apply exactly to the hydrated compounds a pronounced tendency t o undergo hydration is evident. Padoa and Matteucci (A. 1915 ii 676) have shown that inGENERAL AND PHYSICAL CHEMISTRY. ii. 89 benzene solution aromatic hydrocarbons exhibit no appreciable power of combiiiing with the solvent. This is borne out by the results of measurements of the diffusion of naphthalene diphenyl and dibenzyl in benzene solution ; the values of the molecular weight found in this way are 121 152 and 180 respectively the theoretical values being 128 154 and 182.T. H. P. Influence of Glycerol Dextrose Alkali Nitrates and Sul- phatee and Ammonium Salts on the Solvent Power of Water. JAMES CHARLES PHILIP and ARTHUR BRAMLEY (T. 1915 107 1831-1837>.-By the method described in a previous paper (com- pare A. 1915 ii 236) experiments have been made to determine the effect produced by the above-mentioned substances on the dis- tribution of ethyl acetate between water and benzene a t 20°. For all the dissolved substances examined excepting ammonium nitrate the equivalent relative lowering of the solvent power increases as the concentration decreases. From a comparison of the values of the lowering of the solvent power with those deduced from earlier observations on the influence of dissolved salts on the solubility of hydrogen oxygen ethylene and acetylene in water it is found that the authors’ values are greater except in the case of the nitrates Since the values are calculated on the assumption that the added substance has no solvent power of its own it follows that they must be regarded as minimum values.For this reason the equivalent lowerings yielded by the distribution method are probably nearer the truth and for the majority of the dissolved substances the specific character of the reference substance is of less significance in the method used by the authors than in other work of the same kind. H. M. D. The Electrical Synthesis of Colloids. H. T. BEANS and HERBERT E.EASTLACK ( J . Amer. Chem. SOC. 1915 37 2667-2683).-The experiments described were made with the object of throwing light on the nature of the electrical method of producing colloidal solutions. I n a preliminary calculation of the conductivity due t o colloidal particles of gold for which the size charge and mobility are known it is shown that the conductivity due to the colloid itself is negligibly small in comparison with the observed conductivities of colloidal gold solutions. Comparative experiments in which the increase in the con- ductivity due to the electrical dispersion of gold and platinum was determined showed that the average increase for sols of approxi- mately the same depth of colour is about eight times as large for platinum as for gold.The platinum sols were invariably more stable than the gold remaining apparently unchanged on keeping f o r several weeks whilst the gold sols coagulated in from two to twenty-four hours. The greater stability of the platinum sols is probably connected with the presence of small amounts of electro- lyte formed by oxidation of tbe metal. during the process of dis- persion.ii. 90 ABSTRACTS OF CHEMICAL PAPERS. I n accordance with this view it lias been found that certain anions have a stabilising influence on red gold sols and this property may be utilised in the preparation of stable colloidal solu- tions of the metal. Such anions are chlorine bromine iodine and hydroxyl and a iiiarked effect is observed in coiiceiitrations ranging from 0.00005S to 0.005,V.The stabilisiiig effect is not observed if the gold is dispersed in pure water and the electrolyte added subsequently. The lower limiting anion concentration appears to be independent of the concentration of the colloid forrned over a wide range and tlie upper limit is t o some extent iiifluenced by the coagulating power of the associated cation. Other anions appear t o have no influence 011 tlie stability of red gold sols negative results being obtained with solutions containing small quantities of fluorides nitrates chlorates and sulphates. I n all these solutions tlie colloidal particles are negatively charged and the stabilisiiig effect of certain anions would seem to be determined by the ability of these ions t o forin stable complexes with gold. Attempts to detect gold it1 the) filtrate after coagula- tion of the sols gave however negative result)s from whicli it is inferred tliat the airiouiit of the gold compound whicli is necessary to produce a stable colloid is extremely minute.The above observations lead to the conclusion that the electrical method of colloid synthesis involves a primary thernio-mechanical dispersion of tlie metals and the subsequent reaction of the highly disperse1 metals with certain ions present. in the surrounding medium resulting in the forniatioii of negatively charged colloidal complexes. H. M. D. Influence of Light on the Stability of Colloidal Solut'ions. H. NORDENSON (Zeitsch. physilial. Chem. 1915 90 603-626).- The influence of light from a quartz mercury lamp on a number of sols has been investigated spectrophotochemically and ultra- microscopically.It is shown that light has a slow coagulating influence on metal colloids which is very similar t o tlie influence exercised by a weak electrolyte. The quantity of light' necessary t o bring about a visible coagulation is very large which in all probability explains the negative results of other investigators. There is no chemical change occasioned in the disperse phase con- sequently so far as this phase is concerned the change is t o be regarded as purely physical. The photo-action does not bring about chemical changes in the dispersion medium and the action only takes place if the colloid is present during the action of the light in the dispersion medium. Various types of rays have an analogous action wliicli is iiidepeiident of tlie charge on tlie colloidal particles.Thus ultraviolet light and &rays act on both negative and positive colloids. The action cannot therefore be regarded as due t o a photo-electric emission of electrons o r t o the supply of certain charges by the light rays. I n all cases the photo-coagula- tion is accompanied by a decrease in the total charge of the colloid. This decrease in the total charge may be due to one of the follow- ing causes (i) a change in the dissociation of the adsorbed electro-GENERAL AND PHYSICAL CHEMISTRY. ii. 91 lytes; (ii) tlie setting up of potential differences after the manner of tlime in tlie Becquerel effect; and (iii) an adsdrption of hydrogen or hydroxyl ions from tlie dissociated water.I n any case there is a specific photo-chemical action wliicli occasions a disturbance of the adsorption equilibrium on the colloid and thus effects an increase in the size of the particles. This can then be continued after the removal of the light. J. F . S. Application of the Idea of Expansibility Tension to t h e Theoretical Study of Chemical Equilibria. L. GAY ( J . Chim. P?iys. 1915 13 303-311. Compare A 1915 ii 326).-A theoretical paper iu whicli the conception of expansibility tension is applied in the derivation of a general formula f o r the displace- ment of the equilibrium in a mixture resulting from a change in the volume pressure or temperature. H. M. D. The Ternary System Carbon Tetrachloride Alcohol and Water HARKY A. CuR'rIs and ESBON Y.TITUS ( J . PhysicaZ CheiiL. 1915 19 739 -752).- il large iiuniber of experiments have been carried out to determilie the critical solubility data of ternary mixtures of the above three coniponents. Further experiments have been made t o establish the relationship between the density composition and refractive index of the homogeneous ternary niix- tures. From tlie experimental data the equilibrium line between the one-liquid phase and the two-liquid phase systems has been located on the composition diagram for the temperature 19.75O. The general shape of the critical solubility surface in the com- position-temperature prism has been determined over a range of about 50°. It has been found that this surface rises abruptly from isotherm t o isotherm that is temperature has but little effect on the mutual solubility of the three components. The index of refraction has been determined f o r eight series of homogeneous ternary mixtures.It' has been found that as water is added to a mixture of carbon tetrachloride and alcohol rich in alcohol the refractive index a t first increases and then decreases. As mixtures richer in carbon tetrachloride are used the maximum refractive index is reached with less and less water until finally with mix- tures containing initially more than 35% of carbon tetrachloride the addition of water causes the refractive index t o decrease con- tinually. The densities have been determined for eight series of homogeneous ternary mixtures. It has been found that the addi- tion of water to a carbon tetrachloride-alcohol mixture rich in alcohol increases the density uniformly whilst the addition of water to a mixture rich in carbon tetrachloride lowers the density. The slope of the density curves does not however change sign a t the point where the density of the initial mixture is unity but a t a point somewhat higher tlian this showing t h a t the volume of the ternary mixture is less tlian tlie sum of tlie volumes of the com- ponents.It is shown that the determiiiatioii of two of the physical properties of a ternary niixture does not always fix its composition. J. F. S.ii. 92 ABSTRACTS OF CHEMICAL PAPERS Equilibria in the Systems of the Higher Alcohols Water and Salts. G. B. FRANKFORTER and STERLING TEMPLE ( J . Amer. Chem. SOC. 1915 37 2697-2716.Compare Frank- forter and Frary A. 1913 ii 685).-In extending thO earlier investigation (Zoc. cit.) the authors have selected the systems n-propyl alcohol-sodium carbonate-water isopropyl alcohol- potassium fluoride-water isopropyl alcohol-potassium carbonate- water allyl alcohol-potassium fluoride-water allyl alcohol- potassium carb ona t e-wa ter allyl alco hol-sodium carbona te-wa ter and allyl alcohol-sodium chloride-water. The method of represent- ing such systems by triangular co-ordinates is described but the results are represented in part by rectangular co-ordinates with the percentage of alcohol in the solvent plotted against the per- centage of salt in the solvent. The n-propyl alcohol used was purified by successive dehydration with potassium fluoride quicklime magnesium amalgam sodium amalgam and again quicklime; it then had b.p. 97*3-97.5O/ 752 mm. D20 0.8032 nH 1.39023 whilst isopropyl alcohol purified by successive treatment with potassium fluoride quicklime sodium amalgam and quicklime had b. p. 82'5O D20 0.7881 nga 1.37960. Potassium fluoride and potassium carbonate were found t o be satisfactory dehydrating agents for the above-mentioned akohols. No evidence was forthcoming as to any relation between the salt- ing-out effect and the chemical constitution of the salts o r of the alcohols and it would appear that the effect is a function of the solubility of the salt in water and in the alcohol concerned together with the amount of water with which the salt unites to form its lowest hydrate and with the ability of the alcohol to replace the water of hydration.Relative Affinity of Metals in Non-aqueous Solutions aDd their Reactivity in Ineulating Media. I. JNANENDRA CHANDRA GHOSH (J. Plzysikal. Chem. 1915 19 720-733).