摘要:

J O U R N A L H. E. ARMSTRONG, Ph.D., F.R.S. HORACE T. BROWN, LLD., V.R.S. J. DEWAR, LL.D., F.R.S. WYNDHAM R. DUNSTAN, hf.A., F.R.S. OF €1. MEI,DOIA, F.R.S. H. FORSTER MORLEY, M.A., D.Sc. A. SC)OTT, D.Sc., F.R.S. T. E. 'FHORI'E, T,L.D., F.R.S. THE CHEMICAL SOCIETY. ON ORGANIC CHEMISTRY. d5:bifor : W. P. WYNNE, D.Sc., F.R.S. sP,xr- &bitax : A. J. GIIEENAWAY. C . P. BAKER, Ph.D., 13.8~. W. A DAVIS. T. EWAN, R.Sc., Ph.D. M. 0. FOKSTER, Ph.D., D.Sc. E. GOULDING, RSc. IV. D. HALLTBUHTON, hl. D., l3.S~. , A. HARDEN, M.Sc., Ph,D. L. M. JONES, B.Sc. L. DE KONINGH. N. LEONARD, R.Sc. H. R. J,E QUELX, 13.S~. c. H. BOTHAI1ILEY. F. R. S. A. LAPWORTH, D.Sc. D. A. LOUIS. N. H. 3. MILLER, Ph.D. G. T. MORGAN, D.Sc. J . C. PHILIP, &LA., Ph.D. R. -€I. PICKAI:D, D.Sc., Ph.1). T. €1. POPE. E. C. ROSSITER. M. J. SALTER. L. J. SPENCEI?, M.A. J. J . SIJIIBOROUGH, Ph.D., D.Sc. J. P. TIIOHPE, Ph.D. E. IT. ~ ~ ' i ~ ~ ~ ~ ~ i , ~ ~ r : r ~ : ~ , ~ , R.A., P1i.r). ir. M. LOWILT, D . s ~ . 1900. Vol. LXXVIII. Part I. LONDON: GURNEY st JACKSON, 1, PATERNOSTER ROW. 1900.RICHARD CLAY & SONS, LIMITED, h K D o N & BUNQAP.

ISSN:0368-1769    

DOI:10.1039/CA90078FP001

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年代:1900

数据来源: RSC

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OF C. F. BAKER, Ph.D., B.Sc. c. I-I. BOTHAMLEY. W. A. DAVIS. T. EWAN, B.Sc., Ph.D. 31. 0. FOI:STEI:, I’h.D., D.Sc. E. GOULDISG, B.Sc. W. D. HALLIBIJIWOK, M.D., B.Sc., A. HARDEN, M.Sc., P1l.D. 1,. M. JONES, B.Sc. L. DE KOSINGH. A. LAPWORTH, DSc. N. LEONARD, R.Sc. F.R.S. H. R. LE SUEVR, B.Sc. THE: CHEMICAL SOCIETY. D. A. LOUIS. T. M. LOWRY, D.Sc. N. H. J. MILLER, P1i.D. G. T. MORGAN, D.Sc. J. C. PHILIP, M.A., Ph.D. R. H. PJCICAI:D, D.Sc., Ph.D. 1’. H. POPE. E. C. ROSSITER. 11. J. SALTER. L. J. SPENCER, M.A. J. J. SUDBOROUGH, Ph.D., D.Sc. J. F. THORPE, P1i.D. E. W. WHEELWRIGHT, B.A., Ph.D. ABSTRACTS O F PAPERS ON PHYSICAL, INORGANIC, MINERALOGICAL, PHYSIOLOGICAL, AGRICULTURAL, AND ANALYTICAL CHEMISTRY. H. E. ARMSTROXG, Ph.D., P.R.S. HORACE T. BROWN, LL.D., F.R.S. J. DEWAR, LT,.D., F.R.S. WYNDHAM R. DUNSTAN, M.A., F.R.S. H. J. H. FENTON, M.A., F.R.S. C. E. GILOVES, F.R.S. R. MELDOLA, F.R.S. H. FOCSTEIL MORLEP, &LA., D.Sc. T. E. THORPE, LL.D., F.R.S. W. A. TILDES, D.Sc., F.R.S. A. SCOTT, D.Sc., F.R.S. 6bitD.r : W. P. WYNNE, D. Sc., F. R.S. Sixzb- 6.b.itD.r : A. J. GREEXAWAY. 1900. Vol. LXXVIII. Part 11. LONDON: GURNEY SS JACKSON, 1, PATERNOSTER ROW. 1900.I~ICIIARD CLAY h SONS, LIMITED, LONDON & BUNGAY.

ISSN:0368-1769    

DOI:10.1039/CA90078FP003

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年代:1900

数据来源: RSC

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INORGANIC CHEMISTRY 13 I n o r g a n i c Chemistry. Production of Ozone by the Decomposition of Water by Fluorine. By HENRI MOISSAN (Compt. Tend., 1899, 129, 570-573). -When fluorine is passed into water cooled at 0", the liberated oxygen contains from10 to12 per cent., or, under the most favourable conditions, as much as 14.39 per cent., of ozone, and is decidedly blue. The pro- portion of ozone is higher the more rapid the current of fluorine, provided that the water is kept at 0", and subject to the maximum limit of 14.39 per cent.; it is markedly less if the temperature of the water is allowed t o rise. By ARNOLD NABL (Monatsh., 189 9, 20, 679--684).-1f dry sulphur dioxide is passed into absolute alcohol in which metallic zinc is suspended, and contained in a flask from which a i r is excluded, a white precipitate is formed.This is left f o r a day, filtered, and the operation then repeated. The solution deposits small, microscopical, rhombic needles which, after drying in vacuum t o eliminate the alcohol of crystallisation, give figures on analysis agreeing with the formula ZnS20,. The other product, in- soluble in alcohol, appears to be a mixture. Isomerism of Salts of Ammonium, Hydroxylamine, and Hydrazine. By ALEXANDER P. SABANEEFF [with A. DSHEWACHOFF, (Clmu. Centr., 1899, ii, 32-33; from J . Rum. Ci~ern. Soc., 1899, 31, 375 -383. Compare Abstr., 1898, ii, 577).-The following pairs of C. H. B. Hyposulphurous Acid. R. H. P. M. EFROSS, z. GINSBURG, J. LEblKE, M. PROSIN, and A. WLASSOFF]14 ABSTRACTS OF CHEMICAL PAPERS.isomeric compounds have been prepared and their molecular weights determined by Raoult's method : (la) ammonium hydroxylamine hydrogen phosphite, (1 b) diammonium hydrogen phosphate ; (2a) hydroxylamine dihydrogen phosphite, (26) ammonium dihydrogen phosphate ; (3a) hydroxylamine formate, (36) ammonium hydrogen carbonate ; (4cc) hydroxylamine acetate, (4b) ammonium glycollate ; (5a) hydrazine oualate, (56) hydroxylamine oxamate ; (6a) hydrazine succinate, (6b) hydroxylamine succinama te ; (7c.5) hydroxylamine benz- oate, (7b) ammonium salicylate ; (8cc) hydroxylamine m a minobenzoate, ( 8 b ) hydrazine salicylate, QIIH,O>N,HG. (2cc) is a syrup which, with absolute alcohol, yields hydroxylamine phosphate. (3cr) crystallises in needles, and is easily soluble in water, forming an acid solution which decomposes on boiling, and does not then give the hydroxylamine reaction.( 4 b ) is prepared by mixing glycollic acid with the calculated quantity of ammonia and evaporat- ing in a vacuum; i f an excess of ammonia is used, diammonium glycollate is formed ; i t separates in needles, is easily soluble in water, giving an acid solution from which the acid salt is obtained on evap- orating. (5a) crystallises in needles, and is very slightly soluble in water. (5b) forms crystals, and is easily soluble in water. (6r.5) separates in very perfect crystals, and is soluble in water. (66) gradually changes into hydroxamic acid ;the same change is brought about by boiling the solution. (76) separates as the anhydrous salt when aqueous solutions of ammonia and salicylic acid are mixed and heated.(8a) is very slightly soluble in water, but more so in alcohol. (86) is prepared from salicylic acid and hydrazine hydr- oxide. (arc), (3a), ( 4 a ) , (5b), (6b), (?a), and (8a) are prepared from the barium salts of the corresponding acids and the sulphates of the nitrogen bases. Whilst measuring the electrical conductivity of hydrazine sulphate, its oxidation by platinum black was observed, and when oxygen is passed into an aqueous solution in which platinum black is suspended, the sulphate is completely oxidised, nitrogen, ammonium sulphate, sulphuric acid, and water being formed. Action of Potassammonium on Arsenic. By C. HUGOT (Compt. rend., 1899,129, 603-605).-The action of excess of potassammonium on arsenic yields a brick-red compound, AsK,,NH,, analogous to that previously obtained from sodarnmonium(Abstr., 1899, ii, 15l),and when this is heated a t 300" in a vacuum, it yields a black compound, ASK,.When the arsenic is in excess, the product is a n orange solid, K2As4,NH3, which, when heated a little below 300°, yields a cinnabar-red compound, K,As,. C. H. B. By HENRI GAUTIER (Compt. rend., 1899, 129, 595--598).-Boron sulphide, B,S,, prepared by the action of dry hydrogen sulphide on dry amorphous boron at a red heat, was decomposed by sodium hydroxide solution, oxidised with bromine water, and precipitated with barium chloride. Four experi- ments give B= 11.041 with a probable error +,0.017. Boron carbide prepared in the electric furnace by the action of c 0, (7a) is very slightly soluble in water.E. W. W. The Atomic Weight of Boron.INORGANIC CHEMISTRY. 15 sugar-charcoal on amorphous boron in presence of copper, was decom- posed by chlorine, and the residual carbon weighed as such, and also in the form of carbon dioxide. Two experiments give B = 10.997. C. H. B. Atomic Weight of Boron. By H E N R r GAUTIER (Coinpt. rend., 1899, 129, 678-681. Compare Abrahall, Trans., 1892, 61, 650; Ramsay and Aston, Trans., 1893, 63, 207 ; Rimbacb, Abstr., 1893, ii, 207).-Boron tribromide, obtained by passing pure bromine over pure boron heated to a dull red heat, was fractionally distilled alone, and then finally over reduced silver, when it distilled quite coiistantly a t 90.5O. A weighed quantity of the boron haloid was decomposed by water, and the halogen determined as silver haloid.The mean value obtained for the atomic weight of boron by nine experiments on the decomposition of the bromide was 11.021, with a probable error of +, 0.006, and from five experiments on the chloride, 11.011, with a probable error of 0.008, The mean of these values is 11.016, a number which the author adopts for the atomic weight of boron in preference to the vdues obtained by analysis of boron sulphide and boron carbide (com- pare preceding abstract). Graphite. By LUDWIG STAUDENMAIER (Be?.., 1899, 32, 2834-2834. Compare Abstr., 1898, ii, 96 ; 1899, ii, 481).-When graphitic acid is heated with sulphuric acid and water a t lSOo, it gives an insoluble pyrographitic acid, which retains the form and appearance of the original graphite.When oxidised with nitric acid, this gives a soluble product containing mellitic acid, a red substance soluble in ether, a dark brownish-red substance soluble in alcohol, and a black residue insoluble in alcohol or ether. When treated with a mixture of fuming nitric acid and potassium chlorate, unlike ordinary pyrographitic acid, i t gives a transparent, yellowish-green pseudo- gmphitic acid ; this resembles graphitic acid but is more soluble, less stable, and more readily oxidised ; it gives a black reduction product with stannous chloride. Treatment of Lepidolite. By JULIUS FORMANEK (Chem. Centy., lS99, ii, 11-12; from 0estes.r. Chern. Zeit., 2, 309--312).-1n order to obtain cEsium and rubidium compounds from lepidolite, the finely powdered mineral is decomposed with concentrated sulphuric acid in an iron pan, and the solution evaporated in a lead vessel.The residue is taken up with water, and the potassium, c;lesium, and rubidium alums which separate are crystallised from water several times, and then treated with barium hydroxide. The excess of the baryta and most of the alumina are removed by means of carbon dioxide, and the solu- tion, after neutralising with oxalic acid, is evaporated until crystals begin t o form. Most of the potassium salt separates on cooling, and the rest is removed from the residue by fractional crystallisation, the czesium and rubidium salts being afterwards separated by the same means. E. W. ?V. Commercial Calcium Carbide. By HENRI MOISSAN (Bull.Soc. Chim., 1899, [ iii], 21, 865-871).-Theoretically, 1 gram Pure boron trichloride was obtained in a similar manner. H. R. LE S. T. M. L.16 ALlSTJtACTS OF C BEMICAL YAPEltS. of calcium carbide should yield 349 C.C. of acetylene, the amounts obtained from seven commercial samples varied from 292.8-318.7 C.C. ; three inferior specimens, which were grey and porous, instead of having a fused, crystalline structure, gave only 228.6, 250.4, and 260.3 C.C. respectively. The gas sometimes contains notable quantities of ammonia, and several specimens of carbide yielded a little hydrogen phosphide. To facilitate the study of the insoluble residue, the carbide was decomposed with a n aqueous solution of sugar, whereby the lime produced is kept in solution. The residue consists principally of the silicides of carbon, calcium, and iron, sometimes mixed with a little graphite and calcium sulphide ; dilute (10 per cent,.) hydrochloric acid extracts iron, lime, and small quantities of aluminium and phosphorus ; the concentrated acid dissolves further quantities of lime and silica, whilst carbon silicide and graphite remain unat tacked.The various forms in which these impurities exist were recognised by microscopical examination. The silicon occurs chiefly a3 carbon silicide, but small quantities of calcium silicide, silica, and a compound containing iron, carbon, and silicon are also formed. Silicon hydride, from the decom- position of calcium silicide, is often evolved in the treatment with con- centrated hydrochloric acid. The total sulphur in three samples of carbide was found t o be 0.37, 0.43, and 0.74 per ccnt.; i t exists as calcium sulphide and aluminium sulphide. Hydrogen sulphide is not liberated when impure calcium carbide is decomposed by water, since it is retained by the calcium hydroxide formed in the reaction ; traces of a volatile organic compound containing sulphur seem, however, to be formed in some cases, since the gas, after being mashed with potash and lead acetate solution, yields a small quantity of sulphuric acid when burnt. Iron is found as silicide and carbosilicide. Phosphorus occurs chiefly as calcium phosphide, but is also found combined with iron and silicon. Carbon is sometimes found as graphite retaining calcium and silicon ; none mas detected in the form of diamond.N. L. Action of Magnesium on Saline Solutions. By DONATO TOM- MASI (Bull. SOC. Chirn., 1899, [iii], 21, S85-887).-When magnesinm wire is placed in a solution of potassium chloride, t h e metal is con- verted into hydroxide, with liberation of hydrogen ; the potassium chloride simply favours the oxidation of the magnesium, and is not itself decomposed. With ammonium chloride solution, a vigorous reaction occurs, hydrogen is evolved, and ammonium magnesium chloride formed. A 30 per cent. solution of calcium chloride attacks mag- nesium, slightlyin the cold and more readily on heating, with the formation of magnesium hydroxide and hydrogen, but a saturated solution is without action unless the metal is finely divided and the liquid heated. A 30 per cent.solution of magnesium chloride has very little action on magnesium, but the boiling solution is easily decom- posed by a magnesium-platinum couple, with t h e formation of mag- nesium hydroxide and oxychloride. The action on magnesium of solutions of various other salts was examined, and the products of the reactions, in addition t o hydrogen, were found to be as follows. Sodium and lithium chlorides : magnesium hydroxide, Barium and strontiumINORQANIC CHEMISTRY. 17 chlorides : scarcely any action on magnesium, Cupric chloride ! cuprous chloride, copper oxychloride, and magnesium chloride. Cadmium chloride : cadmium oxychloride, metallic cadmium, and magnesium chloride. Cobalt chloride : cobalt hydroxide and magnesium chloride. Lead chloride : lead oxychloride, metallic lead, and magnesium chloride, Mercuric chloride : mercurous chloride, mercury oxide, and magnesium chloride.Ferric chloride : ferric hydroxide, ferric oxychloride, and magnesium chloride ; ferric chloride is not reduced by magnesium. Chromic chloride : chromium hydroxide and magnesium chloride, Platinic chloride : metallic platinum and magnesium hydroxide. Gold chloride : metallic gold, magnesium hydroxide, and magnesium chloride. Copper sulphate : metallic copper, cuprous hydroxide, basic copper sulphate, and magnesium sulphate ; at 0", cuprous hydroxide only is obtained. Zinc sulphate : metallic zim, zinc hydroxide, basic zinc sulphate, and magnesium sulphate. Ferrous ' sulphate : ferrous hydroxide, and magnesium sulphate. Mangmese sulphate : manganese hydroxide and magnesium sulphate.N. L. Anhydrous Magnesium Carbonate. By RODOLPHE ENGEL (Conzpt. rend., 1S99, 129, 59S--600).-When magnesium ammonium carbonate is gradually heated in a current of dry air a t a temperature not exceeding 1 30-140°, it yields anhydrous magnesium carbonate which differs from the natural mineral, and from the carbonate pre- pared by Senarmont, but resembles that obtained by the action of heat on magnesium potassiumsesquicarbonate (Abstr., 1886,821). It retains the crystalline form of the double carbonate, is very hygroscopic, sets like plaster when mixed with water, and absorbs almost instantly about 100 times its own volume of ammonia gas. Attempts to prepare an ammonium magnesium seaquicarbonate gave negative results, and the compound, MgCO,,NH,HCO, + 4H,O, ascribed to Pavre, was never described by him.C. H. B, Dicarbonyl Cuprous Chloride. By WILLIAM APP JONES (Arne?*. Chenz. J., 1899, 22, 287-31 l).-Carbonic oxide is not absorbed by dry cuprous chloride, but in presence of sufficient hydrochloric acid to form a thin paste, an amount of gas is absorbed at 0' which corre- sponds with the formation of dicur6onyZ cup?*ous chZo?*ide, Cu2C1,,2C0, + 4H,O ; on adding ice-water, white plates having this composition separate which rapidly decompose in the air. The compound prepared by passing carbonic oxide into cuprous chloride in presence of water or dilute hydrochloric acid (1HC1: 2H,O) is not decomposed by diminishing the pressure until the latter is reduced to 135-125 mm., when complete decomposition occurs ; in presence of concentrated hydrochloric acid, decomposition begins at 410 mm.pressure and gradually increases as the pressure is reduced to 160 mm., when it takes place more rapidly and is colnplete a t 130 mm. pressure. Curves are given showing these results. On passing carbonic oxide into a solution of cuprous chloride in pyridine at Oo, the compourtd 2Cu2C1,,3C0 appears to be formed, but could not be isolated ; on raising the temperature, decomposition occurs VOL. LXXVIII. ii. 218 ABSTRACTS OF CHEMICAL PAPERS. regularly, until a t looo it is nearly complete. The resnlts are plotted in the form of a curve. When oxygen is passed into dicarbonyl cuprous chloride a t Oo, the latter is decomposed, giving rise to a small quantity of carbon dioxide ; the formation of this cannot be due to increased activity of the oxygen brought about by the cuprous chloride undergoing oxidation, and thus splitting the molecular into atomic oxygen, for when a mixture of oxygen and carbonic oxide is passed through ferrous sulphate or chloride these compounds are oxidised, but no cgrbon dioxide is formed.I n discussing the decomposition of dicarbonyl cuprous chloride by reducing the pressure or raising the temperature, it is pointed out that this takes place similarly to that of compounds the ‘‘ atomic” nature of which cannot be doubted; its properties are compared with those of other inorganic compounds containing carbonic oxide, and the conclusion is reached that i t must be regarded as a true chemical compound.The behaviour of dicnrbonyl cuprous chloride with oxygen, chlorine, hydrogen, and nitrogen shows that, a t the moment of its liberation from the compound, carbonic oxide possesses no increased chemical activity. W, A. D. Spectroscopic Analysis of Neodymium and of Praseo- dymium. By WILHELM MUTHMANN and L. STUTZEL (Bey., 1899, 32, 2653-2677, Compare Abstr., 1898, ii, 518 ; von Scheele, Abstr., 1898, ii, 519 ; 1899, ii, 291 ; Bettendorf, Ahstr., 1890, 851).-Accord- ing to Crookes’ ‘‘ one band one element ” theory, praseodymium must contain 37 different elements, whereas according to von Scheele the sub- stance is homogeneous. The authors themselves consider that the composite nature of praseodymium is probable, although not established, and that even if true the separation of the constituents, on account of the similarity in their chemical behaviour, presents an almost im- possible task.Specimens of praseodymium from Bastnas cerite and from Australian and Brazilian monazite have been compared with Shnpleigh’s preparations and no differences have been detected, The composite nature of neodymium is even still more in doubt, as, so far, pure neodymium has not been obtained ; the product obtained by the sulphate method of Reparation contains 2 per cent. of praseodymium. A new separation by the aid of the chromaies is quicker, and it is hoped will give better results. Neodymium has the most complex absorption spectrum of all the earths, the number of bands in neutral chloride solution being 24. All these are riot necessarily visible a t the same time; in certain con- centrated solutions, the six yellow bands become one, similarly for the green ; on dilution, several groups disappear completely, particularly the narrow bands at the red end of the spectrum.Numerous instancesof change in the configuration of bands of the rare earths are known, but the causes have not been determined. A notable instance is found in the case of praseodymium; ordinary didymium gives the blue line X 469 of praseodymium as a well-defined, not over broad, absorption band ; when the earth is fractionated by Welsbach’aINORGANIC CHEMISTRY. 19 method, the line loses in intensity, broadens and moves towards the violet end of the spectrum ; on further fractionation, the band becomes smaller and more intense, but even in the purest specimens is never so sharp as in the crude didymium.Bunsen (Annalen, 1866, 128, 190) pointed out that the bands in the spectra of didyminm salts vary considerably, according to the nature of the acid constituent. Further variations have been found in the case of both praseodymium and neodymium. Neodymium nitrate and chloride give different absorption spectra, especially in the green part of the spectrum ; the nitrate in dilute nitric acid gives a single pale band about A = 522, whereas in the chloride there are two bands, 525.5 and 521.5, and a pale band 520.5; the yellow bands in the chloride are sharper than in the nitrate. Still greater differences are observed when the spectra of salts derived from carboxylic acids are examined. A solution of carbonate, probably containing the metal as the hydrogen carbonate, has not the characteristic dark red colour of the nitrate, but a fairly intense blue, due to the fact that the yellow absorption band has increased consider- ably in intensity, whilst the violet band X 432-424 has completely disappeared ; the green bands are more pronounced than in the nitrate, and all bands are some 7.5 h nearer the red end of the spectrum, and, i n addition, a new orange band, X = 600.5, has made its appearance.Somewhat similar differences have been observed in the case of praseodymium, not merely does the relative luminosity of the bands vary with different salts, but also the order in which the lines dis- appear on diluting the solutions. It is obvious that the absorption spectrum is not simply de- pendent on the molecular weight of the anbydrous salt, as Bunsen suggested.The authors have employed a spectroscopic method for the estimation of praseodymium and neodymium, although, according t o Schottlander (Bey., 1892, 25, 569), this method is inapplicable. The observations were ma.de with a special Kriiss apparatus, and in calculating the results, Vierordt’s equation, A = c/ - log J, was em- ployed, where A = constant, c = concentration, and J= intensity of light after passing through a 10 mm. layer of the solution when the original intcnsit,y of the light = 1. In the following minerals-orthite from Miask, cerite from Riddar- hyttan, and orthite (allsnite) from Llano Go., Texas, it was found that the percentage of neodymium was practically twice that of praseo- d y miu m.J. J. S. Radio-active Barium Salts and Polonium. By FRITZ GIESEL (Ann. Phyls. Chem., 1899, [ii], 69, 91--94).-The author has independently obtained from uranium ores other than pitchblende a substance, consisting chiefly of barium sulphate, which emits Becquerel rays. The substance is similar t o that obtained by P. and S. Curie, according t o whom it contains a n active element radium, Freshly crystallised barium salts containing radium are only slightly active, but in the course of a few days or weeks the activity increases to a maximum ; the portions which crystallise first are more active than 2-220 ABSTRACTS OF CHEMICAL PAPERS. those subsequently obtained from the mother liquor. The chloride, bromide, and iodide phosphoresce without any previous illumination, especially when anhydrous; in moist air, they gradually lose this property, but renewed heating restores it to them.The stronger the phosphorescence of any particular specimen, the feebler is the emission of Becquerel rays. Barium platinocyanide, prepared from active barium chloride and potassium platinocyanide, shows strong, spontaneous phosphorescence, which grows less intense as time goes on, the green colour of the double salt changing to yellow and finally t o brown. By dissolving and crystallising the brown product, the green salt can again be obtained, The active constituent of the barium salts has not been isolated, and it seems impossible to effect a separation by fractional cry stallisation alone. Strongly active products containing polonium are also being investigated. Hydrogen sulphide produces in them a precipitate which surpasses in activity the best barium salt preparation. The chloride prepared from this sulphur compound is equally effective, as is also the metal deposited from the chloride solution by metallic zinc or an electric current. The penetrating power of polonium raysis much less than that of radium rays, and consequently the shadow produced by a hand or metallic object is much sharper and deeper with the former than with the latter. J. C. P. A New Radio-active Substance. By A. DEBIEERNE (Compt. rend., 1899, 129, 593--595).-The constituents of pitchblende which are not precipitated by hydrogen sulphide from an acid solution, but are precipitated by ammonia or ammonium sulphide, include a small quantity of a substance which emits radiations capable of acting on a photographic plate, making barium platinocyanide phosphorescent and accelerating the discharge of electrified bodies. Apart from its radio-activity, which seems to be about 100,000 times tls great as t h a t of uranium, it resembles titanium in general properties, It differs from radium in not being luminescent. C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA9007805013

