摘要:

J O U R N A L H. BRERETON BAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CBOSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN &LA. Ph.D. F.R.S. BXRNARDYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.R.S. F. R. S. OF A. HARDEN D.Sc. Ph.D. F.R.8. T. M. LOWRY D.Sc. J. C. PHILIP D.Sc. Ph.D. F. L. PYMAN D.Sc. Ph.D. A. Scow M.A. D.Sc. F.R.S. G. SENTER D.Sc. Ph.D. S. SMILES D.Sc THE CHEMICAL SOCIETY. E. F. ARMSTRONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. H. W. BYWATERS D.Sc. Ph.D. R. J. CALDWELL D.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. W. GODDEN B.Sc. E. GOULDING D.Sc. W. D. HALLIBURTON M.D. F.R.S. H. B. HUTCHINSON P11.D. L. DE KONINGH. G. D. LANDER D.Sc. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. G. F. MORRELL Ph.D. D.Sc. ABSTRACTS OF PAPERS T. S. PATTERSON D.Sc. Ph.D. T. H. POPE B.Sc. T. SLATER PaIcE D.Sc. P1i.D. E. H. RODD D.Sc. S. B. SCHRYVER D .Sc. Ph.D. W. P. SKERTCIILY. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc. Ph.D. ON ORGANIC PHYSIOLOGICAL AND AGRICULTURAL CHEMISTRY. 1915. Vol. CVIII. Part I. LONDON 1915. GURNEY & TACKSON 33 PATERNOSTER ROW E.C,PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMITED BRUNSWICK ST. STAMFORD ST. S.E. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91508FP001

出版商:RSC    

年代:1915

数据来源: RSC

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J 0 U R N A L H. BRERETON BAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. BERNARDYER D.Sc. M. 0. FORSTER D.8c. Ph.D. F.R.S. F.R.S. OF A. HARDEN D. Sc. Ph.D. F.R.S. T. RI. LOWRY D.Sc. J. C. PHILIP D.Sc. Ph.D. F. 1,. PYMAN D.Sc. Ph.D. A. SCOTT &LA. I).Sc. F.R.S. G. SENTER D.Sc. Ph.D. S. SMILES D.Sc. THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON PHYSICAL INORGANIC MINERALOGICAL ANALYTICAL CHEMISTRY. AND E. F. ARMSTRONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. H. W. BYWATERS D.Sc. Ph. D. R. J. CALDWELL D.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. W. GODDEN R.Sc. E. GOULDING D.Sc. W. D. HALLIBURTON M.D. F.R.S. H. B. HUTCHINSON Ph.D. I,. DE KONINGH. G. D. LANDER D.Sc. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. G. F. MORRELL Ph.D. D.Sc. T. S. PATTERSON D.Sc. P11.D. T. H. POPE B.Sc. 1’. SLATER PRICE D.Sc. Pl1.D. E. H. RODD D.Sc. S. R. SCHRYVER D.8c. Pl1.D. W. P. SKERTCHLY. F. SODDY M.A. F.R.S. J. F. SPEKCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STANFORD M.Sc. l’h. D. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS P11.D. H. WREN M.A. D.Sc. P1i.D. D. F. rrWISs D.s~. 1915. Vol. CVIII. Part 11. LONDON GURNEY 5z JACKSON 33 PATERNOSTER ROW E.C. 1915.PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMITED BRUNSWICK ST. STAMFORD ST. S.E. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91508FP003

出版商:RSC    

年代:1915

数据来源: RSC

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ii. 16 ABSTRACTS OF CITEMTCAT PAPERS. Inorganic C he mi s t r y. Isalation of Oxygen from Air. L. BeEaFEm (Brit. Pat. 2121 1 of 1913; from J. Soc. Chem. Ind. 1914 33 S31).-The vapour of nitric acid is passed over heated sulphuric acid t o form oxygen water and nitrosylsulpliuric acid. The last substance is treated with water to form sulphuric acid and nitrogen trioxide the latter being t'hen reconverted into nitric acid by means of water and atmospheric oxygen. The equations are (i) 4IIN0 = 4N0 + ZH,O + 0 ; (ii) 4H,SO + 4N0 = 4H(NO)SO +,2H,O + 0 ; (iii) ZH(NO)SO + H,O = 2H,XO + N,O,; (iv) N,O,+ O,+H,O = ZHNO,. The cycle of operations is completed continuously in a system of refractory and acid-proof tabes acting as heat interchangers on the counter-current' principle the tubes being preferably packed with quartz grains or the like which offer resistance t o the flow Preparation of Thionyl Chloride.FAEBENFABRIKEN YORM. FXIEDRICH BAYElt & Co. (Brit. Pat. 27830 of 1913 ; from J. Xoc. Chem. I n d . 1914 33 SSO).-Thionyl chloride is obtairted by the reaction of sulphur or sulphur chloride with chlorine and cliloro- of liquids and facilitate the iiitercliange of heat c. s.INORGANIC CHEMISTRY. ii. 17 sulphonic acid or of sulphur dichloride with clilorosulphonic acid with or without the addition of a catalyst such as antimony tri- chloride or mercuric chloride. c. s. Preparation of Thiony 1 Chloride. FARBEE FABRIKEN VORM. F. BAYER & Go. (D.R.-P. 275378; from J. Xoc. Chern. hd. 1914 33 831).-Thionyl chloride is produced by the interaction of sulphur trioxide and sulphur dichloride a t the ordinary temper- ature and pressure in presence of suitable catalysts such as antimony trichloride mercuric chloride or chlorides of other heavy metals.T. €1. P. Preparation of Hydrazoic Acid or Azides. H. STAUDINQER (D.R.-P. 273667; froui J. SOC. Chem. lnd. 1914 33 693).-When hydrazine hydrate or a hydrazine salt is treated witlh the nitroso- amine of a secondary amine such as diphenylamine in alcoholic solution and in presence of alkali hydroxide or carbonate the following reaction takes place slowly in the cold but more rapidly on heating NPh,*NO + N,H + NaOEC=NHPh2 + N,Na,+ 2H,O. T. H. P. Thermal Dehydration of Stilbite Thaumasite and the Hydrates of Magnesium Sulphate and of Copper Sulphate.H. E. MERWIN (J; IVaehingfon Acad. Xci. 1914 4 494-496).- Small quantities of the substances mentioned above were heated between the walls of thin glass tubes in an oil-bath a t a series of temperatures and the rate a t which the water was expelled a t the various points was determined. Copper sulphate is shown to lose first two molecules of water then two more and finally the last a t a much higher temperature. Stilbite loses 17.6% of water without any evidence being obtained of a break in the dehydration curve. Magnesium sulphate gives four maxima in the rate of epolution of water corresponding with the expulsion of 4H20 and three single molecules. Thaumasite CaSO,,CaCO Ca SiO 1 5H,O loses first of all 14 molecules of water the last one being held much more firmly.J. F. S. Hydrolysis of Zinc Chloride. ALFREDO SORDELLI ( A n d . Soc. Quito. Argentina 1914 2 97-112).-The addition oE water t o concentrated solutions of zinc chloride does not cause any separa- tion of the basic chloride 2ZnC12,11ZnO; the latter is formed when the solution contains an excess of zinc oxide. The pre- cipitation is exothermic. The hydrolysis constant as determined by means of methyl acetate or sucrose is small,,even a t looo. G. D. L. Complex and Barnic Lead Salts. Cause of the Solubility of Lead Sulphate in Ammonium Acetate. C. BLOMBERQ (Chem. Teekblud 1914 11 1030-1034).-From the results of determinations of the freezing point and electrical conductivity VOL. CVIIT. ii. 2ii. 18 ABSTRACTS OF CHEMTCAL PAPERS. of solutions of lead acetate the author draws the conclusion that the solubility of lead sulphate in such solutions is due t o the formation of either complex or basic salts.Supposed Crystalline Compound of Ferrous Chloride and Nitric Oxide. I. EELLUCCI (Qcczzetta 19 1 4 ii 384-389).-The experiment'al conditions employed by Thomas (A.? 1896 ii 26) give a yellow microcrystalline mixture! of ferric chloride with a small proportion of nitric acid and not the compound FeGl,,NO which has not yet been prepared. Manchot's ferronitricoxide phosphate (compare A. 1914 ii 567) is therefore the only corn- pound of the type [Fe(NO)]X2 as yetl known. Ternary Alloys of Nickel-Copper-Lead. N. PARRAVANO [with c. MAZZETTr] (G'azxetta 1914 44 ii 375-384).-The author has traced the fusion diagram of these alloys which exhibit partial miscibility in the liquid state.Nickel-copper alloys form a con- tinuous series of mixed crystals with melting points falling con- tdnuously from that of nickel to that of lead. With lead-nickel alloys the melting-point curve falls from 1451° at which nickel melts t o 1338O the temperature of the invariant equilibrium between a solid and two liquids one containing about 30% and the ot,her about 85% of lead; subsequently the curve falls rapidly to a eutectic which consists of practically pure lead and solidifies at 3 2 7 O . Similar behaviour is exhibited by copper-lead alloys the limits of miscibility being about 36-85% of lead. Given the existence of two miscibility gaps in the binary alloys two simple hypotheses present themselves with reference to the manner in which these gaps are continued into the! triangular diagram of the ternary alloys (1) the two gaps may undergo restriction each exhibiting a critical point; (2) the two gaps may be continued one into the otlher giving rise to a whole zone of liquid gap which interrupts the continuity of the fusion surface and divides the latter into two clearly distinct parts.Experiment shows that case (2) is verified with nickel-copper-lead alloys this result' being in accord with that furnished micrographically. The results indicate the following method of removing nickel and copper from lead. The ternary eutectic virtually coincides with the lead vertex of the triangular diagram so that mixtures in the neighbourhood of lead at temperatures intermediate to those corresponding with the beginning and end of solidification con- sist of a solid part containing the greater part of the nickel and copper in the form of mixed crystals and of almost pure liquid lead; the mixed copper-nickel crystals are lighter than the liquid and can be readily removed.Since the quantity of crystals gradually increases as the te'mperature is lowered from that corre- sponding with the commencement of the crystallisation t o that of the eutlectic plane the temperature of the bath should be as low as possible. The rapid fall of the surface of fusion in the neighbourhood of the lead point ensures the success of the opera- tion sins i t allows of moderately wide variations in the temper- A. J. W. T. 11. P.ISORGANIC CHEMISTRY.ii. 19 ature of the bath without rendering possible the failure of the separation. T. H. P. Artificial Macles of Tin. P. GAUBERT (Compt. rend. 1914 159 680-682. Compare Ewing and Rosenhain Phil. Trans. 1900 193 [A] 353; 1901 195 [ A ] 279).-A study of the conditions governing the formation of bands of twin crystals in tin. The sheets of tin are prepared of the required thickness by melting and casting them between two smooth well-polished plates of glass. On suddenly piercing such a sheet of tin with a needle thelre are produced (1) on the side remote from where the needle entered a cross in relief the branches being very broad and equal or unequal according to t#he crystalline orientation of the sheet of tin; (2) two or three series of brilliant parallel bands about 0.5 mm.broad and extending from the point of penetration to the edges of the crystal. Their exterior face at first in the plane of the sheet makes an angle of several degrees with it. The crystals of tin do not always arrange themselves in the same manner with respect to the sheet of glass and the angle which the two or three series of bands make between them is variable. Some sheets of tin give bands making an angle of 8 7 O others give two kinds of bands making an angle of 71° whilst others give three series of bands of which the angles are 4 5 O 71° and 6 4 O . The folding or twisting of a sheet of tin results in the forma- tion of twinned bands. The “cracking” of tin is probably due to the formation of these macles. W. G. Electrolysis of Antimony Chloride in Presence of Colloids.ARRIGO MAZZUCCHELLI (Gaxzetta 1914 44 ii 404-419).-The presence of antimony chloride in electrolytic antimony cannot be prevented by carrying out the electrolysis of the chloride in a solution containing a colloid. Many colloids including resorcinol tannin molybdic acid starch and gum have no influence on the aspect and properties of the metallic deposit but the presence of proteins especially of gelatin results in the separation of antimony which exhibits increased lustre and fragility and is explosive towards heat but only slightly so towards shock. Quinine’ with which antimony chloride forms a double chloride sparingly soluble in concentrated hydrochloric acid has an effect similar t o that of the proteins; the cationic function of the alkaloid appears to favour its absorption by the met’al. Lowering of the temperature at which the electrolysis takes place renders the metallic deposit pitted and less adherent owing to increase in the cathodic evolution of hydrogen. From these results the conclusion is drawn that in explosive electrolytic antimony the metal and the chloride form a true not a colloidal solution. Such a solution is formed by antimony with its chloride bromide or iodide but not with the fluoride. T. H. P. 2- 2