-The author has studied the action of a number of metals on solutions of salts in a series of nonconducting solvents with the object of ascertaining whether chemical replacements take place in solutions of salts which are not ionised. Solutions of ferric chloride mercuric chloride mercuric cyanide cadmium iodide and lead oleate in benzene toluene nitrobenzene aniline chloroform amyl alcohol amyl acetate and ethyl acetate were shaken in sealed glass tubes a t 21° with the metals mercury copper lead iron tin nickel zinc and magnesium. The specific resistance of each solution was measured by the replacement method.I n every case the resistance was very high the value varying between 45 x 1O1O and 0.25 x 106 ohms. It is shown that magnesium zinc and lead replace iron in ferric chloride in all the solvents used; tin replaces iron in most cases; copper replaces iron in aniline solution and probably in amyl alcohol solution. Mercury does not replace iron in any solvent but reduces the ferric chloride t o ferrous chloride in all the solvents except aniline in which case there is no action. Magnesium zinc and copper replace mercury in mercuric chloride in all cases. Iron D. F. T.GENERAL AND PHYSICAL CHEMISTRY. ii. 93 replaces mercury in mercuric chloride in ethyl acetate amyl acetate and amyl alcohol solutions.Lead has no action on mercuric chloride in chloroform solution but in all other cases it reduces mercuric chloride to mercurous chloride. Copper replaces mercury in mercuric cyanide in all solutions. Iron replaces mercury in nitrobenzene and amyl alcohol solutions magnesium replaces mercury only in amyl alcohol solution and lead replaces mercury in the cyanide in amyl alcohol and amyl acetate solutions. I n other cases there was no action. Magnesium replaces cadmium in cadmium iodide in all solutions whereas zinc does not replace it in any; iron replaces cadmium in aniline chloroform and amyl alcohol solutions and copper replaces cadmium in aniline chloro- form amyl alcohol and amyl acetate solutions. Magnesium copper and zinc replace lead from lead oleate solutions in all the solvents; iron has no action in benzene chloroform nitrobenzene and ethyl acetate solutions of lead oleate and mercury has no action on any of the solutions of lead oleate.It is thus shown that the replacement series is not at all a characteristic of the replacing metal but is dependent on the mutual relationship of the metals the acid radicles and the solvent present in a given com- bination. A series of experiments was carried out with solutions of mercuric iodide and mercuric chloride in ethyl ether ethyl acetate glycerol carbon tetrachloride chloroform benzene toluene and carbon disulphide. These solutions were shaken with silver and in every case mercury was deposited thus showing that the order of replacement is the same in all cases as in water.J. F. S. Dynamic Researches on the Formation of Some Aromatic Sulphones Under the Influence of Aluminium Chloride in a Medium of Benzenesulphonyl Chloride. S. C. J. OLIVIER (Rec. trav. chim. 1915 35 166-179. Compare A. 1914 i 676 818; ii 846).-The author has determined the velocity of forma- tion of sulphones from benzene and chlorobenzene on adding them to a solution of aluminium chloride in benzenesulphonyl chloride a t 30°. The velocity constant K was calculated assuming that the compound C,H,*SO,C1,A1Cl3 reacts with the benzene or chloro- benzene the solvent not being able to remove any of the aluminium chloride from its combination. The results show that one molecule of aluminium chloride cannot transform more than one molecule of benzenesulphonyl chloride and that for low concentrations of aluminium chloride the values of K tend to decrease during the reaction.A t high concentrations the formation of sulphone is a true bimolecular reaction. An increase in the concentration of the aluminium chloride or of the chlorobenzene causes a diminu- tion in the value of IZ. The molecular weight of the combination C,H,*SO,Cl,AlCl in solution in benzenesulphonyl chIoride was determined by cryoscopic methods and gave no indication of association with increase in concentration of the aluminium chloride. On combinations of sulphones with aluminium chloride the above solvent exerts aii. 94 ABSTRACTS OF CHEMICAL PAPERS. greater or less dissociating action. The results show that for the same solvent the relative velocities of introduction of a secoiid substituent are shown by C,H > C,H,Cl.W. G. Determination of Ionisation Constants and the Titration of Weak Bases by the Conductivity Method. CH. DE ROIIDEN ( J . Chim. Phys. 1915 13 261-301).-The methods usually employed in the determination of the ionisation constants of weak acids and bases depend on the measurement of the degree of hydro- lysis of their salts in aqueous solution. The equilibrium relations in solutions of such salts are discussed and attention is drawn to the essential difference between tlie hydrolysis constants (1) when the acid and base are both weak and (2) when the acid is strong and the base weak or vice vers2. The difference gives rise t o little ambiguity so long as the salt falls into one o r other of these limit- ing groups but the hydrolysis constant of a salt which occupies an intermediate position is a quantity which cannot be defined by either of the ordinary formulze.The magnitude of the hydrolysis constant is determined by the ionisation constants of the acid base and water and on this account hydrolysis constants are not of primary significance. A detailed description is given of a method for the determina- tion of the ionisation constants of weak bases from measurements of the electrical conductivity of solutions after the addition of successive quantities of a standard solution of hydrochloric acid. This addition was effected without aiiy appreciable change in the volume of the solution. The results obtained for aniline and f o r 0- 712- and pchloro- aniline are recorded.H. M. D. Reaction Velocity in a Viscous (Eeterogeneous) Medium. RAPHAEL H. CALLOW (Trnns. Fnmday Soc. 1915 11 55-59).- The effect' of the presence of gelatin on tlie velocity of hydrolysis of methyl acetate has been determined. Results cannot be obtained with sodium hydroxide on account of its reaction with the gelatin but with hydrochloric acid the change in the velocity constant is small in comparison with that of tho viscosity being only 10% below the normal even in tlie case of a jelly which is completely set. The form of the relation between viscosity and velocity has not been fully determined. C. H. D. Aspirin. 111. Anqmalies of the Decomposition of Aspirin by Water. TI. E. TSAKALOTOS and S. HORSCII (BzLZZ. Soc. c l i i m 1915 [iv] 17 401-406. Compare A.1915 ii 47 433).-A quantitative study of the decoiriposition of aspirin in aqueous solu- tion a t 23O 50° and 60° the rate of decomposition being measured by removing 25 C.C. of the solution a t given intervals and titrating this against N/50-barium hydroxide. At 50° tlie reaction was also followed by electrical conductivity measurements. I n each case the velocity curve shows two minima the times a t which these occur varying with the temperature. W. G .GENERAL A N 0 PHYSICAL CHEMISTRY. ii. 95 The Indirect Determination of Velocity of Hydrolysis by the Polarimetric Method. JAMES CODRINGTON CROCKER (T. 1915 107 1762-1765).-A mixture of sucrose formamide and hydro- chloric acid was made up and the change in the rotation of the solution a t constant temperature followed in the polarimeter.The acid liydrolyses the formamide and is partly used up in the process. It also liydrolyses tlie sucrose remaining unchanged in amount by this reaction. The rate of hydrolysis of the sucrose being dependent on the amount of acid present gradually diminishes in proportion as the formamide is decomposed. From tlie rate a t which the velocity of inversion of the sucrose decreases the velocity of hydrolysis of the formamide can be arrived a t . For the method of calculation the original must be consulted. The rota- tion of the sucrose solution is not appreciably affected by form- amide. Data are given showing t h a t a satisfactory value for the velocity constant for the hydrolysis of formamide can be obtained by this method the principle of the metho-d being applicable to any reaction during which the hydrolyst changes i n concentration and a t the same time can act as a simple catalyst on a third substance present in the solution.T. S. PA. Velocity of Crystallisation of Supersaturated Solutions. ERNESTO CABALLERO Y L ~ P E Z (Anal. Fis. Qzcim. 1915 13 350-375).-An investigation of the effect of mechanical physical physico-chemical and chemical influences on the velocity of crystal- lisation of supersaturated solutions of tlie sulphates of sodium potassium copper zinc ferrous iron magnesium and potassium aluminium. A. J. W. The Catalytic Hardening of Fats by Means of Nickel Oxidee. W. MEIGEN ( J . pr. CIzem. 1916 [ii] 92 390-411. Compare Meigen and Bartels A. 1914 i 482).-Jn reply to- Bedford and Erdmanii (A.1913 i '701) and Siegmund and Suida (A. 1915 ii 626) the author submits the evidence as to the activity of an unisolated nickel suboxide during tlie catalytic reduction of fats t o a critical survey and confirms the opinion already expressed by Meigen and Bartels (Zoc. c i t . ; Normann and Pungs A. 1915 ii 159; Bosshard and Fischli A. 1915 ii 788) t h a t oxides of nickel exhibit activity as catalysts only when they contain a certain amount of the free metal. Further experimental evidence with other oils is adduced in support of this view and stress is laid on the u n t r u stw o r t hi ness of specific gravity or e 1 ec t r i c a 1 conductivity data as evidence of the coinposition of the catalyst after a reduc- tion experiment.Such results must be dependent on the nature and amount of the organic impurities included in the finely divided nickel and these indeed also can affect the sensitiveness of the carbon monoxide test for the presence of free nickel. The free nickel can be removed fairly satisfactorily from a used nickel oxide catalyst by a magnet and in this way the author obtained frac- tions which contained more nickel than could be present' even inii. 96 ABSTRACTS OF CHEMICAL PAPERS. it suboxide of the formula Ni,O so that the presence of free nicker can scarcely be denied. From the facts that metallic nickel is known t o be an effective accelerator and that it can be found in nickel oxide which has been used as a catalyst the author is unable to accept the suggestion that nickel oxide owes its apparent catalytic activity to the forma- tion of a suboxide the presence of which is not proved and the catalytic properties of which are merely postulated. D. F. T. [Determination of] Molecular Weights of Gases by an Evaporation Method. H. L. TRUMBULL ( J . Amev. Chem Xoc. 1915 37 2662-2667).-Measurements have been made of the rate a t which water evaporates in contact with dry air carbon dioxide and hydrogen at atmospheric pressure. The entire apparatus was immersed in a thermostat maintained a t constant temperature (25'07O k O*0lo). The rate of evaporation (dwldt) multiplied by the barometric pressure ( B ) is constant for a given gas. The values of B . dw/dt f o r the three gases %re approximately in the inverse ratio of the square roots of the densitdes of thO gases indicating that the rate of vaporisation is determined by the rate of diffusion. H. M. D. The Valency Theoryof J. Stark from a Chemical Point of View. DOROTHY A. HAHN and MARY E. HOLMES ( J . Amer. Chenz' SOC. 1915,37,2611-2626).-An account is givemn of Stark's electron theory of valency in its application to the interpretation of chemical phenomena. The account represents an abstract of a treatise by P. Ruggli (" Die Valenzhypothese von J. Stark von Chemischen S tandpunkt," Stuttgart 19 1 2). H. M. D. An Improved Form of Gas-washing Bottle. F. R,. VON BIGHOWSKY and H. STORCH ( J . Amer. Chem. Soc. 1915 37 2695-2696).-In its simplest form the apparatus consists of an ordinary wash-bottle which in operation is laid on its side. The tube which reaches t o the bottom of the bottle is slightly con- stricted below the cork and given a very slight inclination to the horizontal. The gas to bO washed enters the bottle through this tube and forms bubbles a t the constriction opposite t o which and on the lower side of the tube is a sufficiently wide aperture t o admit freely the entrance of the liquid in the bottle. H. M. D. An Automatic Vacuum Pump. OTTO MAASS ( J . Amer. Chenz. SOC. 1915 37 2654-2656).-A form of Topler pump which works automatically in conjunction with an aspirator. No mechanical spring or valve is involved and experience has shown that it can be allowed to run with perfect safety for an indefinite period. H M. D.