出版商:RSC    

年代:1900

数据来源: RSC

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20 ABSTRACTS OF CHEMICAL PAPERS. Miner a 1 o gical Chemistry . Dopplerite. By C. CLAESSEN (Jahrb. f . Min., 1899, i, Ref., 424 ; from Chem. Zeit., 1898, 523).-Analysis of dopplerite from an Olden- burg moor gave : C. H. 0. Ash. Total. 52.96 4-67 34.1 0 8.27 100~00 New Zealand Coal and Ambrite; Barbados Manjak. L. J. s. By P. PHILLIPS BEDSON (Tvans. Fed. Inst. Mining Eng., 1899,16,388-390). -Coal from New Zealand gave analysis I (by A. Dodds); the com- position of the dried ash-free coal is given under Ia; 10-13 per cent.MINERALOGICAL CHEMISTRY. 21 of the coal is soluble in pyridine. Ambrite, a brown, transparent resin, associated with this coal, gave T I (Dodds). An asphalt from Barbados, locally known as manjak, gave I11 (by R. L. Treble) ; it resembles albertite in appearance, but is completely soluble in pyr- idine.Fixed carbon. Volatile matter. Moisture. Ash. S. I. 46.44 47.80 4.66 1.10 0.54 11. - - 0*59 0.18 c 111. 36.52 61.90 1.58 c C. H. 0. N. - I I U . 80.95 9.87 9.1s - IIICC. 81.18 8.43 10.39 - ICC. 74.32 9-67 20.0 1 L. J. S. Identity of Binnite with Tennantite : Composition of Fahl- em. By GEORGE T. PRIOR and LEONARD J. SPENCER (iwin. Mag., 1899, 12, 184--213).-The small, briIliant crystals of ‘ I binnite” are of rare occurrence in the white, saccharoidal dolomite of the Binnenthal in Switzerland. They are cubic and hexakistetrahedral, and the formula usually assigned to them is 3Cu2S,2As,S,. It is now shown that they are crystallographically, physically and chemically identical with the less perfectly developed crystals of Cornish tennantite.Analysis I was made on eleven crystals (weighing 0.3101 gram), of which the streak is chestnut-brown ; thin splinters are translucent and crimson by transmitted light. This analysis gives the formula 3Cu2S,As2S,=Cu3AsS,. Analysis I1 is of crystals, of which the streak is black, and which, in thin splinters, are opaque; formula [S(Cu,Ag),S,As,S,] + g3[ GFeS,As,S,]. The variation in the colour of the streak of the mineral depends on the amount of iron present. Analyses I--V by G. T. Prior. I n each case, detailed descriptions are given of the crystallographic and physical characters and of the associations of the material analysed. Cu. Ag. As. Sb. Bi. Fe. Zn. Pb. S. Total. Sp. gr. r. 49.83 1-87 19.04 - - 1.11 - 0-17 27.60 99-62 4’62 11.44’12 4.77 [20.49] - - 3’68 - - 26‘94 100*00 4.598 1x1. 45.39 - trace 28735 - 1’32 - 0.11 24’48 100.15 4‘921 IT. 41.55 - trace 28.32 0.83 1.02 2.63 0‘62 24.33 99.30 4.969 V. 30’56 15-26 trace 27.73 - 3’51 trace 0’05 23.15 100’26 5.047 The results of these analyses of ‘ I binnite,” as well as the published analyses of Cornish tennantite, differ considerably from the figures required by the accepted formula for fahlerz (tetrahedrite and tennant- ite), namely, 4R”S,R”’,S,, where R” = Cu,, Ag,, Fe, Zn, and R ” = As, Sb, Bi. Very few of the published analyses of fahlerz agree with this formula, and minerals which have given the formula 3R”S,R”,S, have often received new names. Three new analyses were therefore made of specially pure tetrahedrite crystals free from copper pyrites, blende and pyrites which are usually so intimately associated with fahlerz ; the fracture of these crystals was smooth and conchoidal and with a brilliant lustre,22 ABSTRACTS OF CHEMICAL PAPERS.Analysis 111 is of material from a large crystal of octahedral habit from Fresney d’oisans, Dauphine ” ; the streak is dark brown ; after deducting the iron as pyrites, the formula is 3Cu,S,Sb2S, = Cu,SbS3. Analysis IV is of the well-known brilliant crystals from Horhausen, in Rhenish Prussia; very thin flakes are crimson by transmitted light, and the streak is dark brown. Analysis V is of tetrahedral crystals, probably from Wolfach, Baden; the streak is black. IV and V give the formula [ ~ ( C U , A ~ ) ~ S , S ~ , S , ] ;t &[G(Fe,Zn)S,Sb S 3.These analyses suggest the new formula 3R ,S,R”’?S3 + x[6R”E!,$”’,S,], where R’ = Cu, Ag ; R” = Fe, Zn ; R ” = As, Sb, Bi ; and x is a small fraction, often =2G and 1 but rising to in the case of the highly ferriferous tetrahedrite ’‘ coppite.” I n this formula, the group (Fe,Zn),S,, and not (Fe,Zn),Sp, is isomorphous with Cu,S3. Only in those cases where iron and zinc are absent does the simple formula SRS,R”’,S, hold good. Numerous previous analyses are discussed and found to agree with the new formula. L. J. 5. Melonite (?), Coloradoite (?), Petzite and Hessite. By WILLIAM F. HILLEBRAND (Arner. J. S’ci., 1899, [iv], 8, 295-298).--MeZonite? -Impure material from the Melones mine, in the Mother Lode region, California, gave the results under I ; after deducting a little hessite and tellurium, this gives the formula NiTe,, I n colour and cleavage, the material agrees with Genth’s melonite from the same locality; Genth, however, gave the formula Ni,Te3. Coloradoite ?-One small specimen from the Norwegian mine in the same district showed dolomite, petzite, hessite, and a mercury telluride, which is probably coloradoite.Petxite.-Analysis of pure material from the Norwegian mine gave 11, agreeing with the formula Au;J!e,3Ag2Te. ETessite.-Material from San Sebastian, Jalisco, Mexico, gave analysis 111; sulphur, iron and zinc are also present. Te. Ni. Ag. Au. Se. Mo. Pb. Total. Sp. gr. 11. 33.21 - 41.87 25.16 trace 0.08 - 100.32 8.925. I. 80.75 18.31 0.86 - - - - 99.92 - 111. 36.11 - 61.16 - - - 1.90 99.17 8.24. L. J. S. Langbeinite from the Punjab Salt Range.By FREDERICK R. MALLET ( M h . Mag., 1899, 12, 159--166).-A potassium magnesium sulphate occurring as a lenticular stratum in the ‘ kallar’ (impure rock salt) of the Mayo mines, Punjab, India, was discovered and analysed in 1873. The material has now been more completely examined, and found to be the same as the cubic mineral langbeinite, 2MgS0,,K2S0,, recently described from the Prussian salt deposits (Abstr., 1898, ii, 168). The Indian mineral is associated with salt, sylvite and kieserite, and sometimes encloses these. It is colourless and transparent, and optically isotropic. The powder is slowly but completely soluble in water. Sp gr. 2.84 ; H = 4. Analysis gave :MINERALOGICAL CHEMISTRY, 23 K,O. MgO. so,. NaCl. H,O.Total. 22.23 19.08 57.27 0-41 0.84 99-83 On exposure to the air, the powder absorbs water, and there is an increase in weight of nearly 57 per cent. ; the decomposition therefore takes place in accordance with the equation : 2MgS04,K2S0, (langbein- ite) + 13H20 = K2S0,,MgS04,6H,0 (picromerite) + MgS04,7H20 (epsomite). Lnngbeinite, as isotropic octahedra , may be artifically produced by fusing together magnesium and potassium sulphates in the proper proportions. L. J. S. Formation of Oceanic Salt Deposits, particularly of the Stassfurt Beds. XIII. Evaporation of Sea Water a t 25'. By JACOBUS H. VAN'T HOFF and W. MEYERHOFFER (Chem. Ceiitv., 1899, ii, 76 ; from Sitxungsbev. Aknd. Wiss. Bedin, 20, 372--383).-The most recent and trustworthy analyses of sea water show that on an average 1000 parts contain NaCI, 47 ; KC1, 1.03 ; NgC12, 7-26 ; and MgSO,, 3-57, When sea water is evaporated at 25', the salts separate out in the following order :-( 1) NaCl ; (2) NaCl + MgS04,7H,0 and NaCl+ MgS04,6H20 ; (3a) NaCl + MgS04,6H20 + KC1 and NaCl + MgS0,,5H20 + KCI ; (371) NaCl + MgSO4,4H2O + MgCl2,KCl,6H2O ; (4) NaCl + MgSO4,4H,O + MgCI,,KCl,GH,O + MgC1,,6H20, and in the following relative quantities : NaCI.MgSO,. KCI. MgCI,, KC1,6H20. BfgC1,. 1. 94.5 2. 2.39 1.63 3cc. 0.59 1-42 0.72 36. 0.50 0.22 1-27 4. 0.02 0.30 0.07 6.02 These quantities, however, are only obtained when the separate crystailisations are removed from the mother liquor. By ERNALD G. J. HARTLEY (Min. Mag., 1899, 12, 152--158).-The formula of pharmacosiderite is uncertain ; it is based on an analysis by Berzelius (1821), and no analysis has since been made.The present analyses mere made on selected green crystals from Uornwall; sp. gr. 2.798. A green crystal placed in ammonia solution very soon becomes red throughout without alteration of the optical characters; on placing such a red crystal in dilute hydro- chloric acid, the green colour is restored to the whole crystal. Two preliminary analyses (I and 11) show a deficit, which mas afterwards found to be due to the presence of potassium. This element is present in all the Cornish specimens examined, but in variable amount (2.68 and 4.12 per cent. K20), and in two specimens from Hungary only traces were found. About 10 per cent. of water is lost a t 100'; at 130', the crystals begin t o turn brown and opaque, and about 14.18 per cent.is lost (= 5H20 in the formula given below). A complete analysis made on another specimen is given under 111. E. W. W. Pharmacosiderite. AszO,. P,O,. Fe,O,. K,O. H,O. Total. I. 37.53 2.04 39.29 - 19.63 98.49 11. 36.85 2.06 38.61 - [19*63] 97-35 111. 37-16 1.20 37.58 4.54 18.85 99.3324 ABSTRACTS OF CHEMICAL PAPERS, The ratios between the iron, arsenic acid and water are fairly constant, and give the formula 3Fe,0,,2As2O,,13H,O = 2FeAsO4,Fe(OH),,5H,O. The potassium is assumed to replace hydrogen in the hydroxyl, and the formula is finally written as 2FeAsO4,Fe[O(H,K)],,5H,O. [Chabaxite] from North Carolina. By JULIUS H. PRATT (JaAr6. f. Min., 1899, i, Ref. 229-231; from JOUY. EZisha Mitchell Sci. Soc., 1897, 14, 61--83).-Analyses by C.Baskerville are given of the small crystals of chabazite associated with wellsite (Abstr., 1897, ii, 565) in the Buck Creek corundum mine, Clay Co., North Citroliua. The simple and twinned rhombohedra occur on felspar, hornblende and corundum. The material for analysis was separated into two portions by means of a heavy liquid ; anal. I on material of sp. gr. 2.147-2.203 ; 11 of sp. gr. 2.203-2.244. SO,. A1,0,. FeO. CaO. RaO. MgO. K,O. Na20. H20. Total. I. 45-08 19-68 2-00 7-22 0'18 0.23 4.34 3.35 18-00 100*08 11. 46'15 20'74 2.00 6'92 0'24 0'22 4.10 3 35 16'30 100-02 This variation in composition and specific gravity supports Streng's hypothesis as to the composition of chabazite. Other minerals from North Carolina, described in this paper, have already been noticed (Abstr., 1898, ii, 342, 606).Constitution of Pectolite, Pyrophyllite, Hemimorphite and Analcite. By FRANK W. CLARKE and GEORGE STEIGER (Amey. J. Sci., 1899, [iv], 8, 245-257).-1n continuing the investigation of the constitution of natural silicates, special importance is attached to the two following reactions : (l), when talc is ignited there is a liberation of one-fourth of the silica (Abstr., 1890, 948) ; this suggests that other acid metasilicates may behave in a similar way ; (2), dry ammonium chloride, a t its temperature of dissociation, acts differently on different minerals (Abstr., 1892, 772). I'ectoZite.-The material used in the experiments was from Bergen Hill, New Jersey ; analysis gave the results under I, agreeing with the accepted formula HNaCa2Si309.Only a small portion of the water is given off below a dull red heat. After igniting the mineral, sodium carbonate solution takes up 8.68 per cent. of silica, or one-sixth of the total amount. This, it is considered, indicates that the mineral is an acid metasilicate as expressed by the above formula. Before ignition, sodium carbonate solution, or even distilled water, has a slow, decom- posing action on the mineral, both silica and bases being withdrawn ; the action is, however, not one of simple solution. PyrophyZZite.-The material used was from Deep River, North Carolina, and gave the results under 11. The empirical formula, AlIISi,O,, is apparently that of an acid metasilicate, but after ignition, only about 2 per cent.of silica is liberated. The formula is therefore written as OH*Al:Si,O,, that is, as a basic salt of the acid H,Si,O,. The mineral is very slightly attacked when heated with dry ammonium chloride. Hemimorphite.--White material from Franklin, New Jersey, gave the results under 111. The formula generally accepted represents the L. J. S. L. J. S.MINERALOGICAL CHEMISTRY. 25 mineral as a basic metasilicate, SiO,(Zn*OH),. Here the hydrogen is all combined in one way, and so, too, is the zinc. In all other possible formuh, the hydrogen, as well as the zinc, must be represented a s present in at least two modes of combination. Several experiments were made with the idea of extracting a definite fraction of the zinc or water, but the results were negative and only tend t o support t h e usual formula, Water and sodium carbonate solution have very litble action either before or after ignition of the mineral.By heating with dry ammonium chloride, all the zinc is converted into zinc chloride. AizaZcite.--Crystals from Wasson's Bluff in Nova Scotia gave analysis IV. Temperature. 100". 180". 260". 300". Low redness. Full redness. Blast. Total. H,O percent. 0.58 1'16 3'64 1.57 1.90 0.11 nit 8.96 Before or after ignition very little silica is extracted by sodium car- bonate solution. Heated a t 350' with dry ammonium chloride, about half of the sodium is converted into chloride, and ammonia is retained ; this ammonia is not given off when the residue is warmed with caustic sodium solution. The composition of the residue, after extracting sodium chloride, is given under V, which agrees approximately with H2Na,Al4SiSO2,,NH,.This ammonia derivative suggests that the analcite formula should be quadrupled, namely, Na4A14S~s02,,4H,0. G. Priedel has previously shown t h a t t h e water of analcite may be replaced by ammonia (Abstr., 1896, ii, 48:). An excess of silica over that required by the accepted analcite for- mula, NaA1Si20,1H,0, is shown by analysis I V and by some previous analyses. This is explained by analcite being, not a metasilicate, but a mixture of ortlzo- and tri-silicate, the general formula being NaAlX, H,O, where X = nSiO, + mSi,O,. This explains the alteration of albite, NaAlSi,O,, and nephelite, NaAlSiO,, to analcite. For normal analcite, the formula is finally written as A1,Ns,(Si0,),(Si,0s),,4H20. This is written structurally t o show the relation between analcite, leucite and the garnet-sodalite group.SiO, AI,O,. Fe,O,. CaO. Na,O. H,O. Total. I. 53.34 0'33 - 33'23 9.11 2-97 ; MuO, 0'45 ; CO,, 0.67 100'10 II. 84.73 29'16 0.49 - - 5.35 ; TiO,, 0'73 ; MgO, trace 100'46 111. 24.15 0.19 0.12 - 7.95 ; ZnO, 67.55 99'96 IV. 57.06 21'48 0.13 0.16 12-20 8'96 99'99 V. 62.59 24-34 - 0.18 S ' l l 2 . 3 2 ; NH,, 2'46 100'00 By ERNST A. W~LFING (Bey., 1899, 32, 2214--2224).-Analyses are given of four samples of Keuper marl from the neighbourhood of Tubingen; some were made by the author, the others by Dittrich. The agreement is fairly close, except in the case of alumina and ferric and sodium oxides. The anthoi- separated the iron and aluminium by running the nearly neutral solution of t21e chlorides into excess of a boiling solution of caustic soda (made from the metal), and found more alumina and less ferric oxide than Dittrich, who fused the mixed oxides with pure caustic soda in a silver crucible j the discrepancy in t h e sodium is unexplained, The water is lost as follows : v L.J. S. Analysis of Rocks.26 ABSTRACTS OF CHEMICAL PAPERS. Stress is laid upon the necessity that the reagents used in a rock- analysis, including the distilled water, should be pure. C .F. B. Experimental Petrology. By K. BAUER (Jalwb. f. Min., 1899, Beil. Bd. 12, 535-580)- I n continuing the experiments of Doelter and Schmutz (Abstr., 1897, ii, 54, 329) on the artificial production of rockq, the main object has been to test whether different rocks can be formed from the same magma.Powdered rocks-mica-schist, granite, diorite, phonolite, leucite-lava, nepheline-basalt and andesite, or mixtures having the same composition as these-were fused in a platinum crucible with various fluxes. The following will serve as a n example of the several experiments made. A mixture consisting of mica schist, potassium fluoride, sodium fluoride, calcium fluoride, sodium tungstate and potassium tungstate was maintained i n a fused condition at 1400' for two hours, in a plastic condition for seven hours, and allowed to cool slowly for five hours. Under the microscope, the product resembled a mica-andesite, and was seen t o contain plagioclase, biotite, augite, magnetite, scapolite, nepheline and glass, The same mica-schist with other fluxes gave a product resembling a melilite-basalt.Using diorite with various fluxes, the products were quartz-basalt, andesite, melilite-basalt, mica- andesite and phonolite-pitchstone. Phonolite-pitchstone was also produced from mixtures having the compositions of granite and of phonolite. This is taken to indicate that different; rocks may be formed from the same magma, and vice vem2. [The chemical composition of the magmas have, however, been considerably modified by the large amount of fluxes used.] Hornblende was formed in three of the fusions, whilst quartz was formed only once. L. J. S. [Mineral Analyses]. By W. TARASSENKO (Jahvb. f. Min., 1899, i, Ref., 458-475 ; from Mem. X i e f Nnturulists' SOC.(Russian), 1896, 15, 1--347).-The following mineral analyses are given in a petr- ological paper on t h e gnbbro and allied rocks in the districts of Radomysl, gov. Volhynia, and Shitomir, gov. Kieff, Russia. Orthoclase (microperthite) in a labradorite-rock from Poromowka, Shitomir district, gave anal. I ; the material analysed contained spindle-shaped enclosures of plagioclase. Labradorite from the same rock gave I1 and I11 ; the former of sp. gr. 2.692-2.686 ; the latter of sp. gr. 2.686-2.677; this material also contained spindle-shaped enclosures, possibly of ortho- clase, Diallage in a, labradorite-rock from Kamenny Brod, Radomysl district, gave IV (also MnO, trace ; X, 0.15). SiO,. TiO,. A1,0,. Fe,O,. FeO. CaO. MgO. K,O. Na,O. H,O. Total. I. 62.58 0.59 20'83 - - 2'10 - 12'24 2'08 0.41 100.33 11.54.78 0.36 28-16 0.27 0.48 10.35 - 1.45 4.84 0.04 100'73 111. 55.32 0'28 28.16 0.05 0.52 10'05 - 0.97 5.20 0.03 10058 IV. 50'11 2-01 1'69 1.15 15.61 15.20 13.68 - - 0'65 99.15 L, J. 8,MINERALOGICAL CHEMISTRY. 27 Trap-rock of Rocky Hill, New Jersey. By ALEXANDER HAMILTON PHILLIPS (Ainer. J. Sci., 1899, [iv], 8, 267-285).-A dyke of dolerite in the Triassic strata a t Rocky Hill, New Jersey, shows, in its width of half a mile, variations in chemical composition a,nd in structure. Analysis I is of the microcrystalline rock a t the margins ; I11 is of the most coarsely crystalline material towards the centre of the dyke, and I1 is of an intermediate rock, Analyses are also given of material separated from the rocks by means of heavy solutions.IT and V are of the diallage from the rocks I1 and IT1 respectively. VI and VII are of felspar (plagioclase) from the rock 11, the former of sp. gr. >2.69, and the latter of sp. gr. <2-69. VIII and IX are of felspar, sp, gr. >2*69 and <2*69, from rock 111; and X is of felspar (anorthoclase), of sp. gr. ~ 2 . 6 0 from the same rock. SiOz. Ti02. AlZO3. Fe20s. FeO. MnO. CaO. MgO. NazO. RJO. + IT. 50.34 1-56 15'23 2.82 11.17 0-14 9.61 5.81 2.93 1.02 111. 56.78 1'44 14'33 5.76 9.27 0.25 5.26 1-58 3.43 1.75 IV. 47.72 - 3'44 5-93 18.34 - 11.40 12.89 0.86 0'37 + V. 48.54 - 5.50 2.77 21.25 - 10.97 7.67 3'10 VJ. 53'84 - 29.30 0.81 - - 10.08 0.28 5.31 1-16 I. 51.46 1'06 13.98 2.66 8.92 - 10.49 7.59 4.75 VIT. 62'26 - 21.87 0.54 - - 6-53 0.15 7.98 1'20 VIII.66.84 - 17.98 2'6C - - 4.02 0.48 5.46 1.72 IX. 71.68 - 15.02 2'48 - - 3.86 0.12 5-52 1.37 X. 66.28 - 16.79 1.60 - - 0.71 0.13 9.76 5'31 P205. HsO. Total. 0-20 0.26 101.09 0-36 0'43 100.64 - - 100'95 - 0.44 101'22 -- 0 3 2 100.85 - 0.72 99'82 - - 100.05 - 0.49 101.07 L. J. S. 0.17 - 101*08 - 0'82 100'62 Analyses of Italian Volcanic Rocks. By HENRY S. WASHINGTON (Amer. J. Sci., 1899, [ iv], 8, 286--294).-Five analyses are given of trachytes from the Phlegman Fields and from Ischia. By LAZARUS FLETCHER (Min. Mag., 1899, 12, 167--170).-This iron was known before 1869 in the neighbourhood of Caperr, Kio Senguerr, Patagonia. It weighs 114 kilograms, and measures 48 x 31 x 27 cm. The structure is octahedral, and the etched surface shows distinct Widmanstatten figures with kamacite, t m i t e and plessite.Schreibersite is embedded in the kamacite. Sp. gr. 7.837. Analysis gave : L. J. S. Meteoric Iron from Caperr, Patagonia. No troilite or silicate was seen. Fo. Ni. Co. P. Cr. Cn. S. Total. 89'87 9-33 0'53 0'24 traco trace nil. 99.97 In composition and structure, this iron resembles the Joel iron from At acama. L. J. S. Cliftonite and Tmnite in the Youndegin Meteoric Iron. By LAZARUS FLETCHER (Min. Nag., 1899,12, 171-1 '74).-Cliftonite is the name given by the author to cubic crystals of graphitic carbon obtained from the meteoric iron found in 1884 in the sub-district of Youndegin, Western Australia. From a fragment weighing 8.32 grams, three milli- grams of cliftonite were isolated (Abstr., 1888, 30). More recently, a larger mass (97.25 grams) of the same iron was dissolved in dilute hydrochloric acid, but no cliftonite was seen.The cliftonite is there-28 ABSTRACTS OF CHEMICAL PAPERS. fore localised in one or more parts of the mass, and not uniformly distributed through it. During the solution of the iron, thin, lustrous, black plates (total weight, 0.0870 gram) were set free; they appeared to be an alloy of nickel and iron belonging to the tzenite group, After being kept for eleven years in a weighing tube, the material had increased in weight and altered in character owing to the formation of a layer of magnetic iron oxide on the surface, Sp. gr. 6-75. An analysis shows the material to be tzenite, with the composition : Fe, 61.87 ; Ni(Co), 38.13. Phosphorus, copper and magnesium were also present in small amount. L. J. S. Fluorine in the Mineral Waters of Portugal and Spain. By ANTONIO J. FERREIRA DA SILVA and ALBERTO D’AGUIAR (Bull. Xoc. CJ~irn., 1899, [iii], 21, 887-890. Compare Abstr., 1899, ii, 501, 602, 675).-The general question of the presence and detection of fluorine in mineral waters is discussed. The Campilho spring at Vidago has been found by one of the authors to contain fluorine equivalent to 0*000942 gram of sodium fluoride per litre, a result which may be com- pared with the corresponding figures for the Gerez spring (0.02288) and for the Spanish mineral waters of Lug0 (0.0242) and Guitiriz (0*0234). According to Gil, the presence of fluorine in many alkaline and sulphurous waters has hitherto been overlooked, owing to the fact that the tests usually applied for this element depend on the formation of hydrogen fluoride, whereas, since silica or silicates are also commonly present, i t is rather silicon fluoride which is produced and should be sought for. N. 1,.