ISSN:0368-1769    

DOI:10.1039/CA9150805016

出版商:RSC    

年代:1915

数据来源: RSC

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ii. 20 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. The Calculation. and Comparison of Mineral Analyses. C. E. VAN ORSTRAND and FRED. E. WRIGHT (J. Wushington Acad. A%. 1914 4 514-525).-A mathematical discussion and criticism of the papers by Schaller and Wells (ibid. 1913 3 97 416) on the calculation of mineral f ormulz and the interpretation of mineral analyses. I n all cases the method of least squares is involved. Several equations and formulze itre given f o r the computation of the probable errors and the adjustment of the data. Identity of Empressite with Muthmannite. WALDEMAR T. SCHALLER (J. Fashinylon Acad. A% 1914 4 497-499).-The two minerals empressite (Bradley A. 1914 ii 737) and muthmannite (Zambonini A. 1911 ii 734) are considered by the author t o be really the same substance.The physical characteristics are very similar the only difference being that whilst empressite is AgTe and contains no gold muthmannitei contains considerable quanti- ties of gold and is expressed by the formula (AgAu)Te. The quantity of gold is however always less molecularly than the silver; the author therefore expresses the opinion that empres- site is only pure muthmannite and could be more accurately named muthmannite whilst the original mineral should be named auric muthmannite. J. F. S. L. J. S. Analytical Chemistry. Symbolical Representation of Analytical Operations. 1,. GOWING-SCOPES (C'hem. News 1914 110 247-250).-8 list of some ninety symbols for representing analytical operations is given ; Dihydroxydistyryl Ketone or Lygosin a New Indicator.ARON FERENEZ (Ann. Chim anal. 1914 19 232 ; from Phnrw. Post. 1913 521).-When 2 mols. of salicylaldehyde and 1 mol. of acetone in alcoholic solution are treated with concentrated sodium hydr- oxide soslution condensation takes place with the formation of a salt which may be crystallised from alcohol; this salt on treat- ment with an acid yields o-dihydroxydistyryl ketone a substance giving an orange-red coloration with alkalis and a turbid opal- escence with acid solutions. The indicator may be used in the form of a 1% alcoholic solution; it is stated to be as sensitive as phenolphthalein and may be employed in the titration of ammonia. w . P. s. their use is indicated by a number of examplw. 'cv. P. S.ANALYTICAL CHEMISTRY. ii. 21 Methyl-red a8 an Indicator.R . T. TROMSON (Analyst 1914 39 518-519).-This indicator is especially useful in the titration of ammonia and weak bases such as quinine (compare A 1909 ii 90); its colour change is sharper than that of methyl-orange and its sensitiveness is but little affected by the presence of neutral salts such as sodium chloride or sulphate. It must not be assumed that methyl-red can be substituted for methyl-orange or that it will act similarly t o the latter; methyl-red is affected by dissolved carbon dioxidel and when used as the indicator in the titration of carbonates the solution must be boiled after each addition of acid in order to expel the liberated carbon dioxide. Methyl-red in this respect most closely resembles litmus (compare also T.w. P. s. Qualitative Test for Water by the Use of the Acetylene- Cuprous Chloride Reaction. E. R. WEAVER (J. Amer. Chum. Xoc. 1914 36 2462-2468).-The presence of water in a substance can be readily detected by bringing it into contact with calcium carbide and a solvent for acetylene and then decanting or distil- ling the resulting solution into an ammoniacal solution of cuprous chloride. Most of the usual organic solvents if carefully dried are suitable for this purpose. The method is applicable t o a great variety of substances and especially to the volatile organic com- pounds. The only compounds which interfere with the test are the stronger acids and substancw such as hydrogen sulphide which precipitat.e cuprous salts from solution. The test is sensitive to less than 0.1 mg.of water. 1910 97 2477). E. G. Rapid Methods of Estimating Water in Crude Petroleum Oil-Fuel and Similar Substances. HERBERT S. SHREWSBURY (Analyst 1914 39 529-831).-A simple method is described for estimating the water by distillation. One hundred C.C. of the oil and a few pieces of pumice-stone are placed in a distillation flask which is so supported that its sideltube passes vertically down- wards into a graduated cylinder surrounded by cold water. After the neck and surface of the flask (uncovered by the oil) have been heated cautiously with a flame the oil itself is heated until all the water and a few C.C. of oil have distilled over into the cylinder and the volume of the water is read. Another method depends on the extraction of the water frosm oil-fuel by glacial acetic acid and on the alteration of the turbidity temperature of the acid with a standard oil caused by the presence of the water.The turbidity temperature of the acetic acid with the oil (equal volumes of arachis and cocoanut oils) is ascertained; 10 C.C. of the stan- dardised acid and 10 C.C. of the d-fuel are then shaken together the acid layer is separat'ed filtered and 2 C.C. of the1 filtrate are lieatled with 2 C.C. of the standard oil until the mixture is clear and its turbidity temperature determined. Standards must be prepared by adding known quantities of water to the acetic acid. A correction is necessary for the effect on the turbidity temper ature of substances other than water dissolved from the oil-fuel;ii. 22 ABSTRACTS OF CHEMICAL PAPERS.bhis is obtained by drying a portion of the oil-fuel by heating it in an open basin and then shaking 2 C.C. of it with glacial acetic acid as described. When the oil-fuel contains more than 2.5% of water the acetic acid extract must be diluted with acetic acid exactly the same dilution being made in the case of the extract giving the figure for the correction. Both methods can probably be used for the estimation of water in substances such as butter lard and other fats and oils. w. P. s. Examination of Sulphur Chloride. F. FRANK and E. NARCRWALD (Gummi-Zeit. 1914 28 1580-1581 ; from J. Xoc. Chom. Ind. 1914 33 749).-Whilst pure sulphur chloride has D15 1.684 samples having D15 1.680 +o 1.690 may be considered as satisfactory. When 105 C.C.are distilled using a standard flask and condenser (of which minute details are given) 95 C.C. should distil within 4O the first 5 C.C. being rejected. The sample should contain at least 98.8% of S,Cl calculated on the chlorine content estimated by the following method From 10 to 15 C.C. of nitric acid (D 1.5) and a quantity of silver nitrate sufficient for the reaction are1 introduced into a small pressure flask having a ground-in stopper secured by a lever. A small weighing bottle contlaining from 0.2 to 0.5 gram of the sample is then dropped into the flask this is shaken until all the sulphur chloride has dis- appeared aad is then heated for thirty minutes on a water-bath cooleld and opened. The precipitate is collected dissolved in ammonia re-precipitated again collected and weighed.The method yields trustworthy results higher than those obtained by the older process. w. P. s. Modifled Kjeldahl Flask for Estimating Soil Nitrogen. H A. NOYES (J. Amar. Chern. Soc. 1914 36 2541-2542).-As the amount of nitrogen in ordinary soil is small a large sample must be employed for its estimation and this usually necessitates the transfereace of the solution from the digestion flask to another flask for distillation t o avoid bumping. I n order t o obviate this transference a modified Kjeldahl flask may be used which has a capacity of about 700 C.C. and differs from the ordinary form in being egg-shaped. The pointed bottom of the flask prevents the solid matter from settling during the heating and frothing does n o t occur as the bubbles are broken against the sides of the1 flask.The flask has proved very satisfactory in practice. E. G. Preparation of Reduced Strychnine Reagent for the Colorimetric EBtimation of Nitrates in Water. G. DENIG~S (Ann. Chime anal. 1914 19 221-222 ; from Bull. Soc. pharm. Bordmux 1914. Compare A. 1911 ii 655 673).-The zinc amalgam used is obtained by immersing 50 grams of zinc foiI cut into small strips in a mixture of 50 C.C. of water and 20 C.C. of hydrochloric acid (D 1-18) and then adding 10 C.C. of 4% mercuric chloride solutio'n; after two minutes' contact the strips are washed vith water placed on a sheet of filter paper until dry and thenBKALY'I'ICAL CHEMISTRY. ii. 23 stored in a closed bottle. The reagent itself is prepared immediately before use as described (Zoc.c i t . ) . The red coloration produced by the action of nitrates on the reagent in the presence of sulphuric acid attains its full intensity only after the reacting mixture has been heated on a boiling water-bath for five minutes. Estimation of Phosphorus in Phosphor-Bronze. E. W. HAGMAIER (Net. aid Chem. Eng. 1914 12 524-525; from J. SOC. Chem. Ind. 1914 33 923-924).-0ne gram of the bronze is dissolved in a mixture of 10 C.C. of hydrochloric acid and 5 C.C. of nitric acid the solution is diluted with 150 C.C. of hot water 10 C.C. of a solution containing 1 gram of cerium chloride in 25 C.C. of hydrochloric acid and 200 C.C. of water are added and ammonia is run in slowly from a burette until a greenish-blue coloration appears. Four C.C. of acetic acid are now added and the mixture is boiled for ten minutes.After settling the clear liquid is siphoned off the precipitate washed by decantation with 100 C.C. of hot water (added in about six successive portions) and dissolved by heating with 15 C.C. of nitric acid and 3 C.C. of hydrochloric acid. When cold the solution is treated with 5 C.C. of ammonia (1 l) and the phosphoric acid precipitated in the usual way with Estimation of Boric Acid and its Compounds in Extract of Tomatoes and Other Preserved Foods. Nrco~lis CAMUS (And. SOC. Quirn. Argentina 1914 2 123-130).-After ashing the residue from which all the carbon need not be burnt off is moistened with strong hydrochloric acid and the boric acid ex- t,racted with acetone. After evaporation of the solvent the resi- due is dissolved in about 3 C.C.of very dilute hydrochloric acid and the boric acid recognised by means of turmeric paper. By standardising the conditiions size of paper strength of turmeric etc. it is possible to obtain approximately quantitative values. W. P. S. ammonium molybdate. w. P. s. G. D. L. Estimation of Cadmium in Zinc. W. COOPER (Chem. News 1914 110 250-251).-Five grams of the sample1 are dissolved in a cold mixture of 150 C.C. of water and 7 C.C. of sulphuric acid and the solution is decanted into a flask any undissolved residue being washed with a small quantity of water. Twenty C.C. of dilute sulphuric acid ar0 then added to the solution the mixture is diluted t o 250 c.c. treated with hydrogen sulphide for twenty minutes and after two hours the precipitated cadmium and zinc sulphides are collected on a filter.Ths sulphides are now dissolved in hydrochloric acid containing bromine 5 C.C. of sulphuric acid are added and the mixture is heated until fumes of sulphuric acid are given off. This residual solution is diluted t o 50 c.c. any lead sulphate is separated and the precipitation with hydrogen sulphide and treatment with sulphuric acid a,re repeated. The solution is once more treated with hydrogen sulphide the cadmium sulphide is collected on a weighed filter washed dried a t looo and weighed. w. P. s.ii. 24 ABSTRACTS OF CHEMICAL PAPERS. Iodate Method for the Estimation of Copper. W. W. BROSTROM (Eng. and N i n . J. 1914 98 215-216; from J. Scc. Cham. Ind. 1914 33 891).-The copper is reduced with sodium sulphite solution in the presence of hydrochlo,ric acid and pre- cipitated with potassium thiocyanate.The precipitate is washed decomposed with hydrochloric acid in the presence of a small quantity of carbon tetrachloride and the solution titrated with potassium iodate solution until the red colour produced a t first is discharged. Results are given showing that the method is trust- Estimation of Cuprous and Cupric Sulphides in Mixtures of One Another. EWEN POSNJAK (J. Amer. Chern. ~ u c . 1914 36 2475-2479).-During an investigation of copper sulphide minerals it was desired to estimate cuprous and cupric sulphides in presence of one another. A method has therefore been devised which depends on the difference in the behatriour of the sulphides towards silver nitrate as shown by the equations Cu,S + 4AgNO,= Ag,S + 2Ag -I- 2Cu(NO,) and CuS + 2AgNO,=Ag,S + Cu(N03),.I n order to carry out an estimation the substance must be fine enough to pass through a sieve of 80 meshes per cm.. About 0-4-0.5 gram of the material is treated with 50 C.C. of 5% silver nitrate solution which is added gradually with vigorous stirring. To complete the reaction the mixture is heated on the steam-bath for three hours and stirred vigorously a t short intervals. The precipitate is collected and washed and then treated two or three times with 6% ferric nitrate solution a t 70° to extract the silver. The extract is filtered and the residue washed with hot water. Nitric acid is added t o the filtrate until it becomes colourless and the silver is then precipitated and weighed as the chloride.The amount of cuprous sulphide is calcu- lated from the silver found whilst the cupric sulphide is calcu- lated from t'he difference bet'ween the silver in the silver sulphide and that precipitated in the metallic form. The method has been found t o be accurate within 1.5% for the analysis of mixtures of the sulphides in any proportions. worthy. w. P. s. E. G . Electrolytic Estimation of Nickel. W. JUDSON NARSH (J. Plip~icd Chem. 1914 18 705-716).-ft is shown that when nickel is estimated electrolytically by deposition from solutions containing an excess of ammonium oxalate the weight of the d e posit is always too high owing t o the presence of carbonaceous material. The present paper deals with experiments made with the object of improving the process.The nickel deposit is shown to contain nickel carbide which is supposed to be formed by the action of acetylene on the freshly deposited metal. The acetylene is produced by the cathodic reduction of carbon monoxide and carbon dioxide formed at the anode. Attempts were made t o reduce the amount of carbon dioxide formed by adding reducing agents to the solution such as hydrazine sulphate hydroxylamine sulphite sodium nitrite and sodium sulphite. Of these substances,ANALYTICAL CHEMISTRY. ii. 25 the first only produced a noticeable effect inasmuch as it caused the deposit to be much darker probably due to the formation of nickel sulphide. This conclusion is rendered likely because when a nickel solution was electrolysed in the presence of ammonium carbonate and sodium sulphite a flocculent precipitate of nickel sulphide was produced and hydrogen sulphide was evolved.Having failed tlo improve the oxalate method of estimation the author has investigated a number of other methods and comes t o the conclusion that the electrolysis of the double ammonium sul- phate solutioas of nickel gives the best results. A solution of nickel sulphzcte containing about 0.2 gram of nickel in 200 C.C. is mixed with 15-20 C.C. of ammonium hydroxide solution (D 0.96) and 5 grams of ammonium sulphate. The electrolysis is effected between an anode of platinum gauze 6 cm. x4.5 em. and a cathode of copper gauze made in the form of a cylinder 5 cm. high and 3 cm. diameter. The cathode is rotat'ed a t 550-6563 revolutions per minute.The electrolysis is carried out a t ordinary temperature with a current of 0.8 ampere and an E.M.F. of 3.5 volts and requires about twenty-five minutes. It is essential that nitrates and chlorides. should be absent. J. F. S. Modificatione of the Reduction Test for Tungstic Acid. G. TOROSSIAN (Amer. S. Sci. 1914 [iv] 38 537-638).-Wheri powdered tungstic acid is placed on aluminium foil and moistened with a drop of dilute hydrochloric acid a blue coloration is obtained; the reaction is also given by thungstic acid after fusion with sodium carbonate and the presence of ferric oxide copper oxide lead oxide sulphur calcium fluoride or sodium nitrate does not interfere with the test. w. P. s. Assay of Crude Platinum. M.SCHWITTER (Eng. and Nin. J. 1914 97 1249-1250; from J. S'oc. Chem. In& 1914 33 751).- Twenty grams of the nuggets are digested with 200 C.C. of aqua regia (lHNO 3HC1) on a water-bath f o r one hour and then boiled f o r two hours. The solution is decanted and again boiled to dissolve any finely divided metal in suspension. The aqua regia treatment is repeated on the residue the mixture is diluted and allowed to settle. After about eighteen hours the clear solu- tion is decanted and the last portion filtered into a litre flask the filter being washed until colourless. Osmn'ri&um.-The residue from the acid treatment is scorified with 10-15 grams of test lead and enough litharge to fill the scorifier. The button is cleaned with as little hammering as possible and dissolved in dilute nitric acid (1 3) ; the solution contlaining the lead is filt'ered the filter washed free from lead and dried.The osmiridium is separated as completely as possible from the paper the latter is burned and the ash added to the metal which is weighed. Platinum.- Twenty-five C.C. of the filtrate are evaporat'ed to dryness the resi- due heated for one hour with occasional stirring wilh 5 C.C. of hydrochloric acid (1 9) 20 C.C. of water and 8 grams of ammonium chloride and then set aside for eighteen hours; theii. 26 ABSTRACTS OF CHEMICAL PAPERS. platinichloride is collected washed with 20% aniinonium chloride solution and ignited in an annealing cup. The metal contains most of the iridium; the quantity of the latter if not more than 5% can be judged with sufficient accuracy from the colour of the platinichloride 0.2% of iridium sufficing to impart a decided red tint.Gold.-The filtrate from the platinichloride is treated with 5 grams of ferrous sulphate the gold collected and ignited. Palladium.-The filtrate from the gold is treated with one-fifth of its volume of hydrochloric acid and 10% potassium iodide solu- tion is added five drops at a time until no further quantity of black precipitate (PdI,) forms. The mixture is boiled cooled the precipitate collected washed with dilute hydrochloric acid (1 4) until free from iron ignited in a porcelain crucible then heated with a few drops of formic acid to reduce any oxide dried and weighed. Rhodium.-The filtrate from the palladium is reduced while hot with zinc and the metallic precipitate is digesteld for ten minutes on a water-bath with 25 C.C.of dilute nitric acid (1 3) ; the residue is ignited reduced in hydrogen and weighed as rhodium; it contains the last traces of iridium. w. 9. s. Detection and Estimation of Combustible Gaaes in Mineral Waters. ENRIQUE HAUSER (Anal. Pis. Quim. 1914 12 155-1 63 256-259. Compare A. 1914 ii 285).-A minute description of the eudiometer devised by the author for the estimation of com- bustible gases in water and of the mode of operating it. Th& gas is ignited electrically in the eudiometer and the products are analysed by means of ordinary absorption pipettes. The solubility of methane varies according to the nature of the saline solution. A. J. W. Rapid Method for the Detection and Estimation of Solid Hydrocarbons Mixed with Fatty Acids.G. VERONA-RINATI (Ann. Chim. Appticnta 1914 2 20L-202).-This method is carried out as follows. By means of a buretbe 7 C.C. of dry a-dichloro- hydrin b. p. 174O are measured into a glass tube having a diameter of about 10 mm. and a capacity of about 15 c.c. and graduated to read easily t o 0.1 C.C. To this are added 1 . 2 C.C. of water and 1.43 grams of the substance t o be tested. The tube is closed tightly by means of a cork and immersed in a beaker of water maintained a t 65* being removed and well shaken from time t o time. When the liquefied mass is no longer diffused uniformly throughout the whole of the liquid the1 tube is left at rest for ten minutes and the volume of the1 undissolved part collected a t the top is read; this reading is repeated after further heating and shaking.Each 0.1 C.C. of this volume corresponds with 5% of fatty matter of mineral origin in the original substance. I n order t o ascertain whether such mineral fat consists of cerasin o r paraffin or a mixture of these about 2-3 grams of the original material are treated in a test-tube with the aqueous a-dichlorohydrin until the fatty acids are completely dissolved. The tube is then allowed t o cool until the undissolved portionANALYTICAL CHEMISTRY. ii. 27 becomes consolidated a t the top whilst the fatty acids remain in solution in the liquid underne'ath. The solid mass is removed and pressed between filter papers tol free it from the solvent; 0.2 gram of it is heated in a test-tube over a naked flame with 10 C.C.of anhydrous a-dichlorohydrin and the temperature is determined a t which the dissolved hydrocarbon begins to' separate again and render the liquid turbid. When this hydrocarbon consists solely of paraffin this temperature never exceeds 92O (88-92O) whilst with cerasin it is never below 1 1 2 O (l12-l15°). With a mixture of paraffin and cerasin the temperature of separation lies between 92O and 112O and its value indicates which of the two pre- dominates in the mixture. T. H. P. Estimation of Sucrose and Lactose in Condensed Milk by means of Acid Mercuric Nitrate. CECIL REVIS and GEORGE A. PAYNE (Analyst 1914 39 476-479).-The acid mercuric nitmte solution employed is prepared by dissolving mercuric oxide in twice its weight of nitric acid I3 1-42 and diluting the solution t o five times its volume with water A quantity of 65.085 grams of con- densed milk is dissolved in about 220 C.C.of water heated in a boiling water-bath for about five minutes (or kept cold for sixteen hours) and then diluted to 250 C.C. a t 1 5 O . One hundred C.C. of this solution are transferred t o a 100 C.C. cylinder 10 C.C. of the mercuric nitrate solution are added the mixture is shaken for thirty seconds filtered after five minutes and the filtrate is polarised a t 20O. Twenty-five C.C. of the filtrate are then placed in a 50 C.C. stoppered flask the flask and its contents are weighed heated in a boiling water-bath for eight minutes cooled the weight is adjusted and the solution polarised.The readings observed are corrected for the increase in volume due to'the added reagent less the volume of the f a t and protein precipitated; this correc- tion (C) will be and the readings are mukiplied by (lOO+C). Then sucrose %= (D-T)100/(E,-t/2) and lactose1 %=((u-S) x RL1x 100/26-034 where B and Z are the corrected direct and invert readings R and RL the inversion and lactose factors and t the temperature of the invert reading. The factors R and R were' found to be 141.71 and 0.3086 respectively; these figures are the results of actual experiment with sugar solutions of the concentration met with in the case of condensed milks thel authors having ascertained that acid mercuric nitrate has an inverting action on sucrose and that it slightly raises the1 rotlation of lactose.When the milk is clarified with phosphotungstic acid the factars are found to be 142.55 and 0.3165 figures which agree with those recorded by other observers Flour. I. Acidity of Flour. 11. Natural and Artificial Bleaching of Flour. 111. Sulphates and Lime in Flour. R. T. THOMSON (Analyst 191 4 39 519-527).-The aqueous extract of flour is acid to phenolphthalein neutral t o methyl-red C z= 10 - [(P x 1.11) + (P x 0*82)/100 x 26.0341 c.c. (compare A. 1907 ii 586). w. P. s.ii. 28 ABSTRACTS OF CHEMICAL PAPERS. and alkaline to methyl-orange. The acidity indicated by phenol- phthalein is not due to the presencc of lactic acid since Lhis acid is also indicated by methyl-red and i t is doubtful whether lactic acid is the acid produced when flour becomes “sour.” There is no support for the usual statement that ordinary flour is acid in reaction.The author gives the results of experiments showing that artificial bleaching of flour by nitrogen peroxide does not have the same effect as natural bleaching that is by exposure to the atmosphere. Although flour absorbs nitrogen oxides from the air the bleaching effect in this case is due to other causes probably oxidation assisted by moisture and light. For the estimation of sulphates in flour it is recommended that 20 grams of the flour should be mixed with 250 C.C. of water containing 15 C.C. of hydro- chloric acid D 1.16 and then heated until the1 starch is liquefied. The mixture is cooled filtered and the sulphates are precipitated in the filtrate by the addition of barium chloride.First-grade flour was found to contain 0.011% of SO and 0.015% of CaO whilst common-thirds ’’ yielded 0.061% of SO and 0.102% of CaO (com- Utz’s Modiflcation of Halphen’rs Reagent for Cottonseed Oil. ENRICO GASTALDT (Ann. Chim. Appliczta 1914 2 203-207).- At no temperature does Utz’s reaction (compare A. 1914 ii 591) give the same coloration with cottonseed oil as Halphen’s reagent and as i t is exhibited a t 250-260° a t which temperature Halphen’s test fails it cannot be regarded as a modification of the latter. A t a temperature exceeding 160° which is usually sur- passed in Utz’s reaction oleic palmitic or stearic acid gives a colora- tion similar t o that obtained with cottonseed oil. This reaction cannot therefore be regarded as characteristic for cottonseed oil.The author’s modification of this test (compare A. 1912 ii 1108) may be carried out very rapidly and reveals the presence of small proportions of cottonseed oil in the following manner five to1 six drops of a 1% solution of sulphur in carbon disulpliide and three to four drops of pyridine are added to 5 C.C. of the oil or fat and the liquid heated directly over a flame for four t o five minutes care being taken that the temperature does not exceed 140O. T. H. P. pare A. 1914 ii 816). w. P. s. The Freezing Point of Milk. J. BROWNLIE HENDERSON and L. A. MESTON (Chem. News 1914. 110 259-261 275 283-284 ; from Proc. Roy. Soc. QueenslacncF 24 165).-The freezing point of fresh mixed milk from a herd of cows varies from -0*55O t o -OV56O the average being -0.555O.The constancy of the freez- ing point affords a means of detecting the presence of added water in milk since a rise of 0*005O indicates the presence of about 1% of water. The freezing point is not however a measure of the proportion of total solids or of non-fatty solids in the milk. As the milk becomes acid the freezing point is lowered but the authors are not yet in a position t o state whether any definite relation exists between the depression of the freezing point andANALYTICAL CHEMISTRY. ii. 29 the increase of acidity. Tables are given showing C.C. of added water per litre to milk corresponding with temperatures ranging from -0.55" t o -0.351" for differences of O*O0lo and ths method of determining the freezing point is described in detail.JV. P. S . [Determination of the] Freezing Point of Milk. G. A. STUTTERHEIM (Phacrm. Weekblad 1914 €5 1 131 1-1 313).-A descrip- tion oE a modified form of Beckmann apparatus for the determina- tion of the freezing point of milk (co,miire A. 1914 ii 169 304). A. J. W. Estimation of the Cineole (Eucalyptol) Content of Euca- lyptus Oils. HENRY G. A. HARDING (Analyst 1914 39 475-476). -The resorcinol method (compare A. 1908 ii 233) for the esti- mation of cineole is unt'rustworthy when applied directly t o euca- lyptus oil but better results are obtained by using the fraction of the oil b. p. 170-190°. for the test. Even then the results tend to be too high especially in the case of oils containing more than 50% of cineole. Turpentine has been suggested as a diluent but since it1 contains substances which are absorbed by resorcinol only that portion should be used which distils between 156O and 160O.One hundred C.C. of the eucalyptus oil under examination are dis- tilled the fraction distilling between 170° and 190" is collected separately and diluted t o 100 C.C. with the turpentine fraction mentioned; a preliminary test will show whether further dilution is necessary to reduce the cineole content t o 50%. Ten C.C. of the solution are then shaken in a flask having a graduated neck with a warm 55% resorcinol solution for five minutes a further quantity of the resorcinol solution is then added so as to bring the oil into the neck of the flask and after cooling the volume of the oil is read. w. P. s. Estimation of Camphor and of Certain Essential Oils when in Solution in Alcohol.W. B. D. PENNIMAN and W. W. RANDALL ( J . I n d . Eng. Chem. 1914 6 926-928).-The method proposed depends on the fact that camphor and the essential oils of pepper- mint lemon orange anise and nut'meg are liberated from their alcoholic solution when this is mixed with from four to ten times its volume of concentrated calcium chloride solution and that the separated camphor or oil is soluble in light petroleum b. p. 40-60°. Within certain wide limits the increase in volume of the light petroleum is equal t o the volume of the camphor or essential oil. A measured quantity of the alcoholic solution under examination is mixed in a flask provided with a graduated neck with calcium chloride solution a definite volume of light petroleum is added (about equal t o the volume of the oil to be dissolved) more of the calcium chloride solution is added t o bring the mixtare into the neck of the flask the whole is submitted t o centrifugal action and the increase in volume of the light petroleum noted.W. P. S.ii. 30 ABSTRACTS OF CHEMICAL PAPERS. Detection of Emodin-bearing Drugs in the Presence of Phenolphthalein. L. E. WARREN (Amer. J. Phovm. 1914 86 444-449).-The red coloratioii obtained when emodin is treated witah an alkali cannot be used for the detection of this substance in mixtures also containing phenolphthalein but if the latter is converted into tetraiodophenolphthalein the emodin may be ex- tracted with chloroform and identified by the alkali test.The substance is extractled with acetone or chloroform the extract is evaporated the residue dissolved in dilute sodium hydroxide solu- tion and a slight excess of iodine solution is added. The mixture is then rendered acid with hydrochloric acid the insoluble tetra- iodophenolphthalein is separated by filtration and the filtrate after the addition of sodium sulphite is shaken with chloroform; this chloroform extract is evaporated and the residuel tested with alkali hydroxide solution. I n the case of preparations containing phenolphthalein a faint red coloration may sometimes bet obtained but' this disappears on the addition of an excess of the alkali whilst the coloration given by eniodin is permanent. The emodin colora- tion is of various shades of red according t o the source of the emodin.Except in the case of aloes the method is trustworthy. A method described recently by Bailey (A. 1914 ii 501) was also Estimation of Prussian-blue in Tea. G. W. KNIGHT (J. Z7,d. Eng. Chern. 1914 6 909-910).-The following method is recom- mended for the estimation of very small amounts (say 1 part per 200,000) of added Prussian-blue in tea. One hundred grams of the powdered sample are moistened with 85%. phosphoric acid and distilled until phosphoric acid begins tor pass over the distillate beiBg collected in a receiver containing dilute sodium hydroxide solution. The distillate if acid is neutralised 3 C.C. of 10% sodium hydroxide are added in excess then a small crystal of ferrous sulphate and a few drops of ferric chloride solution and the mixture is boiled for one minute.The solution is then acidified with hydrochloric acid the precipitate collected washed with alcohol and dissolved in a small quantity of sodium hydroxide solution. After this solution has been acidified with acetic acid a few drops of hydrochloric acid and ferric chloride solution are added followed by more hydrochloric acid if necessary. The whole is then evaporated t o about one-half its bulk the precipitated Prussian-blue is collected on a filter washed with dilute hydro- chloric acid water alcohol and ether dried a t looo and weighed. w. P. s. found to yield €rustworthy results. w. P. s. Reactions of Alanine and Glycine. L. CHELLE (Ann. Chim. and 1914 19 67-68; from Bull. SOC. pharrn. Bordeaux 1913).- Ah.nine.-About 10 mg.of the substance are dissolved in water 1 C.C. of glacial acetic acid and 0.5 C.C. of 5% sodium nitrite solu- tion are adde'd and the mixtare is boiled until nitrous vapours cease to appear; 0.1 gram of hydrazine sulphate is then added the solutJon is again boiled and 4 C.C. of concentrated sulphuric acid are added gradually. The resulting solution is divided into threeANALYTICAL CHEMISTRY. ii. 31 portions; the addition of a drop of an alcoholic guaiacol solution to one portion produces a red coloration; a yellow coloration is obtained on treating another portion with a drop of an alcoholic codeine solution whilst the third portion yields an orange colora- tion on the addition of a drop of p-cresol solution. GZycine.-The sulphuric acid solution of the diazotised substance yields a reddish- violet coloration with guaiacol a violet coloration with codeine and a green coloration with p-cresol.The reactions may be Estimation of Morphine. Lloyd’s Reagent. H. 11. GORDIN and J. KAPLAN (Amer. J. Phurm. 1914 86 461-464).- When morphine is extracted from a saturated potassium carbonate solution by shaking with a mixCure eonsisting of equal volumes of alcohol and chloroform the weight of alkaloid found is always too high (from 2 t o 15%); this method of extracting the alkaloid is therefore untrustworthy. Morphine is precipitated completely by Lloyd’s reagent but only about 90% of the alkaloid can be recovered from the precipitate by shaking this with ammonia and methyl alcohol. It is also impossible to recover the whole of the alkaloid from the precipitate formed when Strychnine salts are treated with Lloyd’s reagent ; this strychnine precipitate is tasteless but behaves physiologically like strychnine diluted with an inactive substance ; the decomposition of the precipitate cannot however be brought about by digesting it in vitro with pepsin ptyalin or F.MARINO-ZUCO and C. DUCCINI (Gccnnette 1914 44 ii 437-447).-The toxicology of e’rgot has been the subject of but few investigations which have led to contradictory results. The authors have elaborated the following method for the detection of ergot in viscera a8nd find that it gives trustworthy indications. The alcohol in which the viscera are usually consigned is separated by filtration rendered distinctly acid with tlartaric acid a8nd evaporated on a water- bath until the bulk of the alcohol is eliminated.The finely divided viscera and the sediment on the filter are heated for six hours at 7 5 O with double their volume of 95-960/ alcohol acidified with tartaric acid in a reflux apparatus; the cold alcoholic extract is filtered through new cloth and the residue firmly pressed. This extraction is repeated with fresh quantities of alcohol until the latter ceases t o become coloured the1 combined extracts being then evaporated on a water-bath t o a small volumes. The liquid is mixed with the residue from the alcohol originally present and the remaining alcohol removed by distillation at a low temperature in a vacuum. The reddish-brown turbid syrup thus obtained is dissolved in water and the solution subjected t o prolonged shaking with the twofold volume of ether in a large separating funnel; this operation is repeated with fresh quantities of ether so long as the latter becomes coloured.The ether dissolves the red colouring matter and small amounts of fat whilst the tartrates of any alkaloids present remain in the aqueous solution. The united obtained with 1 mg. of glycine. w. P. s. t r ypsin. w. P. s. Toxicological Investigation of Ergot.ii. 32 ABSTRACTS OF CHEMICAL PAPERS. ethereal extracts arc reduced t o a small volume o n a water-bath a t as low a temperature as possible and the residual liquid filtered if necessary vigorously shaken in an extractor with a small quantity oi cold saturated sodium hydrogen carbonate solution. After a long time the alkaline layer separates and exhibits a ye,llowish-red colour with a faint violet tint o r a distinct violet- red colour if the viscera contained a small or large proportion of ergot.Since this colour reaction may be masked by extraneous colouring matters the extractdon with the alkali is repeated several times and the total extract carefully acidified with concentrated hydrochloric acid and extracted with ether. The ethereal liquids which will have a more or less intense orange-yellow colour are evaporated to a small volume and the residual liquid is examined speckroscopically; in presence of the red colouring matter of ergot three absorption bands with h = 538 499 and 467 respectively are observed. Prior to the spectroscopic examination it is well to repeat the extraction with sodium hydrogen carbonate acidifica- tJon and extraction with ether a t least five o r six times in order to obtain a sufficiently pure ethereal solution of the colouring matter.The aqueous tartaric acid liquid remaining after the extraction with ether is rendered distinctly alkaline by means of saturated sodiun; carbonate solution and the liberated alkaloids dissolved by shaking several times with ether. The faintly yellow ethereal solution is concentrated Lo a m a l l volume a t as low a temperature as possible the residue being washed with a little water in which ergotinine is insoluble. The ergotinine is then either purified by Tanret’s method (A. 1878 679) or converted into its citrate by shaking the ethereal liquid several times with aqueous citric acid; the aqueous solution of the citrate is rendered distinctly alkaline by addition of sodium carbonate and the ergotinine extracted with ether. Keller’s reaction for ergotinine is next applied in the following manner. The residue left on gentle evaporation of the ether is heated slightly on a water-bath with 2-3 C.C. of 8 0.1% solution of ferric chloride in glacial acetic acid. The cold liquid filtered if necessary is placed in a testrtube and 2-3 C.C. of con- centrated sulphuric acid slowly introduced. I f ergotinine is pre- sent a blue ring appears at the surface of separation of the two liquids and the upper layer assumes a violet colour. If Keller’s reaction gives negative results the ethereal liquid which was ex- tracted with aqueous citric acid should be evaporated and the residue subjected to the same test. The above method has always been found to give certain results provided that the amount of ergot present is not less than 1 gram and that the examination of thO viscera is carried out not later than seven days after the interment of the body. Advanced putre- faction of the viscera alters the colouring matter so profoundly as to prevent its recognition. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9150805020