ISSN:0368-1769    

DOI:10.1039/CA9161005065

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

INORGANIC CHEYISTRT. Inorganic Chemistry. ii. 97 The Boiling Point of Aqueouls Solutions of Nitric Acid at Different Pressures. 11. The Influence of Water-retaining Agents on the Gomposition of the Mixture of Maximum Boiling Point. HENRY JERMAIN MAUDE CREIGHTON and HERSCHEL GASTON SMITH ( J . Franklin Inst. 1915 180 703-709).-1n con- tinuation of earlier experiments (A. 1915 ii 446) which showed that the composition of the maximum boiling mixture changes only from 66.80% of nitric acid a t 110 mm. t o 68.18% a t 760 mm. the effect of the presence of potassium hydrogen sulphate and of sulphuric acid has been examined. The composition of the mixture of maximum boiling point is not appreciably altered by the addi- tion of 10% or 20% of potassium hydrogen sulphate. On the other hand sulphuric acid causes a decrease in the nitric acid content of the maximum boiling mixture the decrease being greater the greater the addition of sulphuric acid.A t 760 mm. the per- centage of nitric acid in this mixture is reduced from 68.18 t o 64.5 in presence of 10% of sulphuric acid and to 59.2 in presence of 20%. A t lower pressures the reduction in the nitric acid content is still larger. The results obtained afford an explanation of the fact that solu- tions of nitric acid can be concentrated t o more than 90% by dis- tillation with concentrated sulphuric acid. H. M. D. Two Reactions of Azoimide with Analytical Importance. FRITZ SOMMER and HEINRICH PINCAS (Ber. 1915 48 1963-1969 2096).-A. Oxidation of Azoimide b y Ceric Salts.-A method for the estimation of azoimide in neutral or acetic acid solutions by measuring the volume of the latent nitrogen was first proposed by Raschig 111 1908 who found t h a t when such a solution is mixed with a slight.excess of iodine and a crystal of sodium thiosulphate the evolution of nitrogen is brisk and complete (compare also following abstract). The authors find that although this method is trustworthy for 0'1N-solutions and therefore for solids it is not so for very dilute solutions the end of the reaction being reached too slowly. On the other hand salts of quadrivalent cerium such as ceric ammonium nitrate ceric sulphate o r the ceric ammonium sulphates immediately effect the complete oxidation of azoimide in neutral o r acid solutions eveln when these are very dilute according to the equation 2N3H + 2Ce0 = 3N + Ce203 + H,O.For 0.1 gram of the sodium salt about 2.3 grams of the cerium com- pound should be used. Free hydrochloric acid or excess of chlorine ions must be avoided however otherwise chlorine gas will be 1 i b era t ed B. Reaction of Azoimide with Nitrous Acid.-According t o Thiele (A. 1908 ii 940) azoimide reacts with nitrous acid thus N3H + HNO = N + N,O + H,O. The correctness of this assumption VOL. CX. ii. 4ii. 98 ARSTRACTS OF CHEMICAL PAPERS. has been proved by adding acetic acid t o a mixture of equivalent quantities of barium nitrite and sodium azide and analysing the gases evolved. The reaction proceeds very smoothly and may be used to estimate simple nitrites. A known excess of sodium azide is added to an acidified solution of the nitrite then the mixture is shaken for a minute or two rendered just alkaline by barium hydroxide and boiled to expel nitrous oxide and finally acidified with acetic acid when the excess of azoimide is estimated as above. Another application of the reaction is the detection of nitric acid in the presence of nitrous.Nitrous acid is completely destsoyed even in a O.OOOlS-solution whilst nitric acid is un- affected when a slight excess of sodium azide is added the solu- tion is acidified and boiled. This method for removing nitrous acid is much better than the old treatment with carbamide or the newer reaction with hydrazine sulphate (Sen and Dey A. 1912 ii 296). J. C. W. Oxidation of Azoimide by Iodine. F. RASCHIG (Bey. 1915 48 2088-2092.Compare Chenz. Zeif. 1908 32 1203).-The oxidation of azoimide by iodine in the presence of sodium thio- sulphate might be regarded as a catalytic effect of sodium tetra- thionate as Sommer and Pincas have done (preceding abstract). This is not justifiable however for just as iodine alone causes no evolution of nitrogen so a mixture of sodium tetrathionate with iodine is also without action. If the reaction between iodine and sodium thiosulphate is con- sidered since no more than two molecules can react a t any given instant the first stage in the reaction will be represented thus Na,S,O + I = NaI + NaIS203. It is this intermediate compound which so easily gives up iodine to' the sodium azide (for example) or to another molecule of sodium thiosulphate thus Na,S,O,+ NaIS,O = Na,S,O + NaI. The actual catalyst is therefore the residue NaS,O which takes up iodine if that is in excess and gives i t again to the azide or under normal conditions condenses to form Na,S,O,.Free mineral acids hinder the reaction and since sulphuric acid is liberated as a by-product it' is advisable t o add sodium acetate. Because of this effect of acids it is always advisable too to keep adding sodium thiosulphate t o the solution and this is best effected by using a crystal about the size of a pea which takes sufficiently long to dissolve. Azoimide seems t o be the only substance which whilst un- attacked by iodine alone is oxidised by iodine in the presence of sodium thiosulphate. Bromine water and thiosulphate have the same effect owing no doubt t o the formation of NaBrS203. The only other iodine carrier which has been discovered among sulphur compounds is a sulphide.A crystal of sodium sulphide has the same effect but the liberation of sulphur which also takes place renders the reaction less neat. J. C. W. The Neutralisation Curve of Boric Acid. F,. B. R. PRIDEAUX (TI*nns. Fcrmdcty Soc. 1915 11 76-78).-A discrepancy is foundINORGANIC CHEMISTRY. ii. 99 between the experimental neutralisation curve and that calculated from the single constant of a monobasic acid. This is attributed to the formation of complexes in the borate solwtions the ion H,BO,’ being tlius,weighted by the complexes. A revised constant k =4.5 x 10-10 is given from which the alkalinity of borate solu- tions may be calculated up t o st,rongly alkaline solutions. C.H. D. The Dissociation of Carbongl Sulphide. GILBERT N. LEWIS ( J . Amer. Chem. SOC. 1915 37 2786).-A correction of an error in sign in the receqt paper by Lewis and Lacey (A 1915 ii 767). The modification thus introduced into the van’t Hoff equation brings the calculated heat of formation of carbonyl sulphide from liquid sulphur and carbon monoxide to 11,000 cal. in good agree- nient with the value of Thomsen. D. F. T. The Supposed Formation of Persilicate by the Action of Air on Solutions of Sodium Silicate. HUGO DITZ ( J . 211’. Glmn. 1916 [ii] 92 412-418).-The author regards the state- ment that the solution of a silicate of an alkali metal when exposed t o air undergoes partial oxidation to a persilicate (Jordis A.1914 ii 200) as highly improbable. A solution of such a persilicate should actually contain the hydrolytic products namely a silicate and hydrogen peroxide but the only evidence mentioned (Zoc. c i f . ) is the presence of a little free chlorine in the carbon dioxide liberated by hydrochloric acid. Such a result might be due to the presence of a little manganese as impurity in the silicate solution. However the author (Ditz also Ditz and Kanhauser A. 1913 ii 958) has shown that after prolonged exposure to the air many alkaline substances are found t o contain sniall quantities of nitrite and nitrate and treatment with hydrochloric acid would give rise t o nitrous fumes with the former and if the acid were concentrated to chlorine with the latter. Experimental test has confirmed the possibility of this result with a solution of a silicate of an alkali metal distinct traces of nitrite being present even after exposure for two days the amount being very appreciable after three months.In the same period the quantity of nitrate formed was relatively small whilst titanic acid failed to reveal any trace of hydrogen peroxide. D. F. T. Thermal Analysis of Mixtures of Alkali Hydroxides with the Corresponding Haloids. 111. Lithium Compounde. GIUSEPPE SCARPA ( A t t i R . Accad. Li72cei 1915 [v] 24 ii 476-482. Compare A. 1915 ii 448 633).-The systems LiOH- LiF LiOH-LiC1 LiOH-LiBr and LiOH-LiI have1 now been investigated. The lithium hydroxide employed contained 98.5% LiOH 0.8% Li,CO and 0.7% H,O and had m. p. 462O; Dittinar (+7.XOC. Chem. Ind. 1888 7 733) and de Forcrand (As 1906 ii 445) found m. p. 445O. Pcr lithium fluoride the author finds m. p. 840O; Carnelley (T. 1878 33 281) gave 801O. Lithium hydroxide and fluoride are 4-2ii. 100 ABSTRACTS OF CHEMICAL PAPERS. completely miscible in the liquid state and form solid solutions containing from about 5 to 85 mols. % of the hydroxide. The eutectic point 430° corresponds with 80 mols. % of the hydroxide. Guntz (Ao 1894 ii 91) gave 600° Huttner and Tammann (A. 1905 ii 229) 600° and Schemtschuschni and Rambach (A. 1910 ii 204) 614O. The curve of primary crystallisation of the system LiOH-LiC1 falls from 605O to a eutectic a t about 290° and exhibits a distinct angle a t 50 mols. % LiOH. The eutectic arrest observed a t about 285O with all mixtures containing from 45 t o 100 mols.% LiOH has its maximum duration a t about 65 mols. % LiOH. Mixtures con- taining 0-50 mols. % LiOH show a second arrest a t 315O this having its maximum duration for 40 mols. % LiOH and corre- sponding with the formation of a compound probably 2LiOH,SLiCl decomposing on fusion. ,. Lithium bromide has m. p. 550O; Carnelley (Zoc. c i t . ) found 547O. The diagram of state for LiOH-LiBr is similar t o that of the pre- ceding system the two branches of the curve of primary crystal- lisation intersecting a t the eutectic point 275O which corresponds with 45 mols. % LiOH. The eutectic arrest is shown with 0-70 mols. % LiOH but not with 75-100 mols. % LiOH; the latter mixtures exhibit however a marked arrest a t 310° this having its maximal duration with 75 mols.