ISSN:0368-1769    

DOI:10.1039/CA9007805020

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

28 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Autodigestion of the Pancreas. By S. PFORRINGER (Vi~chow’s h c h i v , 1899,158, 126--147j.-Previous authors have called attention to the possibility of self-digestion being a cause of pancreatic cysts and necroses. Chiari (Zeit. IIeiZk, 1896, IT), in particular, has directed attention to the fact that the pancreas is often found partially digested after death, and he considers that this may begin in the last hours of life. The present investigation confirms Chiari’s views; it contains records of a hundred autopsies ; the pancreas was examined microscopically, and evidence of digestive necrosis was found in forty- five, and this was very marked in eleven cases. The conditions of the patients (age, disease, &c.) appear to be as varied where such necrosis is found as in those cases where it is not found.By D. LAWROFF (Zeit. physiol. Chem., 1899, 28, 303--306).-The presence of arginine is helpful to the tryptic digestion of proteid. This appears to be connected with its alkalinity; an equivalent amount of sodium carbonate acts similarly. Arginine, like sodium carbonate, aids the W. D. H. Action of Arginine on the Tryptic Digestion of Proteid.PHYSIOLOGICAL CHEMISTRY. 29 emulsification of fats; excess of arginine, as OF sodium carbonate, is harmful. W. D. H. The Fluorine in Tootb- and Bone-ash. By HEINRICH HARMS (Zeit. Biol., 1899, 38, 487-498).-Fresenius’ method with certain small modifications is well adapted for the detection of quite minimal quantities of fluorine.The amount of fluorine in bones and teeth as given by Carnot, T. Wilson, and Gabriel is much too great. The amount varies from 0.022 to 0.005 per cent. The variations in the amount of fluorine, as compared with the other constituents of the ash, which are fairly constant, show that the fluorine is not chemically combined with these, but is rather an accessory constituent ; this view is confirmed by the presence in the bone of microscopic crystals of calcium fluoride. W. D. H. Composition of the Cartilage of the Shark. By GUSTAV VON BUNGE (Zeit. physiol. Chem., 1899, 28, 300--302).-The cartilage removed from the fish Scymnus borealis, which had been packed in ice, gave the following analytical results: water, 92.8 per cent. ; organic material, 5.9 ; inorganic material, 1 *3.Of the inorganic material, sodium and chlorine were the most abundant constituents ; details are also given of the other inorganic constituents. Petersen and Soxhlet (J. pr. Chenz., 1873, [ii], ‘7, 181) state t h a t the fresh cartilage contains 16.7 per cent. of sodium chloride; their specimen, however, had been packed in salt. Substances present in the Liver which are converted into Sugar by Acids. By JOSEF SEEGER (Chent. Centr., 1899, ii, 58; from Centr. Physiol., 13, 115-120. Compare Abstr., 1898, i, 619).- After liver-extract has been heated with hydrochloric acid, more sugar is found than corresponds with the sugar and glycogen contained in the extract. The substance prepared from liver- extract by means of 90 per cent. alcohol contains nitrogen, reduces alkaline copper solutions, and, when heated with acids! yields a sugar with reducing properties, but the quantity so obtained is far too little to account for the excess of sugar formed from the extract by acid, hence the liver must contain yet another compound which is easily converted into sugar.The carbohydrate groups of the albumin are supposed to be affected by the action of the liver in such a way that they easily form sugar by the action of hydrochloric acid. W. D. H. E. W. W. Amount of Urea in the Liver. By RUDOLF GOTTLIEB (Chem. Centr., 1899, i, 1298 ; from Arch. expt. Path. Phcc~m., 42,238-249)- See this vol., ii, 57. Human Bile. Ey RICHARD PON ZEYNEK (Chew,. Centr., 1899, ii, 213-214 ; from Tien. klin. Tach,, 12, 568-569).-The quantity of bile secreted in a day amounts to 300-400 grams, containing 7-12 grams of solid matter ; it is strongly alkaline, and has a sp.gr. 1.011-1.012. The bile pigments are completely precipitated by basic30 ABSTRACTS OF CHEMICAL PAPERS. lead acetate, but only partially by the normal salt ; the bile acids, mucin, and the colouring matter are throtvn down by saturating with ammonium sulphate. Only a slight precipitate is formed by super- saturating with magnesium sulphate. Hydrochloric or sulphuric acid gives an amorphous precipitate and the liquid becomes deep green and gradually deposits the bile acids. Bile gives a yellow coloration with alkalis ; this is shown best by samples which have become of a greenish tinge by exposure to the air. The precipitate obtained by means of alcohol, when rubbed with glycerol, is capable of converting starch into sugar, but does not digest albumin.The bile secreted by the patient during each hour of a day was examined and found to be of a sp. gr. 1.011 and to contain in 1000 parts, 21.88 of solids, 2.39 of mucin, 13.8 of alkali salts of the bile acids, 8.96 of soluble salts, and 0.23 of insoluble salts. Another sample had a sp. gr. 1.012 and yielded 30.76 of solids, 2.087 of mucin, 18.31 of alkali salts of the bile acids, 0.7'8 of lecithin, 2.307 of cholesterol and fat, 9.10 of soluble salts, 0.31 of insoluble salts, 0.054 of ammonia and trimethyl- amine, and 2.087 of acid ethereal extract, On one day when 336.73 grams of bile were secreted, the solid residue amounted to 10.69 grams ; the amounts of the former per hour varied from 2.01 to 30.25 grams, and of the latter from 0.054 to 0.99 gram, The ash is principally made up of sodium chloride, the insoluble portion containing traces of iron and copper.By adding zinc chloride and excess of ammonia to a very dilute aqueous solution of bile, a green coloration is formed in +--l hour, and the liquid shows a characteristic band in the red part of the spectrum about 650 p p wave-length. Human urine containing bile pigments and bilirubin also give this reaction. E. W. W. Degradation of Caffeine in the Organism of the Dog. By MARTIN KRUGER (Bey., 1899, 32, 2818--2824).--On administering 50.5 grams of caffeine during a period of 20 days to a dog which was fed exclusively on flesh, there was found in the urine excreted during this period 7.4 grams of 4 : 6-dimethylxanthine (theophylline), 6.6 grams of unchanged caffeine, 4.6 1 grams of 4-methylxanthine, 1.9 grams of 1 : 4-dimethylxanthine (theobromine), and about the same quantity of 1 : 6-dimethylxanthine (paraxanthine)-per 100 grams of caffeine orginally administered.For the method of separation adopted, the original paper should be coneulted. The results obtained show that all three methyl gpoups of caffeine are attacked simultaneously, and that the group in position 1 offers least resistance to elimination ; so that theophylline is the principal initial degradation product of caffeine, just as 4-methylxanthine is the principal product in the case of theobromine (Kriiger and Schmidt, following abstract).The small quantity of theobromine obtained, taken in conjunction with Kriiger and Schmidt's results, explains why heteroxanthine (1-methylxanthine) is not formed by the degradation of caffeine, and suggests that the 4-methylxanthine isolated owes its origin to theophylline rather than t o theobromine. It is pointed out that theophylline and theobromine have hitherto never been isolated in the animal organism, but only from plant extracts. W. A. D.PHY SIOLOGIICAL CHEMISTRY 31 Decomposition of Theobrornine, Paraxanthine, and 4-Me thy1 - xanthine in the Animal Organism. By MARTIN KRUGER and PAUL SCHMIDT (Ber., 1899, 32, 2677-2682, Compare Albanese, Abstr., 1S99, ii, 777).-Bondzynski and Gottlieb’s experiments (Abstr., 1895, i, 434) have been repeated. Theobromine, when introduced into the bodies of dogs or rabbits, is excreted in the urine partly iu an unaltered condition, but mainly as 1- and 4-mcthylxanthine. Para- xanthine is converted in the body of rabbits into 6-methylxnnthine, identical with that found in human urine.Neither 1-methylxanthine nor xanthine could be isolated. Although theobromine is converted into 1-methylxanthine in the animal system, attempts t o obtain xanthine from 4-methylxsnthine were abortive. The separation of the purine derivatives from urea was accomplished by precipitating them with sodium hydrogen sulphite and copper sulphate ; the purine derivatives obtained from the copper precipitate were treated with manganese peroxide in dilute acetic acid solution in order to destroy uric-acid (compare Abstr., lS9S, i, 699).J. J. S. Intestinal Absorption and Saline Cathartics. By GEORGE B. WALLACE and ARTHUR R. CUSHNY (PJiiger’s Archiv, 1899, ’7’7, 202-209. Compare Abstr., 1898, ii, 442).-Hober (ibid., ’74, 346) describes the absorption of saline solutions in the small intestine as depending on purely physical factors. This theory is opposed to the results previously published by the authors ; the present paper re- states their views, and adds some further confirmatory experiments, W. D. H. Passage into the Urine of Chloroform administered by Inhalation. By DIOSCORIDE VITALI (L’O~)’osi, 1899, 22, 145-14!3).- Prom the results of tests made on the urine of four patients before and after the administration of chloroform, the conclusion is drawn that chloroform does not pass into the urine.The presence in the urine of organic chlorine compounds produced from the chloroform could not be detected. T, H. P. By WACLAW VON MORACZEWSKI (PJEiigeim’s A r c h , 1 S99,77, 200-31 O).-The excreta from a number of normal fasting frogs kept in a clean vessel were collected, and in them the nitrogen, phosphorus, chlorine, ammonia, potassium, sodium, calcium, and magnesium were estimated. The results aregiven in full and compared with what occurs in frogs whose blood had been replaced by an iso-osmotic solution of sodium chloride; in these animals, which often live a considerable time, the metabolic changes are slow as evidenced by the reduction in the various substances excreted and mentioned above, When sodium nitrate is used instead, the amount of nitrogen is high from the ex- cretion of nitrates, but the amount of potassium and sodium is high also.Sodium acetate is more fatal. Sodium sulphate raises the excretion of nitrogen, but the other substances are diminished, as when sodium chloride is used. Excretion in Blood-free and in Fasting Frogs.32 ABSTRACTS OF CHEMICAL PAPERS, If a urea solution is substituted for the blood, there is a n increase in the excretion of nitrogen, and of some of the other substances also. If sugar solution is used, the frogs stand it exceedingly well ; all ex- cretion diminishes except that of calcium; this probably depends on the ready solubility of calcium phosphate in solutions of sugar. Frogs can stand considerable dilution of their blood without interference with nitrogenous metiabolism.Fat of Normal and of Degenerated Heart Muscle. By W. L~NDEMANN (Zeit. Biol., 1 S99, 38, 405-41 8).-The question always arises in connection with fatty degeneration, whether the fat is pro- duced from proteid in the cells, or whether it has been merely trans- ported from other parts and stored there. The comparison OF the heart-fat in cases of fatty degeneration, mostly from cases of anzemia, with that in normal hearts, and with that in other parts of the body, appears to support the former view. The following table summarises the resultsobtained : column 1 gives the acid number, coluinn 2 the saponification number; column 3 the iodine number, and column 4 the Reichert-Meissl number. W. D. H. 1. 2. 3. 4. Degeneration fat ............... 18.35 257.4 108.5 23.9 Normal heart fat ...............7.3 202.3 61.1 2.0 Kidney aiid subcutaneous f a t .., 3.76 201.8 70.8 0.9 The degeneration fat, in its high saponification number and large percentage of volatile fatty acids, resembles butter fat and the fat in the so-calleci tears of marine mammalia. [Physiological Action of] Acetonedicarboxylic Acid and Citric Acid. By LUIGI SABRATANI (Chem. Centr., 1899, ii, 22-23; from Atti Real. Accad. Tovino, 34).-Experiments on dogs and rabbits show that the stupefying effect of acetone is not shared by citric, acetone- dicarboxylic, or acetoacetic acids, which are only injurious in large doses. When acetonedicarboxylic acid is administered to healthy animals, it is partly decomposed in the stomach wi1,h liberation of carbon dioxide, but only very small quantities of acetone or of un- changed acid are found in the urine. Citric acid, under similar con- ditions, does not yield ketonic acids, or a t most traces which escape detection in the urine. Acetone may be separated from acetoacetic acid, et,hyl acetoacetate and acetonedicarboxylic acid by the following method. Insoluble bromine compounds, such as ethyl aa-dibromoacetate, pentabromo- acetone, &c., are precipitated from the urine acidified with sulphuric acid by adding a slight excess of bromine water and allowing the mixture to remain 12 hours. The acetone itself is not attacked, and is distilled from the filtrate after removing the excess of bromine by means of powdered iron. Its amount is then determined by means of Lieben's method of conversion into iodoform. The amount of acetone, together with that derived from the ketonic acids, is similarly estimated In the liquid obtained by directly distilling a second portion of the acidified urine. Acetoacetic acid cannot be separated from ethyl acetoacetate, or acetonedicarboxylic acid by this method. W. D. H. E. W. W.