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

ii. 33 General and Physical Chemistry. The Ideal Refractivities of Gases. WILLIAM JACOB JONES and JAMES RIDDICK PARTINGTOX (Phil. Mag. 1915 [vi] 29 28-35).-A full account of work of which an abstract has already appeared (P. 1914 30 201). The Magnetic Field of an Atom in Relation to Theories of Spectral Series. H. STANLEY ALLEN (Phil. Mag. 1915 [vi] 29 40-49).-On the assumption that the atom may be regarded as a central core carrying an electric charge and producing a mag- netic field similar to that due t o an elementary magnet the core being surrounded by electrons in orbital motion it is shown that a formula for the distribution of lines in spedral series may be derived which is of the same type as the Ritz formula. The energy of radiation as in Bohr’s theory is supposed to be given out in quanta which represent the differences between the energies in two steady st’ates of motion.From a consideration of the numerical values of the constants in the derived formula i t is found however that the magnetic forces set up by the atom are insufficient to account f o r more than a small fraction of the effect that would be necessary t o give the observed distribution of lines in spectral series. The Series Spectrum of Hydrogen and the Structure of the Atom H. STANLEY ALLEN (Phil. Mag. 1915 [vi] 29 140-143. Compare Curtis A 1914 ij 761).-According to) the measurements of Curtis the series lines of hydrogen cannot be exactly represented by Balmer’s formula. An attempt has been made t o ascertain whether the inclusion of the effect of a magnetic field (compare preceding abstract) would lead t o results in agreement with observation.The result of this inquiry shows that it is possible to’ account for the series spectrum of hydrogen on the lines of Bohr’s theory if i t is assumed that the core of the atom can pro- duce a magnetic field equivalent t o that set up by either five or six magnetons. I n support of the number 5 is the fact that the mag- netic moment produced by an electron moving in a circular orbit with angular momentum h/2n is exactly 5 magnetons. On the other hand tlhe hypothesis of a core of 6 magnetons appears to be supported by the diamagnetic properties of hydrogen. Spectroscopic Investigations in Connexion with the Active Modification of Nitroger. IV. A Band Spectrum of Boron Nitride WILFRED JEVONS (Proc.Roy. Soc. 1915 [ A ] 9 1 120-134. Compare A. 1913 ii 813).-When the vapour of boron trichloride is introduced into active nitrogen a very pale bluish-green glow is obtained the d o u r of this being very readily distinguishable from the vivid green of the boron flame. The investigation of the spec- H. M. D. H. M. D. H. &I. D. VOL. CVIII. ii. 3ii. 34 ABSTRACTS OF CHEMICAL PAPERS. trum of the glow has shown that i t consists of the three boron lines A 3451'50 h 2497.83 and A 2496.89 and of a new system of bands with well-defined heads degraded towards the red end which extend from A6371 to at least h2140. The same band spectrum is obt'ained when methyl borate is allowed to come in contact with active nitrogen. Analysis of the spectrum indicates that it contains two distinct systems in the less refrangible of which each band consists of four heads forming two close doublets whilst the more refrangible system is characterised by single-headed bands and thus resembles the band spectrum of silicon nitride described in a previous paper.These bands are not observed in a vacuum tube containing the vapour of boron trichloride and evidence has been obtained that the band spectrum is duel t o boron nitride. Boron carbon and silicon com- pounds behave similarly therefore in that all give rise t o nitride spectra in the nitrogen after-glow. The boron nitride bands like the cyanogen bands are produced in the arc spectrum where they occur together with the headless wavy bands of the oxide. Measurements of the wave-lengths of the heads of the bands are recorded and formulz have been deduced t o represent them.H. M. D. The 8pectrurn of Palladium. EMIL PAULSON (Phil. Mag. 1915 [vi] 29 154-157).-A discussion of the relations exhibited by the wave-numbers of lines in the palladium spectrum. It is shown that a large number of lines fall into four vertical groups the corre- sponding members of which exhibit constant differences in the wave-length numbers. Denoting the four groups by A B C and D the wave-numbers of these lines are represented by the relations B=A+ 1628'33 C=A+3968.00 B=d 4-5159-14. The Absorption Spectra of Organic Substancee in the Light of t h e Electron rheory. N. P. K. J. O'N. MCCLELAND (Phil. Mag. 1915 [vi] 29 192-206).-A theory of absorption is put forward which is based on certain views relative t o the constitution of the atom and it is claimed that this theory makes it possible t o predict with reasonable accuracy the positions of the absorption bands of organic compounds from the constitution when certain fundamental constants are given.I n the model of the atom from which these results are obtained i t is supposed that the valency electrons move in circular orbits round a central nucleus. The radius of the orbits is influencled by the mode of combination of the atoms in the mole- cule and when light is allowed t o act on the system the electrons are caused t o vibrate in their appropriate orbits. Since an electron moving in an orbit represents an electric current the vibrations of one will affect those of another in accordance with the laws of electrodynamics and the problem of ascertaining the position of an absorption band is therefore reduced t o compounding such vibrations by the mutual induction method.The method is applied t o a number of different systems contain- ing respectively one two three and four vibration centres and H. M. D.GENERATJ AND PHYSICAI; CHENISTRY. ii. 35 also to the benzene system in which there are six identical vibra- tion centres arranged in a ring. Other atomic systems correspond- ing with more complex aromatic compounds are also briefly coil- sidered. I n this way a number of constants have been derived with the aid of which it has been possible t o locate the positioii of the absorption bands in a considerable variety of organic corn- pounds.Except in the case of very complex substances the diner- ence between the observed and calculated positions is as close as can be expected. Quantitative Meaaurements of the Absorption of Light. I. The Molecular Extinctions of the Saturated Aliphatic Ketones. PRANCIS OWEN RICE (Proc. Roy. SOC. 1914 [ A ] 91 76-42. Compare Stewart and Baly T. 1906 89 489).-The ultra-violet absorption of fourteen saturated aliphatic ketones has been investigated. I n most cases the ketones were purified by conversion into the bisulphite compounds in others by transformation into the semi- carbazones. The experimental data show that the wave-lengths of the centres of the absorption bands depend on the number of methyl groups in the u- and @-posit'ions relative to the carbonyl group.Snbstitu- tion of hydrogen atoms in the y or further positions has no influence on the position of the band. For ketones of the general formula C€I,*CO*CW,-CH,R in which R is a saturated alkyl radicle the position of the centre of the band is a t ~ 2 7 9 0 and for those represented by the formula RCH,*C1FI,*C0.CH,*CH2R the centre is a t A 2820. The substitution of an a-hydrogen atom by methyl causes the centre of absorption t o shift towards the red and from the data for acetone methyl ethyl ketone methyl isopropyl ketone and pinacolin i t is found that the shifts corresponding with the successive substitution of the three a-hydrogen atoms are 23 50 and 30 Angstrom units respectively. The author considers that these measurements show the existence of a relationship between the optical and the chemical properties.The general results exhibit a certain parallelism with the observations on Lhe magnetic rotation of the ketones for whereas the magnetic rotatory power is normal in the case of methyl isopropyl ketone and the higher homologues it is abnormal for methyl ethyl ketone and still more abnormal for acetone. Spectrophotometric measurements of the extinction-coefficient (E) have also been made and these data show that the molecular extinctdon M=E/c where c is the molar concentration of the ketone has the same value (21.2) f o r all the ketones examined with the exception of acetone and methyl ethyl ketone. Moreover the molecular extinction curves are1 absolutely identical for ketones of the general formula CH,*CO*CH,-CH,R whilst f o r the remainder excepting acetone and methyl ethyl ketone the curves are geo- metrically similar. On the assumption that the smaller absorption power of acetone is due to association the author obtains 1.24 f o r the association €1.M. D. 3-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. factor. This is in close agreement with the value 1.26 derived from the temperature-coefficient of the molecular surf ace energy. I n a similar way the association factor of methyl ethyl ketone js found t o be 1.09. The observations are said t o be in agreement with the theory that' the ultra-violet absorption is due to the electromagnetic field of the carbonyl group as influenced by the substituents in the immediate neighbourhood. H. 11.D. Coloration of Some Derivatives of Picrglmethylamine with Alkalis. A. P. N. FRANCHIMONT and H. J. BACKER (Proc. K. Akad. Wetensclh. Amstsrdarn 1914 17 647-653).-1n continuation of an investigation of the colour of picrylalkylnitroamiiies (A. 1914 ii 84) the authors have investigated the absorption of alcoholic solu- tions of a number of derivatives of pirrylmethylamine of the general formula C,H,(NO,),*NMe*X i n wliich X represents one of the groups KO COMei C02Me CO,Et C,H,. As was found in the case of the nitro-group the nitroso- and the acyl-groups greatly diminish the colour of picrylmethylamine and according t o the absorption curves the absorption bands a t 1 / A = 2390 and 2875 com- plet'ely disappear. The same effect is observed if picrylmethyl- amine is dissolved i n concentrated sulphuric acid.On addition of alkali the absorption curves for the acyl deriv- atives show well-marked bands with their heads a t about l/h=2000 and 2350 which are therefore practically identical with the bands exhibited by picrylmethylnitroamine. Plienylpicrylmethglami~~e in the absence of alkali shows an absorption in this region but the addition of alkali intensifies the absorption? and the curve for the alkaline solution shows maxima a t l/h=2070 and 2400. The ebsorption curve for picrylmethylnitrosoarnine in alkaline solution indicates that it is rapidly decomposed with the formation of the picrate of the alkali metal. The same change occurs with the acyl derivatives but much more slowly. The authors consider t h a t the absorption.bands are due to the interaction of the base with one o r more of the nitrogoups of the benzene nucleus. Confirmation of the Law of Bunsen and Roscoe for the Photochemical Reaction of Hydriodic Acid. E. JIrYrENo GIL (Anal. Fis. Quim. 1914 12 534-539).-8 fitudy of the photo- chemical oxidation of hydriodic acid. The results are in agreement with the law of Bunsen and Roscoe it=const. in wliich i repre- sents the intensity of the illumination and t its duration. Both an electric arc and a mercury vapour lamp were employed as the source of light. Organic Syntheses by means of Sunlight. XI. General Considerations. E. PAT ERN^ (Gazxettct 19 14 44 ii 463-475)- The author mrns up in general terms the results of his investi- gations on this subject during the past' six years.The principal types of readion observed t o occur under the influence of sunlight are as follows 11. &I. D. A. J. W.GENERAI AND PHYSICAL CHEMISTRY. ii. 37 (1) Carbonylic compounds such as aldehydes and ketones react on olefinic hydrocarbons with rupture of the double linking of the latter and formation of the closed-chain trimethylene oxide and its derivatives This so-called trimethylenic condensation takes place generally but not universally and does not occur with oxygenated compounds other than aldehydes or ketones. (2) Ketones react with aromatic hydrocarbons and other aromatic compounds thus 2C,,H1,0 + 2C,H,Et -+ C,,H,,02 + CHPhMe-CHPhMe the ketone undergoing reduction t o pinacone. This doubling of the carbon atom chain takes place also with such compounds as P-phenylpropionic acid which forms j3 y-diphenyl- adipic o r ap-dibenzylsuccinic acid.I n no instance has the1 author been able to prove the union of two aromatic nuclei in this way (see A. 1914 ii 321; Ciamician and Silber A. 1912; i 537). (3) Between ketones and aromatic hydrocarbons and other aromatic compounds a second reaction occurs at the same time as and perhaps more generally than the preceding one. In this direct addition takes place with formation of a tertiary alcohol benzophenone and phenylacetic acid f o r example yielding aflfl-triphenyl-lactic acid. This change termed enolic condensa- tion takes place principally between the carbon of the ketonic carbonyl and the methylene group the aromatic nuclei playing no part. Enolic condensation is observed also between bases and ketones benzophenone giving with benzylamine the compound OH*CPh,*CHPh*N€I with nicotine a new alkaloid C,,H13N CP h 2* 0 €1 and with p-toluonitrile the compound OH*CPh2*CH,-C6H,*CN.(4) Further ketones react with hydrocarbons more especially with the paraffins and with some of their derivatives in a manner which has not yet been clearly characberised (compare A. 1909 i 240) but probably consists in the conversion of two mols. of the ketone into pinacone and the union of a third molecule of ketone with one of the paraffin t o form an oxytrimetliylene coinpoutid 3C,3Hlo0 + C,H +2 = CU,,H,,O + C'lsHl,O:C,H,,,. This reaction is given also by cyclic hydrocarbons and by ethers acetals and similar compounds. The formation of numerous synthetlic resins the preparation of colloidal substances from sparteine and from strychnine the trans- formation of pyrone into a carbohydrate similar t o the pentosans the formation of nitrogenous organic compounds by the reduction of nitrates the synthesis of photo-acetophenone and its analogues and the possibility of introducing complex side-chains into the molecules of the vegetable alkaloids with formation of derivatives of pharmacological applicability are all important points resulting from the author's investiga.tions.T. H. P. Reduction of Aromatic Ketones. 111. Photochemical Phenomena. J. BOESEKEN and W. D. COHEN (Proc. K. Akad Wetensch. Amstevdaml 1914 17 849-870. Campare A. 1913 i 1062).-The reduction of an aromatic ketone in a perfectly neutralii.38 ABSTRACTS OF CHEMICAL PAPERS. medium dom not proceed any further than t o the pinacone. A series of ketones dissolved in a great variety of anhydrous alcohols and a few other substances have been exposed t o sunlight or t o the light of a mercury lamp; in all cases where reduction occurs not a trace of the hydrol is formed the ketones being quantita- tively changed to the pinacones. The addition of sodium ethoxide to the alcoholic solution results in the formation of the hydrols as is t o be expected (Zoc. cat.). The authors deduce therefore that in the reduction of aromatic ketones the hydrogen unites ex- clusively with the oxygen ; the resulting half-pinacoiie polymerises to the pinacone and the latter in the presence of hydroxyl ions is transformed into an equal molecnlar mixture of the ketone and the hydrol.Water acts as a powerful negative catalyst; in 80% alcohol reduckion of benzophenone does n o t occur after exposure for months whereas in absolute alcohol under the same conditions 40% of benzopinacone is obtained after ten hours. The reduction of benzophenone has been investigated in methyl ethyl propyl isopropyl isobutyl mheptyl sec.-octyl hexadecyl allyl benzyl and cinnarri yl alcohols in geraniol cy clohexanol benzhydrol and in fl-methylbutan-fl-ol y-methylpentan-7-01 and 6-methylheptan-8-01. Reduction does not occur in hexadecyl or cinnamyl alcohol proceeds very slowly in the last. three alcohols and in geraniol; and takes place rapidly and quantitatively in the saturated alcohols ; the reaction in methyl alcohol however (and also in allyl alcohol) is milch slower than in the other primary and secondary alcohols.Under the influence of light toluene or cyclohexane reduces benzophenone whilst hydrogen itself does not. By employing a constant source of light and allowing this to act on the different solutions under the same conditions relatively quantitative results are obtained. The experiments lead t o the following generalisations. The velodity of pinacme-f ormation appears to be independent of the concentration of the benzo- phenone and proportional t o that of the alcohol. The temperatare- coefficient is small 1*06-1+11 per loo. The velocity is greatly dependent on the ketone; benzophenone is attacked rapidly most of the other aromatic ketones as yet examined are reduced less rapidly and many of them are not reduced a t all..The ratio of the velocities of pinacone-form ation in different alcohols is constant. The ratio of the velocities of pinacone-forniation in sunlight and in the light of the mercury lamp is the same. When two ketones are present in one solution one of them absorbs a part of the rays required by the other; the same is true when the light passes through a solution of the one ketone and falls on that of the other. The light which is active in the reduction of aromatic ketones is situated in the spectrum between 400 pp and 430 ,up and very probably in o r adjacent to the rays 404'7pp and 407.8pp of the mercury lamp. c. s.GENERAL AND PHYSICAL CHEMISTRY. ii. 39 Acquired Radioactivity.SIR W ILLJAM CROOKES (Phil. Trans. 1914 [ A ] 214 433445).-Experiments extending over several years are described on the action of radium and its emanation on various substances with especial reference t o the diamond. Bom- bardment of a large number of crystals and phosphorescent sub- stances by cathode rays in a vacuum confers no radioactivity on them and the substance both t o electrical and photographic tests remains inactive. The phosphorescence of the diamond under the action of radium is due to the P- and y-rays but these produce no coloration. Placing a diamond in contact with a radium com- pound for long periods produces a coloration usually bluish-green which is an effect of the a-rays. Diamonds so treated acquire an enduring activity in which no apparent diminution occurs after ten years and neither the colour nor the radioactivity is removed by long treatment with a hot mixture of potassium chlorate and nit'ric acid.After being cut the diamond became quite colourless and free from radioactivity. Experi- ments with glass quartz and other materials buried in radium preparations for long periods and deeply coloured by the action of the rays showed that the diamond behaves differently from other substances and alone retains its acquired radioactivity after chemical treatment. Lead glass so treated became almost inactive after boiling in dilute nitric acid but diamond retained the greater part of its activity after boiling with fuming nitric acid mixed with potassium chlorate. A difference also appeared in the distribution of the radiations from the surface.A quartz crystal rendered radioactive and laid on a photographic plate gave an image of the geometric pattern arising from the superficial activity of the kind studied by Rutherford but the image from a radioactive diamond suggested rather a brush discharge from the corners of the crystal. The activity so acquired consists of u- P- and y-rays. F. S. Application of the Theory of Allotropy to Electromotive Equilibria. 111. A. SMITS and A. H. W. ATBN (PY~Jc. K. A h d . 1f%tansch. Amsterdam 1914 17 680-694. Compare A. 1914 ii 165 420 611).-The theory of allotropy described in previous papers is applied in explanation of the phenomena of electrolytic polarisation and of the passive condition of metals. Experiments are described which are said t o support the view that the seat of the polarisation effects and of the passivity is not in the boundary layer separating the metal and the electrolytle solution but in the surface of the metal itself.For the most part the observations consisted in measuring the changes in the E.M.F. of cells of the type :-metal 1 salt solution [ calomel electrode after the metal had been subjected t o the action of acids of anodic or cathodic polarisa- tion or of bromine water. The metals used were cobalt nickel iron and chromium which according to previous experiments are characterised by the slow rate a t which the internal equilibrium is re-established when this equilibrium in the surface layer of the metal has been disturbed by electrolytic o r chemical action.ii. 40 ABSTRACTS OF CHEMICAL PAPERS.Under the influence of the above-mentioned agencies the four metals investigated become distinctly less electropositive as would be expected according to the theory put forward by Smits. Of particular interest are some of the observations made with iron. After anodic polarisation and after etching with strong nitric acid t'he potential difference between iron and 0.W-ferrous sulphate solution decreases fairly rapidly then remains constant f o r a time before beginning t o fall again. The temporarily constant pot,ential difference has the same value whether the passivity of the metal is brought about4 by anodic polarisation or by the action of strong nit'ric acid. It is claimed that none of the older views on passivity affords such a satisfactlory explanation of the observed facts as that which is based on the theory of allotropy.I n certain respects Finkel- stein's theory offers a certain resemblance t o the theory put for- ward by the authors but there is a fundamental difference between the two. Whereas Le Blanc's theory considers that passivity is determined by retardation of the process of ionic hydration the new theory attributes the effect t o retardation of changes occurring in the surface layer of the metal. H. M. D. Allotropy of Cadmium. IV. ERNST COHEN and W. D. HIELDERMAN ( PYOC. K. Akccd. Wetensch. Amsterdum 1914 17,638-641. Compare A. 1914 ii 652).-As a result of the examination of a large number of cells arranged according to the scheme electrolytic cadmium 1 cadmium sulphate solution 112.5% cadmium amalgam it has been found that some show an E.1M.F.a t 25O of 0.050 volt o'thers 0.048 volt and others again 0-047 volt. The E.M.F. of cells of the first group decreases spontaneously to 0.048 volt a t which value the E.M.P. remains constant. I n the expectlation that cells giving 0.048 volt would be found to contain &cadmium and those giving 0.047 volt a-cadmium two such cells were examined at' 2 5 O and 64.5O. The two cells were connected up so as to have an amalgam electrode in common and readings were taken until the E.M.F. became constant. The final readings show that the cell with the lower E.M.F. a t 25O has the higher E.H.F. at 64.5O. From this observation the authors draw the conclusion that the E.N.F.of 0.048 volt corresponds with P-cadmium; i t is also probable that the cell giving 0.047 volt contains a-cadmium and that giving 0.050 volt y-cadmium. H. M. D. Electro-deposition of Lead. F. C. MATHERS and B. W. COCKRUM (Met. and @hem. #fig. 1914 12 714-715; from J. SOC. Chem. Ind. 1914 33 1158-1159).-A smooth finely crystalline deposit of lead is obtained as follows. Twelve and a-half grams of aloes are shaken with 500 C.C. of warm water and the insolubls gum o r tar is dissolved in 25-50 C.C. of glacial acetic acid. The acid solution is added to thel bath which contains 100 grams of lead acetate and 40 grams of ammonium perchlorate per litre. AGENERAL AND PHYSICAL CHEMISTRY. ii. 41 current density of 3.6 amperes per sq. f t . for thick deposits and 7-2 amperes per sq.f t . for thin deposits may be used. With lead lactate or formate solutions the baths should contain 4% af lead as lactate or 2% as formate 1-576 of lactic or formic acid 4% of ammonium perchlorate and 0.25./; of Barbadoes aloes the mixture being warmed and filtered before use. A current density of 3.6 amperes per sq. f t . may be used. Sodium naphtha- lenesulphonate may be used instead of ammonium perchlorate. c. s. Hermann's Phenomenon. GEORGE STANLEY WALPOLE (PYOC. Roy. Xoc. 1915 [ A ] Q1,134-147).-1t has been shown by Hermann that when a current is passed from a dilute solution of a salt t o one more concentrated acid is liberated a t the boundary layer and that alkali is set free a t the same place when the current is passed in the opposite direction.These observations have been confirmed and extended by the author. The experiments were made with a special form of transport apparatus designed to facilitate the formation and investigation of the boundary layers. The results obtained show that the quantities of acid and alkali liberated bear no relation t o the quantity of electricity passed through the circuit. For all the neutral salts examined the acid is always liberated when the current passes from the more dilute to the more concentrated solution and the alkali when the current passes from the concen- trated t o the more dilute. Other conditions being the same the same quantity of acid and alkali is liberated whatever neutral salt is present in the solutions. The explanation suggested for this phenomenon is based on the difference in the velocity of the hydrogen and hydroxyl ions on opposite sides of the boundary layer.This difference is determined by the fall of potential per unit length which depends essentially on the conductivity of the two solutions. The quantities of acid and alkali set free can be calculated from the potentiad gradients in the two1 sclutions the time for which the difference of potential is maintained the resistance constant of the apparatus the dis- sociation constant of water and the mobilities of the hydrogen and hydroxyl ions. Actual experiments afford numbers which are in approximatie agreement wit'h the calculated quantities. H. M. D. Luminous Vapours Distilled from the Arc with Applications to the Study of Spectrum Series and their Origin.11 Hon. R. J STRUTT (Proc. Roy. Soc. 1914 [A] 91 92-103. Compare A. 1914 ii 599).-The vapour of mercury distilling from the arc into a vacuum exhibits luminosity when the vapour has traversed con- siderable distances beyond the range of the electric field of the arc. The luminosity may be caused t o disappear by application of an independent electric field and the' experiments described by the author were made in order t o elucidate the nature of this effect in mercury and certain other meballic vapours.ii. 42 ABSTRACTS OF CHEMICAL PAPERS. From experiments in which the conducting properties of the luminous jet were examined by means of an auxiliary electrical circuit it is found that the conductivity depends essentially on the shape and position of thel cathode and is independent of the position of the anode. The fall of potential is almost completely confined t o the immediate neighbourhood of the cathode.These facts indicate that the electrical properties of the glowing vapour are similar t o those of a flame which is characterised by the great mobility of the negative ions compared with the positive. The luminosity is not affected when the stream of mercury vapour passe6 the anode but is more or less completely quenched whm it reaches the cathode. AltJiough the removal of negative ions at the anode is incomplete it is considerable enough t o show conclusively that the luminosity is independent of the number of negative ions present. It lolloms from this that the luminous emission is not due t o recombination of ions and it is supposed that the luminous centres are positively charged ions which are survivors of those which are generated in the arc itself.Since the time required for the vapour to travel down the tube is of the order of 1/1000 of a second it must be assumed thab the ions remain luminous for what must be considered as a very consider- able interval of time. Experiments with the vapours of sodium potassium calcium magnesium zinc cadmium and thallium have also shown that the line spectra are extinguished when the luminous vapour passes through a negatively electrified net. I n some cases (sodium mag- nesium zinc) the lines of one series are more easily extinguished than those of another. Thus the sodium lines of the subordinate series are all influenced to about the same extent but thO D-line is much less affected.From this it is inferred that the centres of emission are not the same for the two series of lines. The luminous jets formed by arsenic and antimony are not quenched by passing through a negatively electrified net. The band spectrum exhibited by these elements is therefore pre- sumably due to uncharged centres whilst the band spectrum of magnesium hpdride is apparently emitted by positively charged centres. H. M. D. Emiesivity of Metals and Oxides. 11. Measurements with the Micropgrometer. GI-. K. BURGESS and R. G . WALTENBURG (J. Wushingto?z Acad. Sci. 1914 4 566-567).-1t has been found t h a t the micropyrometer described in a previous paper (ibid. 1912 3 No. 7) may be empIoyed for the determination of the mono- chromatic emissivities of substances in very small quantities (of the order of 0.01 gram) with an accuracy of about 1%.The data obtained with red light of wave-length h=O*65 p and h=0*55 p are recorded for a number of metals and metallic oxides the emissive powers being compared with that of solid platinum. The temperatiire-coefficient of the emissivity is very small for all the metals investigated and for most this coefficient is negligible. I n the case of the white metals the emissive powerGENERAL AND PHYSICAL CHEMISTRY. ii. 43 shows very little or no change a t the melting paint but there is a marked discontinuity for gold silver copper and uranium. The behaviour of palladium is anomalous in that the emissivity proper t o the liquid may persist after solidification thus affording an instance of an undercooling radiation effect).The fact that platinum shows a change in emissive power on melting is of some consequence since the Violle standard is usually defined in terms of the luminous radiation from platinum at its nielting point. H. M. D. Experiments with Liquid Helium. Preliminary Determina- tion of the Specific Heat and the Thermal Conductivity of Mercury at Temperatures Obtainable with Liquid Helium and Meamremeots of Thermo-electric Forces and Resistances for the Purpose of these Investigations. H. KAMERLINGH ONNES and G. HOLST (Proc. K. Akad. Wetensch. Amsterdam 1914 17 760-767. Compare A. 1914 ii 832).-As a reault of the investigation of a number of thermo-electric couples it is found that these are un- suitable for the measurement of temperature at liquid helium temperatures. I n accordance with theoretical anticipations the thermo-electric power of all the couples investigated approaches zero a t helium temperatures.On the other hand it is found that satisf actory measurements of temperature may be obtained with resistance thermometers of manganin and constantin. The apparatus employed in the measurement of the specific heat of mercury was similar t o that described by Nernst (A 1910 ii 263). The value obtained wzs 0.00142 f o r the mean specific heat between 4.26* and 6'48O (abs.) and 0.000534 between 2 * 9 3 O and 3-97O (abs.). By making use of Debye's formula for the variation of the specific heat c with the temperature 21 c=kT3 in which k is a constant the authors' data are compared with the results obtained by Pollitzer a t higher temperatures.It is found in this way that the specific heat a t helium temperatures cannot be satis- factorily represented by the formula in question. The measurements of the thermal conductivity gave k = 0.27 between 4.5O and 5*1° (abs.) and 0'40 between 3 ' 7 O and 3 . 9 O (abs.). No evidence of the discon_tinuity which is shown by the electrical conductivity olf mercury a t 4*19O (abs.) was found in the case of the specific heat or of the thermal conductivity. H. M. D. Heat of Fusion and the Periodic System. JULIO GUZMBN CARRANCIO (Anal. Pis. Quim. 1914 12 526-534).-The results of experiments on the heat of fusion of the elements indicate that the heat of fusion per gram is a periodic function of the atomic weight and for analogous elements of the same group of the periodic system decreases with increase of atomic weight.A similar periodicity is displayed by the quotients obtained by dividing the absolute temperatures of fusion by the atomic weights. The atomic heats of fusion do not exhibit a corresponding periodicity. A. J. W.ii. 44 ABSTRACTS OF CHEMICAL PAPERS. The Correction of about 1/66 in the Determination of the Freezing Point of Dilute Aqueous Solutions Supercooled by lo M. C. DEKHUYZEN (Chem. Weekblad 1915 12 24-28).-The author advances arguments and experimental evidence in support of his contention that a correction of about 1/66 should be de- ducted from the reading in cryoscopic determinations with aqueous solutions.The correction must be determined for each apparatus independently and the volume of solution employed should be 15-20 C.C. A. J. W. Determination of Vapour Tensions at Low Temperatures. E. JIMENO GIL (Anal. Pis. Quint. 1914 12 469-4S2).-An account 07 results obtained in the determination of vapour tension a t low temperature. The values obtained for each substance a t the highest and lowest point of observation on the absolute scale are ethyl alcohol 0*00126 (173.1O) and 0.8349 (243.1O) ; ethyl ether 0.005156 ( 1 6 0 . 1 O ) and 0.6963 ( 1 9 5 . 1 O ) ; toluene 0.00170 (183*1°) and 0.8937 (246'1O) ; acetone 0.00837 (18O*lo) and 0.8763 ( 2 1 2 - 1 O ) ; methyl acetate' 0.00354 (138*1°) and 0.6240 (213.1O). A. J. W. Variation of the Triple Point of a Substance with Hydro- static Pressure. ALFRED W.PORTER (Phil. Ma3. 1 915 [vi] 29 143-149).-Since the saturation vapour pressure of any liquid or solid is a function of the hydrostatic pressure it follows that the triple point will vary with change in the hydrostatic pressure. It is shown t h a t the variation of the triple-point temperature with hydrostatic pressure is equal t o the corresponding change of the melting point. Under atmospheric pressure the triple point is therefore identical with the melting point. 33. 14. D. The Surface Tension of Molten Metals. SYDNEY W. SMITH (J. Inst. Metah 1914 12 168-213).-The method used is that of measuring the depression in a capillary tube electric light carbon. Ths metal is melted in a plunibago crucible in an electric furnace a reducing atmosphere being maintained. The level is measured by means of an insulated steel wire which is lowered vertically into t;be carbon tube by a micrometer depth gauge until an elec- trical contact is made.The results are sufficiently concordant. The metals examined are mercury tin bismuth lead zinc anti- mony aluminium silver gold and copper. The1 surface tension of molten metals is a periodic function oE their atomic weight metals with the largest atomic volumes having the least surface tensions. The metals which are known to have the greatest effect in lessening the cohesion of gold are those which are nearest to' gold in atomic weight but with much larger atomic volumes and therefore lower surface tensions such as lead and bismuth.The effect of other metals in dilute solution on the surface tension of mercury is also a periodic function of their atomic weight (Schmidt A. 1913 ii 190). C . H. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 45 Coefficient of Diffusion in Dilute Solutions. BASIL W. CLACK (Proc. Physical SOC. London 1 9 14 2 7 5 6-68).-The apparatus described in previous papers (ibid. 1908 21 863 ; 191 1 24 40) has been improved with the result t>hat accurate measurements of the diffusivity of salts in aqueous solution can now be obtained in a few days. The special feature of the apparatus consists in the suspension of flasks filled with the solution under examinatioii from the arms of a delicate balance in a large volume of water the t’emperature of which is kept consbant. Each flask is fitted with a battery of narrow tubes through wliich the salt diffuses upwards.The diffusion tubes attached t o t’he two flasks are of equal length but differ considerably in sectional area and ail arrangement is provided whereby the concentration of the solution is kept constant a t each end of the tubes. The actual maiiipula- tion during the process of diffusion consists in determining the rate of change in weight of the flasks which in the improved apparatus attains a constant value after a very short time. It is in fact possible t o obtain fairly accurate values for the coeficient of diffusion in experiments which only last one day. The results obtained show that a t 18O the coefficient of diffusion A?. 105) for potassium chloride increases from 1.388 in 0.05.N- solution t o 1.584 in 2*ON-solution; for potassium nitrate it de- creases from 1.453 in 0.05~7~- to 1.190 in 1’ON-solution; and for sodium chloride i t increases from 1.165 in 0*05.iV- to 1.253 in 2 O N - solution. H.31. D. W. J. JONES and J . R. PART- INGTON (Phil. Mag. 1915 [vi] 29 35-40).-The authors discuss the question of the influence of surface energy on the solubility of solids in liquids and on the formation and stability of super- saturated solutions. The’ theoretical argument indicates that the size of ‘(active ” particles of solid that is such as induce crystal- lisation in a given solution decreases with fall o r rise of tempera- ture according to whether the solid dissolves in its nearly saturated solution with absorption or development of heat.The spontaneous crystallisation of supersaturated solutions of the first more fre- qucntly occurring type when these are cooled below a certain temperature is attributed to this reduction in the size of the ‘( active” particle. At a sufficiently low temperature it may be assumed that the necessary size is only a relatively small multiple of the size of the molecule of the dissolved substance. The Widmanatkitten Structure in Alloys and Metals. N. T. BELAIEW (J. Inst. Net& 1914 12 46-55).-The Widman- statt’en structure which is characteristic of meteorites is not’ con- fined to alloys of iron. It may be produced either by transforma- tions in the solid state o r by crystallisation from solid solution. Several examples are given. The Metastable Continuation of the Mixed Crystal Series of Pseudo-Components in Connexion with the Phenomenon of Allotropy.A. SMITS (Proc. K. Bkad. Wetsnsch. Amaterdarn 1914 17 672-678. Compare A. 1914 ii 546).-A theoretical paper in A Theory of Supersaturation. H. M. D. C. H. D.ii. 46 ABSTRACTS OF CHEMICAL PAPERS. which the author discusses the transition from monotropy t o enantiotropy under the influence of pressure. It is also shown that a system which shows no sign of phase allotropy under its own vapour pressure’ may become monotropic when the pressure is raised and that’ enantiotropy may be exhibited a t higher pressures i n the absence of monotropy under the characteristic vapour pressure of the system. H. 3%. D. Gas Equilibria and a Test of van der Waals’ Formula.I. F. E. C. SCHEFFER (Pvoc. K Akad. Vetmzsch. Amsterdam 1914 17 695-703).-The formulz for the equilibrium constants of gaseous systems derived by van der Waals Sackur and Tetrode have been examined by reference t o the data for the system I 21. Or1 the assumption that the iodine molecule is represenbed by two spheres the masses of which are concentrated in centres separated by a distance d these formulz give limiting values for d equal t o 1.6 x 10-8 and 0.7 x 10-9 cm. van der Waals’ formula which takes into account the variability of the specific heat with the tempera- ture yields for the atomic distance d=0.82 x 1 0 - 8 cm. H. M. D. Unmixing in a Binary System for which the Three-Phase Pressure is Greater than the Sum of the Vapour Tensions of the Two Components.F. E. C. SC‘HEFFER (Proc. K. Akad. Vetensch. Amsterdam 1914 17 834-839).-1t has been shown previously (A. 1914 ii 40) that the three-phase pressure in the system hexane-water is greater than the sum of the vapour pressures of the pure components when the temperature is not far removed from the critical solution temperature. Further investigation of liquid pairs has shown that the same behaviour is exhibited by I f normal pentane” (a mixture of n- and iso-pentane) and water and also by benzene and water. The difference f o r the first pair increases from 0.4 atmosphere a t 150° t o 1.8 atl 187.1° which is the critical end-point. For the second pair the difference increases from 0.45 atmosphere a t 210° to 2.95 a t 267.8O (critical end-point). It is supposed t h a t the relation in question is characteristic OF systems f o r which the critical end-points are lower than the critical temperatures of the two components.Binary systems f o r which the critical end-point falls between the critical tsmperatures of the components do not exhibit the above relationship according t o the data which are available for examination. For such systems the three-phase pressure is less than the sum of the vapour pressures of the components. Equilibria in Ternary Systems XVII. F. A. H. SCHREINE- MAKERS (Pvoc. K Akad. Wetensch. Amsterdam 1914 17 767-782. Compare A. 1914 ii 807).-A further discussion of the equilibrium relations for the case in which two of the three com- ponents are volatile and in which a solid binary compound is formed by combination of the non-volatile with one of the volatile components.H. M. D. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 47 Equilibria in the System Pb-S-0; the Roasting Reaction Process. \v. REINDERS [with P. GOUDRIAAN] (Proc. l<. Akad. Tvetensch. Arr~sterdam 1914 17 703-718).-1n order to obtain information in regard t o the nature of the changes which occur during the inanu- facture of metallic lead from galena by the roasting process the authors have investigated the equilibrium relations in the ternary system with lead sulphur and oxygen as components. For tho most part the experiments consisted in the deteriiiination of the vapour pressures air temperatures between 500° and 800° and in the examination of the solid phases present under varying con- ditions of temperature and pressure.The collective data indicate t h a t when sulphur dioxide is re- moved from a mixture of lead sulphide arid lead sulphate the following univariant systems characterised by the presence of three solid phases are successively met with (I) PbS-PbSO,- PbO,PbSO ; (2) Pb-PbS-PbO,PhSO ; (3) Pb-PbO,PbSQ,- 2Pb0,PbS04 ; (4) Pb-2PbQ,PbS04-3Pb0,PbS0 ; (5) Pb- 3PbO,PbSO,-PbQ. The metallic phase probably contains a little dissolved lead sulphide the proportion of which varies in the different equilibria. The vapour pressures corresponding with the five systems and the variation of the pressure with the tempera- ture are shown in a series of curves. From the vapour-pressure curve for the first system the authors find t h a t the thermal value of the reaction PbX+PbSO,= 2Pb+2S02 is -99,543 cal.The value calculated from the heats of formation of the compounds involved in this equation is -92,470 cal. a t 20°. H. M. D. Aspirin. I. Decomposition of Aspirin by Water. D. E. TSAKALOTOS and S. HORSCH (Bull. Soc. chin?,. 1914 [iv] 15 743-747). -A study of the rate of decomposition of aspirin by water alone or in the presence of certain acids. The velocity of tlie action was measured by determining the increase in acidity using X i 50- sodium hydroxide and phenolphthalein as indicator. The decom- position of aspirin by water is very slow a t the ordinary tempera- ture being compIete in about 100 days. Acids exert a catalytic influence on the decomposition which is accelerated by hydro- chloric and sulphuric acids. With acetic o r citric acid the action is accelerat’ed up to about the eighth day afLer which the velocity of the action is diminished. W. G. Number Relations Amongst the Elements. F. H. LORING (Chenz. ,!ews 1915 11 1 13-15).-A discussion of certain relations exhibited by a periodic arrangement of the elements which has been deseribed in the author’s “ Studies in Valency.” H. 31. D. Theory of the Metallic State. F. A. LINDEMANN (Phi2. Mag. 1915 [vi] 29 127-140).-A theoretical paper in which the author discusses tlie interpretation of the physical propertie@ of metals in terms of t’he electron theory. It is shown that the free electrons in a metal may not be treated as a gas for a gas can only be aii. 48 ABSTRACTS OF CHEMICAL PAPERS. good conductor of heat if its heat capacity is large. Experiment shows that the free electrons conduct heat well but t h a t their heat capacity is too small to be measured. I t is suggested that the free electrons forin a space-lattice corresponding with a crystal a t a very low temperature. The application of this view to thO int'erpret ation of the various phenomena which are exhibited by metals is considered in detail. It explains the exceptional behaviour of alloys and in general outline the photoelectric effect but special assumptions are necessary for the derivation of the Wiedemann-Franz law. H. &I. D. Goossen van Vreeswyck a Mining Engineer and Chemist of 250 Years Ago. W. P. JORISSEN (Chern. Weei%6Zad 1914 11 1075-1086; 1915 12 2&-30).-An account of the life and publi- cations of Goossen van Vreeswyck (ca. 1630-1690) celebrated for his investigations in the animal vegetable and mineral kingdoms in many parts of the globe. A. J. W.