% LiOH and corresponding with the formation of a decomposable compound probably 3LiOH,LiBr. Lithium iodide (probably containing a little oxide) has m.' p. 440O; Carnelley (loc. cit.1 found 446O and Sandonnini and Scarpa (A 1914 ii 204) 450O. The curve of primary crystallisation of the system LiOH-LiI exhibits a eutectic a t 45 mols. % LiOH and a pronounced change of direction a t 75 mols. % LiOH. The eutectic arrest occurs a t about 180° and is a maximum a t 45 mols. % LiOH. Mixtures with more than 75 mols. % LiOH show an arrest a t about 310° probably owing to the formation of the com- pound 4LiOH,LiI unstable a t the melting point. Comparison of these results with those previously obtained (A. 1915 ii 448 633) shows that the tendency of an alkali hydroxide to form compounds with the corresponding haloids increases with diminution of the electro-affinity of the cation (compare Abegg and Bodlander A.1899 ii 542). For lithium chloride m. p. 605O is found. T. H. P. Preparation of Phosphorescent Calcium Sulphide. PIERRE BRETEAU (Compt. rend. 1915 161 732-733; J. Yharm. Chim. 1916 [vii] 13 33-37).-Contrary t o the views of Verneuil (com- pare A. 1887 2 539) i t is shown that the presence of sodium chloride and carbonate in small quantities is not essential for the phosphorescence of calcium sulphide. A phosphorescent sulphide can be prepared by heating a mixture of calcium carbonate (100 parts) and powdered sulphur (30 parts) in a crucible a t a dull red heat for one hour allowing the mixture to cool mixing it with alcohol to a paste and adding basic bismuth nitrate in alcoholic solution in sufficient quantity to give 1 part of bismuth to 10,000INORGANIC CHEMISTRY.ii. 101 parts of sulphide. This mixture is dried in the air and then heated a t a dull cherry-red heat for two hours and allowed t o cool slowly. The sulphide so prepared shows a violet phosphor- escence. The bismuth as phosphorogen can be replaced by molybdenum or vanadium or better still by tungsten. W. G. The Derivatives of Perceric Oxide. If. C. C. MELOCHE ( J . Amer. Chem. SOC. 1915 37 2645-2652).-It has not been possible t o prepare perceric sodium carbonate by a method analogous to that used in the preparation of the potassium com- pound (A. 1915 ii 776). A solution of perceric ammonium carbonate may be prepared by this method but the substance has not been obtained in the crystalline form.The solution is less stable than that of the potassium compound and decomposes when kept with the formation of a yellow precipitate presumably ceric carbonate. I f the dark red solution of perceric ammonium carbonate is treated with excess of solid sodium carbonate and the solution evaporated slowly in a vacuum well-formed crystals of perceric sodium carbonate of the formula Ce,0,(C03)2,4Na,C03,30H20 are obtained. It is only sparingly soluble in cold water and effloresces in dry air. Contact with moisture above Oo results in hydrolysis and with larger quantities of water the crystals are completely decomposed with the formation of a gelatinous orange- red precipitate. A perceric rubidium carbonatel was obtained in crystalline form by the method which served for the preparation of the potassium compound but this substance has not been analysed.The action of hydrogen peroxide on a saturated solution of potassium acetate in presence of cerous nitrate yields a solution which probably contains perceric potassium acetate. It liberates iodine from potassium iodide gives a blood-red solution with potassium carbonate and a reddish-brown precipitate with hydrogen peroxide. I n all these perceric compounds half the total oxygen combined directly with the cerium is available for oxida- tion under certain conditions. H. M. D. Soma New Rare Earth Compounds. A. J. GRANT and C. JAMES (1. Amer. Chem. SOC. 1915 37 2652-2654).-With a view to the improvement of the methods employed in the separation of the rare earths a number of new salts have been prepared.Terbium pyromucate (C,H,0.C0,)3Tb,5H,0 radiating crystals very soluble in water ; terbium l-bromo-2-nitrobenzene-4-sulphonate ( N02*C,H3Br*S0,)3Tb,10H20 very small crystals the solubility of which differs little from that of the gadolinium salt; terbium propionate (C,H,*C02),Tb,2H,0 white powdery voluminous crystals ; ferrous lanthanum nitrate 3Fe( N0,),,2La(N03),,24H,0 flat green hexagonal crystals fairly stable' in the1 absence of air. Lanthanum pyromucate ( C,H30~C0,),La,2H20 ; and yttrium pyro- mucate (C,H,O*CO,),Yt,SH,O were also prepared. H. M. 9.ii. 102 ARSTR 4CTS OF CHEMICAL PAPERS. The Separation of Yttrium from the Yttrium Earths.111. J. P. BONARDI and C . JAMES ( J . Amer. Cheni. Soc. 1915 37 2642-2645. Compare A. 1914 ii 370 657)-Further experi- ments have been made with the object of finding a rapid efficient and economical method for the separation of yttrium from the yttrium earths The results of fractional precipitation by the addi- tion of various reagents are briefly described. These reagents include ammonium sebacate azcbenzenesulphonic acid potassium sulp hite sodium citrate tartrate tungstat e p henoxyacetate and m-nitrobenzoate ammonium camphorate and potassium cobalti- cyanide. The use of a cobalticyaiiide solution appears the most promising for the purposes of the required separation and this method is t o be further examined. H. M. D. Decomposition of Mineral Sulphides and Sulpho-salts by Thionyl Chloride.H. B. NORTH and C. B. CONOVER ( A w r . J . Sci. 1915 [iv] 40 640-642. Compare this vol. ii 28).- Mineral sulphides react in general in a similar manner t o the pre- cipitated sulphidea with thionyl chloride according t o the general scheme MS + 2SOC1, MC1+ SO + S2C12. The reactions take place a t 150-175O and require from a few hours' heating in the case of easily decomposed sulphides such as galena pyrites cinnabar orpiment stibnite and arsenical pyrites to one or two days in the case of pyrargyrite proustite covellite sphalerite and tetra- hedrite. Of the minerals examined only argentite molybdenite and cobaltite were notl attacked by thionyl chloride under the above conditions. G. F. M. Reaction of Gases with Lead and Silver.W. STAHL (Clic m. Zeit. 1915 39 885-886).-A summary of published work on the behaviour of lead and silver a t high temperatures towards oxygen sulphur dioxide hydrogen nitrogen the oxides of carbon hydrocarbons argon and helium. G. F. M. Supposed Allotropy of Copper. G. K. BURGESS and I. N. KELLBERG ( J . IVashington Acad. Sci. 1916 5 657-662).-From dilatometric observations Cohesn and Helderman (A. 1914 ii 205 654) have drawn the conclusion that there are two enantiotropic forms of copper with a transition temperature a t 69.2O t o 71'7O. I n support of this view the change in the electrical conductivity of copper after heating a t looo has been put forward. Comparative measurements made with copper and platinum wire resistance thermometers wound on the same frame and exposed alternately t o Oo and looo show that platinum exhibits similar changes in conductivity and thatl in both cases constancy is obtaineld after a few alternations of temperature. A detailed examinatioln of the resist.ance1 of copper ovelr the range 00 t o 1000 by the method described in a previous papelr (A.1914 ii 794) lias also giveii entirely negative results in respect of the alleged allotropic transformation in the1 neighbourliood of 70°. Within the above range the rwistance of copper changes in a continuousIh'OltGANIC CU EMISTHY. ii. 103 niaiiner and there is no evidence of the copper being in a iiieta- stable condition. H. M. D. Sulphides of Copper. EUGEN POSNJAK E. T. ALLEN arid H. E. MERWIN (Economic Geology 1915 10,491-535).-A general physico-chemical investigation of the sulphides of copper and of the various copper-iron sulphide minerals carried out with the object of ascertaining tlie conditions of formation and alteration of the more important minerals of the copper sulphide deposits.Cuprous sulpliide prepared in a vacuum furnace has m. p. 1130O f lo. No dissociation occilrs when cuprous sulphide is heated up to 1200O. Synthetic cuprous sulphide has I):? 5.785 a value which is almost identical with t h a t of the' purest mineral sulphide examined. The copper sulphides formed by fusing together copper and sulpliur are of v::riable composition and always contain more sulphur than is demanded by tlie ,ratio( 2Cu:S. They are micro- scopically homogeneous and vary continuously both in colour and specific gravity with composition.As the sulphur increases they become darker in colour and have smaller specific gravities. The specific volumes of these products lie within the limits of experi- inental error on a straight line connecting tlie specific volumes of cuprous and cupric sulphides. It is shown that all such products are solid solutions of the two sulphides. Cuprous sulphide melts a t 1096O in an at'mospliere of hydrogen sulphide and a t 1057O in an atmosphere of sulphur vapour. The lower melting point as com- pared with that of cuprous sulphide in a vacuum is clue to dis- solved cupric eulphide which increases in amount with the increase of pressure of the sulphur vctpour surrounding it. When cuprous sulpliide is heated in an atmosphere of hydrogen sulphidel a t various temperatures below its melting point the sulphur content increases.For each temperature the1 products contain a definite amount o f sulphur. This sulphur content increases with decrease of temper- ature until a t 358O the product becomes cupric sulphide. Solid solutions of cuprous-cupric sulphide can be prepared by heating compressed powde'rs of tho two sulphides a t about looo. The analysis of a number of natural chalcocites showed that such solid solutions sometimes occur in nature. I n this connexion the nature of the mineral pyrrhotite has been discussed. Cuprous sulphide is dimorphous and has an inversion temperature1 a t 91O. The inversion temperature is considerably influenced by the size of the grains of the sulphide.Increasing amounts of cupric sulphide dissolved in cuprous sulphide raise the