ISSN:0368-1769    

DOI:10.1039/CA9007805028

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 33 Chemistry of Vegetable Physiology and Agriculture. [Effect of Mineral and Nitrogenous Nutritive Matters on the Fermenting Capacity of Yeasts.] By R. KUSSEROW (Ried. Centr., 1899, 28, 630-632 ; from Brennerei-Zeit., 1897, 14, Nos. 318-320 ; and Centr. Bakt. Parasit., 1898, 4, ii, 154).-Addition of superphosphate, potassium phosphate, and magnesium sulphate in- creases the productive power of yeast in bad mash-material. Yeast distilleries should employ lower mash temperatures, to avoid separation of proteids with phosphates ; in thick mash distilleries, the temperatures should be higher in order to separate froth-producing proteids, and to convert peptones and albumoses, as far as possible, into amides. N. H. J. M. Yeast. By CARL BOTTINGER (Chem.Zeit., 1899,23, 313 and 645).- Solutions of grape sugar (5-6 per cent.) to which yeast was added were treated with lime (0.25 t o 2 per cent.), with copper sulphate (0-17-1 per cent.), and with both substances toget,her. I n every case, there was a partial or complete destruction of the sugar in a few days, either with or without evolution of gas. With glycollic acid (0.33 per cent.) all the sugar fermented with abundant liberation of carbon dioxide, With glyoxylic acid, the production of carbon dioxide was only slight and soon ceased ; further addition of yeast induced renewed liberation of gas, and in 30 days nearly half of the sugar was re- covered; oxalic acid was found to be present. Pyruvic acid acts similarly to, but less energetically than, glyoxylic acid, and gives rise to an intense odour of Lotus.Further experiments were made with paraldehyde, acetone, acetic acid, benzaldehyde, tartaric, citric, and oxalic acids. As regards the effect of sugar on the fermentation of grape juice, i t was found that addition of 10 per cent. of grape sugar delayed the production of mould. I n both cases, evolution of gas was very limited, and on distilling on the 20th day, there was only enough alcohol produced, both with and without sugar, to allow of detection by the iodoform test. The effect of sugar was rather physical than chemical. By H. MARSHALL WARD and JOSEPE REY- NOLDS GREEN (Proc. Roy. Xoc., 1899,65,65--84).--The bacteriumoccurs along with a t least one yeast in a mixture of organisms said to have come from Madagascar, where it occurs as an “ excrescence on the sugar cane.” The clumps induce vigorous fermentation in sugar solutions (15-20 per cent.), liberating relatively enormous amounts of carbon dioxide and some acid; oxygen is not necessary in any quantity.The bacterium will practically only grow in presence of sugar, and only certain sugars are suitable : sucrose (after undergoing inversion) is far the best, Iaevulose is utilised t o a slight extent, and dextrose is not a favourable medium. Dextrin, maltodextrin, maltose, lactose, N. H. J. M. A Sugar Bacterium. VOL. LXXVIII. ii. 334 ABSTRACTS OF CHEMICAL PAPERS. and soluble starch are all unsuitable or useless. Negative results were also obtained with glycerol and yeast extract, starch treated with diastase, potato, carrot, and milk.I n order to throw some light on the r6Ze of the bacterium and the yeastsrespectively in the fermentation produced by the mixed organisms, a number of experiments were made in which different solutions (such as sucrose, a mixture of sucrose and ltevulose, dextrose, &c.) were sown with pure cultures of (1) the yeast, (2) the bacterium, (3) the yeast and bacterium separately, and (4) the yeast and bacterium as ordinarily associated. It was found that production of alcohol was due to the yeast alone, the bacterium being without influence. The acid (acetic and succinic) was produced mainly by the bacterium ; of the two acids relatively more acetic acid was produced by the bacterium than succinic acid. I n sucrose, and in dark brown sugar containing lz?vulose, the conjoint organism produced less acids than the bacterium alone, whilst in dextrose the contrary was the case.The presence of the bacterium is of no advantage, but rather disadvantageous to the yeast, whilst the yeast is of use to the bacterium in excreting nitrogenous food. The bacterium does not affect alcohol like ordinary acetifying organisms, and seems to act directly on the sugar with production of acid, the immediate antecedent of which is probably laevulose. In sucrose, the bacterium produces a viscous material containing two carbohydrates in many respects similar to, but not quite identical with, Scheibler's dextran. N. H. J. M. Permanent Forms of Nitric and Nitrous Organisms. By ALFREDBEDDIES (Chem. Zeit., 1899,23,645-647).-Sterilised solutions containing the nutritive substances present in manure heaps, the percen- tage of nitrogen being raised to 3 per cent.by the addition of ammonium sulphate, in which the alkalinity was made suitable by the addition of sodium carbonate or of phosphoric acid, were inoculated with soil, After being kept for several weeks in diffused light a t 20--25O, the cultures in which nitrification was complete were employed for inocu- lating a fresh nutritive substance containing 1 per cent. of a strong solution of humus and 0.25 per cent. of sodium silicate. Cultivations of nitrifying organisms prepared in this manner proved to be much less sensitive than those obtained by Winogradsky in absence of organic matter. Four stable varieties of nitric and three varieties of nitrous bauteria were isolated.The strongest form of the nitric bacterium resisted the action of steam a t 100' for 2 minutes ; and one form of nitrous bacterium lived for 1 minute in steam a t looo. Nitric and nitrous bacteria can be cultivated together and do not interfere with each other, and an inoculating material was prepared by drying previously sterilised calcareous soil to which both forms had been added. P o t experiments are described in which grasses and cereals were grown in sterilised sand to which sterilised humus, ammonium sulphate, and minerals were added, with and without the addition of the inoculatingrnaterial. With inoculation, the growth was stronger and more luxuriant.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 35 Evidence was obtained that, in presence of an abundance of nitrifying organisms, denitrification is hindered and there is no loss of free nitrogen, When, however, denitrifying organisms predominate, the nitrifying bacteria are injured, especially if aeration is limited.N. H. J. M. Germination of the Carob Bean (Ceratonia Siliqua) : Pro- duction of Mannose by a Soluble Ferment, By EMILE BOURQUELOT and HENRI HI~RISSEY (Compt. rend., 1899, 129, 614-616).-1n the germination of the carob bean, a soluble ferment is produced which acts on the albumin in the seed and produces from it mannose and galactose. Since saliva does not act on this albumin, i t follows that the ferment in question is distinct from diastase. This is the first instance of the production of mannose by a soluble ferment (compare Abstr., 1899, i, 839, 968). Action of Anasthetic Vapours on the Vitality of Dry and Moist Seeds.By HENRI COUPIN (Compt. rend., 1899, 129, 561-562).-The germinating power of the seeds of wheat and clover is not in the least affected by exposure, in the dry state, to the satu- rated sapour of ether or chloroform for 680 hours. These liquids may therefore be safely used for the destruction of insects in grain, and are to be preferred tocarbon disulphide, which has an injurious action on some seeds, such as wheat. Experiments with white lupin, purple clover, hairy spring vetch, buckwheat, wheat, barley, maize, and hemp show that moist seeds are much more susceptible to the action of anzesthetics. I n an atmosphere containing 1 C.C. of ether per 10 litres, germination takes place as usual; with a larger quantityof ether, growth is more or less retarded, purple clover being the most resistant of the seeds examined, and with 3.7 C.C.of ether per 10 litres all the seeds are killed, and will not germinate even when removed from the action of the ether and washed well with water. Absorption of Water ,and Dissolved Substances by the Stems of Plants. By EMILE BR~AL (Ann. Agron., 1899, 25, 449--458).-The absorption of different substances by plants was effected by inserting in the stemaglass tubes drawn out to a suitable size, containing the solutions. Whilst nitrates can accumulate inplants, i t was found that ammonium salts, although absorbed, are soon converted into other substances, Nitrates accumulated abundantly in the stems, but could not be detected in the roots. Potassium humate was absorbed by lupins, and was afterwards visible when the stems were cut open.In the case of maize, it was observed that absorption of potassium humate resulted in the destruction of the nitrates present, Potassium humate, in con- junction with ammonium phosphate, diminished the amount of nitrate in amaranth without causing its entire disappearance ; in the case of lupins, all the pre-existing nitrate disappeared. Food-stuffs of the Leaves of the Plane-tree and their Migration during the Growth and Decay of the Leaves. By G. M. TUCKER and BERNHARD TOLLENS (Ber., lh99,32,2575-2583).- The leaves examined were picked at intervals during the summer ; 500 C. H. B. N. L. N. H. J. M.3-236 ABSTRACTS OF CHEMICAL PAPERS. being taken on each occasion; to obtain comparable results, only the two oldest leaves on any one twig were selected. After weighing and measuring the surface of an average sample, the leaves were dried, burnt, and the ash analysed, the constituents determined being SiO,, Fe,C),+Al,O,, CaO, -MgO, P,O,, SO,, K,O, Na,O, C1, and N, The results show that the weight and also the amount of ash of the leaves increased until the leaves died, and then slightly decreased. The amounts of silica and lime show a similar behaviour, but the chlorine and sulphuric acid show a continuous increase, leaves plucked in November containing three times as much sulphuric acid as those plucked in June. Those constituents regarded as the more important food-stuffs show a quite different behnviour ; the phosphoric acid and the potash increase very slightly until the leaves die, after which they diminish to less than half their original amounts.The amount of nitrogen steadily falls, having a t the end a value less than one-fourth of the initial value. Young leaves gathered in November show the presence of large quantities of potash, phosphoric acid, and nitrogen, the amounts of which are sufficient to account for the loss in these constituents suffered by the older leaves after death; any backward motion of these food-stuffs from the leaves to the stem or wood of the twigs the authors regard as of small amount. Comparative experiments with leaves protected from rain and others non-protected show that rain has little, if any, washing-out action on the food stuffs of the leaves.The Replacement of Potassium Salts by Rubidium Salts in Lower Fungi. By OSCAR LOEW (Bied Centr., 1899, 28, 646-647 ; from Rot. Centr., 1898? 74,202-205).-Whilst the author has shown that rubidium can take the place of potassium in putrefaction bacteria, yeast, and Penicillium, the results of Gunther’s experiments indicate that such substitution can take place to some extent in Botrytis cirnerea, but not in Rhixopus nigricans. The experiments now described confirm Gunther’s observation that differences exist in the case of various fungi as regards the power of utilising rubidium. Rucillus coli develops equally well in the presence of rubidium and of potassium ; B. pyocyaneus grows twice as quickly in the presence of potassium as with rubidium.Clccdothrix failed to develop in the presence of rubidium, whilst a moderate growth was obtained with potassium (the organic food was 1 per cent, dextrose and 0.5 per cent. sodium ace tat e). Yellow Colouring Matters accompanying Chlorophyll and their Spectroscopic Relations. By C. A. SCHUNCK (PTOC. Roy. SOC., 1899, 65, 177-186. Compare Abstr., 1899, ii, 540).-Alcoholic extracts of healthy green leaves contain two yellow colouring matters : (1) chrysophyll which separates in lustrous, red crystals, usually in minute quantities, and (2) an amorphous substance to which the author would restrict the name xanthophyll. This is obtained by spontaneous evaporation of the solution, after removing the chloro- phyll by means of animal charcoal, and is impregnated with much T.H. P. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 37 fatty matter. Another yellow colouring matter sometimes occurs witti the xanthophyll; this gives no absorption bands, but only 8.n obscuration in the violet and ultra-violet portion OF the spectrum. Other yellow colouring matters may exist, but xanthophyll seems to predominate, and is also the principal yellow colouring matter of autumn leaves. The absorption spectrum of chrysophyll consists of three bands, that of xanthophyll of four bands, in the violet and ultra-violet portions. The author concludes that the spectrum of crude chloro- phyll (four bands in the less refrangible region and three in the violet) are due to chlorophyll alone, and not, as usually supposed, in part to the accompanying yellow colouring matters.Phyllocyanin and phylloxanthin have bands in positions identical with the three chlorophyll bands in the violet part of the spectrum. Wheat. By GEORGE B. FRANKFORTER and E. P. HARDING (J. Amer. Chern. Soc., 1899, 21, 758-769).-The germ of wheat was found to contain on the average 11.6 per cent. of oil. The sp, gr. of the oil is 0.9292 a t 15" and 0,9374 a t 0". At O", the oil is a cloudy semi-solid, at 15' it is milky, and a t 100' it becomes reddish-brown. When dried a t the ordinary temperature, it increases slightly in weight during the first 45 days, and loses rather more during the next 30 days. The index of refraction of the oil when purified is 1048325, 1.47936, and 1.47447 at Z O O , 30°, and 40' respectively.As regards solubility, 1 gram of the oil dissolves in 1 C.C. of ether, 1 C.C. of chloroform, 30 C.C. of absolute alcohol, or 350 C.C. of 90 per cent. alcohol. The saponification value, according to Kottstorfer's method, is 188.83 mg. of KOH to 1 gram of oil. Iodine number (Hubl) 115.64. Acid value, 40.7. Five determinations of glycerol gave an average per- centage of 7.35. The oil contains 2.0 per cent. of lecithin and 2.47 (mean of 5 analyses) of paracholesterol. The elaidin method gave 1.8 and 2.2 per cent. of paracholesterol. By JULES WOLFF (Chem. Centr., 1899, ii, 211-212; from Ann, chim. anal. appl., 4, 157-162, 187-193). -The root of Cichorium Intybus contains inulin, 6C,H,00, + H,O, but no starch. The inulin obtained from the aqueous extract of the root by precipitating with 90 per cent.alcohol has a specific rotatory power [ a J u -36.57' (Lescceur and Morelle) and does not reduce Fehling's solution. It is completely inverted by boiling for 20 minutes with 5 C.C. of hydrochloric acid, and the laevulose formed may be estimated by reduction or polarimetrically. An optically inactive sugar, ZcevuZin or synanthrose, which does not reduce Fehling's solution, is also present, and is decomposed by hydrochloric acid into dextrose and lzevulosa. Chicory only contains a very small quantity of a sugar which reduces Fehling's solution directly, and this is probably lmw- lose derived from the inulin. The sugars are practically unchanged by drying the root, but by roasting, the quantity of reducing sugars which consist mainly of laevulose with some dextrose is increased, a large portion of the inulin is changed, and caramel and dextrin are formed.The inulin contained in chicory may possibly be of use as a food in N. H. J. M. N. H. J. M. Constituents of Chicory.38 ABSTRACTS OF CHEMICAL PAPkRS. cases OF diabetes. The fresh root contains about 13-15 per cent. and commercial chicory from about 11-16 per cent, of inulin. Analyses of the fresh root, the dried material, and samples of commercial chicory are quoted. Constituents of Flores Kosso. By IWAN L. KONDAKOFF (Arch. Pharm., 1899, 237, 481--493).-An historical account of previous investigations, serving as an introduction t o the following abstract (compare especially, Fluckiger and Buri, Abstr., 1875, 468 ; Levin, Diss., St.Petersburg, 1892 : Leichsenring, Abstr., 1894, i, 424 ; Daccomo and Malagnini, Abstr., 1899, i, 158). Kossin or Taeniin of Pavesi and V6e. By IWANL. KONDAKOFF and N. SCHATZ (Avch. Phurm., 1899, 237, 493--507).