ISSN:0368-1769    

DOI:10.1039/CA9150805033

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i 34 ABSTRACTS OF CHEMlCdL PAPERS. Physiological Chemistry. Effect of Inhalation of Alcohol on the Viscosity of the Blood. R. BURTON-OPITZ (Arne?.. J. Phy&oZ. 1914 35 265-267. Compare A. 1905 ii 98).-The inhalation by dogs of air charged with methyl or ethyl alcohol is associated with a marked increase in the viscosity of the blood The general appearance of the blood as well as the decided increase in its specific gravity indicates that the change in the viscosity is due t o an accurviulatioii of excretory material rather than tot a direct destructive action of the alcohol on the cellular constituents of the blood. The action of methyl alcohol is as great as that of ethyl alcohol and the changes in both cases result very soon after the beginning of the inhalation. H.W. B. Changss in the Hydrogen Ion Concentration of the Blood Produced by Pulmonary Ventilation. T. H. MILROY (Quart. J. expt. Phpsiol. 1914 8 141-154).-Pulmnnnry ventilation with air or with air and o'xygen produces a rapid fall in the hydrogen ion concentration of the blood especially if the period of ventila- tion is short. This results in apncea during which the hydrogen ion concentration rises. Subsequeint ventilation with air rich in carbon dioxide raises the hydrogen ion co'ncentration and noPHYSlOLOGICAL CIiEMISTIiY. i. 33 cessation of breathing takes place. The hydroEen ion concentra- tion is closely related to carbonic acid concentration and influences the activity of the respiratory centre. Blood and Urinary AmylaEe. C. E. Kmc (AWLOT. J. I’hysiol.1914 35 301--332).-The amylolytic power of the blood and urine of the dog cat pig rabbit woodchuck raccoon goat opossum and man under various conditions has been estimated by a modification of Wohlgemuth’s method (A. 1908 ii 444). The amylolytic power o;f’ the blood-serum and urine of different species of animals varies in a manner that is not accounted for by differences in diet and feeding habits. The serum of the goat which is entirely herbivorous has only about one-twelfth of the amylolytic activity of that of either the dog or the cat. Those animals which secrette an amylolytic enzyme in the saliva have generally as compared with those the salivary secretion of which is inactive a larger proportion of amylase in the urine. Feeding with a high carbohydrate diet does not increase the quantity of urinary amylase.A t birth the pancreas in the case of the dog or cat contains only a little amylase and the urinary amylase is also low. As the animal grows the increase in pancreatic amylase is found t o run parallel with the output of urinary amylase. Removal of the pancreas leads to an almost complete disappearance of amylase from the urine and diseases of the pancreas which depress its activity are also associated wilh a decrease in urinary amylase. These considerations and the fact that amylase injected into the blood reappears in the urine lead the author t o the conclusion that urinary amylase arises chiefly by the passage of the amylolytic enzymes from the salivary gland and the pancreas into the blood and their subsequent elimination by the kidneys.Wi. D. €1. H. 147. B. Prothrombin. W. H. HOWELL (Arnar. J. PX?ysioZ. 1914 35 474-482. Compare A. 1912 ii 1078).-The author brings for- ward evidence in supportl of the view that the failure of blood t o clot in the blood vessels is due to the presence of antithrorrlbin and not’ t o the absence of thrombokinase. Prothrombin is pre- pared free from all the other constituents of the blood which take part in blood coagulation with the possible exception of traces of antithrombin by precipitating oxalated plasma with acetone and then extracting the dried precipitate with water. The solutions of prothrombin so obtained are fairly stable and can be heated a t 60° without entirely losing their coagulating power. The addi- tion of calcium salts is found to be sufficient to enable this pro- thrombin t o transform fibrinogen into’ fibrin the addition of kinase being unnecessary.The objection that the prothrombin is accompanied by kinase has been ruled out by testing with peptone plasma which is coagulated by kinase but not by thrombin. The prothrombin extract did not coagulate peptone plasma. An extract of blood platelets is said t o contain both prothronlbin VOL. CVIIT. i. ei. 36 ABSTRACTS OF CHEMICAL PAPERS. and thromboplasti~i (the substance which neutralises the action of antithrombin) because of its clotting action 011 peptone plasma. The presence of prothrombin in the circulating blood is indi- cated by the clotting which follows the addition of calcium salts and tissue extract to centrifugalised oxalated plasma.I n shed blood disintegration of the platelets furnishes an additional supply of prothrombin and thromboplastin both of which are factors tending to hasten the coagulation of the blood. Coagulation of Lymph. W. H. HOWELL ( A m e y . J. Pltysiol. 1914 35 4 8 3 4 9 1 . Compare preceding abstract).-Lymph plasma contains antithrombin in the same concentration as in blood plasma. When freed from corpuscles by long centrifugalisa- tion the lymph plasma clots with great slowness owing to a relative excess of antithrombin. Addition of tissue extract or of kephalin solution to such plasmata. causes prompt clotting. The presence of antithrombin in the lymph prevents the activation by calcium salts of the prothrombin of the circulating lymph into thrombin.I n shed lymph a supply of thromboplastin is furnished by the lymphocytes but more slowly than in the case of the blood in which the additional thromboplast'in is derived from the unstable platelets (Zoc. cit.). H. W. B. H. W. B. The Effect of Temperature on Thrombin and Antitbrombin. W. H. HOWELL (Amw. S. Physiob. 1914,36 1-7).-At temperatures approximating to the body-temperature the action of antithrombin is greatly augmented and this may be a factor of importance in maintaining t@e fluidit~y of blood during life. The effect of high temperatures (60-100°) in weakening or destroying the activity of thrombin is greatly increased by the presence of neutral salts such as sodium chloride. W. D. H. Effect of Filtration Through a Berkefeld Filter on the Coagulability of Oxalated Plasma.C. H. GODDARD (Arrrev. J. Physinl.. 191 4. 35 333-339. Compare Cramer and Piingle A. 1913 i 417).-The auhhor finds that the various proteins in oxalated plasma filter a t different rates through a Berkefeld filter. The first portion of the filtrate does not contain any fibrinogen and therefore does not clot on the addition of soluble calcium salts or of an active solution of throlmbin. The last portion of the filtrate clots promptly when calcium chloride is added whilst intermediate portions may either not clot a t all on the addition of calcium salts or may show a delayed coagulation. Since the filter thua holds back not only the suspended blood-platelets but also the proteins concerned in the coagulation process it follows that the views of Cramer and Pringle (Zoc.c i t . ) regarding the essential function of the platelets in the coagulation of the blood are not confirmed. The plasma of oxalated lymph which does not contain any blood-platelets behaves as regards the coagulation of thePHYSIOLOGICAL CHEMISTRY. i. 37 successive filtrates in the same way as oxalated blood- plasma. €€. 'cy. B. Immunisation Against the Anti coagulating Efftct of Hirudin. MIGUEL VERA and LEO LOEB (J. Biol. Chem. 1914 19 305-321).-A full account of work of which a preliminary note has already appeared (A. 1914 i 617). H. W. B. The Effect of Shaking on Serum. HANS SCHXIDT ( J . Hygitne 1914 14 399-416).-Shaking serum with air prduces coagula- tion and denaturation of the euglobulin due to alteration in the surface energy of the serum leading to adsorption of albumin thus rendering the euglobulin labile which then coagulates and becomes insoluble. The process is not due to oxidation; it is shown that conditions which render the euglobulin more stable such as previous heating and the presence of a hypertonic medium tend tlo inhibit the effect of shaking whereas dilution with water or storage rendering the euglobul& labile favours the effect of shaking.W. D. H. Serological Tests. L. G~ZONY E. HINDLE and P. H. Ross ( J . Hi~gierts 1914 l4,354-359).-Sera and antieera kept in the dark in sealed tubes occasionally give specific reactions after twelve years. I n most cases the results are negative especially in anti- sera. Fowl or human blood gives specific precipitin and comple- ment-fixationyeactions after being in the alimentary canal of blood- sucking arthropods for a t least twenty-three months.W. D. H. The Chemical Control of the Gastric Hunger Contractione. A. B. LUCKHARDT and A. J. CARLSON (Amerr. J. Physiol 1914 36 37-46).-Blood from starving animals and from animals with- out a pancreas transfused into normal animals acts as a tern- porary stimulus to the gastric hunger mechanism. Excessive hzemorrhage has a similar effect. Starvation pancreatic diabetes and possibly large hzemo'rrhages increase some substance or sub- stances which act as stimuli t'o hunger contractions of the stomach. Acidosis is not responsible f o r the result since injection of the acetone group of substances is ineffective in this direction. W.D. H. The Influence on Metabolism of Small Amounts of Thyroid Uland and of Anterior Lobe of Pituitary. JAMES ARTHUR HJCWITT (Quart. J. expt. Yhgsiol. 1914 8 113-124).-0*5 Gram of fresh ox thyroid per diem in an adult rat causes loss of body- weight and increases the appetite. Double this dose lessens appetite. The smaller dose causes more retention of nitrogen than the larger. Simultaneous administration of smail amounts of anterior lobe of ox pituitary has no influence on tnese results. W. D. H. e 2i. 38 ABSTRACTS OF CHEMICAL PAPERS. The Influence on Metabolism of Small Amounts of Thyroid Gland and Porsterior Lobe of Pituitary. JAMES Arm UR HEWITT (Qucwt. J. expt. Z’IqsioZ 1914 8 29’7-302).-Do~es less than 0.25 gram of fresh ox thyroid in a rat cause an increase of weight and increase the appetite; a dose of 0’25 gram at first diminishes the appetite and later increases the food consumed.The smaller dose causes a greater retention of nitrogen than the larger. Doses of 0.125 to 0.25 gram increase the excretion of ammonia in the urine and tihis is still f urtlier raised by simultaneous administra- tion of small amounts of posterior lobe of ox pituitary. W. D. H. Water Drinking. XX. P ~ I L I P €3. HAWK (Biochenz. Bull. 1914 3 420434).-Mainly a rBsum6 of tlhe autlior’s previous work and conclusions; the main result is that the drinking of a reasoiiable amount of water with meals will promote the secretion and activity of the digestive juices the digestion and absorption of food will retard the growth of intest,inal bacteria and lessen the putre- factive processes in the intestine.W. D. H. Water Drinking. XXI. Direct Demonstration of the Stimulatory Power of Water in the Human Stomach. OLAF BEROEIM MARTIN E. REHFUSS and PHIL~P B. HAWK (J. Bid. Chem. 1914 19 345-371. Compare A. 1914 i 1107).-Experiment~ on human subjects are described in which the variations in the acidity of samples of the contents of the stomach are determined after the ingestion of varying quantities of water. It is found that water (ordinary or distilled) either cold 01 warm is a very strong gastric stimulant and in some cases lead! to a flow of gastric juice containing in less than twenty minutes sufficienti acid t o neutralise its own volume of AT/lO-sodiun hydroxide. The acidity of the gastric juice secreted after wate stimulation ranges from 0.18 t o 0.44% of hydrochlorlc acid wit1 an average value of 0.28%.As small a volume of water as 50 c.c is shown tol have a pronounced and immediate stimulatory powe in the human stomach. I n the normal individual water produce fully as great a stimulation as does an Ewald test meal and th acidity values follow a similar type of curve. Evidence of “ latent period ” or of “ fatigue ” could not be di( covered in the case of the gastric glands of the human stoniacl The flow of gastric juice sometimes continued after bhe water whic had evoked its secretion had passed on intol the intestine. Tk stimulatory power of the water is not influenced in a uniform wa by the volume of fluid introduced into the’stomach. I n son instances a small volume of water gave a pronounced stimulatio whereas in others the response was relatively less pronounced whc a larger volume of water was employed.The authors draw the conclusion that t o drink water betwet meals appears t o result in a waste of “glandular energy.” seems that watier can best further the digestive processes whc taken with instead of between meals. H. W. B.PIIYSIOLOGICAL CIIEMLSTNY. i. 39 Vttlue of the Proteins of the Cereal Grains and of M~lk for Qrowth in the Pig and the Influence of the Plane of Protein Intake on Growth. E. V. MCCOLLUM ( J . B ~ o l . C'hem. 1'314 19 323-333. Compare A. 1913 i 549).-The author has deter- mined the amount of nitrogen retained by pigs fed on various grains for periods of forty to sixty days.The results show that in the young pig the growth tendency is so great that the synthesis of body protein is effected a t the maximum rate possible with the particular mixture of amino-acids yielded by the food protein. The more protein given in the food the more rapid is the growth of the animal and the larger is the absolute quantity of nitrogen retained. The constancy of the proportionate amount of ingested protein which is retained in the body a t different planes of protein intake indicates that the rate of retention of nitrogen is limited by the chemical composition of the food proteins and not by the physiLlogica1 capacity cE the pigs to grow. There appears t o be very little difference in the value for growth of the protein mixtures contained in thel three cereal grains wheat oat and maize. A maximum of 23-24% of the ingested nitrogen from any one of these sources can be retained for growth.Feed- ing with mixtures of these grains did not lead to a greater reten- tion of nitrogen than was attained by restricting the diet t o a single source for the protein. I n two experiments in which the source1 of nitrogen was milk protein the retention of nitrogen amount.ed to as much as 60% of the nitrogen absorbed. Influence on Growth of Rations Restricted to the Maize or Wheat Grain. E. B. HART and E. V. MCCOLLUM (J. Biol. Chew. 1914 19 373-395. Compare A. 1914 i 620).-When pigs are restricbed to a diet of maize meal and gluten little or no growth is secured; but' with an addition of salts making the entire ash content of the ration very similar in quality to that of milk approximately normal growth is attained.When the diet consists wholly of wheat growth is again limited with both pigs and rats. The addition of salts induces more growth but the beneficial effect is now found to be only temporary (compare McCollum and Davis A. 1913 i 551). The further additlion of butter-fat to the diet of wheat and salts results in the attainment of an almost iiormal growth. The animals remain vigorous and stroiig for a long period but in some individuals a partial decline mainly character- ised by stiffness ultimatlely sets in. The addition of casein to the wheat-salts-butter-fat diet secures a completely normal growth for pigs and rats. Normal reproduction as well as normal growth has been obtained with such rations.The Digestibility of Maize Consumed by Swine. S. C. GUERNSEY and JOHN M. EVVARD (Biochem. Bull. 191 4 3,369-372). - Maize was prepared in five differentl ways and the food and fxxes were analysed. The results are given in tabular form. Digesti- bility and the time required for digestion are closely correlated. W. D. H. H. W. B. H. W. B.i. 40 ABSTHACTS OF CHEMICAL PAPERS. Toxicity of Phenolic Compounds on Amphibian Eggs. Ross A . GORTNER and ARTHUR Bf. BAKTA (Biochem. Em?/. 1914 3 357-368).-Amphibian eggs and embryos are killed by an 0.05% solution of “ tricresol ” within three days; smaller doses kill in a longer time or retard development; there is some difference of resistance between frogs’ eggs and salamanders’ eggs. Similar details are recorded for orcinol resorcinol catechol phloroglucinol tannin guaiacol tyrosine and tyrosol.Pigment formation is inhibited by most of the reagents mentioned. Tyrosine which is very slightly toxic increases pigmentation. The Viscosity of Bile. R. BURTON-OPITZ (Biochem. Bull. 191 4 3 351-356).-Ox bile is less viscous than dog bile; the former contains only traces of mucin. High viscidity and viscosity do not however always go together. Lowering the temperature raises the viscosity (and the specific gravity). A slight decrease in viscosity occurs on autolysis. Tables of illustrative measure- ments are given. W. D. H. W. D. H. The Origin of the Active Material of the Posterior Lobe of the Pituitary. P. T. HERRING (Quart. J. expt. Physiol. 1914 8 245-266).-Any action in stimulating the uterus and milk secre- tion produced by extracts of the anterior lobe of the pituitary is a product of the cells of the pars intermedia; extracts of this pa.rt have very little pressor action or action on the kidney.Repeat’ed doses confer no immunity in reference to uterine contraction. Ex- tracts of the pars nervosa act on blood pressure as described in previous communications on the uterus kidney and mammary gland. This action may be due t o separate principles but these are all formed in the pars intermedia; their hyaline secretion is stored in the pars nervosa and may pass into the cerebro-spinal fluid. W. D. H. The Physiological Activity of the Pars Intermedia and Pars Nervosa of the Ox-pituitary Compared. P. T. HERRING (Quart.J . expt. Physiol. 1914 8 267-274).-The action of extracts of the pars nervosa in the uterus is from 2 to 5 times more powerful than that of extra’cts of the pars inhermedia. The former have no action a t all on blood pressure and on the kidney. This sort of evidence although not conclusive suggests that the actions are due to more than one substance. The substance acting on the uterus is possibly an early result of the breaking down of the pro- duct formed in the cells of the pars intermedia and that acting on the kidney and on blood pressure is formed later. W. D. H. Differential Fat-Staining. E. T. BELL (J. P n h Bact.. 1914 10 105-1 13).-Ths dichromate-Sudan I11 stain demonstrates fat droplets in thin paraffin or frozen sections. The annular droplets are probably triolein; the solid spheres are mainly lipoids.I n most moderately fatty human kidneys the fat is chiefly lipoid; inPHYSIOLOGICAL CHEMIS'l'1LY. i. 41 the liver it is chiefly triolein. I n rats fe,d heavily on olive oil the convoluted urinary tubules may become filled with droplets which are mainly triolein. W. D. H. Acidosis in Omnivora and Herbivora and its Relation to Protein Storage. H STEENBOCK V. E. NELSON and E. B. HART (!. Biol. Chem. 1914 19 399-419).-Cerexl grains when hydrolysed and oxidised in the body yield a preponderance of acid radicles. On such rations the ammonia content of the urine is high with a compensatory fall in the output of urea. The addition of basic salts to the food is followed by a diminution in the urinary ammonia and an increase of urea.The conclusion drawn by the authors is that naturally acid rations such as the cereal grains if otherwise satisfactory are as effective for growth and reproduction as those of basic character. The ingestion of mineral acids results in a large output of ammonia to effect its neutralisation and it is only when the amount of acid ingested is excessive that the skeleton is drawn on and decalcification cd the bones takes place. On returning to a normal diet there is a rapid storage of calcium and also of nitrogen. H. W. B. Fasting Studies. XIV. The Excretion of Urinary Indican During Two Fasts of One Hundred Days Each. CARL Y. SHERWIN and PHILIP I;. HAWK (Biochem. Bull. 1914 3 416-419. Compare A. 1914 i 222).-The first fast in a dog lastled 117 days and the indican output was continuous and fairly high throughout; the second fast in the same animal lasted 105 days; the indican was less and entirely disappeared after fifty-seven days.As previously shown (( repeated fasting " leads to greater resistance in an animal. W. D. H. The Pressor Bases of Normal Urine. WILLIAM BAIN (Quart. J. expt. P?t,ysioZ. 1914 8 229-24 I).-The pressor bases of t'he urine can be best separated by adsorption by charcoal from which they can subsequently be extracted. The most abundant base present is soluble in ether and volatile with steam. It was isolated as an oxalate which in physical characters and elementary analysis was shown to be identical with isoamylamine oxalate. After thorough extraction by ether there is evidence of a second pressor base in some urines which is however not tyramine.Its nature is not yet determined. The pressor effect of this second base may be preceded by a fall of pressure which may possibly be due to Abelous' uroliypotensine. Trimethylamine is not a pressor substance; such action if present in commercial specimens is due to impurities. W. D. H. Metabolic Factors in Beri-Beri. I. The Effect of Increasing the Carbohydrate Ration on the Development of Poly- neuritis in Birds Fed on Polished Rice. W. 1;. BRADDON and E. A. COOPER ( J . Hygiene 1914 14 331-353).-1n the preparationi . 42 A llST It ACTS OF CEl EM ICA 1 PAPERS. of a dietary t o obviate beri-beri not only the amount of anti- neuritic material must be considered but also its calorific value.Especially i t is necessary to maintain a proper proportion of carbo- hydrate intake. The amount of antineuritic substance required increases with the quantity of carbohydrate metabolised ; the pmcise proportion is not yet determined. The Iron of Organs in Bronzed Diabetes (HEmochro- matosis). ROBERT MUIR and JOHN SIIAW DUNN (J. Pdh. I h c t . 1914 19 226-238).-This condition is associated with cirrhosis of the liver and pancre’as. Hzemosiderin is deposited in the skin and other organs; there is a large increase of iron in the organs especi- ally in lymph glands liver and pancreas. There appears t o be no increase in hzemolysis but the source of the iron appears t o be twofold normal hzemolysis and iron from the food; the cells have an increased affinity for iron.JOHN P. KINLOCEI ( J . Yuth. Buct. 1914 19 77-101).-Tn the glomeriilsr nephritis of scarlet fever and diphtheria the water and nitrogen excreted arc lessened ; in interstitial nephritis this does not cccur. Detzils arc also given in reference t o the salts. The glomerulus is regarded as secreting more nitrogen than has been previously assumed. The glomerulus also has a special secretory function towards chlorides. but not towards phosphates. It excretes sulphates independently of nitrogen. Nitrogen and phosphate excretion are not affected by degeneration of the tubular epithelium. Re-absorption in the tubules does not explain all the variations in chloride excretion neither does it definitely influence the output of phosphates and sulphates. W. D. €1. Regulation of the Blood Volume in Experimental Nephritis. R.A. CHISOLM (J. Path. Bact. 1914 19 265-275).- Extracts made with Ringer’s fluid of kidneys rendered nephritic by uranium nitrate or potassium chromate contain a substance which hinders the passage of fluid from the vessels to the tissues when infused into rabbits. This substance which is not a coagulable protein is absent in normal kidneys. The Thermoprecipitin Method in the Diagnosis of Bubonic Plague in Cadavere. C~ARLOTTE E. WARNER (J. Hygiene 1914 14 360-371).-This reaction between plngue- immune serum and ext’racts of plague bacilli is specific and can be used t o diagnose plague in cadavers butl doubtful and negative reactions do not exclude plague>. The method although useful as a confirmatory reaction can therefore not replace the usual bacteriological methods.W. D. H. JACOB L ~ O S E N - BLOOM (Biochsm. Bull. 1914 3 373-374).-Tbis much discussed method gave in the author’s hands trustworthy results. W. D. H. W. D. I€. The Urinary Solids in Nephritis. W. D. H. The Abderhalden Serum Test for Pregnancy. W. D. H.PHYSIOLOGLCAL CHEMISTRY. i. 43 Landau’s Test for Syphilis. J. BRONFENBKENN ~ i i and J. ROCKMAN (Biochem. Bull. 1914 3 375-:BO).-This test is based on the property of syphilitic serum of combining with iodine. The test is found not t o be specific but is given frequently by normal serum. W. D. H. Purified Antigen of Besredka in the Serum Diagnosis of Tuberculosis. J BRONFENBRENNEIC and J. ROCKMAN (13ochcm. Bull. 1914 3 375-376).-Removal of the lipoids does not affect the antigenic properties of Besredka’s tuberculin.What protein or protein derivative is the really active agent is not yet determined. W. D. H. Besredka’s Tuberculin. J. BRONFENBRENNER and J. ROCKMAN (Biochsm. BUZZ. 1914 3 381-385).-Further work in attempts to ascertain the active substance. The tuberculin was found t o pre- sent many differences in activity in different preparations. Possi- bilities to explain these are discussed but no conclusion is reached. W. D. H. Resistance of the Vaccine Virus to Filtration. A. 13. GREEN (J. Hygiene 1914 14 182-1S5).-The virus in vaccine lymph (calf) does not pass through a Herkfeld V filter; either its mole- cules are too large or it is contained within a. substance with large molecules. It is improbable that passage through a filter destroys its activity.W. D. H. The Effect of Radiant Energy on the Lens and Humors of the Eye. W. E. BURGE (Amer. J. Physiol. 1914 36 21-36). -Radiation from a quartz mercury vapour lamp intense enough to coagulate egg-albumin and similar proteins in an hour does not coagulate the proteins of the lens or of the humors 09 the eye or affect their transparency after 100 hours’ exposure. The most effective region of the ultra-violet spectrum in coagulating egg- white lies around 265 pp. Solutions of calcium or magnesium chloride sodium silicate or dextrose too weak to affect the traas- parency of the lens in themselves modify conditions so that ultra- violet light can precipitate the lens protein and produce opacity. Lenses affected by cataract contain excess of such substances ; hence the prevalence of cataract in diabetes.The same substances decrease the fluorescenoe of the lens. Radiation from the infra- red and visible region of the spectrum has no such effect provided coagulation by heat is excluded. W. D. H. Is the Antagonistic Action of Salts Due to Oppositely Charged Ions? JACQUES LOEB (J. BioZ. Chena. 1914 19 431443).-The author ascertains what are the concentrations of various salts which are just sufficient to prevent the formation of embryos from FzmduZics eggs. These limits are termed the toxic concentrations and it is found that in the presence of a given quantity of a bivalent cation the toxic concentrations for thei. 44 ABSTRACTS OF CHEMICAL PAPERY. various salts are altered in varying proportions.Further the toxicity of the bivalent magnesium ion is antagonised just as easily by a univalent as by a bivalent anion. The valency of the anion does not appear to have any determining influence on the power of a salt to antagonise the toxicity of the magnesium cation. Moreover the univalent anion in potassium chloride reduces the toxicity of the bivalent cation in magnesium chloride much more than does the multivalent anion in sodium citrate. From these and similar considerations the author draws the conclusion that the antagonistic action of Salk is not due to oppositely charged ions but that the mixture of sodium chloride potassium chloride and calcium chloride in the right proportion and concentration has a specific membrane-forming or membrane- preserving effect on all cells and that solutions different from this mixture have a destructive effect which is the greater the higher the concentration and the more the composition of the solution deviates from that of the optimum solution.13. W. B. Pharmacological Study of the Aminopyridines. I. 2- Aminopyridine and its Acetyl Derivative. A. PITINT (Ann. Chim. Applicata 1914 2 213-217).-The toxicity of %amino- pyridine is equal t o that of stovaine whilst 2-acetylaminopyridine is less toxic than nirvanine but more so than novococaine. The anzesthetic effects of the two compounds are described. T. H. P. Pharmacological Investigations on Certain Derivative8 of Morphine and Codeine. A. PITINI (Ann. Chim. Appliccrtn 1914 2 208-213).-Sodium morphineoxidesulphonate and potassium codeineoxidesulphonate (compare Freund and Speyer A.191 1 i 909) have no pharmacological action whilst sodium morphine- sulphonate and codeinesulphonate exert in the frog toxic effects similar to but less marked than those of the alkaloids themselves. T. H. P. Fixation of Arsenic by the Brain after Intravenous Injec- tions of Salvarsan. JAMES MCINTOSH and PAUL FILDES (I'roc. Boy. Soc 1914 [ B ] 88 320-326).-The authors find by experiments in uitro that brain tissue fixes neosalvarsan as readily as does liver tissue. Moreover injection of neosalvarsan into the cerebro- spinal fluid of rabbits rapidly produces paralysis or death. The conclusion drawn is that the absence of arsenic in the brain after int'ravenous injections of salvarsan and neosalvarsan in man and in animals is due not to a lack of affinity between brain tissue and the drugs but to an inability on the part of the drugs to penetrate into the substance of the brain.It was further observed that penetration of neosalvarsan into the brain cannot be obtained by frequently repeated intravenous injections. An explanation is thus given of the lack of success which often attends the treatment of syphilitic lesions of the brain by the administration of salvarsbn. a. w. B,PHYSIOLOGICAL CHEMISTRY. i. 45 Effdctive Principle in Thyroid accelerating Involution in Frog Larvze. MAX MORSE (J. Biol. Chent. 1914 19 421-429)- The author finds that the rapid metamorphosis of tadpoles first observed by Gudernatsch (Arch. Entwicklungsm. 1912 35 457) on feeding with thyroid gland can also be accomplished by feeding with iodothyrin iodised blood-albumin or 3 5-di-iodotyrosine.Inorganic iodides starch iodate,” and iodine-containing a l p are ineffective. The metamorphosis takes place in three days instead of requiring the normal fortnight. The suggwtion is made that the observed positive results are dependent on a rise in the opsonic index associated with increased phagocytosis such as is known t o occur in other organisms after feeding with thyroid extract. Effect of the Intramuscular Injection of Pituitary Extract on the Secretion of Milk in the Human Subject. REUBEN L. HILL and SUTHERLAWD SIMPSON (Amer. J. Physiol. 1914 35 361-366).-The injection of pituitrin equivalent to 20 mg. of the dried infundibular portion of the gland into a female subject in lactation was followed in t’en minutes by a marked increase in the amount of milk secreted. The milk withdrawn after the injec- tion was rich in fat the average figure for three experiments being 5.5% as compared with 3.4% f o r three days when no pituitrin was administered. I n the milk yielded twenty-four hours after injection the fat content was still somewhat above t h s normal. Although no quantitative estimations were made it would appear that the quantity of milk secreted naturally on the morning after the injection wils less than normal. H. W. B. H. W. B. The Effect of Pituitary Extract on Milk Secretion in the Goat. REUBEN L. HILL and SUTHERLAND SIMPSON (Quart. J. expt. Physiot. 1 If 14 8 103-1 12).-Siibcutaneous or intravenous injection of ox-pituitary extract into the goat produces a marked increase of milk secretion when the milking is performed fifteen minutes after the injection; the next milking several hours later shows a corresponding decrease. I n the first milking the milk fat (but not the other solids) is increased but no sudden fall in the fat was observed (as stated by Hammond) at the second milking. W. D. 13’. Bleached Flour. FRANK L. HALEY (Iliochem. Bull. 1914 3 440443).-Experiments on guinea-pigs lead the author t o the conclusion that although nitrite is present i t is not enough in quantity t o cause the formation of rnethzmoglobin and that bleached flour is not detrimental t o health. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9150800034