inversion temperature. This takes place until a concentration of cupric sulphide of 876 is reached after which an inversion is no longer observed. Crystals of chalcocite were repeatedly formed in the dry way a t various temperatures but only above about 250° were they large enough f o r crystallographic investigation. These crystals were isometric. Isometric crystals of cuprous sulphide were also obtained from solutions; a t 250° by the reaction of cuprous chloride with sodium sulphide'; and at ZOOo 170° aiid 1 2 5 O by Frystallisation of cuprous sulphide from solutions of hydrogen sulphide. Crystals formed byii. 104 ABSTRACTS OF CHEMICAL PAPERS. the action of ammonium sulphide on copper which have generally been described as orthorhombic cuprous sulphide are in reality a double polysulphide of the formula Cu,(NH,)S and are tetragonal. Covellite has been prepared in many ways and a crystallographic and optical study of its properties carried out.It is hexagonal and optically positive; the optical dispersion of o is extremely high wLi<l.0 wNa = 1-45 and orl = 1-80. Two very pure samples of covellite have been found to have DY 4.683 and 4.676 respectively. This value is higher than any value previously given for this sub- stance. The highest value found for synbhetic covellite was 4.652. Covellite can be heatled in an atmosphere of hydrogen sulphide up to 358O; i t is then in equilibrium with the gas and a t this temperature and below it chalcocite can be completely converted into covellite.J. F. 8 The Nature of Subsidiary Valencies. XII. Ammines of Copper. FRITZ EPHRAIM and EDOUARD BOLLE (Ber. 1915. 48 1770-1777. Compare A 1915 ii 166 441 454).-Details are given of the preparation of various ammines of copper salts in addition to those previously described ; the ammonia tension has also be'en measured a t various temperatures. The cupric salts of dibasic acids in no case give a hexammine compound even a t the te'mperature of an ice-salt freezing mixture the highest ammine formed being the pentammine. Many of the salts of mocobasic acids give a hexammine compound. I n many cases where the hexammine is capable of existence only a t very low temperatures tlie triammine is nevertheless stable a t fairly high temperatures.The order in which the anions exert an effect on the stability of the ammine is quite different from that observed in the case of the nickel salts; it resembles rather that observed with the zinc salts (A. 1915 ii 454) although with many differ- wcee. The theoretical discussion of the results is t o be given later. The following new compounds are described Copperhexammine nitrate blue crystals; the ammines with 5 and 23/4 molecules of ammonia which have been described by other investigators could not be obtained. Copperhexammine perchlorate. Copperpent- ammine dithionate; the ammine with 9 molecules of ammonia could not be obtained. Coppertetmmmine tetrathionate light blue crys- tals ; copperhexammine thiocyanate ; coppertetrammine formate ; coppertriamrnine benzoate copper-red crystals ; coppertetrammine benzoate dark blue crystals; and copperpentammine benzoate greyish-blue crystals.The ammonia tensions of the following salts were also deter- mined coppertetrammine nitrate coppertetrammine thioimlphate coppertetrammine dithionate coppertetrammine thiocyanate and copperpentammine oxalate. A table is given shotwing the absolute dissociation temperatures and the heats of formation of all the copper ammines hitherto examined. T. S. P. .Thermal Reactions sf Aluminium. RAFAEL LUNA NOGUERAS (-4naZ. Fis. Quim. 1915 $3 390-420).-A historical account oflNORGANIC CHEMISTRY. ii. 105 the production of aluminium and of its applications as a thermal agent. A. J. W. Investigation of the Carbides of Aluminium Nickel and Copper. E.BRINER and R. SENGLET ( J . Chim. Phys. 1915 13 351-375).-A study of the conditions under which carbon com- bines directly with the three metals and of the dissociation of the resulting carbides. The formation of aluminium carbide from the elements has been observed a t 750° and 900°. This compound is exothermic and represents theref ore the stable form a t lower temperatures. Dis- sociation of the carbide was found to occur howevex a t 540° and when heated in a current of air carbon dioxide and aluminium oxide are obtained. This change has been followed a t various temperatures between 540° and 900°. Nickel carbide Ni,C is an endothermic compound and the optimum temperature of formation is in the neighbrourhoiod of 2100O.A t lower temperatures the carbide dissociates relatively rapidly a t 1600° and slowly a t 900°. The carbide must conse- quently be cooled rapidly if a good yield is required. Some evidence has been obtained of the direct combination of copper and carbon to form a carbide a t high temperatures. It is endothermic and dissociates rapidly a t about 1600° more slowly a t lower temperatures. Identification of Tervalent Manganese in Glass. S. It. SCHOLES ( J . Ind. Eng. Chem. 1915 7 1037).-The author coii- siders that the violet tint of manganese glass is due to compounds of the trioxide MnzO3! deducing as evidencie in support of this theory the fact that pirlk solutions were obtained by extracting a lead glass of low m. p. and a water-soluble potash glass with hydrofluoric or 30% sulphuric acids.On diluting the extracts with water a light brown precipitate separated out similar to that obtained by diluting a manganic sulphate solution. Their behaviour towards oxalic acid was also the same. H. M. D. G. F. M. A Magnetic Study of the A3 Transformation in Pure Iron. K ~ T A R ~ HONDA and HIROMU TAKAGI (Sci. Rep. Tohoku Imp. Unb. 1915 [ii] 4 261-269).-Four different specimens of pure iron fro'm the Bureau of Standards Washington have been examined thermomagnetically. The specimens weighing about 0.4 gram are tested in an atmosphere of nitrogen. Both the beginning and end of the transformation may be readily traced on the curves and the critical points thus determined are in good agreement with those found by thermal analysis.The magnetic value of Ac3 for pure iron is 908-911° and of Ar3 889-898O. The number of magnetons is not usually an integer and varies for different speci- niens. These facts are opposed t.0 Weiss's theory. The Magnetic Transformation of Cementite. K ~ T A R ~ HONDA and HIROMU TAKAGI (Sci. Rep. Tohoku Imp. Unniv. 1915 [ii] 4 161-167).-A thermaI and magnetic examination of a series C. H. D.ii. 106 ABSTl1ACTS OF C11EX1 ICAL l’.\t’EltS. of white pig jroiis containing from 2.90% to 3.49‘;; of combined carbon shows that the magnetic transformation of cementite begins on cooling a t 215O and ends on heating a t the same temperature. The temperature range is about 50°. The magnitude of both the thermal and magnetic changes increases with the proportion of cementite.The critical temperature is the same in steels containing as little as 0.14% of carbon so there is no indication of the presence of more than one carbide. It is small in a grey iron. C. H. D. Presence of Platinum in Spain. S. P I ~ A DE RUBIES ( A d . Pis. Qciina. 1915 13 420-433).-A summary of the records as to the occurrence of platinum deposits in Spain. A. J. W. The Series of Triamino-aquo Salts of Bivalent Platinum [Pt3NH,,H2O]X2. L. TSCHUGAEV and I. TSCIIERNJAEV (Compt. relid. 1915 161 792-794). Compare this vol. ii 42).-0ii pass- ing a current of air through a solution of the chloride [OH.&P‘<JyH h’H S H,.OH 1% containing ammonia and ammonium. sulphate or any other sulphate and a small amount of any copper salt oxidation occurs a colourless crystalline precipitate being obtained which is soluble in warm dilute sulphuric acid.Addition of potassium platino- chloride to this acid solution gives a precipitate of the plcitino- chloride [Pt3NH3,H,0]PtCl green needles which when warmed with hydrochloric acid or a soluble chloride is converted into Cleve’s platinochloride [Pt3NH3,Cl],PtCl,. Addition of potassium platino- bromide to the acid solution gives the ylatii~obron~ide [Pt,3NH3,H,0],PtBr green needles which is converted by hydrobromic acid or soluble bromides into the platinobromide [Pt3NH3,Br],,PtBr,. Analysis of the original oxidation product points to its composition being remesented by the formula L in which case i t is allied to Werner’s binuilear diol complexes the index of co-ordinat,ion of the platinum being equal to 6.W. G. The Series of Rydroxy-pentarnminoplatinic Salts. L. TSCHUGAEV and W. CHLOPIN (Compt. rend. 1915 161 699-700. Compare Tschugaev and Vladimirov A. 1915 ii 569).-Tlie authors have prepared a series of salts having the general formula [Pt,5NH3,(OH)]X,. The carbonate is readily prepared by pass- ing a current of ozone through a mixture of Peyrone’s chloride (1 part) and ammonium carbonate (2 parts) in an excess of ammonia for two or three hours with continual stirring. The carbonate is precipitated being insoluble in water and is readily decomposed by acetic acid giving t’he rrcetafe [Pt,5NH,,(oH>](CH3*Co,),.MINERALOGICAL CHEMISTRY. ii. 107 This salt in solution is decomposed by mineral acids to give tlie corresponding salts. In this way the chloride [Pt,5NH3 (OH)]%H20 rhombic plates and the nitrate [Pt,5NH3,(OH)](NO,) crystal- lising in anhydrous needles were prepared. Both these salts are soluble in water and are ionised. The hydroxyl group like the chlorine atom in the series [PtC1,5NH3]X is completely masked and apparently not capable of being directly replaced by a halogen or any other negative atom o r group. [ Pt,5NH3,(OH)]”! is tervaleiit is shown by a study of the coagulating power of the chloride the results of which agree with those of the luteocobalt- aminines which give by dissociation tervaleiit ions. Like the members of the series [Pt75NH,,C1]X and the series [Pt,GNH,]X the salts of this series give carbonates and sulpliates wliich are practically insoluble in water but soluble in the fixed alkalis. Further the chlorides of all these three series are readily reducetl by zinc in dilute hydrocliloric acid giving in each case the chloride of Reiset’s base I [Pt,4NH3]CI,. That the group W. G.