--FZores Kosso, the female flowers of Hagenia abyssinica, are used as a vermifuge ; the sample examined contained moisture 10.5 and ash 10.3 per cent. The flowers were !treated with lime, 90 per cent. alcohol, and water, after the method of Pavesi (Journ. Yhurm. d'Amers, 1858, 472) and VBe (Neues Rep. Pharm., 8, 325); the alcohol was distilled off from the extract, and the residue decomposed with acetic acid, when kossin separated. When a solution of kossin in cold acetic acid or in alcohol is allowed t o remain, crystals of kosin separate.If a solu- tion of kosin in caustic alkalis is acidified with phosphoric acid, or a solution in baryta water decomposed with carbon dioxide, an amorphous variety of kosin, melting at 142q separates ; probably kossin contains a good deal of this. The ethereal extract of another sample of the flowers contained ( a ) an amorphous substance mixed with ( b ) another substance, which was insoluble in cold alcohol, and formed crystals melting a t 63", ( c ) an amorphous substance, characterised by acid and reducing properties, and melting at 155-157" ; ( d ) a wax-like substance, melting at 55" ; (e) a resinous substance, and ( f ) kosotoxin. The latter amounted to 6 per cent. of the dry extract (which itself formed 4.7 per cent. of the drug). As regards kosotoxin, Leichsenring's results were not entirely confirmed ; the melting point is 76'; the molecular formula, as deter- mined by analysis and cryoscopically, is C,,H,,O,, and the acid formed, in addition to kosin, when kosotoxin is boiled with 5 per cent.aqueous barium hydroxide, is not wholly a butyric acid, but contains another acid (valeric 2) admixed. The residue left after extraction of the flowers with ether yielded to alcohol an amorphous tannin, the amorphous substance (a), koso- toxin, and other substances which mere not separated. Detection of Sulphur Dioxide in the Atmosphere of the Tharandt Forest. By HANS WISLICENUS (Bied. Centr., 1899, 29, 643-644 ; from Fharundt forst. Jahrb., 1898, 173--184).-Experi- ments made by the Ost process from May to October in different parts of the forest, a t a distance of 10 kilometres from any source of smoke, showed the presence of sulphur dioxide inside the forest, although in less quantity than a t the edges.The results of previous experiments indicate, however, that in consequence of the limited amount of light in the forest the sulphurous acid is comparatively harmless. E. W. W. C. F. B. C. F. B. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 39 Maize as Food in Servia. By ALESANDEE ZEGA and R. MAJSTOROVI~ (Chern. Zeit., 1899, 23, 544-545).-Maize is the most important food in Servia, and in some districts nothing else is used. Besides boiled and roasted maize, different kinds of bread (including “ famine bread,” an inferior kind in which carrots, nettles, &c., are employed as well as maize), cakes, and other kinds of food, and a beverage, prepared from maize meal and wheat bran, are described.Maize meal (1) yellow, and (2) white, has the following composition : Nitrog. Carbo- Crude Water. subst. Fat. hydrates. Sugar. fibre. Ash. P203 1. 12.69 10.11 4.23 67-44 2.70 1.43 1.40 0.74 2. 13.36 9.56 4-84 66.36 2.68 1-72 1.48 0.68 The composition of the various foods is given. Determination of the Action of some new Foods on the Secretion of Milk, with Special Reference to the Amount of Fat in the Rations formed with these Foods. By EBERHARD RAMM and W. MINTROP (Bied. Centr., 1899, 28, 614-616 ; from Milchzeit., 1898, No. 33).-The following conclusions are drawn from the results of the feeding experiments. A high percentage of fat in food does not result in higher percentage of fat in milk, but the different concentrated foods, in rations differing very little in composition, pro- duced considerable variations in the percentage of fat in the milk As regards the various foods, i t was found that cocoa-molasses (cocoa- husk meal mixed with molasses) was consumed in large amounts and, in conjunction with oil-cake rich in proteids, increased the yieId of butter-fat above the average, Maize bran had no injurious effect on the health of the cows, even when consumed in large quantities.Blood molasses (blood, molasses, and offal of cereals) in quantities of 6-8 kilos. mas not injurious, was in every respect favourable to milk secretion, and is a very valuable food for cows. Value of various Concentrated Foods. By WALDEMAR VON KNIERIEM (Bied.Centr., 1899, 28, 616-618 ; from Landw. Jahrb., 1898, Heft. 3 and 4).-The constituents of cocoa-nut cake show, according to results obtained with rabbits, the following percentage digestibility : crude protein, 95.7; crude fat, 99.1 ; crude fibre, 89.1 ; non-nitrogenous substance, 95.2. With a ram, the results were very similar (except in the case of crude fibre) to those obtained by Kuhn with bullocks. The cake is one of the best concentrated foods. Hemp cake causes indigestion with rabbits as well as with sheep and horses; it can, however, be given to cows in conjunction with considerable amounts of roots, potatoes, malt-germs, or brewers’ grains, and is of importance in the feeding of young cattle. Sun- flower cake gave lower results with rabbits than those given by Wolff, which were obtained with sheep.Rape cake in small quantities favours the digestion of non-nitrogenous constituents ; in the case of cows, it must be employed with care to avoid indigestion, especially when the cake develops mustard oil. Palm cake resembles cocoa-nut cake and is chiefly useful in promoting milk production. N. H. J. M. (2.327-3.437). N. H, J. M. N. H. J. M.40 ABSTRACTS OF CHEMICAL PAPERS. In Feeding with Sesame Cake, do Substances which give the Baudouin Reaction appear in the Butter ? By H . WEIGMANN (Bied. Centr., 1899, 28, 629-630 ; from Milchzeit., 1898, 529)- Experiments with cows in which sesame cake was given in increasing qlxantity (up to 3 kilos. per day) showed that the butter was quite free from sesame oil.I n examining butter for sesame oil, i t is important to employ only 0.1 C.C. of 1 per cent. furfuraldehyde solution; with 1 per cent. sesame oil or 10 per cent margarine, the coloration appears at once, whilst any other coloration can only appear in the course of about half an hour. The results obtained by Scheibe (Milchxeit., 1897, ’745) and Siegfeld (Bied. Centr., 1899, 28, 415), which are opposed to those just described, are attributed t o the employment of unsuitable amoiints of furfuraldehyde, and to the correct conditions as to time and temperature not having been observed. By FRANK W. TRAPHAGEN and W. M. COBLEIGH (J. Arner. Chem. Xoc., 1899, 21, 753-757).-The bare patches of soil incrusted with white, red, or yellow salt which occur in Montana, and are known as ‘‘ alkali ” soils, are of two kinds, the “ white,” consisting mainly of sodium sulphate, and the ‘‘ black,” of sodium carbonate.The appearance of the latter is due to the solvent action of the carbonate on humus which, on evaporation, is left as a shiny black coating on the surface. As little as 0.1 per cent. of sodium carbonate at the surface is deleterious, whilst crops will thrive in the presence of as much as 0.6 per cent. of ‘‘ white alkali.” Larger quantities of white alkali are injurious rather by interference with the process of osmosis than through any chemical action. Analyses of different soils and crusts are given, showing that the amounts of soluble salts differ widely ; there is, however, a very con- stant relation of the amounts of different salts in the extracts.In virgin soils, the alkali occurs at considerable depths, and is mostly concentrated in a particular zone. Under the influence of irrigation, the salts rise to the surface. The best remedy would seem to be under-drainage, but, in the case of land of insufficient value, much can be done by careful surface flooding and suitable cropping. N. H. J. M. AJkali Soil in Montana. N. H. J. M. Distribution and Biological Importance of Furfuroids in Soil. By JULIUS STOKLASA (Bied. Centr., 1899, 28, 5 8 8 4 8 9 ; from Zeit. landw. Versuchswesen, Oesterr., 1898, 1, 251-266. Compare Abstr., 1898, ii, 132).-The furfuroids in soil are produced by algae and bacteria. The dry substance of Pleurococcus oulyaris, which grows on rocks, contains 3.43, that of Nostoc, 5.06 per cent.of pentosans. Cultures o f Bacillus rnesentericus, which is very common in soils, contained 2.31 per cent. of pentosans in the dry substance. Par- rnelia, Lecanora, H y p u m Xchreberi and H. dieramurn, and Sphagnum cymbifolium contain respectively 3-46, 3.43, 6-1 9, 10.78, and 15.44 per cent. of pentosans. Other plants of importance in peat production were found to contain the following amounts o f pentosaus : Pteris uquilina, 18.S ; dspidium, 19.1 ; Equiseturn arvense, 33.5 and 21.1 ; Lycopodiurn, 24.6 ; Cnrex acuta, 19.6 in above-ground growthVEGETABLE PHYSIOLOGY AND AGRICULTURE. 41 and 26.5 in roots ; Calluncc uulgccris, 17.3 and 23.2 per cent. in above- ground growth and roots respectively.Peat was found to contain 17.4 per cent. of pentosans in the first 10 cm., 10.38 per cent. at a depth of 50 cm., 5.34 per cent. at 100 CM., and 1.60 per cent. a t a depth of 2 metres. The surface soil of forest land yielded 3.27, the soil at a depth of 50 cm. 0.83 per cent. of f urfuraldehyde. Observations on the Growth of Maize continuously for Nine Years. By EDWARD H. JENKINS (Ann. Rep. Conn. Agric. Exper. Stat. for 1896, No. 20, 335--341).-The four plots received: (1) cow manure, (2) hog manure, (3) chemical manures, and (4) no manure. The average relative yield'of dry produce from 1890-1896 was as follows : plot 1, 100 ; plot 2, 100.4 ; plot 3, 81.8 ; and plot 4, 51.0. Taking the produce of each plot as 100 in 1890, the following amounts were obtained in 1896.The average composition (6 years) of the kernels and stalks was practically the same in the case of plots 1 and 2. In plot 3 (1,500 lbs. of chemical manure), the kernels contain rather less ash and fat, and 0.5 per cent. less proteids than those of plots 1 and 2, but more nitrogen-free extract. The stalks show similar differences. The kernels of the unmanured plot contain 2 per cent. less proteids, rather less ash and fat, but more fibre and nitrogen-free extract than those of plots 1 and 2. The calculated gain or loss of manure constituents in the soil after 9 years cropping with maize was as follows in lbs. per acre: Plot 1. Plot 2. Plot 3. Plot 4. N. H. J. M. (l), 116 ; (a), 101 ; (3), 79 ; (4), 31. - -- N P,O, K,O N P,O, K,O N P20, K20 /N P,O, K20 A \ +1283 +893 t-156 +2174 +3987 - 7 +611 + l l l l +171 -338 +46 - 7 3 N. H.J. M. Manurial Experiments with Barley. By JOSEPH HANAMANN (Bied. Centr., 1899, 28, 638 ; from Zed. Zccndw. Versuchswesen Oesterr., 1898, 1, 277-285).-The experiments were conducted in zinc vessels containing 12% kilograms of sandy soil, loamy sand, loam, and clay soil respectively (five pots in each case). One pot of each soil was without manure, whilst pots 2-4 received sodium nitrate and potassium chloride. The third pots had in addition superphosphate, the fourth pots basic slag (containing the same amount of phosphate as was given to No. 3), the fifth pots basic slag in double quantity. The results indicate that spring manuring with basic slag is only advisable in the case of sandy soil, loamy sand, and peaty soil, but not in the case of loamy and clay soils, and the amount applied should be twice as great as that of superphosphate.Manurial Experiments with Lucerne. By MAX MAERCKER (Bied. Centr., 1899, 28, 635 ; from Lundw. 2uhrb., 1898, 2'7, 155).-It is thought that liberal application of phosphates mill not only increase the yield of lucerne, but will be of use in preventing the injurious effects of lucerne on a succeeding cereal crop (liability to be laid, fungus attack, k c . ) . N. H. J. M. N. H. J. M.42 ABSTRACTS OF CHEMICAL PAPERS. Experiments on the Availability of Fertiliser-Nitrogen. By SAMUEL W. JOHNSON, EDWARD H. JENKINS, and W. E. BRITTON (Ann. Rep. Conn. Agric. Zxper. Stat. for 1896, No. 20, 178-204. Compare ibid., No.19, and Abstr., 1896, ii, 620).-The nitrogen availability of the different manures for maize grown in coal-ashes and peat, compared with that of sodium nitrate as 100, was found to be as follows (average of three years, 1894-6) : collier castor pomace, 77 ; cotton seed meal, 74 ; red seal castor pomace, 70 ; linseed meal, 70 ; dried blood, 68 ; dry fish, 69 ; dissolved leather, 65 ; horn and hoof, 67 ; tankage, 61 ; steamed leather, 13 ; roasted leather, 9 ; raw leather, 2. On comparing the nitrogen availability of some nitrogenous super- phosphates, determined by vegetation experiments, with the solubility in chemical agents, the following results were obtained : Available Soluble in Soluble in permanganate. for maize, pepsin. Acid. Alkaline. Blood ..............47 47 47 47 Horn and hoof ... 43 28 42 52 Leather ............ 3 8 14 25 The chemical methods would therefore seem to be of value as indicating the probable relative effect of inferior nitrogenous manures. The agricultural value cannot, however, a t present be fixed without vegeta- tion experiments. By MAX MAERCKER (Bied. Centr., 1899, 28, 637; from Landw. Jahrb., 1898, 27, 151).- The effect of potassium phosphate and of kainite was to increase the percentage of proteids in the hay owing, as a botanical separation of the herbage showed, to increased growth of more nitrogenous plants, especially Legurninom. By BRUNO TACKE (Bied. Centr., 1899, 28, 589-611 ; from Landw. Jahrb., 1898, 27, ivy 1-258. Compare Abstr., 1897, ii, 515).-Manure salts con- taining 38 per cent.of potash as potassium chloride gave very good results with potatoes, and had practically no injurious effect when applied in the spring in amounts of as much as 200 kilos. of potash per hectare. Carnallite and kainite (225 kilos.) applied in the spring considerably diminished both the yield of tubers and the amount of starch; in some cases there is a decrease of starch in the dry matter, in otbers the lower percentage of starch in the tubers is due to an increase in the amount of water. Application of lime seems to lessen the injurious effect of spring manuring with potash on potatoes. Application of lime or marl to the soil for all kinds of crops is very beneficial for a time, and is even necessary when artificial manures are employed, but is subsequently injurious owing to the shrinking of the comparatively shallow layer of the surface soil.The injury can be overcome by subsoil liming. Phosphoric acid in the form of phosphorite should only be applied to peat land which retains a certain degree of acidity. Tankage ............ 45 39 45 43 N. H. J. M. Manurial Experiment on Meadow Land. N. H. J. M. Field Experiments on Peat Land, 1892-1897. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 443 Manurial Experiments with Phosphorite and Basic Slag. By A. SEMPOLOWSKI (Bied. Centr., 1899, 28, 637-638; from Zeit. Zandw. Versuchswesen Oesterr., 1898, 1, 267--276).-Whilst hard crystalline phosphorite has to be converted into superphosphate, the so-called soft, non-crystalline mineral, if finely ground, can be employed, without further treatment, as manure. Experiments in which barley was grown in sandy loam and in peaty soil (contained in bottomless wooden boxes) manured with phosphorite meal and basic slag respectively, in addition to other manures, showed that the phos- phorite was decidedly effective, the increased production of barley, over the unmanured plots being not much less than that obtained under the influence of basic slag, N.H. J. M. Comparison between Bone- and Mineral-Superphosphate. By ANQELO MENOZZI (Bied. Centr., 1899, 28, 635; from Agricolt. moderna, 1897,50).-Maize grown in large zinc vessels was manured with equal amounts of phosphoric acid in the form of superphosphate from degelatinised bones and Florida phosphate respectively, in addition t o other manures.The results indicated only slight superiority of the bone as compared with the mineral super- phosphate. N. H. J. M. Phosphate Deposits in Japan. By I(. TSUNETO (Chem. Zeit., 1899, 23, 800 and 825--827).-In 1894, large deposits of phosphates were discovered in the miocene formation, extending over 720 square kilometres, in the south-west of the island Kiushu. The phosphates occur in nodules and aggregates in the lime-sandstone, in marl veins, and in dark brown veins of sandstone situated between the calcareous fine-grained sandstone. The nodules are generally rich in phosphates in the inner portion, whilst the outer layer is rich in iron ; they contain organic remains. The following is the percentage composition of (1) grey nodules, (2) light brown nodules, (3 and 4) aggregates, (5) balls, and (6) breccia : Water and organic. K20. NazO. CaO. MgO. FeO. Fe2O3. A1203. MnzO3. P2O5. 803. C02. Insol. 1. 1'26 - - 9'62 2.28 8.77 2-93 2-14 0.35 3-35 0.29 8.26 55-65 3. 0'65 - - 11.73 2.36 7.37 2.46 1.65 0'23 5'85 0'63 7-92 54-22 6, 2.15 1'04 0'42 16.76 1.20 - 3-89 1.98 - 9-47 trace 2'28 47.15 2. 1-48 -- - 12.71 2'28 8-95 2-99 2.88 0'39 4.76 0.53 7-08 55.25 4. 0.89 - - 10.56 1.14 7.88 1'64 2.00 - 7-14 0.51 6-81 57.43 5. 2.21 2-25 0.42 30.28 1'30 - 3-76 3-72 - 20'29 1'23 1'82 28'38 I n (5), a trace of chlorine and 2-09 per cent. of fluorine were found, and in (6) C1= 0.06 and F = 2.13 per cent. Although the percentage of phosphoric acid is generally low, the deposits are of importance in Japan where manures with very low percentages of phosphates are utilised. The best method for utilising the minerals containing 5-10 per cent. of phosphates seems to be extraction of the ground substance with 12.45 per cent. sulphuric acid (avoiding too great a rise of temperature) in amounts sufficient to decompose the phosphates and carbonates present. N. H. J. M.44 ABSTRACTS OF CHEMICAL PAPERS. The Reversion of Soluble Phosphoric Acid in Superphos- phates. By LUDWIG SCHUCHT (Chem. Cent?'., 1899, i, 1165-1166 ; from Chem. Ind., 22, 152--155).-Reversion does not take place unless the superphosphate is closely packed and consequently sub- mitted to pressure. Ferric and aluminium compounds are harmful as their phosphates act on the undecomposed calcium triphosphate and so yield insoluble phosphates. Silicates are also a source of loss in phosphoric acid ; their amount may be lessened by adding a regulated quantity of fluor-spar during the preparation of the superphosphnte. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9007805033