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i. 46 ABSTRACTS OF CHEMICAL PAPE LtS. Chemistry of Vegetable Physiology and Agriculture. Nitroeo-Bacteria. H. S. FREMLIN (J. l l g g i s n e 19 14 14 149-162).-The nitroso-bacterium grows readily in or on ammonia agar especially if 5 or 10% of beef broth is added. Potassium phosphate agar containing bouillon gelatin but not ammonia also leads t o the formation first of ammonia and then of nitrite. Urine is also a good culture medium so also are peptone water peptone beef broth and milk or blood-serum. Thc nitroso-bacterium is a powerful nitrite-forming organism ; i t is not readily destroyed and a certain amount of organic niatt'er is essential to its better development. w. D. H. Purification of Silk Peptone for Bacteriological Purposes. I. WALKEK HALL (J. Path. Bact. 1914 19 286-304).-The tetra- peptide sold as silk-peptone has certain advantages for bacterio- logical purposes over complex mixtures like IVitte's peptone. Methods are described for purifying the crude product; the pig- ment may be removed by filtration through ,iI r!/i77u ctllrcc.The product has the same optical rotation and amino-acid content as that obtained by phosphotungstic acid precipitation. W. D. H. Organisation of the Cell with Respect to Permeability. the marine alga Grifithsia are placed in hypertonic sea water a withdrawal of water takes place and the protoplasmic sack con- tracts; on replacing the cells in sea water the sack expands to its original size. With hypertonic ammonium chloride the sack also contracts but the inner wall contracts much more than the outer wall; so t h a t there are two' surfaces the outer (plasma membrane) and the inner (vacuole wall) which do not actl in the same way with respect'to permeability.This may be dire t o the outer surface being more permeable to ammonium chloride and partly to a change in permeability produced by the) salt. With more dilute amnioniuni chloride there is x rriarkecl coiitrac- tion of the inner surface alone. As protoplasm is composed of a variety of structures i t seeins possible t h a t many kinds of semi-permeable surfaces exist within the cell. W. J. V. OSTERHOUT (Xcience 1913 38 408-409).-When cells Of N. H. J. M. Effect of Alkali on Permeability. W. J. V. OSTERIIOUT (J. Bio?. Chem. 1914 19 335-343) -The author bas determined the effect on the electrical resistance of the addition of small a,mounts of sodium hydroxide to solutions containing the living tissues of Larninnrio acrccZ),ccrirro.Concentrations of sodium hydroxide greater than l / l O O O l V lead to a diminution in the electrical resistance and the author draws the conclusion that concentra-VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 47 tions of sodium hydroxide below l j l O 0 O S do not have any effect on the permeability of the cell walls whilst above this limit the permeability is increased associated with injury of the cells if the exposure is sufficiently prolonged but not when the exposure is short. H. W. B. Chemical Dynamics OF Living Protoplasm. W. J. V. OSTERWOUT (Science 19 14 39 544-546).-An experiment in which living tissue of Lamiiinnk was placed in 0*52JT sodium chloride which has the same conductivity as sea water and the electrical resistance measured every ten minutes showed a rapid fall from 980 to 320 ohms in 200 minutes when the cells were killed.The results showed that the rate of the reaction was almost constant indicating that the sodium chloride reacted with one substaiice so little of it being used up that its concentration changed only slightly. The loss of resistance might also be due t o the spon- taneous change of some substlance in the protoplasm a process which goes on with extreme slowness until catalysed by the sodium chloride. This implies that even in a healthy and living cell the process of death is always going on. N. H. J. M. Vitality and Injury as Quantitative Conceptions.W. J. V. OSTEREIOUT (,Ycience 191 4 40 488-491).-The vitality of a tissue is so dependent on the maintenance of its normal permeability that the permeability of protoplasm may be employed as a sensitive and trustworthy indicator of its vitality and this may be done by estimating the electrical resistance. In this way a quantitative treatment of injury becomes possible. The degree of injury may be defined as the amount expressed as percentage of thO normal net resistance by which the resistance falls below the normal. The method of plasmolysis may be used not. only to distinguish between living and dead cells but between cells of normal vitality and those in which vitality is impaired. N. H. J. &I. Quantitative Criteria of Antagonism. W. J. V. OSTERIIOUT (/jot.Gaz. 1924 58 178-186).-'I'he hest criteria of antagonism are obhained by mixing equally toxic solutions as the effect' of each mixture if there is no antagonism is known at the outset. Mix- tures of two- equally tloxic solutions must have the same effect as the pure solutions themselves if the effects of the salts are additive. Where antagonism exists there is increased growth and the amount of the increase expressed as percentage of the growth in pure solutions is the most satisfactory measure of antagonism. It is desirable to employ uniform seeds; and only such portions of the plants as are in contact with the solution should be measured. N. H. J. M. Measurement of Antagonism. W. J. V. OSTERHOUT (Bot. Gax. 1914 58 272-276).-1t is shown that the measurement of antlagonism in solutions containing more than two components pre-i.48 ABSTRACTS OF CHEMICAL PAPERS. sents no difficulty when equally toxic pure solutions are mixed. Methods for the graphical expression of antagonism in mixtures of three or more components are suggested. N. IT. J. 31. Forms of Antagonism Curvts as Affected by Concentration. W. J. V. OSTERHOUT (But. Gax. 1914 58 367-371).-It was found with antagonism curves of different types that dilution of the solutions to half strengths results in very marked alterations in the form of the curve. An example given of four curves obtained with different dilutions shows that as the solution becomes more dilute the curve becomes flatter so tlhat finally a straight line would be obtained. The two1 ordinates a t the ends of each curve are equal in height showing that the pairs of pure solutions were in each case equally toxic.A solid model is describsed which gives a complete description of the changes in the antagonism curve as dilution increases. Strong solutions usually furnish a much more satisfactory criterion of antagonism than weak solutions. N. H. J. M. Creatinine in Leguminous Seeds. K. OSHIMA and M. ARIIZUMI (J. Coll. A9ric. Toliokzl Imp. Univ. 1914 6 17-25).-Creatinine was found in seeds of Adzuki beans kidney and soja beans and in smaller amounts in horse beans and green peas. N. H. J. M. Occurrence and Significance of Manganese in the Seed Coat of Various Seede. 3. S. MCHARGUE (J. Amw. Chenz. Soc. 1914 36 2532-2536).-During an investigation on the occur- rence of barium in plants (A.1913 i SOS) the author observed the presence of manganese in the ash of hazel-nut shells. S'everal nuts and seeds havel now been examined and i t has been found that manganese is of very general occurrence. The amount of manganese present varies considerably in different parts of the same seed and the seed coat surrounding the kernel contains a much larger proportion than the kernel or the outer coats. Ex- periments are recorded which show t'hat there' is a close connexion between the amount of manganese and the presence of oxydases in plant tissues and it is therefore considered probable that the accumulation of manganese in the seed coat bears an important relation t o the vital processes in seed formation and germination.E. G. Oxydaaes of Acid Tissues. G. B. REED (Bot. Gaz. 1914 57 528-530).-The acid tissues of Citrus fruits contain oxydases which are evidently protected in some way from the action of the acid. It is suggested that the protection may be afforded by a semipermeable tissue through which the acid cannot pass. It seems evident that the membranes are not normally permeable to acid because lemon seeds frequently germinate while in the carpels; in lemon juice even when several times diluted they fail to germinate. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 49 Bitter Principle of Common Ragweed. BURT E. NELSON and GEORQE W. CRAWFORD (J. Amar. Chem. Soc. 1914 36 2536-2538). -An examination has been made of the common ragweed (Ambrosia artemisifoEia). Two substances have been isolated one m.p. 208* crystallising in white needles or prisms and the other m. p. 65-70° an amber-coloured amorphous substance. The former is tasteless and physiologically inactive whilst the latter has a bitter taste and is probably identical with absinthin from wormwood. It is considered that there are no reasonable grounds for administering ragweed preparations for hay-f ever. E. G. Oxidation by Catalysts of Organic and Inorganic Origin. Compare Moore and Whitley A. 1909 i 623).-The author has investigated the action of the oxydases of the apple potato carrot parsnip beetroot orange and lemon and of the inorganic salts of copper iron chromium manganwe lead etc. on guaiacuni pphenylenediamine quinol pyrogallol gallic acid tannic acid and tyrosine.The correspondence between the action of these organic and inorganic catalysts is found to be extremely close. Both classes of catalysts may be accelerated in the presence of sensitisers such as sodium or potassium chloride or phosphate or retarded or prevented by a variety of inhibitory substances (barium chloride sodium fluoride organic and inorganic acids). With increasing concentration an accelerating substance may become inhibitory whilst a substance which accelerates the action of one oxydase may antagonise the action of another. Strong metallic poisons will arrest the action of organic oxydases and destroy them if immediate contact or rapid penetration is assured. The pulp of apples turns brown when soaked in bulk in metallic poisons because the slowness of penetration allows the cell to be killed and browning to occur before the oxydase is destroyed.Any poison which destroys the oxydase also removes the power of turning brown. The browning is due to the action of the oxydase on a compound of tannic acid in the apple pulp. I n the potato the oxydase acts on a compound of tyrosine. The oxydases of the beetroot and potato appear to be related to one another and to be among the strongest plant oxydases the nearest analogies to them being ferric salts and ferricyanides. The apple carrot and parsnip contain oxydases of the same type but of a feebler grade. The author considers that oxydases and peroxydases do not constitute distinct classes of enzymes. A peroxydase is regarded as a weak or attenuated oxydase.Strong oxydases cause direct oxidation from the oxygen dissolved in a wakery solution; weak oxydases can only use the oxygen from labile oxygen compounds such as hydrogen peroxide or dissolved oxygen in the presence of sensitisers such as the chlorides or phosphates of sodium or potassium. Various intermediate grades of activity occur. An oxydase may be a ‘‘ peroxydase ” to certain oxidising agents or may ALFRED J. &WART (PTw. I / o ~ . 86C. 1914 [B] 88 284-320.i. 50 ABSTRACTS OF CHEMICAL PAPERS. become so when attenuated. The supposed separation of oxydase and " peroxydase " by fractional precipitation with alcohol may be merely the result of attenuation. Attention is drawn to the influence which sensitising substances may have on special oxidations and on respiration in general.It is suggested that they exertl a stimulatory o r controlling action on plant metabolism and thah the sodium chloride always present in the ash of plants may have1 special significance in this connexioa. This view also explains why small doses of salt stimulate the growth of many plants and why phosphates in addition to being food substances act as stimuli to growth. The stimulating action of many metallic salts on growth may be due to' their functioning as oxydases. Exposure of apple or potato pulp to the action of ether o r chloroform leads t o a gradual diminution in the activity of the oxydases present. Chloroform attenuates the oxydases more rapidly than ether does. This is not an oxydase reaction but is an admirable test f o r lignin especially valuable for demonstrating the wood elements in pulpy tissue.H. W. B. Ursol tartrate turns lignified walls red or reddish-brown. Effect of Salicylaldehyde on Plants. J. J. SKINNER (Biochtm. BuIZ. 1914 3. 390-402).-E'ull details are given of the harmful effect produced by various concentrations of salicylaldehyde when added tol soil or solution cultures; wheatl maize rice and other plants were employed. The action is not attributable t o acidity; calcium carbonate appeared to ameliorate the effects. W. D. H. The Phosphoric Oxide Content of Maize Flour. J. ATCCKAE (J. ZIygienP 19 1 4 14 395- 398).-Fmeer and Stantnn have suggested that the estimation of phosphoric oxide in rice may be usefully employed as a criterion of the amount of vitamine present the two substances running approximately parallel in amount.Analyses of maize are given here which show that in the conversion of the grain into flour a loss of phosphoric oxide occurs; concomitantly i t is assumed there is a loss of vitamine. The loss is not so great as in the process of rice polish- ing. Improved processes of milling in the1 Transvaal have still further reduced the loss. The miners certainly are in better health who use the ffour made this way. W. D. 13. Saccharogenesis in Beetroot. H. COLIN (Compt. rend:. 191 4 159 687-689. Compare Girard A 1884 476; 1885 75).-An endeavour to determine the form of sugar which passes from the leaves t o the roots of the beet and is there stored as sucrose. A t all stages in the growth of the plant the aut'hor finds a certain amount of reducing sugars in the roots the amount diminishing as the plant matures.The disappearance of the sucrose from tlie leaves during tlhe night is not necessarily due to migration t o theVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 51 root since it similarly disappears from detached leaves kept in the dark with their stems in distilled water; the water does not con- tain a trace of sugar a t the end of the experiment. Further an examination of the petiole a t its base where it joins the neck of the root shows that the ratio of reducing sugar to sucrose is always much greater than unity. Contrary t o the views of Girard (Zoc. cit.) the author considers that the1 root receives from the leaf both sucrose which it stores and reducing sugars which it poly- merises the entrance of these two types of sugar being regulated by the osmotic pressure of each in the mixture.The amounts of the respective sugars formed in the leaves and taken up by the roots vary with different varieties of beetroot. W. G. Variation in the Nitrate Content of the Soils in Scania Sweden. M. WE~BULL (Bull. dgric. Irhtell. Plant Diseuses ; K. landtbr. Hmdl. Tidrtky. 1914,53,65-73).-Si t t t ates were estimated at intervals of seven to ten days from 1907 t o 1911 in the soil of a field on which different crops were'grown successively; from 1909 to 1911 estima- tions were also made in soil from fallow land. As regards the cropped plots those under beet contained up to 14 per million of nitrogen as nitrates; under wheat and peas 8-9; and under grass only 1.5 per million. On fallow land the amount rose to 33 per million.When the grass was ploughed up the nitrates increased up to November (N=21 per million). This was followed by a fall due to assimilation by the succeeding wheat crop and to loss in drainage. I n the spring the amount of nitrates was low and in the1 early summer there was an increase both in nitrifica- tion and assimilation. To ascertain the effect of vegetation and cultivation a grass plot was divided into three portions one of which remained under grass whilst the second was freed from vegetation and the third dug to a depth of 30 cm. On the grass soil the nitrogen as nitrates averaged 2.4 per million on the second portion 6.5 and on the third 11.3 per million.The amount of moisture in the second and third divisions was about equal being about 1*5-2% higher than in the grass soil. I n order to ascertain whether it is possible to detect the point a t which nitrogenous manuring becomes necessary nitrates were estimated during July and August in eight unmanured plots growing sugar beet. The yields were estimated both on the un- manured and on manured plots. Indications were obtained that where the nitrogen as nitrates fell to 2 per million by the end of July applications of nitrogenous manures resulted in a fairly large increased yie'ld. With a later fall in nitrates the effect of nitrogenous manures is less. Similar results were obtained with otjher crops. N. H. J. M. Nitric Nitrogen Content in the Country Rock. ROBERT STEWART And WILLIAM PETERSON f Utah.Agric. Coll Exper. Stut. Bull. 1914 134).-The results of analyses of numerous samples of Cretaceous and Tertiary soil-f orming materials and some ofi. 52 ABSTRACT8 OF CHEMlCAL PAPERS. Jurassic origin confirmed the view that the abnormally high aixounts of nitrates which sometimes occur in Utah and Colorado soils are derived from the brackish waters of tho old Cretaceous and Tertiary inland seas. Tho average amounts of sodium nitrate found in the different materials were as follows Sandstone. Shale. Clay. Ash. Alkali. Cretaceous. .. . . .. 0 *055% 0’104% 0’039% 0.870% 0.074% Tertiary .....,...... 0.074 0.147 0.053 0.236 0.021 Jurassic . .. . . . .. . . . . 0.008 0’005 - 0.175 0-017 Many of the shales and sandstones contained as much nitrate as the “ nitre spots ” in the cultivated soil ; and calculations based on the average amount of nitsates in fifty-eight shales show that the Cretaceous shale exposed from Palisades Colorado to Emery Utah contain 90 million tons of sodium nitrate.The conclusion is drawn that the nitrate deposits in Colorado Utah and Wyoming are far greater than those of Chile although so far as is known i t is nowhere in sufficient concentration to be worked. N. H. J. M. Comparison of Silicates and Carbonates as Sources of Lime and Magnesia for Plants. W. H. MACINTIHE and L. G. WILLIS (J. Ind. EThg. Chsrn. 1914 6 1005-1008).-The long-continued effects of liming in small or moderate amounts are to be attributed to the conservation of lime as silicates and not to the carbonate remaining unchanged. Untrustworthy methods for the estimation of carbonates will indicate their presence in soils where none exists. Calcium silicate hydrolyses in the soil and acts like calcium carbonate furnishing lime to the soil solution. With the exception of phosphates calcium exists in soils almost entirely in the form of silicates ; magnesium also exist’s as silicatel. Large quantities of magnesium carbonate have a toxic effect on plants whilst the equivalent amount of magnesia applied as finely-ground serpentine is beneficial. Calcium and magnesium silicates wollastonite and Serpentine applied separately or together are very beneficial to plants and calcium silicate is decidedly superior to calcium carbonate. w. P. s. Manuring Experiments with Manganese Sulphate and Carbonate. G. D’IPPOLITO (Alan. Chinz. App&icatc6 1914 2 342 ; from Staz. sperim. ugrcw. ital. 1914 67 621).-Experiments on the manuring of wheat and lucerne with (1) manganese sulphate; (2) a fertiliser containing 15% of manganese sulphate; (3) natural manganese carbonate containing 35% of the pure carbonate ; and (4) manganese carbonate as in (3) but containing 11% of phos- phoric oxide show that the addition of manganese gives increased yields. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9150800046