ISSN:0368-1769    

DOI:10.1039/CA9161005097

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 99 Relation between Temperature and Oxygen Consumption in the Animal Organism. ARISTIDES KANITZ (Intern. Zeitsch. phys. - chem. Bzol. 1915 2 273-278. Compare Krogh A. 1915 i Polemical. The author shows that Krogh's results are in harmony with Arrhenius's law. Pharmacology of the Respiratory Centre. 11. ARTHUR R. CUSHNY and CHARLES C. LIEB (J. Pharm. expt. Ther. 1915 6 451-471).-Morphine slows respiration with little o r no effect on its depth; urethane induces no change except that azising from general narcosis. Under morphine carbon dioxide inhalation produces the usual results,both rate and depth of breathing being increased ; under urethane there is acceleration but this dimin- ishes as the dose of urethane increases. Lack of oxygen produces the same effects.The carbon dioxide concentration in the blood increases under urethane and to a less degree under morphine but this cannot be the cause of the reversed action of carbon dioxide under urethane. After rapid inflation of the lungs the apnoeic pause is lengthened under morphine but only slightly under urethane. Morphine affects the intrinsic rhythm of the respiratory centre but the cent're is less depressed by urethane. I n both case8 the reaction t o reflexes remains normal. I n death from morphine the rhythm of the centre is abolished whilst in urethane poisoning the centre responds by slowing and finally by arrest owing tom the accumulation of carbon dioxide. Both drugs mainly act on the rhythm of the centre but the depth of the breathing depends on the concentration of the carbon dioxide in the blood. W.D. H. Combustion in the Lungs and the Estimation of the Blood Qases. V. HENRIQUES (Biochem. Zeitsch. 1915 71 481-491).- To get concordant results in blood analyses i t is necessary that H. W. B. e 9i. 100 ABSTRACTS OF CHEMICAL PAPERS. the blood (oxalated or defibrillated) should be kept well agitated as i t is withdrawn so that the corpuscles do not settle. Analyses made on blood withdrawn in this manner are more satisfactory than on blood withdrawn slowly from animals with hirudin injec- tions as in this case there is a tendency of the corpuscles t o sink in the connecting tubes and the samples obtained are1 not there- fore ui;iform. Blood withdrawn simultaneously from the right side of the heart and from the pulmonary artery contains the same amount of carbon dioxide and oxygen.The blood in the right side of tlie heartl corresponds in composition theref ore with that perfusing the lungs. Experiments were carried out in which the carbon dioxide excretion and oxygen consumption by the lungs were estimated a t the same time as the gas-content of tlie blood passing to and the blood passing from the lungs. Before and after the experiment the rate of flow of the blood through the lungs was also estimated. The results do not support the conception of Bohr and Henriques of a special combust,ibL process in die lungs. S. B. S. The Influence of Osmotic Pressure on the Volume of Red Blood-corpuscles and the Problem of Permeability. H. J.HAMBURGER (Bzochenz. Zeztsch. 1915 7 1 464-467).-The author claims that he was the first t o call attention t o tlie relationship between osmotic pressure and cell volume and also that he was a pioneer in the investigations on the permeability of cells. These facts are not recognised in some of thel most recent text-books. S. B. S. Biology of Phagocgtes. Influence of Hydrogen Peroxide on Phagocytosis. H. J. HAMBURGER (Intern Zeitsch. phys.-chem. Bigl. 1915 2 255-265).-Hydrogen peroxide has a stimulating action on phagocytes suspended in serum o r saline solution which is made apparent by an increase in the number of phagocytes which ingest particles of starch o r of charcoal suspended in the medium. If after treatment with hydrogen peroxide the’ phagocytes are well washed with saline solution before being brought into contact with the suspended particles the enhanced pliagocytosis is still observed.A similar action is not observed with other oxidising substances such as potassium chlolrate and potassium ferricyanide. The strength of the hydrogen peroxide employed was about 1 3000 and was shown t o be incapable! of causing disintegration of the inactive phagocytic cells. The enhanced phagocytosis was theref ore abso- lute and not merely apparent. H. W. B. I. 11. and 111. E. HEKMA ( I n t e m . Zeitsch. phys.-chena. Biol. 1915 2 279-298 299 -351 352-3G9).-€1istorical survey. H. W. B. GEORGE R. MINOT (Arrzer. J. Physiol. 1915 39 131-138).-Antithrombin is rendered inactive by chloroform and ether thus allowing free thrombin if present in oxalated blood-plasma to produce a clot.Prothrombin is not converted into thrombin by chloroform neither does chloro- Fibrin and the Coagulation of the Blood. The Effect of Chloroform on Coagulation.PHYSIOLOGICAL CHEMISTRY. i. 101 forin weaken the action of thrombin solutions ; ether does slightly. Antithrombin could not be recovered from chloroform or ether extracts of serum or plasma. Cliloroform can precipitate both fibrinogen and protlirombin from an oxalated plasma. I n one rabbit poisoned with chloroform the antithrombin was decreased. W. D. H. Adaptation of Ferments. I. KOOPMAN (I?zto*?z. Zcitsch. p1zys.- chenz. Bzol. 1915 2 266-Stl).-The diastatic activity of the saliva in man remains the same whether the diet is restricted entirely to carbohydrates or consists largely of proteins or is a mixed one.The percentages of dry matter of ash chlorine and nitrogen also re'm aiii fairly constant. The1 enzyme is inactivated by heating a t 6 5 O more quickly on the protein than on the other diets. whilst re-activation occurs onlv when the diet< has consisted chiefly of carbohydrates (compare Griamenitzki A. 1911 i 98). H. W. B. The Acid of the Gastric Juice and Gastric Ulcer. CHARLES BOLTON (J. Path. Bact. 1915 20 133 -15Y).-Experinientsl and clinical evidence is adduced t h a t it is the acid and not the enzyme of gastric juice which produces and increases the nematic condition of gastric ulcers. The damage done is in proportion t o the strength of the acid; 0*3-0*4% is t'aken as evidence of hyperacidity W.D. H. Metabolism of Amino-acids in the Organiem. IX. Uuo Lo~ultoso (Atti R. Accnd. Lincci 1915 [v] 24 ii 401-408).- The results previously obtained are summarised and discussed (compare A . 1915 i 917). The experiments with Ringer's solution and still more those with blood show t h a t different amino-acids exhibit different behaviour and that those which are utilised most by one tissue are least utilised by another. Thus glycine is utilised well by functioning muscle but less by the liver whilst alanine is readily utilised by the kidneys and intestine but not so well by muscle. It seems therefore t h a t no particular amino-acids are generically better utilisable than others but rather t h a t each tissue1 exhibits specific selectivity with reference t o the amino-acids ; asparagine is how- ever withdrawn in larger quantity from the circulating liquid and shows a tendency t o become deaminated.The more or less marked disappearance of amino-acids observed in almost all experiments made with blood is not accompanied by the formation of such compounds as ammonia and acetone in quantities sufficient t o justify t h e conclusion t h a t such disappear- ance is due to deamination; complexes of the amino-acids are tlieref ore probably formed. The experiments with Ringer's solu- tion especially in the intestine and liver reveal the opposite tendency that is the withdrawal of amino-acids with formatioli of ammonia. Since the ability of the liver to synthesise amino-acids by couplingi. 102 ABSTRACTS OF CHEMICAL PAPERS.ammonia with the carbonyl group of ketonic compounds is known i t is evident that complex and antagonistic phenomena take place in the various tissues. T. H. P. Influence of Calcium Salts on Reproduction. RUDOLF ELMMERICH and OSKAR LOEW (Lawdw. Jahr. 1915 48 313-330; from Chem Zentr. 19 15 ii '71 '7).-Experiments with mice rabbits and guinea pigs indicated that an increase of calcium in the diet led to an increased number of litters and an increase in the number of individuals in e'ach litter accompanied by a decreased individual weight. Sodium chloride had a similar action but the increased fertility of the animals resulted in this case in a great decrease in weight (12%) of the mother. Magnesium chloride was without action and potassium chloride worked very unf avourably.G. F. M. The Effects of Aqueous Extracts of Organs on Unstriated Muscle. GEORGE G. FAWCETT JESSIE 31. RAHE GEORGE S. HACKETT and J o m ROGERS (Amer. J. Physiol. 1915 39 154-161).-The residues (that is aqueous extracts minus nucleo-proteins and coagulable proteins) of pituitary pineal thyroid parathyroid thymus and adrenal glands liver pancreas and spleen contain most if not all of the internal secretions of these organs; each produces a characteristic stimulating effect on the plain muscle of the cat's uterus which is paralysed by adrenaline. There are differences in the activity of the various extracts; each is supposed to act on some portion of the sympathetic nerveendings by a different chemical or physico-chemical action. W. D. H. The Feeding of Young Chicks on Grain Mixtures of High and Low Lysine Content.G. D. BUCKNER E. H. NOLLAN and J. H. KASTLE (Amer. J. Physiol. 1915 39 162-171).-0sborne and Mendel have shown that lysine is largely responsible for the stimu- lation of growth. The present experiments on various lots of chickens support this view. Analytical tables of the food supplied are given the main difference being in the lysine content. Other conditions of rearing were kept constant. The failure to grow on a food mixture poor in lysine is strikingly shown by tables of body-weights and by photographs. This failure is not made good by adding growth-producing fat (butter) t o the rations. W. D. H. Quantitative Observations on Antagonism. A. R. CUSHNY (J. Phnrm. expt. They. 1915 6 439-450).-The experiments were performed with atropine and pilocarpine on the salivary secretion of dogs.I n different dogs a constant amount of atropine was necessary to oppose the action of a constant amount of pilocarpine and in the same dog the ratio of the two drugs remained the same however much the actual amounts injected might vary; that is the antagonism proceeded according to the laws of mass-action and not according t o those of chemical combination. There wasPHYSIOLOGICAL CHEMISTRY. i. 103 evidence that when one poison had been allowed to act f o r some time its antagonist was less effective than if it had been injected simultaneously. W. D. H. Kyrines. HANS FREUND (Phann. Ze?ztr.-h. 1915 56 663-667). -In extension of the work on blood proteins (A. 1914 i 447) the author has examined some kyrines in order to determine whether they differ in toxicity from their parent proteins.Pure globinokyrine sulphate was obtained from hzmoglobin and glutokyrine sulphate from gelatin by the usual processes which are dwcribed. These were injected intravenously and sub- cutaneously into rabbits and guinea-pigs and were found to be less toxic than the parent globin or gelatin. J. C. W. Antiphenol Serum ( MLLE.) JANINA WISZNIEWSKA (Compt. rend. 1915 161 609-612).-Dogs fed on meat preserved by artificial methods and rendered aseptic by a careful process of tyndallisation show an increase of phenols in the animal economy. In this process of putrefaction important variations are noticed due t o the quality of the ingested food. With a basal diet of albumin and protein substances phydroxyphenylacetic acid is found in the urine to the extent of 0*004-1.5 grams per litre.A dog fed on decomposed meat shows after the seventh day an average of 1.619 grams of phenol in the urine. I n the case of dogs under normal conditions carefully fed so as t o avoid intestinal putrefaction on administer- ing phydroxyphenylacetic acid in small doses it is found that the phenols are eliminated without being fixed in the tissues. An attempt was made to isolate phenols resulting from putrid intoxication and an amorphous substance was obtained which did not pass through a dialyser membrane. It gave the biuret reaction and showed the general characteristics of the leucomaines whilst yielding some reactions peculiar to phenols.It was strongly alkaline and its toxic coefficient was fixed a t 0.00012 per kilogram. It is thermostable. When fed to animals at intervals in suitable doses it produced an intense sclerosis a t the end of four or five months particularly in the renal and cephalic arteries. When injected intravenously into a horse it furnished characteristic anti- toxins which could be used therapeutically. Animals immunised by means of this serum survived a five months’ feeding with the substance mentioned above. When a 0.1% solution of the antigen is mixed with a few drops of a solu- tion of ethyl nitrite and a few drops of strong sulphuric acid an intense red coloration is produced which passes into blue on the addition of a few drops of ammonia. The red coloration can be detected a t a dilution of 1 in 2,000,000.The following test is given for the phenol antigen. W. G. Albuminuria Produced by Intravascular Injection of Oval- bumin. A. CH. HOLLANDE M. LEPEYTRE and J. GATB ( J . Pharm Chim. 1915 [vii] 12 345-350).-The physiological albuminuria following the intravascular injection of white of egg can bei. 104 ABSTRACTS OF CHEMICAL PAPERS. differentiated from pathological albuminuria by means of Maurel’s soIution which is a mixture of 25 C.C. of sodium hydroxide (33% solution) 5 C.C. of a 3% copper sulphate solution and 70 C.C. of glacial acetic acid. This solution coagulates ovalbumin whilst serum albumin and serum globulin are unaffected. Ovalbumin may also be distinguished from serum albumin by adding form- aldehyde t o the urine and then heating to the boiling point; serum albumin coaguIates whereas ovalbumin remains in solution. H. W. B. The Relationship between Toxic Doee and Body Surface. KARL KIssKAm (Biochenz. Zeitsch. 191 5 7 1 468-478).-From numerous experiments on the injection of caffeine into rats the conclusion is drawn t h a t Dreyer’s statement as to the relationship between lethal dose and body surface does not hold true. S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9161000099