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

44 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Standardising Acids. By ANTON SEYDA (Chem. Centr., 1899, i, 1164 ; from Zed. ofentl. Chem., 5, 141--151).-Sodium carbonate, used for stsndardising acids, is likely to retain excess of carbon dioxide, or if overheated it may contain sodium hydroxide. A suitable article is, however, obtained by heating sodium hydrogen carbonate for a n hour a t 220” in an air-bath. The results then perfectly agree with those obtained by standardis- ing the acid with the aid of potassium hydrogen tartrate or ammonium By STEPHEN I?. PECKIIAM and H. E. PECKHAM (J Amer. Cihem. Xoc., 1899, 21, 772--776).-1n reply to Hodgaon, the authors state that in order to get accurate estimations of sulphuric acid, any iron or aluminium oxides should be first removed.The following method has been finally adopted for the estima- tion of sulphur in bitumen. A quantity of the substance representing about 0.5 gram of real bitumen is mixed with 15 grams of pure dry sodium carbonate and 15 grams of potassium nitrate and the mixture then fused by degrees in a platinum crucible. The product is dissolved i n dilute hydrochloric acid, evaporated to dryness, and gently ignited to render any silica insoluble ; the residue is then treated with dilute hydrochloric acid and the solution precipitated, while boiling, with a slight excess of ammonia t o remove iron and aluminium. If desired, any calcium may be precipitated as oxalate. The filtrate is now acidified with hydrochloric acid and the boiling liquid precipitated with barium chloride solution added carefully from a pipette.chloride. L. DE K. Estimation of Sulphur in Bitumens. L. DE K. Estimation of Hyposulphurous Acid. By N. FRADISS (Chent. Centr., 1899, i, 1223 ; from Bull. Assoc. Chimistes, 16, 453).-The solution is neutralised and added from a burette to an ammoniacal standard solution of copper sulphate until this is quite decolorised. The presence of sulphites does not interfere. 1 mol. of hypo- sulphurous acid reduces 2 mols. of copper oxide to the cuprous state. L. DE K.AN A L Y TI C AL C H EM IST R T . 45 Volumetric Estimation of Sulphuric Acid. By FRANZ LITTERSCHEID and KARL PEIST (Arch. Pharrn., 1899,237, 521-525).- The authors have developed independently the method described by Griitzner (this vol., ii, 530).The solution of the sulphate is acidified with hydrochloric acid, heated to boiling, treated with a measured excess of N/4 barium chloride solution, stirred well, and allowed to remain in a warm place for half-an-hour; the liquid is then made strongly alkaline with ammonia, excess of ammonium carbonate solution added, and the whole stirred and allowed to remain a t 50-60' for ten minutes. The precipitate is then collected on a small filter, washed three or four times with hot water, and transferred to a conical flask, when the barium carbonate is titrated with N/10 hydrochloric acid. It may be titrated directly when methyl-orange is employed as an indicator ; if phenolphthalein be used, excess of N/10 acid must be added, the carbon dioxide driven off by boiling, and the excess of acid titrated with N/10 caustic potash.On multiplying by 0.4 the number of c c. of N/10 acid neutralised and subtracting the product from the number of C.C. of N/4 barium solution taken, the remainder multiplied by 0.01 gives the weight of SO, present, or multiplied by 0.004 the weight of S. The solution of the sulphate must not contain any acid of which the barium salt is insoluble, such as phosphoric and oxalic acids; neither must it contain substances which are precipitated by ammonium carbonate, or, like 'tartaric and citric acids, hinder the precipitation of the barium. Alkaloids, if insoluble in ammoniacal ammonium carbonate solution, must be removed by extraction with a suitable solvent. The sulphates of potassium, sodium, ammonium, rubidium, czsium, copper, zinc, cadmium, nickel, and cobalt, may be estimated directly ; so also that of lithium! provided the solution be dilute enough t o retain the lithium carbonate in solution (solubility : 1 in 75 parts of water a t 50') Iron sulphate, and the solution obtained by oxidising copper pyrites with nitric acid and potassium chlorate, may also be estimated, if the iron is first removed as hydroxide. With magnesium sulphate, good results have not yet been obtained.Titration of Persulphates. By MAX LE RLANC and M. ECKXRDT (Zeit. Elektrochern., 1899, 5, 355-357).-The reaction between a persulphate and a ferrous salt in solution is comparatively slow at the ordinary temperature ; erroneous results may therefore be obtained in the analysis of persulphates by treating the solution with ferrous sulphate and titrating the excess with permanganate.These errors are very easily avoided by warming the acidified mixture of persulphate and ferrous ammonium sulphate to 60-80' before titrat- ing with permanganate T. E. Estimation of Tellurous Acid in Presence of Haloid Salts. By FRANK A. GOOCH and C. A. YETERS (Arner. J. Xci., 1899, 8, 122-1 26). -Tellurous acid is generally estimated by adding to its alkaline solution a slight excess of standard potassium permangannte. A definite volume of standardised ammonium oxalate is added, and then a sufficiency of dilute sulphuric acid (1 : 1) so as to have about 5 C.C. of the acid in excess. After heating at 60--80°, the excess of oxalic acid is estimated by standard permanganate.C. F. B.46 ABSTRACTS OF CHEMICAL PAPERS. The authors find that the presence of chlorides does not interfere if before the final titration about 1 gram of crystallised mangnnous chloride is added. Bromides are also harmless if the same precaution is taken and the temperature not allowed to rise above 2 5 O . I n the case of iodides, the process breaks down, so another method was successfully tried. The alkaline solution is mixed with a known volume of potassium permanganate, previously standardised with a standard solution of arsenious acid, and, after a while, a slight excess of dilute sulphuric acid is added, with, if necessary, some more potass- ium iodide; after adding a slight excess of potassium hydrogen car- bonate, the liberated iodine is titrated with the standard solution of arsenious acid, the end reaction being the disappearance of the yellow colour ; starch need not be used as an indicator.Supposing the two solutions balance each other-the difference in the two titrations equals the number of C.C. of permanganate consumed by the tellurous acid. L. DE I(. Detection of Nitric Acid in Cadaveric Matter. By DIOS- CORIDE VITALI (Zeit. anal. Chem., 1899, 38, 539-541 ; from Oesterr. Chemikerxeit., 1, 330).--For the detection of free nitric acid in animal matter in which nitrates may already be present, either as normal constituents or by introduction in food, it is useless to distil with water, for the mineral acids combine with albumin, forming acid- albumins, which in many cases are not decomposed at 190'.The substance is therefore digested on the water-bath with freshly preci- pitated barium carbonate, the solution evaporated to dryness, and the residue boiled repeatedly with absolute alcohol for the removal of calcium and magnesium nitrates. The alcoholic solution will also contain the soluble acid-albumin. It is evaporated to dryness, the residue dissolved in water, and exactly neutralised with barium hydroxide solution, which decomposes the acid-albumin. The solution is again evaporated and the nitrates separated by absolute alcohol. The residual barium nitrate is then dissolved in water, decolorised with lead acetate, freed from lead by hydrogen sulphide, and the concentrated solution finally crystallised in the desiccator. The residue from the first treatment with alcohol contains the barium nitrate derived from the presence OF free acid as well as insoluble acid-albumin, and possibly some calcium nitrate.It is treated with a dilute solution of sodium carbonate until an alkaline reaction is just obtained. The acid-albumin and the barium nitrate are by this means converted into sodium nitrate, the calcium nitrate remaining undecomposed. The filtered solution is evaporated to dryness and the residue boiled with absolute alcohol. The sodium nitrate dissolves, but it is stated that the calcium nitrate remains undissolved. The sodium nitrate is purified and identified in the same way as the barium nitrate above, [W. Fresenius expresses grave doubts as to the correctness of some of the above reactions, and points out that the author contradicts himself, as well as established fact, in stating that calcium nitrate is undissolved by boiling alcohol.] Another method consists in treating the animal matter with freshly precipitated strychnine, when strychnine nitrate is formed.ThisANALYTICAL CHEMISTRY, 47 can be purified by solution in boiling alcohol, the colour removed with lead acetate, and the nitrate finally obtained as crystals. A very sensitive reaction for nitric acid is obtained by adding salicin and 8-10 drops of concentrated sulphuric acid to the residue of an evaporated solution. A blood-red coloration is produced, which becomes violet on dilution. By THORNSMITH (J. A.mei*. Chem. Soc., 1899,21, 769--772).-Two grams of the sample are boiled with 100 c.c.of water and 2 grams of sodium hydroxide; when cold, the liquid is made up t o 250 c.c., well shaken, and filtered through a dry filter.50 C.C. are then concentrated t o 25 c.c., and after cooling to 80°, 25 C.C. of hydrochloric acid and 3 grams of potassium iodide are added. After remaining for 10 minutes, any arsenic acid will be completely reduced to the arsenious state and the liberated iodine is removed by diluting with water and carefully decolorising with solution of sodium thiosulphate. After first neutralising with, and then adding a n excess of sodium hydrogen carbonate, the arsenious acid is titrated in the usual maner with N/lO solution of iodine. M. J. S. Estimation of Arsenic in Paris Green. L. DE K. Estimation of Boric Acid in Tourmaline. By GEORGE W. SARGENT (J.Amer. Chem. Xoc., 1899,21,858-887).-The paper contains a summary of all the chief methods proposed for the estimation of boric acid, and the author’s opinion as to their respective merits. When dealing with tourmaline and similar minerals containing alum- inium, the chief difficulty arises from the incomplete separation of boric acid and umina, the only way of effecting complete separation is by the method proposed by Gooch, namely, volatilisation of the acid by means of methyl alcohol, coupled with the titration of the volatilised acid by By LOUIS C. JONES (Amel.. J. Xci., 1899, 8, 127-132. Compare Abstr., 1899,ii, 332).-Under certaindefinite conditions, a mixture of boric acid and mannitol possesses an acidic power sulticiently strong t o liberate iodine from a mixture of potassium iodide and iodate.The iodine is readily estimated by means of sodium thiosulphate, and represents the amount of boric acid. To obtain correct results, the following mode of procedure should be used: the borate is dissolved in the smallest possible quantity of hydrochloric acid and then diluted with water so that 50 C.C. of liquid shall contain about 0.1 gram of boric acid. The greater part of the free acid is then neutralised with sodium hydroxide and 5 C.C. of a 40 per cent. solution of potassium iodide and 10 C.C. of a 5 per cent. solution of potassium iodate are added and the liberated iodine at once removed by a few drops of a stror;g solution of sodium thiosul- phate. After restoring a very faint yellow colour by means of stand- ard iodine, 15 gramsof mannitol are added, and when dissolved, a stand- ard solution of sodium thiosulphate is added until the colour is bleached, when an extra 10 C.C.are added. A little more mannitol is added and after standing in a cool place for an hour, the excess of thiosulphate is carefully titrated by means of standard iodine solution. Thornson’s glycerol method. L. DE K. Iodometric Method for the Estimation of Boric Acid. L. DE K.4s ABSTKACTS OF CHEMICAL PAPERS. Stutzer and Hartleb’s Process for the Estimation of Com- bined Carbon Dioxide (Calcium Carbonate) in Soils. By H. SCHUTTE (Zeit. angew. Chem., 1899, 854--858).--The author criticises this process (Abstr., 1899, ii, 521) and states that, although good enough for marls, it is not sufficiently accurate for the estimation of small quantities of calcium carbonate in soils.The chief objection to the process is that ammonium chloride also acts on calcium in combination with silicic acid, and so causes the results to be in excess of the truth. Ferrous carbonate is also stated t o interfere with the accuracy of the method, and cannot always be Gas Washing Apparatus : Rapid and Accurate Process for the Estimation of Carbon Dioxide. By ROBERT SCHALLER (Zeit. angew. Chem., 1899,878-880).-The apparatus is essentially a U-tube 17 cm. long, one side of which is very narrow and serves to admit the current of the gas. The other side is filled with glass beads 2 mm. in diameter, which are moistened with the absorbing liquid. I n the new apparatus for estimating carbon dioxide, the substance is decomposed in a kind of test-tube with hydrochloric acid, and the carbon dioxide is swept out by means of a current of air which has been freed from this gas by passing through two of the U-tubes containing a solution of potash.The gas then passes through a similar tube containing sulphuric acid before it reaches the absorber. The latter consists of one or two similar weighed U-tubes con- taining 10 C.C. of 50 per cent. solution of potassium hydroxide. These tubes are, in addition, fitted with a small test-tube 8 cm. long con- taining 1 C.C. of strong sulphuric acid, and provided with a doubly perforated rubber cork. Through one of the holes passes a tube with a bulb in its centre and drawn to a narrow point a t the bottom, the object being t o prevent any escape of moisture from the apparatus.The other hole is fitted with a small beut tube t o allow the air to By HERMANN NOLL (Zeit. angew. Chem., 1899,859 -86O).-The process recommended by Tacke is found to answer for the estimation of calcium carbonate in marls, as it is not affected by the presence of small quantities of ferrous and aluminium compounds or of calcium silicate. The details of this process are briefly as follows : 0-2 gram of the powdered sample is mixed with 200 C.C. of warm water, 25 or 50 C.C. of N/5 normal sulphuric acid are added, and the carbon dioxide expelled by boiling. The excess of acid is then titrated with standard baryta, using phenolphthalein as indicator. New Volumetric Method for the Estimation of Magnesium.By I~ICHARD K. MEADE (J. Amer. CILem. Soc., 1899, 21, 746-752).- The process is fin indirect one. The ammoniacal solution free froin calcium is precipitated with a solution of sodium arsenate, and the excess of the reagent removed by washing with dilute aqueous ammonia (1 : 3). The arsenical precipitate is then dissolved in 75-100 C.C. of dilute completely decomposed by boiling. L. DE R. escape. L. DE I(. Estimation of Calcium Carbonate in Marls. L. DE K.ANALYTICAL CHEMISTRY, 49 hydrochloric acid (1 : l), potassium iodide added, and the liberated iodine titrated with standard solution OF sodium thiosulphate. L. DE K. Double Ammonium Phosphates of Beryllium, Zinc, and Cadmium in Analysis. By MARTHA AUSTIN (Amer. J. Sci., 1899, 8, 206--216).--When salts of these three metals are precipitated by boiling with excess of sodium ammonium hydrogen phosphate, double ammonium phosphates are obtained, which, on ignition, yield the corresponding pyrophosphatee.It has, however, been found impossible to accurately estimate beryllium in t h i s manner. Zinc may be estimated if care be taken to precipitate the metal from a neutral solution containing 10 per cent. of ammonium chloride. The process is also well adapted for cadmium ; the solution should contain 10 per cent. of ammonium chloride, be practically neutral, and be allowed t o remain several hours before By P. A. MACKAY (J. Amer. Chem. Soc., 1899, 21, 940-941).-The metal is treated with dilute hydrochloric acid in sufficient quantity t o dissolve the bulk of the zinc ; the undissolved portion then contains all the lead and cadmium present.After dissolving the residue in nitric acid, the lead is recovered in the usual way as sulphate, and in the filtrate the cadmium is pre- cipitated by hydrogen sulphide; the cadmium sulphide is then col- lected, washed, and redissolved in boiling hydrochloric acid and titrated with potassium ferrocyanide. It has been noticed, however, t h a t small quantities of cadmium can only be accurately estimated in the presence of zinc, and also that 1 gram-mol. of cadmium requires 3.676 gram-mols. of potassium ferrocyanide, instead of 3.767, as required by theory. A solution containing 10 grams of zinc per litre is prepared, and 50 C.C. of this titrated with a solution containing 36.76 grams of potassium ferrocyanide per litre, using uranium acetate as indi- cator. Another 50 C.C.is then added to the liquid containing the cadmium, and the titration is repeated; each C.C. excess of ferrom cyanide solution used in this titration represents 0.01 gram of cad- Electrolytic Estimation of Zinc in the Presence of Manganese. By EMIL J. RIEDERER (J. Amer. Chm. SOC., 1899, 21, 789-792).- Zinc may be conveniently separated from manganese by electrolysis. The solution, which should not contain chlorides or nitrates, but only sulphates, is mixed with 5 grams of ammonium lactate, 0.75 gram of lactic acid, 2 grams of ammonium sulphate, and then made up t o 230 C.C. ; the amount of zinc should not exceed 0.17 gram. The cathode, which should be 1& cm. distant from the anode, should consist of a platinum dish on which silver has been deposited, and during the action of the current it is advisable to use a mechanical stirrer so as t o obtain an even and uniform deposit of zinc ; the current may vary from 0.20-0*26 ampkres and the temperature from 15-26'.The time required for the complete deposition of the zinc does not VOL. LXXVIII. ii. 4 filtering. L. DE K. Analysis of Zinc for Cadmium and Lead. mium. L. DE K.50 ABSTRACTS OF CHEMICAL PAPERS. exceed 54 hours; the deposit is free from manganese. It is rapidly washed first with water, then successively with alcohol and ether, dried Direct Estimation of Aluminium in the Presence of Iron, Manganese, Calcium, and Magnesium, By WILLIAM H. HEM and EDWARD D. CAMPBELL (J. Amer. Chem. SOC., 1899, 21, 776-780).-A convenient bulk of the liquid, preferably containing the metals as chlorides, is heated to boiling and dilute ammonia is added so long as the precipitate readily redissolves; to reduce the ferric salts, a saturated solution of ammonium hydrogen sulphite is added drop by drop until the liquid is colourless. The aluminium is now precipitated by adding a few C.C. of phenylhydrazine and is washed with hot water containing about 10 per cent. of phenylhydrazine hydrogen sulphite free from excess of sulphur dioxide, On ignition, it leaves pure alumina. Chromium may also be separated from iron, calcium, mag- nesium, cobalt, or nickel in this manner. If, however, the mixture also contains phosphoric acid, the alumina will be contaminated with phosphoric oxide, which must be estimated By RODOLFO NAMIAS (Chem.Centr., 1899, i, 1224; from Annzcar. SOC. chirn. Milano, 1899, 54--56).-The author uses Volhard’s process when estimating man- ganese in samples of iron or steel. Use is made of carefully selected crystals of potassium permanganate which are reduced by boiling with hydrochloric acid ; the manganous chloride so obtained is precipitated with sodium carbonate, the precipitate is converted into manganoso- manganic oxide, and this is titrated with ferrous sulphate. It is recommended to first dissolve the steel, or iron, in hydrochloric acid before oxidising with nitric acid t o prevent the formation of By PORTER W. SHIMER (J. Anzer. Chern. Xoc., 1899, 21, 723-’724).-A new form of the reductor used in the estimation of iron and phosphomolybdate solutions.It is essentially a plain glass tube g-inch in diameter and 20 inches long drawn out and cut off at the lower end. It is united with a 4-inch funnel by means of wired rubber tubing fitted with a screw clamp. The lower end passes through a soft two-hole stopper of a thick-walled pint gas bottle connected with a filter pump through an intermediate safety bottle and valve. The passage of the solution through the reductor may be effected either by use of the pump or by Bunsen’s device of condensing steam. The tube is filled by placing a few small pieces of broken glass in the drawn out portion, then a little clean sand and finally about 3 ounces of amalgamated zinc. The speed of filtration isregulated by the upper clamp; a reduction takes about five minutes.i n the water oven for 5 minutes, and weighed. L. DE K. and allowed for. L. DE K. Volumetric Estimation of Manganese. organic compounds, which reduce permanganate. L. DE K. A Simplifled Reductor. L. DE K. Separation of Iron from Chromium, Zirconium, and Beryl- lium by the Action of Hydrogen Chloride on the Oxides. By FRANKE S. HAVENS and ARTHUR F,WAY (Am. J. Sci., 1899,8,217--215). -Gooch and Havens (Abstr., 1897, ii, 232) have shown that ironANALYTICAL CHEMISTRY. 51 oxide may be readily separated from alumina by heating the mixed oxides in a current of hydrogen chloride a t a temperature of 450-500' ; if to the mixture of sodium chloride and sulphuric acid a small quantity of manganese dioxide is added so as to also generate a little chlorine, the decomposition may be effected a t 200-300'.The authors now state that this method may be used successfully for the separation of oxide of iron from the oxides of chromium, zirconium, By GEORGE W,,SARGENT (J. Amer. Chem. Xoc., 1899, 21, 854-857).--The metal is dissolved in hydrochloric acid, oxidised with nitric acid, and the solution evaporated to dryness; the residue is taken up with a little dilute hydrochloric acid, and filtered into a separating funnel. The bulk of the ferric chloride is now removed by agitating the liquid with ether (Chase's method) and the solution, after removal of the dissolved ether, pre- cipitated by bromine water and ammonia ; the precipitate is freed from nickel by a second solution and precipitation.The combined filtrates containing the nickel are acidified with hydrochloric acid, freed from any copper by hydrogen sulphide, the filtrate boiled to expel hydrogen sulphide, and, when cold, a slight excess of ammonia added, and the liquid titrated with standard potassium cyanide, with silver iodide emulsion as indicator (Campbell and Andrew's method, Abstr., 1895, ii, 421). L. DE K. [Estimation of Chromic Acid in Acetylene Ririfiers.] By FRITZ ULLMANN and IRMA GOLDBERG (Chem. Centr., 1899, ii, 19-20 ; from J. Gashel., 42, 374--377).-See this vol., i, 1. By THOMAS BROWN, jun. (J. Arrrer. Chem. Soc., 1899, 21, 780--789).-Assu~ of soluble oves such, as Stibnite and Senarnzontite.--l gram of the finely powdered sample is boiled in a covered beaker with 25 C.C.of strong hydrochloric acid until about 15 c.c are left. 2 grams of tartaric acid are then added, and when dissolved, about 4-6 drops of strong nitric acid are intro- duced, and the boiling continued for a minute. The mixture is then diluted with water, the insoluble residue well washed on a filter, and the filtrate diluted to about 250 C.C. The liquid is now saturated with hydrogen sulphide and gently heated, and after remaining for an hour, the antimony sulphide is collected and washed with cold water, If there is any probability of lead being present', the precipitate must be dissolved in ammonium sulphide and the filtrate reprecipitated with dilute hydrochloric acid. The precipitate is collected on a counterpoised (double) filter, washed, dried at 1 lo', and weighed ; the bulk of the crude antimony sulphide is transferred to a weighed platinum boat, and then placed inside a piece of combustion tube and heated in a current of carbon dioxide, so as to convert i t into black antimony sulphide, which is then weighed.A correction is finally made for the small amount of sulphide not removable from the filter. Assay of insoluble ores such us Cewantite.--l gram of the powdered ore is mixed in a covered porcelain crucible with 10 grams of a mixture of equal parts of sulphur and dry sodium carbonate, covered with a little more of this flux, and fused for 10 minutes in a muffle. The mass and beryllium. L. DE K. Estimation of Nickel in Nickel-steel. Estimation of Antimony in Ores.52 ABSTRACTS OF CHEMICAL PAPERS. is extracted with water, and in the filtrate the antimony is precipitated as sulphide by means of hydrochloric acid ; the crude sulphide is then treated as previously directed.Assay of pccrtiably soluble ores : 0xysdphides.-These are assayed by the combination of the two processes described. The fire assay (fusion with potassium cyanide), although easy of execution, seldom agrees with the wet assays, and is particularly un- suitable for ores containing sulphur. Apparatus for the Preparation of Plant-Ash for Analysis, By G. M. TUCKER (Ber.. 1899, 32, 2583-2585).-This is A simplified form of Shuttleworth's apparatus (Dim. Gottingen, 1899, and J . Landwirtlmhajt, 1899, 173) designed to give a control over any loss of potash, chlorine, &c., by vola,tilisation. The platinum vessel, in which the plant is burnt, is of a conical form and is provided with a closely-fitting cover having two apertures.I n the central aperture is soldered a tube passing t o the bottom of the vessel and down this tube, by means of which air enters, passes the handle of a stirrer. By means of the other aperture, the gases from the combustion chamber are led through a small wash-bottle, beyond which is an aspirator which draws air through the whole apparatus. Any ash mechanically carried by the air stream is stopped by a loose movable cap fitted to the exit tube. The conical shape of the vessel allows of more uniform heating, which is carried out first in a conical sand-bath, and, later, over a bare flame, the vessel being then fitted into a hole in a n asbestos card.T. H. P. Ammoniacal Copper Solutions and Hydroxylamine as a Test for Acetylene. By LUDWIG ILOSVAY YON NAGY ILOSVA (Bey., 1899, 32, 2697-2699).