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

ii. 48 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Formation of Ammonia and Hydrogen Cyanide in the Distillation of Goal. OSKAK SIMMERSBACH (b'hhl uncl &ise?z 19 14 34 1153-1159 1209-1213).-The coal to be tested is enclosed in a porcelain tube which is provided with a tlie8rmocouple and is heated in an inclined position in an electric furnace. Before beginning an experiment the air is displaced by carbon dioxide previously purified and dried. The upper end of the tube is con- nected with a manometer containing liquid paraffin with a gas- sampling vessel and with the absorption apparatus. The latter consists of two U-tubes containing glass beads and 1 1 sulphuric acid a tube packed with cotton wool and a long 10-bulb tube containing suspended ferrous hydroxide. Beyond this is the gasometer.A t the end of the experiment the carbon dioxide is washed out by means of purified nitrogen. Tar is recovered by washing out the porcelain tube sampling vessel absorbing vessels and connecting tubes with chloroform and washing this solution with dilute sulphuric acid to remove ammonia. The acid solutions are united and used for the ammonia estimation. Hydrogen cyanide is estimated in the contents of the ferrous hydroxidei tube. A Kjeldahl estimation of nitrogen in the tar and coke is also made. For coke i t is necessary to boil vigorously with concentrated sulphuric acid then add potassium sulphate and after thorough boiling complete the solution by the cautious addition of small quantities of potassium chlorate. Various analyses are given and it is shown from experimentsINORGANIC CHEMISTRY.ii. 49 with a cod from Upper Silesia that the percentage of nitrogen in the coke steadily falls with increasing temperature of distillation whilst that in the gas passes through a minimum a t 850° and then rises rapidly. The percentage of ammonia is a maximum a t 850-900° and o,nly diminishes slightly up to 1200O; 3.5 to 476 of the total nitrogen is found in the tar. The proportion of hydrogen cyanide increases slowly with the temperature. The presence of water vapour increases the proportion of cyanide and diminishes that of ammonia. C . H. D. The Vapour-Pressure Lines of the System Phosphorus. A. SMITS and S. C. BOKHORST (Proc. K . Akad. Wetensch. Amsterdam 19 14 17 678-680. Compare A. 1914 ii 533).-Furtlier investigation of the vapour pressure of red and of violet phosphorus indicates that these cannot be considered as enantiotropic modifications.%'hen equilibrium between solid and vapour is attained the data yield a continuous vapour pressure-temperature curve and the authors draw the conclusion that the red and the violet forms of phosphorus differ only in respect of the size of the particles the violet represent- ing the more coarsely crystalline form. The behaviour of red or violet phosphorus on volatilisation is considered to afford strong evidence in support of the theory of allotropy put forward by Smits (A. 1910 ii 195 400). Accord- ing t o this theory red or violet phosphorus consists of a mixture of two or more kinds of molecules in equilibrium and these pseudo- components are supposed to exhibit very considerable differences in volatility. The observed fact that abnormally high vapour pressures are recorded when red o r violet phosphorus is rapidly heated to the temperature of the measurement is readily accounted for by the absence of internal equilibrium and the excessive volatnilisation of the more volatile pseudo-component.Above 450° the rate a t which the internal equilibrium is reached becomes con- siderable and the abnormally high vapour pressures are no longer observed. H. AT. D. A Spongy Modification of Sodium Amalgam. ENRIQUE V. ZAPPI (Anal. SOC. Quim. Argentina 1914 2 210-211).-A specimen of 20% sodium amalgam contained in an imperfectly closed vessel for more than a year gradually lost its metallic appearance and developed a lead-grey colour and foliated structure.Water de- composed it with formatio'n of mercurous oxide and a spongy sub- stance similar in appearance to ammonium amalgam. A. J. W. Influence of the Gaseous Impurities of Silver on the Values of the Atomic Weights Determined by Classical Methode Atomic Weights of Chlorine and Phosphorus. PH. A. GUYE and F. E. E. CERMANN (Compt. rend. 1914 159 992-996).-Taking into account the amounts of carbon monoxide and water vapour recently found by them t o be prelsent in highly purified silver after fusion in hydrogen (compare A. 1914 ii 727 740) the authors VOL. CVIII. ii. 4ii. 50 ABSTRACTS OF CHEMTCAL PAPERS. consider that the values obtained by the use of such silver in determinations of the atomic weight of this metal may be 0.0045 too high.They further discuss the effect of such an error on the atomic-weight determination of a number of other elements based on the use of silver as a standard and find the necessary correc- tions t o be of the order 0.005 t o 0.020 and exceptionally as much as 0.040. Thus for chlorine the atomic weight should be 35.460 instead of 35-455 and for phosphorus 31,007 instead of 31.028. W. G. The Hydration of Portland Cement. A. A. KLEIN and A. J. PHILLIPS (J. Washington Acad. Sci. 1914 4,573-576).-1n connexion with the investigation of the hydration of Portland cement ex- periments have been made on the hydration of mono-calcium aluminate 5 3-calcium aluminate tricalcium aluminate niono- calcium silicate P-orthosilicate y-orthosilicate and tricalcium silicate.Observations were also made with lime burned at different temperatures and ground t o various degrees of fineness and with commercial cements cliaracterised by a high silica a low silica a high iron and a high magnesia content. The only crystalline product observed in the hydration of the aluminates was hydrated tricalcium aluminate (3CaO,Al,O,,xH,O) and this is only formed with a large excess of wat.er. The 5 3- aluminate and th2 mono-calcium aluminate eliminate amorphous hydrated alumina and form the crystalline hydrated tricalcium aluminate. I n contact with a solution of calcium sulphate the three aluminates also yield a compound of the composition 3CaO,A1,0,,3CaSO,,xH,O (" sulpho-aluminateI "). It crystallises in long prismatic needles.Monocalcium silicate and the y-orthosilicate do not undergo hydration and the P-orthosilicate oiily takes up small quantities of water after long periods. Tricalcium silicate hydrates readily and quickly yields crystallised hydrated lime and amorphous hydrated orthosilicatle. I n the hydration of c'ement the first constituent t o react is the aluminate which forms amorphous hydrated tricalcium aluminate and sometimes amorphous hydrated alumina. The sulpho- aluminate crystals are also formed and hydration of the low burned or finely ground lime also takes place. These changes occur within a few hours after the gauging of the cement. Within twenty-four hours the tricalcium silicate begins t o hydrate and this change is generally completed within seven days.Between seven and twentyeight days the amorphous aluminate commences to crystallise and the 6-orthosilicate which is the least reactive compound also begins to react. Reference is also made t o the' influence of these changes on the mechanical properties and t o the action of small quantities of electrolytes on the initial setting of the cement. The Ternary System Ca0-A120,-Si0,. G. A. RANKIN [with Optical Study by FRED. E. WRIGHT] (Amer. J. Sci. 1915 [iv] 39 1-79).-The equilibrium relations exhibited by the binary com- H. M. D.IN ORGANIC CHEMISTRY. ii. 51 binations of these three substances have been described in previous papers (A,) 1906 ii 770; 1909 ii l015) and a partial account of the ternary system has also been given (A. 1911 ii 725) in which certain quintuple points and boundary curves were provisionally located.As a result of further experimental work the equil- ibrium relations have been more exactly defined and the present paper gives a detailed record of the results. The plane projection of the concentration-temperature model shows the existence of fourteen different regions each of which corresponds with a different solid phase. The characteristic points in this diagram are recorded in a series of tables which give respectively (1) the composition of the compounds their melting points and transition points; (2) the temperature and composition of the binary eutectics; (3) similar data for quadruple points other than eutectics ; (4) the temperature and composition of ternary eutectics ; (5) similar data f o r quintuple1 points other than eutectics. A further table is given in which the optical-crystallo- graphical properties of the various unitary binary and ternary compounds are recorded.The temperature-concentration diagram permits of the prediction of the course of crystallisation of any fused ternary mixture. Applied to the case of Portland cement clinker the results indicate that this is essentially a mixture of the compounds 3CaO,SiO 2Ca0,Si02 and 3CaO,A1,0 together with some 5Ca0,3A1,03 and possibly a small amount of free lime. This conclusion is in agree- ment with the results obtained in recent work on commercial Port- land cement clinkers. H. M. D. The Supposed Allotropy of Zinc. CARL BENEDICKS and RAQNAR ARPI (Zeitsch. anorg. Chem.1914 ‘88 237-254).-Several authors have described a transformation point of zipc between 300° and 350O. A further point atl about 170° was observed in commercial “zinc puriss.” by Benedicks in 1910 but was not confirmed by Werner (A. 1913 ii 1057). Kahlbaum’s distilled zinc containing only 0.008% of impurities has been examined in the cast and also in the drawn condition. The drawn metal after annealing a t 350° is almost as flexible as lead wire. The electrical resistance-temperature curves are not well suited to showing small irregularities so that a different graphical method is employed. The abscisg being t the ordinates are W - k t where k is a constant. The highly purified zinc gives a smooth curve without any transformation point. Between 15O and 300° the resistance is closely represented by the formula W=5.45(1+ 0.0039t + 0~0000017t~). The additio’n of 0.5% of cadmium or lead gives rise to1 breaks in t3hei curve those for the cadmium alloy being at about 170° and 350° respectively. These points are attributed to the formation of limited solid solutdons of cadmium in zinc the upper temperature’ being that a t which the solidus is intersected and the lowcr that a t which the curve of solubility in the solid state is crossed.Lead has a similar but smaller influence and is usually present in smaller quantities. 4-2ii. 52 ABSTRACTS OF CHEMICAL PAPERS. Tlie experiments of Colien and Heldernian (A 1914 ii 127) are criticised on the ground that the1 ziiic used becomes partly con- verted into a basic salt by contact with the zinc sulphate solut$ion and that the washing with dilute acid may have caused a loosening of texture which would account for the diminution of density. c'.H. D. Allotropy of Zinc 111. ERNST COHEN and W. D. HELDERMAN (t'roc. K. Akud. Wetensch. Amslerdam 1914 17 641-644. Compare A. 1914 ii 127 65Z).-A criticism of the conclusions drawn by Benedicks and Arpi (preceding abstract) from their observations on the influence of temperature on the electrical conductivity of zinc. The change in the physical propertiea of zinc at higher temperatures cannot be attributed to the presence of impurities. That the change is due t o allotropic transformation has been shown by the authors in experiments with pure zinc. 13. M. D. The Allotropy of Lead. I. EENST COHEN and W.P HELDERMAN (PFOC. A'. Akad. Wetensch. Amsterdam 1914 17 822-828. Compare A. 1914 ii 652).-Experiment# are described which are said t o indicate that ordinary lead consists of a metastable mixture of several allotropic modifications of the metal. The lead used in these experiments was very pure containing only 0.001?6 of copper and 0.0006% of iron. The metal was melted chilled in water and cut into small blocks which were immersed in a solution prepared from 400 grams of lead acetate 1000 C.C. of water and 100 C.C. of nitric acid (D 1.16). After remaining for some days a t the ordinary temperature it was found that the lead shows marlred signs of structural change and after three weeks this becomes so pro- nounced as to suggest complete disintegration of the metal.The change is illustrated by a series of photographs of the metallic surface. The transformation is notl due to chemical action but by means of pyknometric measurements and observations with a dilatometer it is shown that the change is accompanied by changes in density. These variations in density are not' always in the same direction and obviously depend on the previous history of the metal. The authors draw the conclusion that there are more than twos allotropic forms of the metal in the samples under examination. Closely connected with the above observatioiis is the fact that when pure metallic lead is immersed in the solution mentioned above or in a concentrated (30%) solution of lead nitrate a lead tree is formed in a few days both a t the ordinary temperature and a t 50°. H.M. D. Tensile Properties of Copper at High Temperatures. GUY D. BENaoUGH and D. HANSON (J. Inst. Metals 1914 12 56-88. Compare A. 1912 ii 763).-Tensil.e tests of copper in a vertical machine the specimen being heated by gas show that the proper- ties of tlhe metal are greatly influenced by the composition of theINORGANIC CHEMISTRY. ii. 53 surrounding atmosphsre. The ductility a t 800° and upwards is increased considerably by the presence of oxygen. Rolled copper which has noti been annealed is stronger but less ductile than the same copper which has not been annealed after rolling a t all temperatures up to 1000° when an atmosphere of carbon dioxide is used. With annealed copper the fracture passes through the crystals a t temperatures below 700° and between the crystals at temperatures above 750O.A t intermediate temperatures i t may take either course. Oxygen or arsenic alloyed with copper de- creases the strength and increases the ductility a t high tempera- tures. An atmosphere of hydrogen has a weakening effect above 720° probably owing t o reduction of oxide. The results are best explained by assuming the existence of an amorphous intercrystalline cement which is stronger than the crystals a t low and weaker a t high temperatures (Zoc. c i t . and aIso Rosenhain and Ewen A. 1913 ii 119; Humfrey ibid. 778). This cement is probably not identical with Beilby's amorphous matrerial formed by mechanical deformation. c f . H. D. Absorption of Gases by Refined Copper. W. STAHL (Metall unnd Erx 1914 11 470-482 ; from J .SOC. Chem. Ind. 1914 33 1158).-The absorption of gases by molten copper increases in general with the temperature up to a certain point with increasing purity of the metal and with the partial pressure of the gas. The presence of nickel or platinum however has a favourable influence on the absorption. Copper in the solid o r liquid state appears not to' absorb water vapour carbon dioxide nitrogen argon or helium. At 1420° 61 grams of copper absorb 0.15 C.C. of carbon monoxide; this small quantity markedly affects the physical properties of the refined metal. Hydrocarbons are not occluded by copper but are decomposed into ca,rbon and hydrogen the latter being absorbed and the former oxidised. The absorption of hydrogen in and its diffusion through copper has been detected even a t 650O.Up t o 1 500° the absorption of hydrogen increases almost linearly with the! temperature exceptl a t the melting point of the metal where a sudden increase occurs. The solubility per 100 grams of copper is 0.1 mg. a t 650° and 1.4 mg. a t 1500O; with both solid and liquid copper the solubility of hydrogen increases as the square root of the pressure. The conductivity of copper is not affected by absorbed hydrogen. By heating copper containing copper oxide in an atmosphere of hydrogen the gas penetrates the metal and reduces the oxide and the steam produced escapes by disintegrating the metal. The dissociation pressure of cuprous oxide is equal t o the partial pressure of atmospheric oxygen 0.21 atmos.a t 1662O. When the oxide is in solution in the copper its dissociation pressure is lowered so that a t 1600O i t is certain that thermal dissociation of the dissolved oxide does not occur and the absorption of oxygen a t this temperature is due to chemical combination not t o physical solution. The preceding results indicate that during the refining of moltenii. 54 ABSTRACTS OF CHEMICAL PAPERS copper the absorption of carbon monoxide predominates during the end of the “hard poling ” period and a t the beginning of the “ green poling ” period whilst the absorption of hydrogen pre- dominates during the latter period when the oxygen has been removed. The disintegration of copper which occurs during solidification has been traced to occluded sulphur dioxide formed by oxidation of the sulphur present; the gas is evolved with (‘ spitting” during solidification but the cold metal still retains a considerable quantity of the gas.Sulphur dioxide does not diffuse through solid copper below 1000°. The reaction CuzS -t 2Cu,O = 6Cu + SO is reversible ; the equilibrium of the four substances at all temperatures has been Behaviour of Copper-Zinc Alloys when Heated in a Vacuum. W. E THORNEYCROFT and THOMAS TURNER (J. Inst. Metals 1914 12 214-229. Compare T. 1912 181 585; 1913 103 1534).- When a-alloys of copper and zinc are heated in a vacuum the rate of volatilisation is nearly proportional to the temperature but this proportionality is not observed in the alloys richer in zinc. With more than 40% of copper in the alloys the separation is quantita- tive but with alloys containing less copper a part of the copper volatilises with the zinc.The volatility of zinc is increased by alloying with small quantities of copper. proved in a number of investigations. c. s. C?. H. D. The Critical Point at 460’ in Zinc-Copper Alloys. 0. F. HUDSON (J. Inst Metals 1914 12 89-110).-The critical point observed a t 460° in brasses containing from 37 to 60% of zinc and regarded by Carpenter as a eutectoid point (A 1912 ii 764; 1913 ii 138 139) is considered to be due to a polymorphic transforma- tion of the j3-constituent. Structural resolution of /3 is not observed on annealing a t 440° even in presence of a slight excess of a o r y. Further when a heterogeneous alloy is prepared by casting a y-alloy on to copper so that a zone of /3 is obtained bordered above by p + y and below by a+@ the zone of p increases on annealing at 435O proving that a phase P’ is stable below the transformation point.The j3’ zone is also formed by diffusion of zinc into solid copper or a-brass a t 450O. It appears that j3 is more readily supersaturated with a than with y. When bronze containing 10% of tin is immersed in molten tin a t 300° diffusion takes place and a zone of the &constituent is formed in immediate contact with the a-bronze without an inter- mediate zone of a + 6 . This condition is also observed in the above experiments with zinc. [The Influence of Carbon on the Corrosion of Brass.] ARNOLD ’PHILIP ( J . Inst. Metals 1914 12 133-167).-1n a series of experiments to det,ermine the influence of contact with carbon on the corrosion of brass sections of condenser tubing containing 29% zinc and 1% tin are placed in close contact with broken coke C.H. D.INORGANIC CHEMISTRY. ii. 55 in a stream of sea-water. A series of similar specimens in contact with pebbles instead of coke is used for control. It is found that the corrosion is in all cases greatly accelerated by contact with carbon owing to local electrolytic action. This conclusion is opposed to that arrived a t by Bengough and Jones (A 1914 ii 366) and the causw of the difference are discussed a t length. C. M. D. Binary Copper-Zinc and Ternary Copper-Zinc-Lead Alloys. N. PARRAVANO (Gaxzatta 19 14 44 ii 475-502)-[ With C. MAZZETTI and R. MoRETTI.]-T~~ melting-point diagram for copper-zinc alloys differs from those of Shepherd (A.1904 ii 662) and of Carpenter and Edwards (A. 1912 ii 1057) only as regards the equilibrium horizontals at 905O 838O TOOo 595O 545O and 425O for which the corresponding durations have been determined. The temperature of the eutectoid transformation 6-y + E which the author finds to be 545O was given by Shepherd (Zoc. cit.) as 450° and by Tafel (A. 1908 ii 846) as 550O. Of the copper-zinc-lead alloys which exhibit a liquid miscibility gap seven series were examined the percentages of lead constant in the members of any one series being 2 4 10 15 20 30 and 50 respectively. I n the first series the lead remains uniformly dis- tributed throughout the whole mass of the metal. I n the series containing 4% Pb the latter remains moderately evenly distributed with the alloys rich in copper; but as the proportion of copper increases beyond 40% pronounced liquation begins and this pheno- menon becomes accentuat'ed as the percentage of lead present is .augmented. Lead is virtually undissolved in either the a- or the y-solution the lead in lead brasses being merely mixed with the crystals of the brass; this conclusion drawn from the durations of the arrests is confirmed by the results of Carpenter's investigation of the influence of addition of lead on the critical point at 470" (A.1913 ii 139). These results are confirmed by photomicro- graphs of three of the alloys containing 20L Pb. T. H. P. The Quaternary System KCl-CuCl,-BaCl,-H,O. F. A. H. SCHREINEMAKERS and (Miss) W.C. DE BAAT (Proc. K. Akad. IVetelzsch. Amsterdam 1914 17 781--783).-The equilibrium relations in this quaternary system have been described in a previous paper (A. 1913 ii 63). The solubility data at 40° and 60O are now com- municakd in detail. €1. M. D. The Basic Sulphates of Copper. H. FONZES-DIACON (Bull. Soc. chim. 1914 [iv] 15 723-727. Compare Smith Phil. Mag. 1843 [iii] 23 500).-A study of the conditions governing the formation of the basic sulphates of copper CuSO,,3Cu0,4~€,0 and CuS0,,3Cu0,5H20 and of the composition of Bordeaux mixture prepared under different conditions. The yield of basic sulphate for the same strength solutions is greater when the sodium carbonate is poured into the copper sulphate than in the reverse process. The precipitate from the same weight of copper sulphate,ii. 56 ABSTRACTS OF CHEMICAL PAPERS.is richer in basic sulphate when a very dilute solution of sodium carbonahe is poured intlo a moderately concentrated solution of copper sulphate. On slowly pouring a solution of sodium carbonate into1 a solution of copper sulphate continuously st’irred i f the Soh- tion is rich in copper sulphate tho basic sulphate C”uSO4,3CuO,4H,O is formed but as tlhe concentration diminishes the basic sulphate CuS04,4Cu0,6H20 is produced. I f an excess of sodium carbonate is used these basic sulphates are converted into’ the basic carbonate CuC‘03,Cu0,2H,0. I f the supernatant liquid is allowed t o remain a precipitate of one of the basic sulphates is formed. W. G.’ Supplement to the Phase Diagram of Aluminium-Magnesium Alloys.H. SCHIRMEISTER (Metall und Erz. 1914 11 522-523; from J. SOC. Chern. Ind. 1914 33 1159).-The alloys (200 grams in each case) were fused in a nickel wire electric furnace and the progress of the cooling was registered by a thermo-element and re- cording galvanometer. The first stationary points were found a t temperatures which gradually fell from 657O to 550° as the mag- nesium increased from 0 t o 2076. Second stationary points denoting a eutectic point were found at 580-590° with alloys containing 2-15% of magnesium and a second similar eutectic point was found a t 455O with alloys containing 12-150/ of mag- Electrolytic Iron. L. GUILLET (J. Iron Steel Inst. 1915 90 66-81).-Elect~rolyt~ic iron deposited on a large scale with a revolving cathode and high current densit’ies using a solution which is neutralised and depolarised by the addition of iron oxide is hard and brittle and contains as much as seven volumes of gas consisting of hydrogen and carbon monoxide.It has a fine struc- ture resembling that of martensite which becomes less distinct on annealing but only finally disappears a t 800-900° giving place to the normal structure of pure iron. Annealing below 700° has velry little effect on the properties. Using a solution prepared from a pig-iron containing 1% of phosphorus the iron has been found t o contain C 0.004 Si 0.007 S 0.006 and P 0.008%. The posi- tion of the critical points is unaffected by the presence of hydrogen but an additional absorption of heat a t 530-690° is observed in the heating curves of tho crude iron which do not recur on cool- ing.The electlrical properties have been examined by Broniewski (A. 1913 ii 288). Solubility of Hydrogen and of Nitrogen in Iron. E. JURISCH (Stahl und Eisen 1914 34 252).-The solubility of hydrogen in iron wire containing 0.0474 of carbon determined a t atmospheric pres- sum increases somewhat more rapidly than the temperature from 416O to 850O. The curve then rises steeply and suddenly until 930° is reached after which it is approximately parallel t o its original direction. The discontinuity is t o be attributed to the allotropio changer in the iron. The hydrogen is practically all nesium (compare Grube A 1905 ii 523). c. s. C. H. D.INORGANIC CHEMISTRY. ii. 57 liberated on slow cooling.Within all three allotropic ranges the solubility of hydrogen in iron is proportional to the square root of the pressure. The golubility of nitrogen in reduced iron powder increases very suddenly a t 930° and then slowly falls. The solubility is propor- tional to the square root of the pressure. Theory of Hardening and Constitution of Steel. EDWARD D. CAMPBELL (J. Iron XteeE Inst. 1914 90 l-l6).-The properties of steel depend largely on the nature of the carbides. It has been shown that the mean molecular weight of the hydrocarbons evolved when annealed steel is treated with an acid decreases as the per- centage of carbon increases. Hardened steel gives hydrocarbons of lower molecular weight than annealed steel. It is likely that carbides of lower molecular weight are more soluble in solid iron than those of higher molecular weight and have a greater harden- ing effect and that with increasing temperature dissociation of the more complex carbides occurs.Austenite may contain almost com- pletely dissociat'ed carbide. The fact that the hardness of hyper- eutectoid steel diminishes when the temperature of quenching is raised much above the p o h t a t which all the carbide dissolves corresponds with the theory as the hardness should be greatest when solution is complete and dissociation is a t a minimum. The facts of specific volume1 and electrical conductivity are also ex- plained qualitatively. c". H. D. The Transformations of Steels. H. DE NOLLY and L. VEYRET (J. Iron Steel Inst. 1914 90 165-180).-DiIatometric curves are given f o r a number of steels in suppotrt of the view that iron carbide is partly dissociated in solid solution (compare Campbell preceding abstract). C.€3. D. The Influence of Coalescence on the Properties of Steel and Alloys. A. PORTEVIN (J. Iron Steel Inst. 1914 90 204-212)- Bronze containing 16% of tin and consisting of the u- and &con- stituentfs is heated in a salbbath a t 525O for an hour and cooled from 5 2 5 O to 475O during five hours. After reheating rapidly to 525O the slow cooling is repeated. The eutectoid structure dis- appears the masses of 6 coalescing and the hardness measured by Brinell's test diminishes. The effect on a steel containing 25% of tin is less marked. Annealing a eutectoid steel a t TOOo for thirty hours causes coalescence of the pearlite and a great diminution of hardness.A steel containing 0.50% of carbon annealed at 800° for ten hours and very slowly cooled t o 700° shows segregation of the ferrit'e into parallel bands without coalescence of the pearlite whilst annealing for thirty hours a t 700° brings about coalescence. Methane is formed between 600° and 9 3 0 O . C. R. D. C. H. D. Behaviour of Slag Occluded in Steel. 11. Supposed Solubility of Inclusions of Slag in Liquid Steel. F. GIOLITTI and G. TAVANTI (Ann. Chim. Applicuta 1914 2 360-366).-Examinaz-ii. 58 ABSTRACTS OF CHEMICAL PAPERS. tion of the condition and quantity of the reaction slag occluded in a small mass of steel coded rapidly from the fused state and of that occluded in the same mass after re-heating followed by slow or rapid cooling renders untenable the theory of the solubility of this slag in the steel a t a high temperature.A marked difference exists between the' behaviour of the reaction slag and that of inclusions consisting largely of sulphides of iron and manganese. T. H. P. Molecular Magnitude of Metals in the Solid Phase. M. PADOA and F. BOVINI (Gaxxetta 1914 44 ii 528-534).-When a solid solution of concentration C separates from a dilute solution of concentration C and the ratio C, C is constant f o r solutions of different concentrations i t may be asserted that the solute has the same molecular magnitude in the solid as in the dissolved state. The authors have investigated three different alloys of tin cadmium and bismuth. The first two metals form a eutectic and limited solid solutions which are transformed at a temperature just above looo into the compound Sn,Cd; tin and bismuth and also cadmium and bismuth give eutectics but no solid solutions.The ternary alloys examined which solidify at about' ZOO" present no further complications. I n the three ca,ses the ratio of the con- centration of the cadmium with respect t o the tin in the crystals to that in the liquid has the values 0.986 0.985 and 0.957 re- spectively. The solid solutions separating from different liquid solutions of cadmium in tin have therefore approximately the same concentration the coefficient of distribution being sensibly constant. The conclusion is drawn that cadmium has the same molecular magnitude in solid solution in tin as in liquid solution that is i t is monatomic.These results tend t o confirm Stoffel's data concerning these ternary alloys (A. 1907 ii 357). T. H. P. The Allotropy of Antimony. ERNST COHEN and J. C. VAN DEN BOSCH (Proc. K. Akad. Wetensch. Amsterdam 1914,17,645-647). -Evidence has been obtained that so-called metallic antimony is a metastable system which consists of more than two allotropic modifications. From experiments with a dilatometer containing metallic antimony which had been melted rapidly cooled and then powdered a transition point was found at about 1 0 1 O . This agrees with the observation that the density of the substance was lowered on heating f o r four days at 102.5O. That the equilibrium relations are of a somewhat complicated character is shown by the fact that a dilatometer which had been heated for fifty minutes a t 150° before being submitted t o ex- amination a t 9 6 O exhibited for some time a diminution in volume a t this temperature but later the volume showed a steady increase.From observations of this kind it is infcrred that a t 96* metallic antimony consists of a mixture of a t least throe allotropic forms. H. M. D.MINERALOGICAL CHEMISTRY. ii. 59 Reduction of the Oxides of Antimony and Bismuth by their Sulphides. W. R. SCHOELLER (J. SOC. Chem. Ind. 1915 34 6-9).- Mixtures of antimony sulphide (Japanese stibnite) and antimony tri- or tetra-oxide (not antimonious oxide) are heated t o incipient; fusion or a t a higher temperature (965O) in a porcelain boat in a current of dry carbon dioxide.The Sb,O in the residue is ex- tracted by 5% tartaric acid and is estimated iodometrically. The sulphur dioxide evolved is oxidised by a solution of iodine and is estimated in the usual manner. Metallic antimony is produced the best yield being obtained by heating the sulpliide and trioxide (1 2 mol.) a t 965O but the process has the disadvantage that both antimony sulphide and trioxide volatilise in the current of carbon dioxide. Reduction to the metal does not occur when t'he mixtures are fused beneath sodium chloride in a crucible. Antimony is pro- duced when stibnite alone is heated gently in a current of air and subsequently at about 950° in a current of carbon dioxide. The observations recorded above are briefly discussed in con- nexion with the metallurgy of antimony. The oxide and the sulphide of bismuth react readily either in a current of carbon dioxide or beneath sodium chloride in a crucible. Sulphur dioxide is evolved a t a comparatively low temperature and globules of metallic bismuth are formed by heating more strongly. The yield is 90%; a small quantity of basic bismuth sulphate is also formed. c. s. The Effect of Hydrogen on the Annealing of Gold. JOHN PHELPS (J. Inst. Metals 1914 12 125-132).-The temperature at which hard-rolled gold is softened by annealing is raised by hydrogen. Thus the tempsrature of annealing when heating is continued for thirty minutes is raised from 150° t o about 300° by the presence of 0.02 t o 0-04 part of hydrogen per thousand. The effect is destroyed by melting the gold in air or oxygen. C. 11. D.