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

i. 104 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Gomparative Effects of Phosphates and Sulphates on Soil Bacteria. E. B. FRED and E. B. HART (dgric. Exper. Stat. Uniu. Wisco"itsiiz Research Bull. 35 191 5).-Ammonification occurs with peptone in solutions and with casein in soils both with pure and mixed cultures. Addition of potassium dihydrogen phosphate to peptone solu- tion greatly increased the production of ammonia especially a t the end of the second day whilst precipitated calcium phosphate stimulated ammonia production in five-day liquid cultures. With tricalcium phosphate or bone-ash there was no increase of ammonia in peptone solutions. Calcium and potassium sulphates slightly increased ammonifica- tion the latter being the more effective.Addition of potassium dihydrogen phosphate results in an enormous increase in the numbers of bacteria followed by a rise in ammonia production which however is not in proportion to the number of bacteria. I n the soil experiments dipotassium hydrogen phosphate stimu- lated ammonification and cell production whilst tricalcium plios- phate gave a slight increase. All phosphates especially di- potassium phosphate increased the numbers of bacteria. Addition of sulphates and phosphates to soil imreased the pro- duction of carbon dioxide ; with ammonium sulphate the increase was very great. The results indicate that the increased crop production following an application of soluble phosphates is partly due to increased bacterial activity. With increased animonification the plantsVEGETABLE PHYSIOLOGY AND AGRlCULTURE.i. 105 obtain more available nitrogen and with increased production of carbon dioxide more available mineral nutrients. Further Investigations on the Proteolytic Activity of Lactic Organisms. I. Influence of the Temperature. CONSTANTINO GORINI (Atti €2. Accncl. Lincei 191.5 [v] 24 ii 369-376).-Further experiments confirm the author’s previous result (.4 nn. Himo- graphie 1897 9 433) that’ the decompositions of the lactose and of the casein of milk by one and the same bacterium are related t o the temperature conditions the lactose being attacked prefer- ably a t a comparatively high temperature whilst peptonisation of the casein occurs best a t a low temperature. All functions of any given organism have therefore not the same optimum temperature.The supposed connexion between the morphology and the physio- logical activity of lactic organisms is found t o be untenable. N. H. J. &I. T. H. P. A New Nitrite-forming Organism. N. V. JOSHI (Jfeem. Dept. Agric. Itidin Rnct. Ser. 1915 1 85-96).-The organism which differs morphologically from those hitherto described produces nitrites from ammoilium salts asparagine and carbamide ; in the case of ammonium carbonate and carbamide the presence of calcium carbonate seems to retard the production of nitrites. Carbon dioxide up t o SO% and coal-gas stimulate the organism whilst dextrose (0.1 gram) and asparagine (0.2 gram in 50 C.C. of Omelianski’s solution) have retarding effects. Magnesium carbonate is much less effective than calcium carbonate as a base for nitrite formation by the organism.The thermal death point of the organism is between 70° and SOo and tlie optimum temperature between 2 5 O and 35O. N. H. J. M. The Assimilation of Carbon Dioxide. RICHARD WILLST~TTER and ARTHUR SrroIIL (Ber. 1915 48 1540-1564).-The first portion of an investigation on the assimilation of carbon dioxide dealing with the rela€ion between the chlorophyll content and the assimi- latory activity of leaves. The method of experiment? was t o pass a current of air containing a known amount of carbon dioxide through a small illuminated glass chamber containing 5-20 grams of leaves a t constantl temperature< and t o determine the carbon dioxide in the issuing gas; a correction was made f o r the quantity of carbon dioxide found to be yielded by the leaves to a similar stream of air in the dark.It is found that the ratio of chlorophyll content t o assimilatory effect is not a constant one the most marked cases being with autumnal green leaves the assimilatory effect of which is relatively low and with leaves of yellow varieties poor in chlorophyll and etiolated leaves regaining their green colour which possess high assimilatory power. During tlie spring growth of the leaves also a gradual diminution occurs in the ratio of carbon dioxide assimi- lated per hour t o chlorophyll-content a similar difference also being observable in the comparison of young and old leaves.i. 106 ABSTRACl'S OF CHEMICAL PAPERS. Tlisse results are attributed to the existence of another factor probably enzyma.tic in the assimilation process.I n leaves rich in chlorophyll the r a t e of assimilation is almost independent of the degree of illumination within certain limits probably because in this case the chlorophyll effect outweighs that of the enzyme; rise in temperature with normal leaves increases the assimilation probably on account of the marked influence of temperature on the enzymatic process. With leaves poor in chlorophyll telmperature change between 15O and 30° causw little alteration in the assimi- latory proce'ss possibly owing t o the enzyme exerting its full effect on the chlorophyll. The duty of the enzyme may be to facilitate the decomposition of an intermediate compound of chlorophyll and carbon dioxide with liberation of oxygen.Swelling and Germination of Plant Seeds. I. TRAUBE and T. MARUSAWA (Intern. Zeitsch. phy:.-chem. Biol. 1915 2 370-393). -The influence of non-electrolytes salts acids and bases on the swelling of starchy seeds such as barley is essentially the same as that exerted on pure starch (see Samec A. 1915 i 76). Bases greatly increase the swelling whilst indifferent narcotics such its ethers and alcohols have only a slight accelerating action. Glycerol sugars salt's acids and the capillary-active higher fatty acids usually inhibit the imbibition phenomenon. Peas and othe'r seeds containing relatively larger quantities of protein are more affected by khe added substances than starchy seeds. The narcotics have an inhibitory action on such seeds possibly due t o their coagulating action on the proteins.The effect of the added substances on germination is usually determined by their action on the enzymes concerned in the germination processes. Indifferent narcotics anzsthetise the enzymes and delay germination and after the removal of the narcotic? germination may proceed undisturbed although in many cases evidence of permanent injury is apparent. When acids are employed germination and growth are usually permanently inhi- bited when a certain limit in concentration is overstepped. I n minute traces however certain acids such as citric acid decidedly increase the rate of germination. The processes of germination and growth are often affected t o different degrees by the added substances. The capillary-active higher fatty acids are specially injurious to germination. The effects of nume'rous bases salts alkaloids and dyes on germination and growth have also been studied.Rate of Absorption of Various Phenolic Solutions by Seeds of Hordeum vulgare and the Factors Governing the Rate of Diffusion of Aqueous Solutions across Semipermeable Mem- branes. ADRIAN J. BROWN and FRANK TINKER (Proc. Roy. SOC. 1915 [ B ] 89 119-135. Compare A. 1909 ii 386; 1912 ii 1086).-Barley seeds were steeped in water and in N / 2-phenolic solutions a t 19O and a t 32*2O and in solutions of phenol of various strengths (N/2 t o N / 3 2 ) a t 2 2 ' 6 O . The increase in weight was ascertained at intervals. D. F. T. H. W. B.VEGETABLE PHYSIOLOUY AND AGRICULTURE. i. 107 The results obtained with N/2-solutions a t 19O showed a gradual falling off in the rate of absorption as the equilibrium point is reached.With the exception of pyrogallol the phenols showed a marked accelerating effect as compared with wabr the greatest effect being produced by phenol then by catechol resarcinol and quinol in the order as given. A t the higher temperature absorp- tion was much more rapid and the equilibrium was attained in two or three days instead of six or seven days. The relative rates with the different solutions remained however the same. With the different concentrations of phenol the rate of absorp- tion decreases with increased dilution and with the N/SZ-solution the results were practically the same as with water. Estimations of the surface tensions of the phenolic solutions a t the diff ersnt temperaturw employed showed a close relationship with the corresponding absorption constants the order in magni- tude of the latter being the same as the inverse order of the former; so that the product of the surface tension and the absorp- tion constant is practically constant.The conclusion is drawn that when osniotic pressures vapour pressures and viscosities of a series of solutions of permeable solutes are equal their rates of diffusion across the barley membrane are inversely proportional t o their surf ace tensions. N. H. J. M. Osmotic Pressure in Plants. IV. Constituents and Con- centration of the Sap in the Conducting Tracts and on the Circulation of Carbohydrates in Plants. HENRY H. DIXON and W. R. G. ATKINS (Sci.Proc. Roy. Dziblin Soc. 1915 [N.S.] 14 374-392).-1n t.he sap in the tracheae of the trees examined mono- or di-saccharides or both are found a t all times usually in greater amounts than electrolytes. The greatest concentration of sugars occurs in the early spring after which there is a rapid dilution for which the rise in transpiration is largely responsible so that a minimum concentration occurs in summer or autumn. Through the winter there is a rise in concentration culminating iu the vernal maximum which coincides with the period of greatmt root-pressure. The upward conveyance of carbohydrates of which sucrose seems to be the most important' is a continual and primary function of the trachm; whilst the sheath of wood parenchymz round the vessels functions as a gland t o secrete carbohydrates into the rising transpiration stream.The presence of large quantities of Carbohydrates in the wood- sap of roots is probably responsible f o r root-pressure and bleeding. I n the evergreen Zlex and the sub-evergreen Cotoneaster the concentration curves of solutes show smaller fluctuations than those of deciduous trees. The concentration of the carbohydrates is usually greater in the trachez of the stem than in the roots except during the summer. I n Zlex however the concentration in the root is the greater except in winter. The columns of the tracheids may be supposed t o afford a permanent channel for the water and salts and to a less degree for organic substances. N. H. J. M.i. 108 ABSTRACTS OF CHEMICAL PAPERS. Osmotic Pressure in Plants V.Seasonal Variations in the Concentration of the Cell-sap of some Deciduous and Evergreen Trees. HENRY H. DIXON and W. R. Q. ATKINS (Sci. Proc. Roy. Dubl. Soc. 1915 [N.S.] 14 445-461).-The osniotic pressure of tissues is mainly due t o dissolved carbohydrates and the variations in the pressure are t o a great extent caused by fluctuations in the amount of carbohydrates in the sap and in a smaller degree to changes in the concentration of the electrolytes. I n the case of leaves there is a progressive rise in osmotic pres- sure due t o accumulation of eldxolytes; whilst in the one root which was examined i t was found t o be due t o the concentration of carbohydrates. The osmotic pressure of Syriuga vulgaris (deciduous) rose irre- gularly from about 13 atm. a t the opening of the buds t o a maximum of about 18 atm.in August. In the case of the evergreens Zlex nquifolium and Hedern helix the osmotic pressure in the leaves was greater in the winter months than in the summer. The osmotic pressure of the sap in the roots of I . apifolium rose from a minimum of about 6 atm. in October to a maximum of 14 atm. in September. There was no concentration of electrolytes in these root's due t o age and the increased osmotic pressure in the older roots is evidently due' to increased concentration of the carbohydrates. N. H. J. M. Studies in Permeability. 11 Effect of Temperature on the Permeability of Plant Cells to the Hydrogen Ion. WALTER STILES and INGVAR J~RGENSEN ( A m . Bot. 1915 29 G11-618).- From the results of experiments with potato discs the conclusion is drawn that the absorption of the hydrogen ion of hydrochloric acid in dilute solution by potlato cells takes place according t o a simple exponential relation betwelen time and the concentration of the acid.The rate of absorption is increased about 2.2 times for a rise of loo between Oo and 30°. N. H. J. M. Presence in Plants of Hmmatoid Compounds of Iron. 11. G. GOLA (Atti R. Accnd. Liizcei 1915 [vl 24 ii 289-291. Compare A. 1915 i 926).