-Ammoniacal copper solutions decolorised by reduc- ing with hydroxylamine can be used for detecting acetylene, but the value of the reagent and the coIour of the precipitate depend on the proportions used. The quantities recommended are, for 50 C.C. of solution, (I) cupric chloride ( + 3H,O), 0.75 gram ; ammonium chloride, 1.5 grams ; aqueous ammonia (20-21 per cent.), 3 c.c., hydroxylamine hydrochloride, 3 grams. (11) cupric nitrate ( + 5H,O), 1 gram ; aqueous ammonia, 4 c.c., hydroxylamine hydrochloride, 3 grams. (111) copper sulphate (+ 5H,O), 1 gram ; aqueous ammonia, 4 c.c., hydroxylamine hydrochloride, 3 grams.The reagent gives a splendid red precipitate with acetylene, but begins to deteriorate after three days. By EDMOND JANDRIER (Chem. Centr., 1899, i, 1296; from Ann. chim. anal. appl,, 4, 156).-Resorcinol recommended by Mulliken and Scudder (Abstr., 1899, ii, 388) gives, with acraldehyde, almost the same colour as with formaldehyde, and is consequently not a safe test for the detection of methyl alcohol ; the test is also interefered with by the presence of furfuraldehyde. It is proposed to use gallic acid instead, as recommended by Barbet and Jandrier (Abstr,, 1898, ii, 265). By WILHELM PRESENIUS and LEO GRUNFIUT (Zeit. and. Chem., 1899, 38, 472-512). -Wines obtained by the fermentation of solutions of glucose in L. DE K. T. M. L. A Colour Test for the Detection of Methyl Alcohol.L. DE K. Recognition of Marc Wines (Tresterweine).ANALYTICAL CHEMISTRY. 53 contact with grape marc ( T ~ e s t e ~ ) have hitherto not been distinguish- able with certainty by chemical analysis from natural wines. The authors believe they have discovered a trustworthy criterion of mch mines in the fact that they contain little or no tartaric acid combined with alkaline earths, whilst natural white wines always contain calcium tartrate to an extent which permits a limit of about 0.1 gram of tartaric acid per 100 C.C. to be established. The recognition of this fact in their composition depends on the estimation of the ratio of the total tartaric acid to the total alkalinity of the ash and the alkalinity of the portion of the ash soluble in water. With reference to the observations of Kulisch, Kohlmann, and Hoppner (Abstr., 1899, ii, 341 ; also 1895, ii, 465) on this subject, they point out that, in the estimation of the soluble constituents of the ash, a very limited amount of washing (30-80 C.C.of hot water for the ash of 100 C.C. of wine) must be employed, so as to leave the calcium carbonate of the ash as far as possible undissolved, Formuls are given for calculating the analytical data. An exception to the above rule occurs in the case of marc mines to which tartaric acid has baen added during manufacture. Red wines also contain much smaller proportions of calcium tartrate than white mines. The above criterion must therefore in all cases be considered in connection with other characteristics of marc wines, namely, a high proportion of ash to total solids, high percentage of tannin, and occasionally also of volatile acids.It can likewise only be employed in cases where the ash of the wine exhibits a normal total alkalinity and the proportion of sulphate is not abnormal, since it is obvious that excessive sulphuring would disturb the relations of the various tartrates in the wine. The alkalinity factor of natural wines, that is, the alkalinity of 0.1 gram of the ash expressed in cubic centirnetres of normal alkali, seldom exceeds 0.8 or 1.0. Wines exhibiting a much lower alkalinity factor should be examined for excessive sulphuration. h much higher factor would suggest a search for added organic acids. The ratio of glycerol to alcohol in marc wines seems generally t o exceed the limit of 7 : 100 laid down for natural wines.With regard to the use of the large proportion of tannin as a criterion of marc mines, it is evident that no limit can be laid down, since the proportion of tannin in natural wines varies widely. Barth has argued that the ratio of total extract (after deduction of sugar, ash, and non-volatile acids) to tannin may be regarded as constant, and employs the factor 5 for multiplying the tannin. The authors show, however, that in a great number of natural wines, even the factor 4 would be too high and point out the need for further in- vestigations of this sub ject. The authors also give a complete analysis of the ash of a marc wine prepared by themselves, and some analyses of raisin-wines, one of which they also manufactured, M.J. S. Volumetric Estimation of Alcohols, especially of Fusel-Oil in “Brandies.” By FRANZ ADAM (Chem. Centr., 1899, i, 1226-1227; from Uesterr. Chem. Xeit., 2, 241-243).-A solution of acetyl chloride in chloroform, after it has been well shaken with water and so54 ABSTRACTS OF CHEMICAL PAPERS. decomposed into acetic and hydrochloric acids, is titrated with normal alkali. Another portion of the chloroform solution is allowed to act on the alcohol, whereby it is partly decomposed into hydrogen chloride and alkyl acetate ; after decomposing the remainder with water, the titration is repeated, and the difference in alkali represents the amount of the alcohol. To estimate amyl alcohol in brandy, the sample is diluted to 20 per cent.strength by volume, and the fuse1 oil then extracted by repeated agitation with pure chloroform, This is re- peatedly shaken with water, then dried over burnt gypsum and treated with standard solution of acetyl chloride, &c. The process is also suitable for the estimation of the alcohol number of ethereal oils. L. DE K. Action of Bromine on Phenol and Cresols with Reference to the Analysis of Mixtures of these Compounds. By Huao DITz and FRANZ CEDIVODA (Zeit. angew. C'hem., 1899, 873-817 and 897-903).-An alkaline solution of a phenol is mixed with a known excess of bromine dissolved in caustic potash, acidified with dilute HCl (1 : l), shaken vigorously for 1 minute, and titrated with standard thiosulphate solution in the presence of potassium iodide ; under these conditions, 1 mol.of o-cresol or p-cresol takes up 2 atoms of bromine, whilst m-cresol and phenol each combine with 3 atoms. I n the case of p-cresol, it is essential that the duration of the experi- ment should not exceed the prescribed time limit, otherwise the amount of bromine required exceeds 2 atoms. When the alkaline solution of a phenol and excess of bromine is acidified with concen- trated sulphuric acid, allowed to remain for 10 minutes, subsequently shaken for 5 minutes, and then filtered through glass wool or sand, it is found, by treating the filtrate with potassium iodide and titrat- ing with thiosulphate, that the amount of bromine taken up corresponds with 3 atoms in the case of o-cresol and p-cresol, and with 4 for m-cresol and phenol.These results are applied to the analysis of mixtures of two or more of these constituents. The mixture of the phenols is separated from other impurities by extraction with ether ; the ethereal extract is dried over calcium chloride or dry sodium sulphate, distilled up to 180' to remove ether and last traces of moisture, the fraction distilling over above this temperature is treated with bromine by the two methods just described, and the amount of phenol, m-cresol and mixed ortho- and para-cresol determined by means of the following equations : (i) x + y + x = a ; (ii) 3Br/94.06.x + 2Br/108*08.y + 3Br/108'08.x = 6; and (iii) 4Br/94*06.x + 3Br/108.08.y + 4Br/l08-08.x = c, where x and x represent the amounts of phenol and m-cresol, y the amount of the mixture of the ortho- and para-isomerides, a the total quantity of phenolic compounds, b the amount of bromine absorbed when the solution is acidified with dilute hydrochloric acid, and G the amount taken up when concentrated sulphuric acid is employed, and the bromo-derivatives filtered off before titration.G. T. M. Simpliftcation of the Phenylhydrazine Test [for Sugar in Urine.] By ALBERT KOWARSKY (Chem. Centr., 1899, i, 1294; from Bed. klin. Wochschr., 36, 412-414)-5 drops of pure phenyl-ANALYTICAL CHEMISTRY, 55 hydrazine are mixed with 10 drops of glacial acetic acid and 1 C.C. of brine, and the mixture boiled for 2 minutes with 3 C.C. of the supposed diabetic urine and then allowed to cool slowly. If the characteristic osazone crystals form after a few minutes, the urine is practically free from sugar.If appreciable traces of albumin are present, these must be first removed by coagulation at the boiling Stability of Gun-Cotton and Smokeless Powder. By C. HOITSENA (Zeit. urzgew. Chem., 1899, 705-710).-A review of the methods in use for testing these explosives as t o their keeping powers. The author thinks that at present there are not sufficient grounds for substituting the Simon-Thomas test for those of Abel and of Guttmann. For comparison, a stock of matrerials of guaranteed make Chemistry of Butter- Fat. 11. Chemical Composition of Butter-Fat. By C. A. BROWNE, jun, (J. Anter. Chem. Xoc., 1899, 21, 807-827. Compare Abstr., 1899, ii, 709).-This is a long investiga- tion as to the true composition of butter-fat ; on the whole, the article does not lend itself to useful abstraction.The following analysis of the fatty acids obtained from 100 grams of butter is interesting as it confirms the result of Hehner and Mitchell (Abstr., 1897, ii, 287) as to the small proportion of stearic acid contained in butter : dihydroxystearic, 1.00 ; oleic, 32.50; stearic, 1-83 ; palmitic, 38.61 ; myristic, 9.89 ; lauric, 2.57 j capric (decoic), 0.32 ; cnprylic (octoic), 0.49 ; caproic (hexoic), 2.09 ; butyric The Reichert Number of Butter. By JAMES H. STEBBINS (J. Amer. Chem. Soc., 1899, 21, 938-940).--From the result of 317 analyses of genuine butters, the author is in favour of placing the lowest allowable limit of the Reichert number at 11.5. Analysis of Bees Wax. By ANGIOLO FUNARO (L'Orosi, 1899,22, 109--123).-The adulterants of bees wax are Japan and Carnaiiba wax, animal fats, stearic acid, resins, cerasin, and paraffin wax.The various methods for detecting and estimating these impurities are described in detail and discussed, By EARL BERNHARD SOHN (Biecl. Celztr., 1899, 28, 298-299 ; from Milchxeit., 1898, 498). -The employment of pure furfuraldehyde which has been recently distilled in a vacuum, and is colourless, is of great importance in testing for margarine by means of the Baudouin test. I n case pure furfuraldehyde is not available, the employment of furfuramide is recommended. The following process for detecting for sesame oil is given : the melted filtered butter (10 c.c.) is extracted with hydrochloric acid of sp. gr. 1.125 three or four times or until the acid remains colour- less.Five C.C. of the butter fat is then shaken with a solution of 1-08 grams of furfuramide in 100 C.C. of absolute alcohol (0.1 c.c.) and hydrochloric acid of sp. gr. 1-19 (10 c.c.) for a t least half a minute. If the fat solidifies, it is heated at 60-'70°, If the hydrochloric acid heat. L. DE K. and of known age should be kept. L, DE K. acid, 5.45; total, 94.75. L. DE I(, L. DE K. T. H. P. The Sesame Oil Reaction and Sesam6 Butter.56 ABSTRACTS OF CHEMICAL PAPERS. shows a red coloration which does not soon disappear, sesame oil is proved to be present ; with small amounts of sesame oil, the colora- tion takes hours to appear. [Testing Butter for Oil of Sesam6.1 By H. WEIGMANN (Bied. Centr., 1899, 28, 629).-See this vol., ii, 40.Detection and Estimation of Formaldehyde in the Free State and in its Compounds. By G. H. A. CLOWES and BERNIIARD TOLLENS (Ber., 1899, 32, 2841-2848).-Formaldehyde is estimated by heating with phloroglucinol and hydrochloric acid at 70-80" and weighing the phloroglucide, C,H,O,, which is produced under these conditions. In most of its compounds, the formaldehyde can be estimated in this way by using hydrochloric acid and water, but in some cases it is necessary to employ a more or less concentrated sul- phuric acid t o hydrolyse the methylene compound. A large number of analytical results are given. [Separation of Acetone from Acetoacetic and Acetonedi- carboxylio Acids]. By LUIGI ~ABBATANI (C'hem. Centr., 1899, ii, 22-23 ; from Atti Red. Accad.Torino, 34)-See this vol., ii, 32. New Reaction of Acetone and a New Method for the Detection of Aliphatic Amines. By ENRICO RIMINI (L'Orosi, 1899, 22, 40-44).-1f to a mixture of an aliphatic monamine with a 10 per cent solution of acetone a few drops of a concentrated solution of sodium nitroprusside are added, a magenta coloration is formed, which gradually becomes more and more intense and lasts for several hours ; the addition of a few drops of acetic acid changes it to an intense violet. When the hydrochloride of the amine is employed, too much alkali must not be added, as in this case the orange tint of Legal's reaction is obtained ; this, however, vanishes much more quickly than the red coloration. By using aniline or phenylhydrazine in place of the aliphatic monamine, no coloration is obtained, whilst benzylamine gives a faint violet colour which forms slowly. With secondary aliphatic monamines, Legal's reaction takes place, whilst tertiary amines act simply as alkalis.No coloration is obtained if, instead of acetone, one of the following substances is employed :-formaldedyde, acetaldehyde, paraldehyde, isobutaldehyde, or valeraldehyde, chloral, benzaldehyde, salicyl- aldehyde, anisaldehyde or cinnamaldehyde, furfuraldehyde, dextrose, acetophenone, benzophenone, ethyl acetoacetate, camphor, fenchone, or tanacetone ; with concentrated solutions of pyruvic acid, a brown coloration forms and changes to green, whilst with dilute solutions a ponceau tint is developed. The presence of 1/10 per cent. of acetone in a solution can be detected in this way,and the formation of the colour is not interfered with by the presence of alcohol or acetaldehyde.Use is made of this reaction of acetone and of that of acetaldehyde formerly described (Rendiconti Amminisir. Civile. Minister0 del Interno, 1898) by the author t o distinguish between primary and secondary aliphatic amines. The formation of an azure coloration on adding sodium nitroprusside and aldehyde to the solution of an amine, shows N. H. J. M. T. M. L.ANALYTICAL CHEMISTRY. 5 7 that the base is secondary, whilst if acetone is added in place of the aldehyde, and a magenta tint is given to the liquid, the amine is primary. These reactions are obtained in mixtures of primary, secondary, and tertiary amines. Volumetric Estimation of Quinones Derived from Benzene. By AMAND VALEUR (Compt.rend., 1899,129,552-553).-The method described is based on the reduction of quinones by hydriodic acid, all secondary reactions being avoided by operating in the following manner. A cooled mixture of 20 C.C. of concentrated hydrocbloric acid with an equal volume of 95 per cent. alcohol is quickly added to 20 C.C. of a 10 per cent. aqueous solution of potassium iodide. The liquid is then poured into the alcoholic solution of the quinone and the iodine liberated is titrated with N/10 sodium thiosulphate solution. The process is expeditious, and is shown to give accurate results in the case of quinone, dichloroquinone, toluquinone, and thymoquinone ; i t is also applicable to unstable compounds of quinones, such as pheno- A Colour Reaction to Distinguish the Hydrochlorides of m-Phenylenediamine and p-Phenylenediamine.By L. CUNIASSE (Chem. C’entr., 1899, i, 1297 ; from Ann. chim. anal. appZ., 4,156-157). -The meta-compound, when heated in aqueous solution with a few drops of a 1 per cent. solution of acetaldehyde in proof-spirit slightly acidified with acetic acid, yields, when cold, a splendid yellow colora- tion with a strongly green fluorescence. The para-compound turns Estimation of Urea in the Tissues: and the Amount con- tained in the Liver. By RUDOLF GOTTLIEB (Chem. Centr., 1899, i, 1298 ; from Arch. Exp. Path. Pharm., 42, 238-249).-The urea is first isolated as a mercuric compound by von Schroeder’s process; finally, the alcoholic solution of the urea is precipitated by an ethered solution of oxalic acid and the acid contained in the urea oxalate found by titration.The blood of starving dogs contains 0*011-0*02 per cent. of urea ; when on meat diet, it increases to 0.033-0-056 per cent. The liver, contrary to expectation, contains only 0.008-0*02 per cent. T. H. P. quinones and quinhydrones. N. L. orange-red without any fluorescence. L. DE K. L. DE K. Detection of ‘( Saccharin ” in Wines. By DIOSCORIDE VITALI (Chem. Centr., 1899, i, 1297-1298; from Boll. Chirn. -Farm., 38, 297-300).--The only trustworthy method is based on the conversion of the sulphur of “ saccharin ” into sulphate. Small quantities of “ saccharin ” may be estimated by precipitation with mercuric nitrate. The precipitate is then weighed and the amount of mercuric oxide in it estimated, the difference representing the saccharin.” L.DE K. Employment of Chloral Hydrate in the Estimation of Alkaloids. By EDUARD SCHAER (Zed. anal. Chem., 1889, 38, 46 9-472). -The author completely confirms Len z’s opinion (A bs tr.,58 ABSTRACTS O F CHEMICAL PAPERS. 1899, ii, 391) as to the value of chloral hydrate for the ex- traction of the vegetable alkaloids from plant products, especially when large proportions of resins and ethereal oils are present. A still more powerful solvent, especially for solid fats and waxes, is a concentrated alcoholic solution of chloral alcoholate. Mauch has made the observation that thesalts of the alkaloids are dissolved by aqueous chloral hydrate as readily as the free bases.A ditliculty is, however, encountered in the extraction of strychnine from nux vomica seeds and Ignatius beans, in consequence of the presence of mucoid compounds, which (in common with certain varieties of starch and also animal gelatin) swell up in chloral hydrate, and render it viscous. Caoutchouc and gutta percha also resist completely the sol- vent action of chloral hydrate, and, when they are present t o a large extent, no advantage results from the use of chloral. Rfauch asserts that when the chloral hydrate solutions of the bases are warmed, the bases are often converted into formates. So far as the author’s experience extends, the chloral solutions of the alkaloid salts exhibit great permanence, and, may be heated on the water-bath without loss of alkaloid. The Chromic Acid Test for Cocaine.By GEORGE L. SCRAEFER (J. Amer. Chem, Xoc., 1899, 21, 936-938. Compare Abstr., 1899, ii, 715).-In reply to the criticisms of Squire (Chemist and Druggist, April 22), Cownley (Plmrm. J. Tmns., April 15), and Merck (Phawn. Zeit., No. 42), the author upholds his own chromate process. M. J. S. L. DE K. The Active Principle of Cayenne Pepper. By KARL MICKO (Chem. Centr., 1297 ; from Zeit. Unters. Nuhr.-Gennussm., 2, 411-412. Compare Abstr., 1899, i, 716).-Capsacutin described by Mijrbitz is probably the same compound as the author’s capsaicin, Ci,~iY03N, the-active principle of Capsicum unnuum, L., and Capsicum fustagautum, BZ. Reactions of cupsuicin.-When moistened with neutral solution of ferric chloride and a little alcohol, insoluble,. greenish-blue drops are noticed, but this test is not parlicularlg delicate. Strong sulphuric acid and a particle of sugar cause, after some hours, a fine violet coloration.When heated on the water-bath with strong hydrochloric acid, an alkaloidal substance is obtained which yields precipitates with platinic chloride, iodine, and potassium mercuric iodide. L. DE K. Detection of Nucleo-albumin in Urine by means of Tannin. By LEON GARNIER and L. MICHEL (J. Phurm., 1899, [vi], 10, 150-1 52).-The precipitate produced when tannin (Almh’s reagent) is added t o urine previously diluted with its own volume of a satu- rated solution of sodium chloride, consists chiefly of tannin with a small amount of sodium chloride and traces of nitrogenous substances. The phosphates present in the urine cause the precipitation of the tannin.Ott’s statement (Jahyesber. fiir Thierchemie, 1895, 567) that the formation of this precipitate is a sure test for the presence of nucleo-albumin is thus proved to be erroneous. H. R. LE S.ANALYTICAL CHEMISTRY. 59 Estimation of the Products of Digestion with Pepsin. By JEAN EFFRONT (Chem. Zeit., 1899,23, 770-771 and 783-784).-A solution of tannin in tartaric acid may be employed for separating proteoses and peptones, as proteoses are precipitated and peptones remain in solution ; its use is suggested as a reagent in the analysis of the products of peptonisation. For a complete analysis, the follow- ing determinations should be made : 1, total nitrogen; 2, total pro- teids ; 3, syntonins ; 4, proteoses ; 5, peptones.For the total proteids, the solution is precipitated with phosphotungstic acid, the precipitate washed with N/2 hydrochloric acid and dried without removal from the filter; the nitrogen in this precipitate is estimated, and the number thus obtained multiplied by 6.25 gives the total proteids. Syntonins may be estimated by exactly neutralising the solution with sodium hydroxide (1 : lo), or even more correctly by estimating the total proteids in the original solution and then in the neutralised solution, the difference between the two determinations giving the percentage of syntonins. Proteoses may be precipitated by a tartaric acid solution of tannin after the albumin is first removed by coagula- tion, and the syntonins by neutralisation.The solution is made by dissolving tannin (50 grams) in water (500 c.c.) adding N-sodium hydroxide (50 c.c.), making up to 1 litre, and then adding 15 C.C. of a 10 per cent. tartaric acid solution. The precipitate is well washed, then dried between filter-paper, and the percentage of nitrogen deter- mined. The peptones which remain in solutlion may be precipitated by phosphotungstic acid. The percentages of peptoses obtained by salting out with zinc sulphate, and by precipitating with a tartaric solution of tannin, are not concordant when the proteid solution has undergone an appre- ciable amount of peptonisation. The results obtained also indicate that phosphotungstic acid is an uncertain reagent for estimating peptones. It appears that, after pro- longed peptonisation, the peptones are no longer precipitated by this reagent, and it is concluded that the compounds known as peptones are really substances of very different characters, some of which are precipitated by the phosphotungstic acid reagent and others not, and, further, that peptones themselves are acted on by pepsin.The process of analysis described above gives accurate results only when peptonisation has proceeded for a short time. J. J. 8. Analysis of Glue and Leather. By WILHELM FAHRION (Chem. Zeit., 1899,23, 452-453).-Glue and leather contain a small quantity of fatty matter, which, however, is partially oxidised, and incompletely soluble in light petroleum, To estimate fat in glue, 10 grams of the cut-up sample are heated with 40 C.C. of S per cent.alcoholic potash on the water-bath, adding some more alcohol if necessary, and finally evaporating to dryness. The residue is then dissolved in hot water and rendered acid with hydrochloric acid. The liquid is heated nearly to boiling for half-an.hour, then transferred to a separating funnel, and, when cold, shaken with ether and then left to settle overnight. The aqueous layer is drawn off, the ether poured off, and the hydroxy- acids which adhere to the sides of the funnel are dissolved in hot60 ABSTRACTS OF CHEMICAL PAPERS. alcohol. Both the ethereal and alcoholic solutions are then evaporated in the same tared dish. The rasped sample is first extracted with light petroleum to obtain the bulk of the fat. It is then treated with alcoholic potash as described, but on faintly acidifying with hydrochloric acid, a precipitate of tannin and its derivatives (phlobaphens) is obtained which occludes some more fat, and also any hydroxy-acids.The f a t may be extracted with ether, but as yet a process is not known for the separation of fatty hydroxy-acids from the tannin precipitate. The latter may be dried and weighed, but as it always contains mineral matters, it must be finally burnt to ash. By C. ASCHMAN and HAROLD FABER (Chem. Zeit., 1899, 23, 61).--25 grams of the finely divided air- dried sample are put into a porcelain dish and heated for 1 hour on the boiling water-bath with 100 C.C. of aqueous caustic soda (50 grams per litre); the liquid is poured off and the extraction repeated several times. The whole, including the deposit, is then made up to 510 C.C. (10 C.C. being occupied by the insoluble matter) and after the supernatant liquid has become clear, an aliquot part is syphoned off and tested as follows : 0.125 gram of humic acid (mid. huminic. pur.) is dissolved in soda solution and diluted to 500 C.C. ; 5 C.C. are diluted to 100 c.c., 10 C.C. of dilute sulphuric acid (1 : 5) added, and the liquid boiled with addition of solution of potassium permanganate (0.32 gram per litre) until the colour is no longer discharged. 10 C.C. of a solution of oxalic acid (0.63 gram per litre) are now added and the excess of oxalic acid titrated back with the permanganate solution. The usual blank experiment is then made, and having thus found the humic acid value of the permanganate, the amount of humic acid in the soil may be ascertained by titration. For the success of the ex- periment,it is necessary that the amount of the humic acid present in the aliquot part of the solution of the sample shall not materially differ from the amount used in the standardising experiment. Alcoholic potash is also useful in leather analysis. L. DE K. Estimation of Humus in Soils. L. DE K. Analyses of Ginger. By EDWY G. CLAYTON (Analyst, 1899,24, 122--125).--The author has analysed 37 samples of ginger from various sources (some of them being again analysed after steeping in water or proof spirit) and has tabulated the results. The analysis comprises the following estimations : soluble and in- soluble ash; the extracts obtained with cold water, ether, absolute alcohol (after complete extraction with ether), and light petroleum respectively ; essential oil ; alkalinity calculated as potash, and chlorine in the soluble ash ; in certain cases, the ash, alkalinity of the ash, chlorine in the cold water extract, water, and silica were also deter- mined. It appears that the commercial processes -washing, scraping, cutting, grinding, and separation of fibre-do not so alter the composi- tion of genuine ginger as to convey the idea that it has been adulterated with spent ginger, except in some cases where excessive washing had occurred. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9007805044