ISSN:0368-1769    

DOI:10.1039/CA9150805048

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i 53 Organic Chemistry. Absorption of Gasolene Vapours i n Natural Gas by Fuming Sulphuric Acid. R. P. ANDERSON and C. J. .hGEr,DER (J. I n d . Eng. Chem. 1914 6 989-992).-Fuming sulphuric acid has a distinct absorbing action on certain specimens of natural gas the absorption increasing with the amount of higher hydrocarbons particularly gasolene vapours present in the gas. The average number of carbon and hydrogen atoms per mol. of hydrocarbon absorbed by fuming sulphuric acid (and consequently the average molecular weight of the hydrocarbons) may be calculated from the composition of the gas before and aft*er absorption and from the decrease in volume which takes place. Application OF this reagent to the study of natural gases for the production of gasolene may be made by determining the absorption under certain uniform conditions ; the composition of the portion which is absorbed should also be ascerbained as a check on the indications obtained from the decrease in volume.w. P. s. Preparation of d h l o r o -E-bromopentan-P-ol and of a Ketone Therefrom. 1114734 and 11 14735 ; from J. Xoc. Chem. Ind. 1914 33 1 171).-Maguesium ( I atom.) is dissolved in an absolute ethereal solution of ethylene dibromide and epichlorohydrin (1 mol.) is added ; treatment with a suitable acid pro- d uces a-chZoro-E-bronzopentm-P-ol CH,Cl*C H (OH) * CH,*C H,*CH2Br. The ketone CH,CI*CO*CH,*CH,*CH,Br is obtained by the oxida- tion of the preceding carbinol for example with potassium dichromate ELI LILLY & Co. (U.S. Pat. and sulphuric acid. c.s. A Compkrison Between the Molecular Weights of Protagon and of the Phosphatide and Cerebrosides Obtainable from it. ALEXANDER LYALL PEARSON (Biochem. J. 1914 8 616-627).- The long-continued argument whether protagon is a mixture or a compound is approached by attempts to determine the molecular size of protagon and its constituents (cerebrosides and sphingomyelin). If it is a compound the molecular size of protagon would he greater than that of its constituents; it should therefore produce little or no elevation of the boiling point of a solvent. The solvent used was chloroform. In two experiments there was no alteration in the boil- ing point in one a lowering of 0.05O. Various mixtures of the cerebrosides with or without sphingomyelin produced elevations of the boiling point of the same solvent of 0.03O 0*13O 0.04' 0*07O 0*07* 0*03O and 0.02O in a series of experiments.The conclusion is drawn that the protagon molecule is very much larger than that of its constituents and therefore that protagon is a compound and not a mixture of them. It is termed a phospho-cerebroside. The question whether protagon is a mixture of several phospho-cerebrosides still remains to be settled. Cramer calculated that protagon has a molecular weight of 5778 from its sulphur-content. The molecular weights of cerebro- VQL. CVIII. i. fi. 54 ABSTRACTS OF CHEMICAL PAPERS. sides and of sphingomyelin are about 1000; one gram of a substance of this molecular weight would in a 4% solution in chloroforrri elevate the temperature of the boiling point of chloroform O*lOo.The smaller figures obtained in mobt of the experiments cited would rather tend to emphasise the author's admission that determinations of molecular weights of substances of high molecular weight can Gnly be approxi mate. W. D. H. The Dissociation of Cl-T;SO,Cl and C,H,*SO,Cl by Aluminium Chloride. J. BOESEKEN and H. W. VAN OCKENBURG (Izec. irctv. chirn. 1914 33 317-323. Compare A 1913 i 334).-Wheri methane- sulphonyl chloride is mixed with aluminium chloride a t t'he ordinary temperature in the absence of a solvent a crystalline additive ccrn- pound CH,-SO,Cl AlCl is formed. On warming this compound sulphur dioxide and methyl chloride are evolved and the aluminium chloride remains behind. If the methanesulphonyl chloride is added to the aluminium chloride in the presence of an excess of benzene hydrogen chloride is evolved and phenyl methyl sulphone m.p. 88* is f orrned. Ethanesulphonyl chloride behaves similarly with aluminium chloride in the absence of a solvent giving an additive cornpound G,H,*SO,CI,AlCJ which on warming gives ethyl chloride and sulphur dioxide and a t the same time a brown resinous product formed by the reaction of the aluminium chloride with hydrogen chloride and ethylene products of a secondary decomposition of the ethane- sulphon yl chloride. W. G. CECIL L. HORTON (Chem. News 1915 111 29-31).-1n a previous paper ( A . 1913 ii 743) attention has been drawn to the directive action of the carboxyl group in the Walden reactiofl This influence of the carboxyl group together with the fact that all the mbstituents and reagents are unsaturated is made the basis of a further attempt to explain the reaction in question.The theory assurses the formation of an intermediate compound in which the position of the addendum depends on the attractive or repulsive action of the carboxyl or ester group. This position determines the distri- bution of the valsncy and the resulting cleavage. The author illustrates the supposed action by reference to a number of special cases. Preparation and Hydrolyeis of Ethyl Hydrscrylate. The Walden Inversion. H. M. D. W. A. DRUSHEL (Amer. J. Sci. 1915 [iv] 39 113-121).-A convenient method for the preparation of hydracrylic acid is described in which glycerol is oxidised by means of fuming nitric acid and glyceric acid liberated from the calcium salt by the addition of oxalic acid.The glyceric acid is converted into P-iodopropionic acid by treatment with iodine and solid yellow phosphorus and the concentrated solution of the sodium salt is then acted on in the cold with silver oxide using a mechanical stirrer Esterification of the acid with absolute alcohol leads to the formation of a mixture of acrylic and hydracrylic esters even if only very small quantities of mineral acid are present but ethyl hydracrylate isORGSNIC CHEMISTRY. i. 55 readily obtained if the acid is boiled with an excess .of absolute alcohol in presence of anhydrous copper sulphate and mineral acids are rigidly excluded. It has b. p. 95-96'/20 mm. D20 1.059 and is completely miscible with water.I n the absence of a catalyst it is hydrolysed only very slowly by water. In presence of O.1N-hydrochloric acid the velocity coefficient ( k . lo5) for the hydrolysis was found to be 16-25 at 2S0 40.65 at 35O and 98.75 at 45O. The influence of the hydroxyl group in the P-position on the rate of hydrolysis is shown by a comparison of the coefficients at 25' for ethyl propionate (71.2) ethyl lactate (76*1) ethyl hydra- crylate (16-25) and ethyl glycerate (18.5). Substitution of the hydroxyl group in the /?-position has therefore a marked retarding influence on the rate of hydrolysis i n presence of acids. The velocity of saponification of the ester by sodium hydroxide was also measured a t 0" and 25'. The velocity coeflicient 1.83 at Oo is compared with the corresponding values for ethyl propionate (1.1 6) ethyl lactate (14.6) and ethyl glycerate (9.02).From there numbers i t is evident that the relations differ in some respects from those exhibited by the coefficients for hydrolysis by acids but are i n general agreement with the results obtained in the saponification of the esters of other oxy-acids (compare Dean A. 1913 ii 187). H. X D. a-Sulphopropionic Acid and its Resolution into Optically Active Isomerides. A. P. N. FRANCHIMONT and H. J. BACKER (Pvoc. K. Akad. Weetensch. Amsterdam 19 14 17 653-658).-a- Sulphopropionic acid hitherto known only in the form of a viscous syrupy liquid has been obtained in the form of large hygroscopic crystals containing one molecule of water of crystallisation. When dried over phosphoric oxide it has m.p. 100.5O. Previous attempts to resolve the acids have given negativo results but it is found that if an aqueous solution of the acid is evaporated with an equimolecular quantity of strychnine crystals of the strych- nine hydrogen salt of the dextro-acid are obtained which may be purified by recrystallisation. From this the neutral barium sait is obtained by decomposition with barium hydroxide and an aqueous solution of t be free acid is obtained from this by addition of sulphuric acid. The solution concentrated in a vacuum over phosphoric oxide does not crystallise spontaneously but crystals were obtained on the addition of a trace of the racemic compound. The acid is exceedingly hygro- scopic m. p. 81-82' and contains one molecule of water.The measurement of the rotatory power of the acid and its salts gave the following values for [MI"," d-acid + 4 9 * 2 O potassium hydro- gen salt + 45.'7' barium hydrogen salt + 79.8' strychnine hydrogen salt - 71.4' normal barium salt - 14.4'. The ltxvo-acid was not ob- tained in perfectly pure condition but the following data are recorded I-acid - 45*8O strychnine hydrogen salt - 135O normal ammonium salt +- 14.8'. It is noted that the molecular rotatory power of a-sulphopropionic acid is greater than that of a-brornopropionic acid (44.4') although the weights of the substituents are practically identical. H. M. D. VOL. CVIII. i. gi. 56 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Acetaldehyde from Acetylene. FARBENFABRI- KEN VORM. FRIEDR. BAYER & Co.(Fr. Pat. 469497 ; from J. Xoc. Chem. Ijzd. 1915 34,49).-Acetylene is passed into a solution or suspension of a n organic sulphonic acid and a mercury compound or of a mercury salt of a sulphonic acid I n either case a free mineral acid may be added. For example 21.6 parts of mercuric oxide are heated with 417 parts of o-chlorophenolsulphonic acid and 583 parts of water and acetylene is passed into this solution a t 30-35" ; when the absorption of the gas has diminished considerably the aldehyde is removed by heating or by means of steam. Solu- tions of sulphonic acids have a high power of hydration considerably greater than t h a t of solutions of mineral acids of the same acidity. The yield is about 300 parts. c. s. Synthesis by means of Mixed Organo-metallic Derivatives of Zinc Polyhalogenated Ketones.E. E. BLAISE (Bull. SOC. chim. 1914 [iv] 15 728-737. Compare A 1914 i 1050 1051).- Certain dichloro- and trichloro-ketones have been prepared through the intermediary of cycloacetals. For the preparation of these cyclo- acetals lactic acid a-hydroxyhexoic acid and a-hydroxyisobutyric acid were tried the last-named being the most satisfactory. Dicbloroacetyl chloride condenses with lactic acid giving a-dichloroacetoxypropionic acid CHCl2*CO*O*CHMe*CO2H m. p. 67O b. p. 164-167'/17 mm. yielding an mid chloride b. p. llso/21 mm ; and with a-hydroxy- hexoic acid giving a-dichlorocccetoxy?~exo?ll chlovide b. p. 147-1 49'1 26 mm. Dichloroacetyl chloride is best condensed with a-hydr- oxyisobutyric acid by heating the mixture on a water-babh until the action is complete when on cooling a-dich2oroacetoxyisobutyric acid m.p. 9 5 O crystallises out ; i t is moderately readily hydrolysed by water. It gives a n anilide needles m. p. 99-100' and a chloride a colourless denbe liquid b. p. 103'/12 mm. This chloride condenses with zinc ethyl iodide in dry toluene giving the cycloacetal CHCI,-CEt<O.&O 0 CMe m. p. 51" b. p. 236-239O or 124*5-125'/16 mm. On boiling this cpclo- acetal with a mixture of acetic and hydrochloric acids i t is decomposed giving a mixture of dichloromethyb ethgl ketone CHCl,*COEt b. p. 138.5 -1 39' or 56.5'/36 mm. yielding with hydroxylamine glyoxal- dioxime and chloroniethyl chloroethyl ketone CH,Cl-CO*CHClMe b. p. 60°/13 mm. (compare Vladesco A 1891 1183) the second ketone beirjg formed by migration of the chlorine atom after the formation of the first ketone.Trichloroacetyl chloride condenses with a-hydroxyisobutyric acid giving a-trichloroacetoxyi8oDut?/ric acid CC13*CO*O*CMe2*C02H m. p. 1 1 7 O giving a chloride b. p. 107'/13 mm. or 113"/18 mm. and a n anilide m. p. 100'. The chloride yields with ziuc methyl iodide the m. p. 98-99' with sublimation cycloacetal CCl,*CMe< which on boiling with the mixture of acetic and hydrochloric acids gives methyl trichloromethyl ketone a colourless mobile liquid b. p. O*$!Me 0-coORGANIC CHEMISTRY. i. 57 57"/48 mm. 60'154 mm. and 134' (compare Schlotterbeck A. 1909 i 533). The author agrees with Cloez that the ordinary trichloroacetone consists almost entirely of aay-trichloropropanone.W. G. I t yields a sernicarbazone m. p. 140". Structure of the Two Methylglucosides; a Third Methyl- glucoside. EMIL FISCHER (Ber. 1914 47 1980-1989).-Nof's statement (A 1914 i 490) that a- and P-methylglucosides are striic- turally different as also are the corresponding a- and P-penta-acetyl- dextroses is not in harmony with the following properties of the com- pounds (i) The penta-acetates are converted into the same p-aceto- chloro(or bromo)-dextrose by hydrogen chloride (or bromide). (ii) Treatment! of P-acetobromodextrose with silver nitrate and sodium yields an acetonitrodextrose which is converted merely by crystal- lisation into the isomeric stable well-known acetonitrodextrose. (iii) By hydrolysis Purdie and Irvine's tetramethyl a- and P-methyl- glucosides (T.1903 83 1081 ; 1904 85 1049; 1905 87 1022) are converted into the same tetramethyl glucose. The latter retains its methyl groups against the attack of hydrogen chloride in benzene a t 105-115O and yet is converted by methylation into the original tetramethyl a- and P-methylglucosides. A structural difference in the methylglucoside~ therefore appears t o be impossible a t all events in the sense of NeE's conception. The reaction between a-dextrose and methyl alcohol containing 1% of hydrogen chloride yields in addition t o the two crystalline methyl- glucosides a considerable amount of a syrup which has hitherto not been purified and has been regarded a s dextrose dimetbylacetal. It is now found that the syrup distils without decomposition in a high vacuum.The purified substance C7III4O b. p. 200-215°/0*2 mm. [a]E - 3.64' in about 10% aqueous solution is named y-methylylucoside (the prefix does not refer too the structure of the compound but is used simply t o differentiate it from the a- and P-isomerides). It is stable to alkalis Felrling's solution or hot water but is hydrolysed to dextrose and methyl alcohol by N-acetic acid a t loo" by N/lOO-hydro- chloric acid at looo and by N/lO-hydrochlaric acid a t 17-16". y-Methylglucoside is scarcely attacked by emulsin or by yeast extract a t 37'. c. s. New Compounds of the Choline Type. P r e p a r a t i o n of the Monoacetate of P-Methylbutane-up-diol. 111. G. A. MENGE (U. S. Hyg. Labop.. Bull. No. 96 37-50. Compare A 1912 i 74 949).-The physiological activity of choline and p- and y-homocholines and their derivatives indicates that the greatest activity and the least toxicity are obtained in those compounds which contain the trimethyl- amine nucleus and in which the alcoholic hydroxyl group is not further removed from the nitrogen than the P-position.Consequently the substitution of the hydrogen atoms in the a- and the @positions of the carbon chain by alkyl and other groups rather than the direct extension of the chain is indicated as the most promising development from the point of view of physiological activity. The preparation and properties of a-methylcholine I' P-homocholine," 9 2i. 58 ABSTRACTS OF CHEMLCAL. PAPERS. '' y-homocholine," and of some of their derivatives have been already recorded (Zoc.cit.). OH*CMeEt*CH,*Nllle,Cl has now been prepared from the crude substance by means of the platinichloyide. P-Phennyl -P-methylcholine chloride OH* CPhMe- CH,*NMe,CI colourless rhombohedra1 plates is prepared by heating P-chloro-a- hydroxyisopropy lbenzene with a small excess of 33% alcoholic tri- methylamine in a sealed tube in boiling water; it forms a platini- chloride (C,,H,,ON),PtC1 decomy. 223*5-224* (corr.) and auri- chloyide m. p. 137*5-138*5O (corr.). In striking contrast to all other attempts to acylate /3P-disubstituted cholines the acetyl derivative of PP-dirnethylcholine chloride OAc*CMe2*CH2*NMe,C1 a colourless waxy substance is readily obtained by gently boiling PP- dimethylcholine chloride with acetic anhydride and pouring the cooled mixture into dry ether; theplatinichloride has decomp.233-234'. The acetyl derivative of P-phenyl-a-metbylcholine chloride prepared by means of acetyl chloride at looo forms a yellow platinichloride. For the preparation of a-mono- and di-substituted cholines chloro- hydrins of the types CHRCl*CH,-OH and CRR'Cl*CH,*OH are necessary Two methods of preparing the latter namely (i) the addition of bypochlorous acid to olefines and (ii) reactions indicated in the scheme Pure P-methyl-P-ethylcholine chloride CH,Cl*CRR'*OH -+ OAc*CH,*CRR'*OH -+ OAc*CH,*CRRCl -+ OH*CH,*CRR'CI have not been practically successful. However the first stage of the second method for example heating anhydrous potassium acetate and a-chloro-P-methylbutan-P-ol to gentle boiling readily yields the acetate OAc*CH,*CMeEt*OH b.p. 92*8-93'/15 mm. (Kling gives LUIGI ROLLA (Ann. Chim. Applicata 1914 2 301-304).-The author has analysed the gaseous products formed by the action of water vapour on barium cyanide at various temperatures ranging from 100' to 500O. A t temperatures below 200° the changes taking place are expressed by the equations (1) Ba(CN) + 3H,O = Ba(OH) + ZNH + 2CO and (2) Ba(OH) + 2CO = (H*CO,),Ba. I n accord with the thermochemical data the absorption of carbon monoxide by brtrium hydroxide occurs more readily at 100' than a t higher temperatures. A t ZSO' the barium formate begins to undergo partial decomposition thus (3) (H*CO,),Ba = BaCO + H + COY and the oxalate which is also formed to some extent is probably decomposed into barium carbonate and carbon monoxide.At 300-400° reactions occur similar t o those observed by Vignon (A. 1911 ii 391; 1914 i 917) in his investigation of the action of carbon monoxide on lime the corresponding equation being (4) 2(H-C02),Ba + BaO = 3BaC0 + CH or (5) 4(H*CO,),Ba + 2Ba0 = 6BaC0,+C2H,+2H,. That reaction (4) should take place at a higher temperature than (2) is indicated by thermochemical data but 145-147O/10 rnm.) DZ5 0.9989. c. s. Action of Water Vapour on Barium Cyanide.ORGANIC CHEMISTRY. i. 59 i t could not be foreseen that above 400' the predominating reactions are (3) and the decomposition of the oxalate into carbonate and carbon monoxide. At temperatures exceeding 250° carbon dioxide is formed in appreciable proportions ; combination of reactions (2) and (3) evidently results in a change analogous to the formation of water gas from carbon monoxide and water vapour.PIETRO FALCIOLA and ANTONIO MANNINO (Ann. Chim. Applicata 1914 2 351-356).- Treatment of olive oil with hydrazine hydrate renders the oil turbid and raises its melting point considerably. The reaction proceeds in the cold and without appreciable development of heat a slight ammoniacal odour being detectable in its early stages. The mass becomes whiter and the elevation of its melting point increases with the proportion of hydrazine hydrate employed. The solid substance separating from the oil is mostly soluble in hot alcohol which deposits a crystalline substance m. p. 110-112°. I t is also soluble in acetone which deposits a white substance m.p. 65-67'. A number of other oils both animal and vegetable exhibit similar behaviour. Such hardened oils and fats either alone or in conjunction with other substances such as naphthalene or anthracene are suitable for the manufacture of candles. Triolein behaves similarly with hydrazine hydrate the resultant product which contains C 74*32-74*47% H 23*56-13-64% and N' 9*03-9*07% having m. p. 110-112° about 76' and 106-108O when crystallised from alcohol acetone and alcohol successively. The iodine number of the substance is 166 and vapours alkaline towards litmus are evolved when i t is heated with potassium hydroxide. The similar substance m. p. 112-114' obtained from fused tristearin has a still higher iodine number ; its percentage composition is C 73.1 H 13.4 and N 9.1 and its molecular weight determined in freezing benzene varies from 178.8 to 320.4 as its concentration increases from 1.2% to 2.6%.Tripalmitin and hydrazine hydrate yield a similar product m. p. 108- logo. T. H. P. Nitration of Mixed Dihalogenbenzenes. A . F. HOLLEMAN (Proc. K. Akad. Wetensch. Amsterdam 19 14 1 7 846-849).-The author at tempts to express quantitatively the directing influence of each of two substituents in a benzene nucleus on a third entrant atom or group. [With W~~Au~.]-\vhen o-chlorotoluene is nitrated the chlorine atom directs the nitro-group to positions 3 and 5 whilst the methyl group directs it to positions 4 and 6. If the proportion is determined (by solidification curves) in which o-chloro-4(and 6)-nitrotoluenes are present in regard to the isomerides o-chloro-3 (and 5)-nitrotoluenes the ratio which is found t o be Mo :GI= 1 1.415 is also the proportion of the substitution velocities caused by methyl and by chlorine [With VAN DEN AREND.]-T~~ preceding ratio applied to the case of the nitration of p-chlorotoluene gives calculated quantities of the isomeric chloronitrotoluenes which agree approximately with those observed experimentally. T.H. P. Action of Hydrazine Hydrate on Fats.i. 60 ABSTRACTS OF CHEMICAL PAPERS. [In part with HEINEKEIT.]-T~~ relative quantities of mononitrated chlorobromobenzenes produced by the nitration of 0- or p-chlorobromo- benzene are determined by estimating the amount of chlorine and bromine displaced by treatment with sodium rnethoxide ; it is well known that only halogen atoms in the ortho- and para-positions to nitro-groups are eliminated by this rexgent. Experiments on the nitration of 0- and p-chlorobromobenzenes show that the ratio of the substitution velocities caused by chlorine and bromine when present together in the benzene nucleus is C1 Br= 1 0.88.The ratio obtained in the case of o-chloroiodobenzene is C1 I = 1 1.84. From these two ratios the authors calculate that the ratio for bromine and iodine should be Br I = 1 2.30 ; the experimental value obtained by the nitration of o-brornoiodobenzene is Br I = 1 1.75. c. s. Action of Potassium Hydroxide on the Nitroamine of 4 6-Dinitro-3-methylanisidine. F R ~ D ~ R I C REVERDIN and ARMAND DE Luc (Arch. Sci. phys. nut. 1914 [iv] 38 410-413).-The authors have determined the constitution of the substance m.p. 1 8 2 O previously obtained by them (compare A 1914 i 831) by heating 4 6-dinitro-3-methylnitroaminoanisole with potassium hydroxide solu- tion. This substance is now shown to be 4 6-dinitro-3-methylmino- phenol its constitution being proved by the fact that on heating its silver salt emulsified in methyl alchol with methyl iodide on a water- bath for fifteen minutep the methyl ether of 4 6-dinitro-3-methyl- arninophenol m. p. 198' (compare Blanksma Rec. truv. chim. 1889 8 276) is obtained. The original substance dissolves in nitric acid (D 1.5.2) giving a violet solution turning to yellow on addition of water and yielding by ex traction with ether a substance cry stallising in small prisms m.p. 173'. W. G. The Three Fluorobenxoic Acids and their Nitration. J. H. SLOTHOUWEB (Kec. trccv. chim. 1914 33 324-342).-The author has prepared the three fluorobenzoic acids by oxidation of the correspond- ing fluorotoluenes with aqueous potassium permanganate. H e has determined the solubility in water a t 32' and the electrical conduc- tivity at 25' of these acids and from them has prepared a number of derivatives. o-Fluorobenzoic acid m. p. 123O gives a chloride b. p. 206O an amide small white needles m. p. 1 1 6 O a rnetlhyl ester b. p. 209' a n ethyl ester b. p. 221' and the following salts sodium salt C,H,F* CO,Na basic magnesium salt CGE4F*CO,*Mg*OH 3H,O calciuin salt (C,H4F*C0J2Ca 2H,O barium salt (C,H,F*CO,),Ba H,O strontium salt (C,H,F* C0,),Sr,2H20 zinc salt (C,H,F*C0,),Zn,3H20 basic zinc salt C,H,F*CO,*Zn*OH cadmium salt ( C,H,F*C0,)2Cd,H,0 and 2iH,O basic coppei.salt C,H,F*CO,*Cu*OH silver salt C,H ,F*CO,Ag. m-Fluorobenzoic acid m. p. 123.6' yields a chloride b. p. 189' an arnide white leaflets m. p. 130° a methyl ester b. p. 1 9 7 O an ethyl ester b. p. 2 0 9 O and the following salts sodium salt C,H,F*CO,Na,ORGANIC CHEMISTRY. i. 61 potassium salt C,H,F'*CO,K calcium salt (C,H,F*C0,),Ca:3H20 barium salt (C,H,F*C02),Ba,3H,0 and 4E20 cadmium salt ( c6 H,F*CO,),Cd 2H20 basic coppev salt C,H,F'*CO,*Cu*O H silver salt C,H4F*C02 Ag. p-Fluorobenzoic acid m. p. 182O gives a chloride b. p. 193' a n amide white leaflets m. p. 154*5" a methyl ester b. p. 198" an ethy? ester b. p 210° m. p. 26" and the following salts sodium salt C,H,F*CO,Na ccclcium salt (C,H,P*CO,),Ca 3H,O barium salt (C6H4F*C02)2Ba and with 2H20 and 4H,O z i n c salt (C,H E'*C0,),Zn,3H20 cadmium salt (C,H4F*C0,),Cd,4H20 basic lead salt C,H,F*CO2=Pb*OH,3H,O copper salt (C6H4F*C0,!,Cu silver salt C,H,F*CO,Ag.o-Fluorobenzoic acid is readily nitrated when slowly added to nitric acid (D 1.52) at 0". The two isomeric nitro-compounds formed are separated by fractional crystallisation of their potassium salts from water the salts being then decomposed with dilute hydrochloric acid. The main product is 2-fluoro-5-nitrober~xoic acid m. p. 138-139' which is almost white and gives a potassium salt crystallising in long needles. I t s constitution was proved by heating it with alcoholic ammonia in a sealed tube at 130-140" the product being 5-nitro- 2-aminobenzoic acid rn.p. 265' (compare Hubner A. 1878 148). The other product of the nitration only present as a trace was 2;fluoro-3-nitrobeszxoic acid m. p. 160". m- Fluorobenzoic acid is nitrated under similar conditions giving 3-fEuoro-6-nitrobenxoic acid m. p. 134.5" which is converted by alcoholic ammonia into 6-nitro-3-aminobenzoic acid (compare Griess Ber. 1872 5 198). A certain amount of resinous products are formed during this nitration. p-Fluorobenzoic acid is nitrated by adding i t slowly to boiling nitric acid (D 1.52) and pouring the product into excess of cold water. The sole product is 4-f2uOrO-3-nitrOhenxOiC acid slender needles m. p. 121-1 22O which with alcoholic ammonia yields 3-nitro-4-amino- benzoic acid (compare Salkoweki this Journ.1875 72). Comparing the four series of fluoronitro- chloronitro- and bromo- nitrobenzoic acids they show in each case R steady rise in the ni. p. on passing from the fiuoro- through the chloro- t o the bromo-deriva- tives. The point of entrance of the nitro-group in all the above nitrations is in every case what would be expected from a knowledge of the behaviour of fluorobenzene and benzoic acid respectively on nitration. W. G. Preparation of Halogen-alkyl Esters of o-Acetoxybenzoic Acid. It. WOLFFENSTEIN (D.R.-P. 276809 ; from J. SOC. C'hem. I d . 1914 33 1172. Compare A 1912 i 556).-Polyhaloidalkyl esters of salicylic acid are treated with acetylating agents. For example tert.-trichlorobutyl salicylate is heated with acetic anhydride and anhydrous sodium acetate at 160-180" and the product is treated with water and with aqueous sodium carbonate the ester being finally extracted by ether c.s.i. 62 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Halogen-alkyl Esters of o-Acyloxybeneoic Acids. R. WOLFFENSTEIN (D.IC.-P. 276810 ; from J. Xoc. Chem. Ind. 19 14 33 11 72. Compare preceding abstract).-Polyhalogen-alkyl esters of salicylic acid are treated with acylating agents other than those which introduce the acetyl group. c. s. cis-Caronic Acid and Some of Its Derivatives. R. LOCQUIN (Bull. Xoc. chim 1914 [iv] 15 747-751. Compare Baeyer and Ipatiev A. 1897 i 83 ; and Perkin and Thorpe T. 1899 75 48),- cis-Caronic acid can readily be distinguished from its isomeride terebic acid by its instantaneous m.p. taken on mercury that of the former rising t o 186" and that of the latter remaining at 174'. Methyl cis- caronate C9H1404 is a colourlees mobile liquid b. p. 111-113°/ 14 mm. Ethyl cis-caronate C,,H,,O bas b. p. 129-330'/13 mm. The acid can be readilyregenerated from the esters by boiling with 15% aqueous hydrochloric acid under reflux until the oily layer dis- appears. Caronic anhydride is best prepared by boiling the cis-acid for some time with a n excess of acetyl chloride or thionyl chloride. 1x1 benzene solution with aniline i t yields an acid anilide CO,H*C,H,*CO*NHPh rn. p. 205' which if kept for some time at 180-190° is converted into the a d C,H,<CO>NPh co m. p. 143'. W. G. Glucosides of Chalkones [P henyl Styryl Ketones].G. BARGELLINI (Gazzetta 19 14 44 ii 520-528).-The author has prepared various glucosides of phenyl styryl ketones by condensation of the glucoside of salicylaldehyde helicin and of the glucoside of vanillin with different hydroxy-ketones. The condensations take place in alcoholic solution a t the ordinary temperature and in presence of either 40% sodium hydroxide solution or piperidioe. The glucosides are not resolved into their constituents by emulsin and therefore belong t o the a-series. They are not hydrolysed by acids but they dissolve in concentrated sulphuric acid giving first an intense red coloration and afterwards an orange-yellow or red solution. The gtucoside of 4-hydroxyphenyl 2-hydroxlystyryl ketone OH*C,H,*CO CH CH C,H,* O*C,H 1105 prepared from the glucoside of salicylaldehyde and p-hydroxyaceto- phenooe forms a felted mass of minute cream-yellow needles m.p. 26 7-25 9 O (decom p.). The glucoside of 2-hydroxy-4-rnethoxyphenyl 2-hydroxystyryl ketone O M e ~ C 6 H 3 ( 0 ~ ) * ~ O * C H C ~ * C H 4 * O * C ~ ~ ~ obtained from the glucoside of salicylaldehyde and 2-hydroxy-4-methoxyacetophenone forms flocks of canary-yellow needles xu. p. 213-215". The glucoside of 2-hydroxy-5-methoxyphenyl 2-hydroxysty~yl ketone C,,H,,O forms small orange-yellow needles m. p. 255-227'. The g Eucoside of 2-h y droxy - 3 4 -dime t hoxypheng l 2 -h y drox ystyry Z ketone OH*C,H,(OMe),* co CH:CH C,H,* o*C6H1,o5 forms bright yellow medles m. p. 195-196' (decornp.).ORGANIC CHEMISTRY. i. 63 The glucoside of 1 -hydroxy- /\A 2-naphthyl 2 - hydroxystyryl 1 I ,,!-GO* CH C H * C,H,*O* C,H1,O ketone (annexed formula) \A/ prepared from 2-acetyl-a- naphthol and the glucoside of salicylaldehydo forms flocculent aggregates of minute ormge-red needles m.p. 264-246' (decomp.). CHO-(~>-O*C6H,05A~ ~~tra-acetylglucovanillin (annexed formula) prepared from tetra-acetyl- bromoglucose and vanillin in presence of sodium hydroxide forms shining colourless prisms m. p. 143-144'. The glucoside of 2-lqdroxy-4-methoxyphenyl 4-hydroxy-3-methoxy- styryl ketone O?il[e* C,H,( OH)*CO* CH :CH*C,H,( OMe)* 0*C,H,,05 prepared from the preceding compound and 2-hydroxy-4-methoxyaceto- phenone forms canary-yellow crystals m. p. 220-225O. OH OMe T. H. P. Preparation of Anthraquinone. CHEMISCHE FABRTK GRIESHETM- ELEHTRON (U.S.Pat. 1119546; from J. Xoc. Chem. lnd. 1915 34 22).-Anthracene is treated with nitric acid in the presence of a mercury salt and an indifferent liquid below 60'. The product which is a mixture of unstable meso-nitro-derivatives of nnthracene is con- verted into anthraquinone by treatment with an oxidising agent in the presence of a mercury salt above 60'. c. s Preparation of Aminoanthraquinones. FARBWERKE VORM. MEISTER LUCIUS & BHUNING (Fr. Pat. 469741 ; from J. Soc. Chem. Ind. 1915 34 22. Compare this vol. i 20).-Organic amino- compounds may be used in place of ammonia. c. s. Constituents of Esential Oils. I. Galbanum Oil. 11. Syntheses in the Sesquiterpene and the Diterpene Series. F. W.SEMMLER and K. G. JONAS (Ber. 1914 47 2068-2082).-1. The oil obtained by the distillation of Galbanum resin has b.p. 55-195O/15 mm. D25 0.9353 !nF 1.49395 and a t8'. By repeated fractional distillation it is separated into nine fractions of which the following have been examined. The fraction b. p. 56.5-75O/15 mm. obtained i n 29.506 yield contains pinene nopinene (P-pinene) and myrcene but no camphene. The fraction b. p. 100-120°/15 mm. (245%) contains a substance CloHl6.O (enolisible ketone?) which can be esterified and yields by oxidation a ketonic acid C,,,H,,O ; from the latter the dicarboxylic acid C9H1404 is obtained by the action of an alkaline solution of bromine. The fractions b. p. 120-150°/15 mm. (5%) contain cadinene. The fractions b. p. 150-170'/'15 mm. (36%) contain a tertiary sesquiterpene alcohol cadinol C,,H,60 which in a slightly impure state has b.p. 155-165°/15 mm. D20 0.9720 nD 1,50702 and uD +22O and yields an acetate C17H2,02 b. p. 160-170°/9 mm. DU 0.9916 nz 1.49870 and a' + 14'. By treatment with potassium hydrogen sulphate phthalic or succinic anhydride or formic acid,i. 64 ARSTRACTS OF CHEMTCAL PAPERS. cadinol is converted into I-cadinene. By reduction with hydrogen in the presence of platinum I-cadinene is converted into 1-tetrahydro- cadinene C15HB8 b. p. 125-128"/10 mm. D20'5 0.8838 ng'5 1.48045 I-Tetrahydrocadinene obtained by the reduction of I-cadi- nene dihydrochloride by sodium and alcohol has b. p. 125-12S0/ 10 mm. D21'5 0.8827 ng'5 1.48094 and ag'5-520. The colour re- actions of cadinene described by Wallach could not be obtained by the authors.11. Octahydro-a-camphorene (Semmler and Rosenberg A. 191 3 i 377) has b. p. 183-186'/14 mm. DzO 0.8331 n 1.46001 and From the liquid products obtained by the action of hydrogen chloride on the diterpene fraction of polymerised myrcene there is produced by the elimination of hydrogen chloride a bicyclic diterpene C,,H, for which the name iso-a-camphorene is proposed. It has b. p. 193-197"/19 mm. DZ1 0.9029 nD 1*50300 and [.]D+o" and is reduced by hydrogen and platinurn to hexahyclroiso-a-carnphorene C20H38 b. p. 180-186"/14 mm. DZ1 0.8588 nD 1.46800 and By heating with anhydrous oxalic acid in a sealed tube linalool has been converted directly into a-camphorene and citronellaldehyde into a diterpene oxide C,,H,,O b. p. 190-200°/17 mm. DZo 0.9193 nD 1,49156 al,+4" which is reduced by hydrogen and platinum to a saturated substance C,,H,,O b p.183-187°/17 mm. DZ0 0.8944 By reduction in dry ether by hydrogen and platinum cyclokoprene- myrcene (Semmler and Jonas A. 1913 i 742) yields hexahydrocyclo- isoprenemyrcene C15Hao b. p. 133-135"/15 mm. DZO 0.8245 nD 1.45497 an +-O' the formation of which is a complete proof of the monocyclic nature of cycloisoprenemyrcene. Since cadinene has a bicyclic structure of the naphthalene type and since the condensation of acyclic terpenes with isoprene yields mono- cyclic sesquiterpenes the authors hoped to synthesise bicyclic sesqui- terpenes for example cadinene by condensing monocyclic terpenes with isoprene. By heating I-a-phellandrene with isoprene in a sealed tube a sespuiterpene Cl5HZ4 is obtained which has b.p. 129-132'1 15 mm. DZ0 0.8976 12u 1,4949 and a - 1 5 O and is probably identical with P-santalene. Limonene and isoprene do not react by heating in a sealed tube but by their reaction in glacial acetic acid at 35" or by treating the two hydrocarbons in the proportion 2 1 with about three times the quantity of ethylsulphuric acid a t - 18' to - loo a sesquiterpene Cl5HZ4 b. p. 120-127°/10 mm. DZo 0.S89 n 1.502 otD +Lo is obtained which appears to be monocyclic. Similar results (and probably tho same sesquiterpene) are obtained with - 20". [.ID k O0* [a]D k 0'. nD 1.47319 a D + 3". isoprene and pinene or sabinene. c. s. The Synthesis of Colouring Mattens. E. NOELTTNG (Arch. Xci. phys. nat. 1914 [iv] 38 244-262 337-343).-An historical survey of the chemistry of dyes containing a classification of those used on a large scale into groups a brief account of the properties of each group being given.W G.ORUANIC CHEMISTRY. i. 65 Vat [Anthracene] Dyes and Intermediate Products for Use in their Preparation. BADISCHE ANILIN- & SODA-FABRIK (1st. Add. t o Pr. Pat. 458949 ; from J. SOC. Chem. Ind. 1915 34 22).- Imines of anthracene-1 9-dicarboxylic acid in which the hydrogen of the imino-group is replaced by a hydroxyl alkyl or aryl group are obtained by treating the acid or its anhydride with hydroxylamine or with an aliphatic or aromatic primary amine. For example the methylimine is obtained by heating anthracene-1 9-dicarhoxylic anhydride with ten times its weight of 13% aqueous methylamine a t 150" for 5 hours.The substituted imines are converted into vat dyes analogous t o those obtained according t o the principal patent by fusion with alkalis. The dyes may also be obtained by treating the dyes mentioned in the principal patent with alkylating or arylating agents. I n general the products dye rather bluer shades than do the substances c. s. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 276808; from J. SOC. Chem. Ind. 1914 33 1151).-Isatin is oxidised by potassium per- manganate in neutral aqueous suepension yielding a compound CI6H8O2N2 m. p. 262O yellow crystals which is converted into indigo- white by sodium hyposulphite and a n excess of alkali hydroxide and is very reactive and therefore suitable for the preparation of indigoid D i k e t o m e t h y l t r i a z i n e and its Derivatives.A. OETROGOVICH (Gazzettu 1914,44 ii 562-585).-4 6-Diketo-2-methyl-1 3 :5-triazine (compare A 1911 i 1036) may be conveniently prepared by heating biuret with acetyl chloride in a sealed tube the isolation and purification of the acetylbiuret being thus avoided The free base crystallises either i n the anhydrous state or with 1H,O and has m. p. 276-277" (decomp.). The marked acidity of the compound shown by the ability of its aqueous solution to decompose carbonates and the fact t h a t all i t s metallic derivatives contain only one equivalent of metal are in from which they are derived. Preparation of an Oxidation Product of Isatin. dyes. c. s. better accord with the enolic structure NH<gf:i?>C*OH than with the diketonic formula previously given.The hydrochloride C,I'I,O,N,,HCl was prepared but the correspond- ing sulphate and selenate could not be obtained the hydrogen sulphate C,H,O,N,H,SO (or + H,O) and hydrogen selerzate C,H ,02N,,H2Se0,,&H,0 being formed under all the conditions employed. When heated a t above 100' or when repeatedly evaporated in aqueous solution on a water-bath the platinichIoride (C,H,O,N,) H2PtCI6,4H2O (compare Nencki Ber. 1876 9 234) loses hydrogen chloride with formation of dichloroplatodiketomethyltriazine C,H,O,N,*PtCl,* C4H402N3 which separates a s a pale yellow powder. Attempts to prepare the aurichloride resulted in the reduction of the auric chloride t o metallic gold which was deposited in shining leaflets.This reaction is very sensitive and may be employed t o detect small quantities of the base either in the pure state or ini. 66 ABSTRACTS OF CHEMICAL PAPERS. admixture with a large proportion of acetylbiuret which does not reduce auric chloride. Diketomethyltriaxilns phosphonaolybdate forms minute lemon-yellow acicular prisms. The sodium derivative of diketomethyltriazine C,H,ON,*ONa crystallises with 14H20 or 2H,O. The silver +&H20 and +H,O the barium + 7H20 and the basic Zeud derivatives O( *Pb*C4H402N3)2 + 8H,O were prepared. T. H. P. Mechanism of F o r m a t i o n of Azo.compounds by the Action of Diazonium Salts on Phenols and on Amines. G. CHARRIER (Gazzetta 19 14 44 ii 503-51 6). -The author discusses the various theories which have been advanced to explain the formation of hydroxy- and amino-azo-compounds by the action of diazonium salts on phenols and on amines.None of these theories explains however the varying reactivity in this respect shown by diazouium salts of phenols and of their ethers. The most secure basis for any explanation of the mechanism of this combination is furnished by the very general diazo-decomposition of the nitrates of (1) hydroxyazo-compounds and of their etherp and (2) aminoazo-compounds and of their alkyl derivatives (compare Charrier and Ferreri A. 1922 i 812; 1913 i 535 1111 1112,1113; 1914 i 597 599 748 1178). One advantage of such an explanation is that i t allows of the reconciliation of Blomstrand’s structural formulae for diazonium salts with certain of their more important reactione such as the formation of hydroxy- and amino-azo.compounds. In the light of the author’s experimental results it is probable that the formation of the so-called diazoamino-compounds or aryldiazoanilideq to which the nitrates of hydroxyazo-compounds show certain analogies in behaviour may be regarded as taking place according to the scheme Ar-NH + NiNAr’Clz N/HAr-..-.NI!YAr’Cl= NHAr*N:NHAr‘C‘l= =NHAr*N:NAr‘+HCl. T. H. P. ,,H .._______.._._ The c o a g u l a t i o n of Albumin by Pressure. P. w. BRIDGMAN (J. Biol. Chem. 1914 19 511-512).-Egg-albnmin was enclosed i n a nickel-steel case and pressure transmitted t o it by mercury. If the pressure is applied slowly any rise of temperature is negligible; a pressure of 5000 atmospheres for thirty minutes rendered the white of egg a little stiff ; 6000 produced coagulation like curded milk ; 7000 made it like a hard-boiled egg.The rate of coagulation is increased at low temperatures. J. A. MENZIES (Proc. physiol. Xoc. 1914; J. Physiol. 49 iv-v).-The blood is mixed with a quarter of its volume of a syrupy solution of potassium carbonate and heated on the water-bath until it sets into a brown coagulum. This is thrown into twice its volume of alcohol and left overnight for thorough extraction of the bEmatin ; on neutralising this dark brown extract with hydrochloric acid hsematin is precipitated and is W. D. H. The Preparation of Haematin.PHYSIOLOGICAL CHEMISTRY. i. 67 purified by washing with distilled water alcohol and ether. Hsma- tin may also be precipitated by ether or by calcium chloride and ammonia or baryta mixture. Calcium and barium compounds respectively are thus obtained. W. D. H. Hzematin Compounds. J. A. MENZIES (Proc. physiol. Xoc. 1914; J. Phyoiol. 49 v-vi).-Hzmatin exists in two forms one which occurs in solutions and moist precipitates is soluble in dilute hydrochloric acid. The other the dry substance is insoluble in dilute acid but is readily soluble in alkali. The first may be a hydrated aubstance and is changed by drying in the same way that a lactone is formed from a hydroxy-acid. Haematin in acid solution is precipitated by dialysis the acid acting as a solvent and not forming a compound. I n alkaline solution it is not precipitated on dialysis although the solution becomes neutral to litmus. Sodium and potassium therefore form compounds with hsmatin which are soluble in water. The calcium and barium compounds are insoluble in water but dissolve in alkali with the formation of the alkali compound. Hsmoglobin is analogous to a salt globin playing the part of a base and hsmatin that of an acid. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9150800053