-In order tot obtain the h;ematoid compounds of iron of plants in a pure condition advantage is taken of the solubility of their picrates. Froin these the picric acid may be removed by treatment with water or by solution in sodium hydrogen carbonate solution and subsequent acidification with acetic acid. A large number of vegetable organisms of different kinds have been examined and the results show that the occurrence of organic compounds of iron may be regarded as general.The principal propezties of t,hese compounds are as follows They are soluble in aqueous alkali solutions but not in dilute acids and they yield picrates soluble in neutral solvents and are soluble in pyridine after they have been detached from the protein molecule. Their iron is removed by the action of aqueous alkali in the hot but they are resistant t o hot aqueous acids and t o alkali even a t 240O. Wit11 hot alcoholic hydrogen chloride they give compounds whichVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 109 still contain iron and have some of the characters of haemin.When heated with zinc dust or aluminium they yield pyrrole derivatives. I t is probable therefore that plants contain iron compounds which are chemically and perhaps also biologically analogous t o €hose characteristic of the blood pigments of many animals. T. H. P. Pigments of Fruits in Relation to some Gienetic Experiments on Gapsicurn Annuum. W. R. G. ATICINS and G. 0. SHERRAHD (Sci. Proc. Roy. Dubl. Xoc. 1915 [N.S.] 14 328-365).-1n Capsicum fruit,s red is dominant t o yellow and seems to be a simple dominant to chocolate and orange. I n unripe fruits the different shades of green are due t o variations in the numbers of chromatophores in each cell. The red and chocolate pigmeats form oily liquids and also differ from lycopin carotin and xanthophyll by dissolving readily in cold alcohol and light petroleum.The solutions become colourless when evaporated in daylight. The amount of pexoxydase in the' fruits seems to diminish during ripening. It is frequently present only in the epidermis whilst the defeper tissues contain a strongly reducing in hibitor. N. H J. M. Content of Amylase in Ripening Seeds of Horse Beans. A. BLAGOVESCHTSCHENSKI ( J . Russ. Phys. Chem. Soc. 1915 47 1529-1532).-Examination of the seeds of Vicia faba L. var. minor a t different stages of their maturation shows t h a t the amount of amylase present changes approximately in the same way as the rate of accumulation of staxch. This result is regarded as a proof of the synthesising action of the amylase in the ripening seeds the apparent incompleteness of the parallelism between rate of synthesis and amount of enzyme being due to the loss of some of the starch from the assimilatory organs.T. H. P. Oxydases and their Inhibitors in Plant Tissues. IV. The Flowers of Iris. W. R. G. ATKINS (Sci. PYOC. Roy. Dub]. Soc. 1915 [N.S.] 14 317-327).-The peroxydase reactions of related species of Iris are similar although the distribution and amount of anthocyanin may be very different. Active peroxydase is absent in the Pogoniris group whilst the reactions are usually well marked in the Xiphion group; in the Apogon group the distribution varies. When negative results are obtained by the usual method the presence of the enzyme can be shown by treatment with hydrogen cyanide or toluencwater which removes an inhibitor probably by diffusion since the protoplasm is rendered permeable by the reagents.When the flowers are kept in darkness the quantity of active peroxydase increases; in one case organic peroxide was produced. It is not possible to correlate the distribution of peroxydase and anthocyanin in Iris owing perhaps to complications introduced by inhibitors. N. H. J. M.i. 110 ABSTRACTS OF CHEMICAL PAPERS. Formation of Alkaloids in Papaver Somniferum L. var. Nigrum and the Opium obtained from the Plant. L. VAN ITALLIE and J. A. VAN TOORENBURG (Phnmz. Weekblad 1915 52 1601-1 606).-The opium from Papver somniferum var. migrum contains thebaine narceine morphine codeine and papaverine but not narcotine. A. J. W. Odoriferous Substances of the Thorn-apple Datura Stra- monium.A. SIVOLOBOV (J. Russ. Phys. Chenz. SOC. 1915 47 15 61-15 69).-The products obtained on distilling disintegrated branches of Datura stramoniam including leaves flowers twigs and fruit cones with water consist principally of methyl and ethyl alcohols mixed with small proportions of trimethylcarbinol ( ?) aldehydes ketones and esters. The aldehydes comprise acetalde- hyde and probably formaldehyde propaldehyde isobutaldehyde and another of considerably higher boiling point. Acetone and another ketone of higher boiling point were found and esters of acetic and formic acids. The small proportion of odoriferous sub- stances is explainable by their volatility which prevents any marked accumulation. T. H. P. Soil Gases. J. WALTER LEATHER (Mem. Dept. Agric.India Chem. Ser. 1915 4 S5-134).-By means of an attachment to a soil-boring cylinder the soil samples could be a t once completely enclosed and the whole of the contained gases could be pumped out. I n addi- tion to the total volumes of gas the amounts of argon nitrogen oxygen hydrogen and carbon dioxide were estimated. Argon was estimated because its ratio to the oxygen or nitrogen in soil gases would show whether these gases had been liberated or combined. When rain falls on a dry soil the volume of gas displaced is not necessarily the same as the volume of water. I n the wettest weather it was found that the soil contained about half as much gas as in hot drx weather. Gases from swamp rice soils were found to contain large amounts of nitrogen in relation to argon indicating liberation of soil nitrogen very little oxygen and considerable amounts of hydrogen and methane.Gases in the neighbourhood of roots contained high percentages of carbon dioxide and commonly contained hydrogen but not methane. Analyses of gases from soils during active nitrification showed normal instead of low amounts of oxygen. These results and others obtained in nitrification experiments in closed vessels seem to point to a rapid diffusion of gases through soil. The conclusion is drawn t'hat tillage of the soil is unnecessary as far as aeration is concerned and that the value of good cultiva- tion must be due t o other effects. N. H. J. M. Adsorption of Potassium and Phosphate Ions by Typical Soila of the Connecticut Valley. HOBERT H. BOGUE (J.Physical Chem. 1915 19 665-695).-The adsorption of phosphate and potassium ions by four typical soils from the Connecticut valleyVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 111 has been exhaustively studied. The soils examined were a Windsor sand a Podunk fine sandy loam a Connecticut meadow silt loam and a Suffield clay. The soils were thoroughly leached with water to remove any soluble salts and then placed in a nickel tube and solutions of potassium chloride and monocalcium ortho- phosphate CaH4(P0& of known strength were allowed to perco- late through them. The change in concentration of the potassium and phosphate ions was determined colorirnetrically. The results of the investigation are expressed in tables and curves. The main results are in agreement with previous work of Cameron Schreiner Failyer and Schloesing.It is shown that when soils are leached the concentration of phosphate and potassium ions in the soil extract approaches a constant value which appears to be fixed and definite for any given soil. When soils are subjected to the action of soluble potassium and phosphate salts the concentration of these salts in the soil extract is a t first not materially increased owing to the power of the soils to adsorb these salts but as adsorp- tion proceeds it becomes weaker and a point is finally reached where the amount of soluble salts extracted in the soil extract is nearly equivalent to the amount applied. The concentration of the potassium and phosphate ions in the soil extract approaches a low constant which appears to be fixed and definite for each soil when only a part of the adsorbed ions has been removed by the leaching action of water.The constants attained by the four soils by the leaching action of water are very nearly alike which seems to indicate that the concentration of the potassium and phosphate ions in the soil solutions of the various soils were practically the same and not a t all dependent on the amount of adsorbed potassium or phosphate they originally contained. This indicates that the concentration of salts in soils is largely dependent on the specific adsorptive capacity of the individual soils. These results tend t o disprove the theory that the composition of the soil moisture and hence the adsorptive capacity of the soil is determined primarily by the composition of the soil.They tend to prove that this quality is dependent on the mechanical texture of the soil. Further since these soils continue to adsorb small amounts of potassium and phosphate ions long after the approximate point of saturation has been reached and they continue to lose potassium and phosphate ions in small amounts long after the soluble forms must have been entirely leached outt and as the latter point is reached long before all the previously adsorbed potassium and phosphate ions have been leached out it would appear that the soils were able to take up these ions from the solution in two distinct ways first by saturating itself with the ions these undergoing no chemical change and thus remaining readily soluble and easily leached out; and secondly by interacting with the salts producing insoluble compounds which are slowly reconverted into soluble compounds on treatment with water.J. F. S. Field Test with a Toxic Soil Constituent Vanillin. J. J. SKINNER (U.S. Dept. Agric. B?ill. 164 1915).-The results of poti. 112 ABSTRACTS OF CHEMICAL PAPERS. experiments in which clover was grown in soil containing 100 mg. per kilo. of vanillin increased by subsequent additions t o 300 mg. showed a reduction in yield of 53%. Similar experiments with wheat showed injurious effects in two soils (sand and sandy loam respectively) whilst in a third soil (loam) no injurious effects were observed. Experiments were also made with different plants grown on small plots. The soil was a silty clay loam of an acid nature with a low percentage of organic matter.Vanillin was applied the day before sowing the seed and three other applications were made the total amount added being 320 kilos. per hectare. ThO final results showed considerable reductions in the yields of cow peas garden peas and string beans. It was found that the soil when kept for six months after the application of vanillin was still harmful to the respective crops. N. H. J. M. The Solubility of the Phosphoric Acid in Powdered Thomas Slag on Repeated Extraction with Water Containing Carbon Dioxide. J. G. MASCHHAUPT (Chew. Zentr. 1915 ii 552; from Verslag. L a n d bouw kwad. Onderxoelc. Ry ks land boziwproefstat. 19 15 41 pp.).-The amount of phosphoric acid which can be extracted from powdered Thomas slag by water containing carbon dioxide depends largely on the relative quantities of the solid and liquid phases. If this relation is fairly constant the' more' marked is the effect of the free lime and calcium silicate present on the solu- bility of the phosphoric acid.Slag- powder characterised by a high solubility with respect t o citric acid gives a higher yield of phos- phoric acid in the earlier extractions but after a certain number of extractions all samples exhibit similar behaviour as to the solu- bility of the remaining phosphoric acid. The content of free lime determined by extraction with a sugar solution is higher in samples of low solubility towards citric acid whilst the content of calcium silicate is higher in samples showing the same characteristic. The varying content of free lime can only in a small degree be responsible for the variable solubility in citric acid because although the removal of the lime raises the percentage of phos- phoric acid extracted by 2% citric acid or by water containing carbon dioxide the differences still persist' and therefore are possibly to be referred to double salts of calcium silicate and calcium phosphate. The results do not indicate any definite relation between the solubility in water containing carbon dioxide and in citric acid considerable differences being observed in the behaviour on the first extraction with the former solvent with samples the difference between which is only slight as measured by the citric acid test. D. F. T.

ISSN:0368-1769    

DOI:10.1039/CA9161000104

出版商:RSC    

年代:1916

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 107 Muscovite with Unusual Optical Characters from a Marble in Maryland. R. W. CLARK ailti W. F. Huw (Ceiztr. .lJi)? . 1915 666-668).--A greyish-brown dolomitic marble knowii in the trade as “Mar Villa” marble occurs in large quantity a t Cockeysville Maryland. It owes its colour to the presence of a brown mica which has the optical characters of phlogopite (markedly pleochroic; optic axial angle very small and optic axial plane parallel to the plane of symmetry) b u t the chemical composi- tion of muscovite (the ratio A1,0, SiO as shown in the follow- ing bulk analysis of the marble being nearer t o t h a t of muscovite 1 2 than to t h a t of phlogopite 1 6). SiO,. A1,0,,. FeO. CaO. MgO. MnO. CO,. FeS2. Total. 3.88 1.24 0.32 30.06 20.41 0.02 43.93 0.06 99-91” The percent age mineralogical composition calculated from this bulk analysis of the marble is dolomite (with MgO CaO = I 1-l) 93.97; muscovite 2-27; tremolite 3.75; pyrites 0.06. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9161005107

出版商:RSC    

年代:1916

数据来源: RSC