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 59 Litharge from Zarshuran Persia. ALEXANDER SCOTT (Min. Mag. 19 14 1 7 143-1 46).-The specimen described is from a mineral vein which has long been worked for orpiment near the Zarshuran River in Kurdistan. It is red with a yellowish-brown streak and is in part crystalline with a laminated structure. The optical characters of cleavage flakes suggest orthorhombic symmetry. Analysis gave PbO. CuO. Sb,O,. P,05. CO,. Total. Sp. gr 97.17 2.61 0.30 trace trace 100.08 8'61 Red and yellow crystalline modifications of lead monoxide haveii. 60 ABSTRACTS OF CHEMICAL PAPERS. been prepared artificially but there is solm0 confusion in the crystallographic descriptions of these. A New Locality for Voelckerite. AUSTIN F. XOGERS (Min.Mclg. 1914 17 155-162).-Careful determinations of the amount of water present in apatites which are deficient in fluorine and chlorine prove that these elements are replaced isoniorphously by oxygen rather than by hydroxyl the general formula of minerals of the group being 3Ca,(P0,),,Ca(F,,Cl,,0JC03). For members of the group in which the oxygen atom predominates the author has proposed the name voelckerite (A. 1912 ii 565). The following analysis by G. W. Jordan is given of voelckerite from a rneta- morphic glaucophane-bearing rock from Calaveras Valley Santa Clara Co. California. The mineral is white and subtranslucent with an imperfect cleavage and faint lustre D 3-06. Deducting a portion of the carbon dioxide as present in admixed calcite the amount of CO is calculated as 0.35 and the excess of oxygen as 1.49% CaO.A1,0,. FeO. P,05. H,O. CO,. Insol. Total. 54-46 1.35 0.24 41'47 0.22 1.03 0.53 99.30 L. J. S. L. J . s. Pintadoite and Uvanite Two New Vanadium Minerals from Utah. FRANK L. HEW and WALDEMAR T. SCHALLER (J. Kashington Acad. Xci. 1914 4 576-579).-Pintadoite occurs as a thin green efllolrescence on the sandstone cliffs of Caiion Pintado San Juan Co. Utah. Under the microscope it is slightly pleochroic and has moderate t o high birefringence. It dissolves slowly in cold water. Analysis I gves the formula 2Ca0,V20,,9€120 U03. CaO. MgO. K,O. V205. P20,. As,O,. H,O. Insol. Total. I. - 2 2 6 - - 42.4 - - 35.0 - 100.0 11. 39.60 1-73 0.04 0-30 37-70 0'06 0-05 18-28 1.24 99.00 Uvanite occurs as a brownish-yellow powder disseminated in sandstone a t Temple Rock Emery Co.Utah. 11; resembles carnotite in appearance and mode of occurrence but i t has not the clear yellow colour characteristic of carnotite. Under the micro- scope the minute crystalline particles show a high birefringence. The mineral is not soluble in water but it dissolves very quickly in ammonium carbonate solution. Analysis I1 agrees with 2U0,,3V20,,15H20. L. J. S. Barkevikite from Lugar Ayrshire. ALEXANDER SCOTT (Mi%. Mag. 1914 17 138-142).-Black lustrous prismatic crystals of barkevikite occur in a rock called lugazite. The optical characters are in agreement with those of the original barkevikite from Barkevik in Norway. SiO,. TiO,. A1,03. Fe,O,. FeO. MnO. MgO. CaO. Na20. K20. H,O. Total. 42.48 2.90 8:58 6-81 15'62 0-39 2-78 13-45 6'32 0.60 0.25 100.18 The relation of barkevikite to other members of the amphibole group is discussed.D 3.298 ; a.nalysis gave L. J. S.ANALYTICAL CHEMISTRY. ii. 61 Meteorites of Uwet and Angela Re-determination of Nickel and Iron in the Baroti and Wittekrantz Meteoric Stones. G. T. PRIOR (Min. Mag. 1914 17 127-234).-A mass of iron weighing absut 55 kilos. fell about ninety years ago a t Uwet in Southern Nigeria. An etched slice shows well-marked Neumann lines together with needles of schreibersite and nodules of troilite. The iron belongs t o the normal hexahedrite group of the type of Braunau. Several masses of iron the largest weighing 4341 grams have been found embedded in the caliche at the Angela Nitrate Works near Santa Catalina Iquique Chili. This iron is an ataxitel con- taining a comparatively low percentage of nickel (anal. 11)) and characterised by its extraordinary richness in schreibersite (amount- ing t o nearly a quarter of the mass); i t is probably identical with La Prirnitiva (A. 1898 ii 391) Analysis I corresponds with Fe,,Ni. Fe. Ni. Go. Cu. P. C. Total. Sp. gr. I. 93.36 5-78 0.75 nil 0.25 0.03 100.17 7.862 11. 95.03 4.52 0.65 - trace trace 100-20 7.892 The separation of iron and nickel by means of ammonia is found to be incomplete even after several precipitations. Triple precipita- tion of the iron with sodium acetate and subsequent precipitation with ammonia gives more accurate results ; the percentages previously given for the Baroti and Wittekrantz meteorites (A. 1914 ii 64) are now corrected. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9150805059

出版商:RSC    

年代:1915

数据来源: RSC