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

61 General and Physical Chemistry. Electrical Conductivity of Alkali Chlorides and Nitrates. By FRIEDRICH KOHLRAUSCH and MARGARET E. MALTBY (Chern. Centr., 1899, ii, 465-466 ; from Xitx. Kgl. Aknd. TViss. Berlin, 1899, 665),- With the view of testing the theoretical connection between molecular conductivity and ionic migration, the conductivities in dilute solution of the chlorides and nitrates of potassium, sodium, and lithium have been determined with the greatest care. The numbers in the follow- ing table give the equivalent conductivities a t 18" for solutions of the concentration rn, and represent the mean of several determinations, which agreed on the average to 1/4000th. m. 0~0001 0~0002 0.0005 0.001 0.002 0-005 0-01 0.02 0.05 0.1 0.2 0.5 1.0 KC1. 129.05 128.76 128.09 127.33 126.29 124.40 122.42 120.00 115.94 11 2.00 107.96 102.40 98.28 NaCl. 108.06 107-80 101.18 106.48 105.55 103.79 101.95 99.66 95.86 92.01 87.73 80.93 74.34 LiC1.98.06 9 7-78 97.13 96-45 95.55 93.86 92.08 89.88 86.22 82-35 77.9 3 70.65 63-30 KNO,. 125.49 125.18 124.44 123.64 122.59 120.47 1 18-20 115.27 11 0.09 104.7'7 98.74 89.23 S0.47 NaNO,. 204.53 106.18 103.53 102.85 101.88 100.07 93-16 95.70 91.60 87.24 82.28 74.05 65-86 LiNO,. 94.38 94.07 93.45 92.80 91.91 90.27 88.55 86.38 82.86 79.24 75.06 68.03 60.80 For solations up to and including the concentration N/500, each ion has a specific conductivity, which depends on the concentration alone; up to N i l 0 solution, the deviations from t h i s rule amount to +, 1 per cent. As a rule, the fall of ionic conductivity with increasing concentration is most rapid in the case of ions with high migration velocity, but no general and simple law can be laid down.Within the same limits, the fall of conductivity is, in the cases of potassium and sodium, more rapid for the nitrate than for the chloride; in the case of lithium, more rapid for the chloride than for the nitrate. J. C. P. Change of Free Energy in Fused Halogen Compounds of some Heavy Metals. By RICHARD LORENZ (Zeit. aizorg. Chenz., 1899, 22, 241-255. Compare Abstr., 1899, ii, 269).-In determining the E.M.F. of polarisation for a number of fused salts (Abstr., 1899, ii, 267), Czepinski found the temperature coefficient abnormally large at higher temperatures. Further investigation by Weber (Abstr., 1899, ii, 724) has shown that this coefficient d E / d T is regular, even up to high temperatures, when the electrodes are kept far enough apart ; the necessity for this is due to the diffusing and penetrating power of the halogen and the metallic vapour. VOL.LxxvIiI. ii, 562 ABSTRACTS OF CHEMICAL PAPERS. Differentiation of the equation E= Q + T.dE/dT leads to the relation - dQ/d17= 5?.d2E/dT2. Thus, when dE/dT is constant, Q must also be constant. This relation is approximately fulfilled in the case of lead chloride, so that the molecular heat of the compound is very nearly the sum of the atomic heats of the components. On the assumption that this relation holds exactly, the E.M.F. may be extrapolated for ordinary temperatures. The value thus calculated for the E.M.F.of the system P b 1 PbCl, 1 C1, is 1.65 volts, agreeing with the value 1.59 volts for the E.M.F. of decomposition of lead chloride in solution, calculated by Bodlander from its solubility. The paper also discusses the ionic concentrations in fused salts, leading to the conclusion that the dissociation of fused silver chloride is rather more than twice that of fused lead chloride. J. C. P. Coagulative Power of Electrolytes, By W. C. DAMPIER WHETHAM (Phil. h?C6g., 1899, 48, 474--477).-The coagulative power of a n electrolyte may be taken as inversely proportional to the number of gram-equivalents necessary to produce immediate coagula- tion in a given solution of a colloid. The coagulative powers of sulphates with uni-, bi-, and ter-valent ions stand in the ratio 1 : 35 : 1023 (compare Trans., 1895, 67, 6 3 ) , those of chlorides in the ratio 1 : 30 : 1650.There is certainly an intimate connection between the coagulative power and the electrical properties of a solution, and it may be supposed that to produce coagulation a certain minimurii electrical charge is necessary. Further, as the electrical charge on an ion is proportional to its valency, equal charges are carried by 293 triads, 3n dyads, or 6% monads. On this basis, i t is shown that the coagulative powers of uni-, bi-, and ter-valent ions in equivalent solution are in the ratio 1 : x : x2, agreeing well with the numbers just quoted. If this view is correct, the coagulative power of a quadri- valent metallic sulphate would be about 30,000 himes as great as that of a sulphate with a univalent ion.J. C. P. Application of the Dissociation Theory to the Electrolysis of Aqueous Solutions of Two Electrolytes with One Common Ion. By JAMES G. MACGREGOR (Chem. Centr., 1899, ii, 8 2 ; from 171-ccn.s. Roy. SOC. Canada, [ii], 4, 117--14S).--The author has cal- culated the values of the dissociation in solutions of mixed electrolytes with one common ion, and obtained from these values the ratio of the transference numbers of the other two ions, the values so resulting being compared with those obtained by Hopfgartner (Abstr., 1898, ii? 151). The agreement was satisfactory in the cases of solutions of sodium and hydrogen chlorides, potassium chloride and iodide, and barium and hydrogen chlorides. Agreement was not obtained in the case of solutions of copper and hydrogen sulphates, but this is explic- able by the dissociation of the acid into H and HSO, ions as well as into H2 and SO”, ions.Theory of the Electrolytic Solution Pressure. By R. A. LEHFELDT (Phil. Mag., 1899, 48, 430- 433).---The electrolytic solu- tion pressure, II, of a met31 is calculated from the observed E.M.F. L. M. J.GENERAL AND PHYSiCAL C€iEMISTRY. 63 between the metal and the solution in which it is immersed by the equation E= RT/E.log,II/P, where E is the quantity of electricity associated with 1 gram-equivalent, and P is the osmotic pressure of the metallic ions in the solution. For zinc, II has the very high value 9.9 x 10ls atmospheres. An expression is obtained for the tension due to the electrical double layer between the metal and the ions in solution, leading t o the equation, x = JJDII/2rc2, where x is the number of gram-equivalents that go into solution per sq.cm. of surface, and D the dielectric constant of the medium, From this equation, it may be shown that in order to produce the solution pressure attributed to zinc, 1.27 grams of the metal would have to pass into the ionic form per sq. cm. immersed, a conclusion which is not borne out by observation. Besides this difficulty with regard t o the electrolytic solution pressure of zinc, there is one of another kind i n the case of palladium, for which 11= 1.5 x ; the smallness of khis value involves the rejection of the molecular theory of fluids. J. C. P. Thermal Conductivity in Gases. By M. SMOLUCHOWSEI R.VON SMOLAN (Chem. Centr., 1899, ii, 353, from Oesterr. Chem, Zeit., 2, 385). -It has been previously shown that, as foretold by Maxwell, the thermal conductivity of a gas is independent of pressure. The author shows, however, that this does not hold for very low pressures, and in this case a temperature difference occurs a t the surface of gas and solid. When the mean wave-length is greater than the dimensions of the containing vessel, the phenomena are very complicated, Brush’s assumption of the existence of etherion is not justified, and the author considers the supposed element to be merely aqueous vapour (compare Abstr., 1899, ii, 287). Thermal Capacity and Colour Changes of Solutions of Cobalt Chloride. By M. WREWSKY (Chem. Centr., 1899, i, 1202; from J.Russ. Chem. Xoc., 1899, 31, 164--171).-0wing to difficulties in calorimetry a t high temperatures, the changes in colour were brought about by the addition of alcohol. The change from a blue to a red solution is accompanied by an increase in the difference between the thermal capacities of solution and solvent. The author considers the results support Berthelot’s hydrate theory. The decrease of thermal capacity by dissolution of salts is a function of both concen- tration and temperature, increase of both acting in the same sense. L. 31. J. L. M. J. NOTE BY ABSTRACTOR.-with regard to the comparison of the heat capacities of a solution and its components, see Tammann, Abstr., 1896, ii, 289. Thermal Capacity of Solutions of Sulphuric Acid. By EUGEN YON BIRON (Chew.Cerztr., 1899, i, 1202-1204; from %ss. Chem. Xoc.. 1899, 31, 171-203).-The author has determined the mean specific heat between 18.6 and 21.8 for solutions of sulphuric acid of the composition H,SO,,nH,O, where rz varies from 0 to 1600, the extreme values for these liquids being 0.3352 and 0.99675. The molecular heat for the monohydrate is 51.17, that calculated from its 5-264 ABSTRACTS OF CHEMICAL PAPERS. components being 50.9, and the difference is ascribed to the heat of dissociation of the hydrate. A t dilutions greater than H,SO,, 100H,O, a linear relationship is found to exist between the equivalent electrical conductivity and the difference between the found and calculated values for the molecular heat, so that it appears probable that both owe their origin to the same cause (compare Tammano, Abstr., 1896, ii, 289).Some Boiling Point Curves. 11. By JOHN K. HAYWOOD (J. Amer. Chern. sbc., 1899, 21, 994--1001).-A continuation of the author's previous paper (Abstr., 1899, ii, 632), the mixtures examined being benzene with chloroform, carbon tetrachloride, ether, acetone, and methyl alcohol ; and methyl alcohol with ethyl alcohol, carbon tetrachloride, and ether. Minima were obtained in the follow- ing cases a t the temperatures and composition given : benzene with methyl alcohol, 58*33 ; 53 to 67 per cent, of benzene ; methyl alcohol with carbon tetrachloride, 55*95', about 18.4 per cent. of alcohol. The law previously suggested that chemically similar substances yield similar boiling point curves again receives support, whilst it also ap- pears that similarity of constitution of the two mixed compounds is unfavourable to the production of a minimum even when the boiling points are close together.L, M. J. By GARNETT RYLAND (Arne?.. Chern. J., 1899, 22,384-396).-.A mixture of methyl alcohol and benzene containing 38 per cent. of alcohol distils at the constant temperature 57-57.5' ; similarly, a mixture of ethyl alcohol and benzene with 32 per cent. of alcoholj distils unchanged a t 67-68', The composition of the mixture with constant boiling point is in both cases dependent on the pressure. Numerous binary mixtures of organic liquids have been examined with the view of discovering mixtures of constant boiling point. Forty-five have been found to boil at a constant temperature a t or below the boiling point of the more volatile constituent, two above the boiling point of the less volatile constituent, and one between the boiling points of the constituents.For these mixtures of constant boiling point, the ratio of the two constituents in the distillate is approximately that of the products of their vapour density and vnpour tension at the temperature of distillation, a result in accordance with earlier researches on the subject. By H. W. BAKHUTS ROOZEBOOM (Proc. K . Akad. Wetensch. Amsteydccm, 1899, 1, 466-468). -Melting point curves for mixtures of the racemic and dextro-compounds were examined in the case of dimethyl tartrate and dimethyl diacetyltartrate. I n the first case, the racemic compound melts at 89.4' and the active compound a t 43*3", and a minimum of 41.6 is reached a t 3 per cent.of racemic compound ; in the second case, the melting point of the racemic compound is 83%" and that of the active compound 104.3'; the minimum of 83.4" is reached at about 86 per cent of the racemic compound. I n both cases, the form of the curve is almost horizontal at the racemic compound, and indicates L. M. J. Liquid Mixtures of Constant Boiling Point. J. C. P. Melting Points in Systems of Optical Isomerides.GENERAL AND PHYSICAL CHEMISTRY. 65 considerable dissociation. The results confirm the author’s previously published theoretical views (Abstr., 1899, ii, 401). By ALBERT DAIIMS (An72. Chim. Phys., 1899, [vii], 18, 140-142. Com- pare Abstr., 1897, ii, 245 ; 1899, ii, 546).-Coppet’s determinations of the freezing points of dilute acetic acid agree closely with the values previously obtained by the author, who has also anticipated the theoretical conclusions deduced by this investigator.A Reply. By LOUIS C. DE COPPET (Ann. China. Phys., 1899, [vii], 18, 142--144).-The author, whilst admitting that Dahms first determined the freezing point of the eutectic mixture of acetic acidand water, claims to have discovered the lower freezing point of a superfused mixture at a temperature about Z0 lower than the eutectic point. The author’s conclusions were originally published over 2 7 years ago. Since binary liquid mixtures having two eutectic points and three freezing points are known, it is highly probable that similar mixtures having three or more eutectic points should be capable of existence.G. T. M. L. M. J. F r e e z i n g Point of Mixtures of Acetic Acid and Water. G. T. M. Freezing Point of Mixtures of Acetic Acid and Water. Test by Freezing Point Determinations of the Dissociation Values obtained by the Conductivity Method in the case of Solutions of Potassium and Sodium Sulphates. By E. H. ARCHIBALD (Chern. Centr., 1899, ii, 7, and Chem. News, 1899, 80, 46, et sep. ; from Trans. Nova Scotia Inst., 10, 33).-Determinations were made of the electrical conductivity of solutions of each of the com- pounds at various dilutions at 1 8 O and at 0”. I n the case of potassium sulphate solutions a t concentrations above 0.35, the dissociation is slightly greater at Oo than a t 1 8 O . The cryoscopic depressions of the solutions were also determined by the method adopted by Loomis, with whose results also the values are in good accord.Comparison of these depressions with those calculated from the dissociation values show the agreement to be close, the differences never exceeding 4 per cent., being, however, for the sodium chloride always in the same directions. For mixtures of equal volumes of solutions containing molecular pro- portions of the two salts, the depression is given by the expression D = 1 sS6, (1 + a1 + a,)iV/2, where N is the number of gram-equivalents per litre of each salt in the solutions mixed, and ala, the dissociation (this expression appears t o involve the assumption that the salts are equally dissociated, which is, however, almost the case for the salts examined], and the depressions so calculated are found to agree well with those determined experimentally.Cryoscopic Behaviour of Substances with Constitutions similar to that of the Solvent. By FELICE GARELLI and F. CALZOLARI (Gaxzetta, 1899, 29, ii, 357-375. Compare Abstr., 1899, ii, 732).-The cryoscopic behaviour of various substances has been studied in solvents, from which they are derived by the substitution of an amino- or a hydroxyl group for a hydrogen atom. I n the following cases, abnormal molecular weights were obtained, indicating the forma- tion of solid solutions between the solvent and the solute; p-hydroxy- L. M. J. V.66 AnSTRACTS OF CHEMICAL PAPERS. azobenzene and p-aminonzobenzene dissolved in azobenzene ; m-nitro- and p-nitro-phenol and o-nitro-, m-nitro-, and p-nitro-aniline in nitro- benzene ; 2 : 4-dinitroaniline in nL-dinitrobenzene ; p-xylidine in p-xylene ; p-hydroxyacetophenone in acetophenone ; triphenylcarbinol in triphenylmethane ; and glycollic acid in acetic acid.With solu- tions of o-nitrophenol in nitrobenzene, 2 : 4-dinitrophenol in m-di- nitrobenzene, and p-aminoacetophenone in acetophenone, normal mole- cular weights are obtained. Influence of the Solvent on the Cryoscopic Behaviour of Phenols. By KARL AUWERS [with W. BARTSCH and H. 3X. SMITH] (Zed physikal. Chenz., 1899, 30, 300--340).-If the abnormal cryo- scopic depressions of hydroxy-compounds are due to association, then an association constant should be obtainable by a calculation similar to that used for obtaining the dissociatioiz constant, Experiments with acetoxime, benzophenoxime, Z-camphoroxime, benzoic acid, and o-bromo- benzoic acid, however, show that, except in the last case, no constant value for the association constant is obtained, a t least not on the assumption of double molecules. Determinations with other com- pounds to high concentrations further show that the molecular weight does not, in general, tend to any constant value; the greatest valueof association hitherto observed is about four, whilst cryoscopic depres- sions of ethyl alcohol in benzene give values leading to seven times the normal molecular weight.It appears, therefore, that the abnor- mal depressions are not due to association, but to some mutual influence of solvent and solute, and determinations were made of the depressions of a number of hydroxy-compounds in various solvents.The following mere employed as solvents, and the cryoscopic constant obtained for each is added :-Nitrobenzene, 70 ; nz-dinitrobenzene, 106 ; p-nitrotoluene, 78 ; 2 : 4-dinitrotoluene, 89 ; 8 : 4 : 6-trinitrotoluene, 115 ; p-chloronitrobenzene, 109 ; p-dichlorobenzene, 77 ; p-chloro- bromobenzene, 92 ; T-dibromobenzene, 124 ; benzil, 105. I n all these solvents, ortho-substitution derivatives of phenol were cryoscopically normal as in benzene or naphthalene ; with para-compounds, however, this is not the case, p-nitrophenol, methyl p-hydroxybenzoate, and p-hydroxybenzaldehyde being abnormal in the halogen conipounds, but almost normal in those solvents containing a nitro-group, so that the halogen increases and the nitro-group decreases the abnormalising influence in the solvent.Other substituted phenols dissolved in p-dic hloro-, p-chlorobromo-, and p-dibromo-benzene were then investi- gated, and it was found that, as in naphthalene, para-compounds are more abnormal than meta-, and the order of the groups arranged according to their influence in giving abnormal values is : aldehyde, cyanide, substituted carboxyl, nitro-groups, whilst the abnormality is greatest in dichlorobenzene, and least in dibromobenzene. The ab- normal cryoscopic depressions are hence the product of two factors, one dependent on the constitution of the solute, the other on that of the solvent (compare Abstr., 1896, ii, 293 ; 1897, ii, 476). Influence of the Medium on the Heats of Solution of Salts.By N. GALITZEI (Chem. Centr., 1899, ii, 469-470 ; from J. Russ. Chem. Soc., 31, 536--5PO).-The effect of increasing quantities of alcohol on T. H. P. L. M. J.GENERAL AND PHYSICAL CHEMISTRY. 67 the heats oE solution of potassium nitrate and potassium carbonate in water has been investigated. By the addition of alcohol to water, the heat of solution is diminished, the diminution ultimately reaching a minimum, which depends on the nature of the dissolved salt. No connection could be traced between this phenomenon and the electrical conductivity of the solutions. By KONRAD DIETERICI (An7~. Phys. ClLem., 1899, 69, 6S5-’705).-For most substances hitherto investigated, the ratio of the actually observed critical density to the ideal density (the density which the substance would have if the law pv = 161’ held for the critical pressure and temperature) is nearly constant, and equal to 3-75,; for ethylene, nitrous oxide, nitrogen, and oxygen, the ratio differs considerably from 3.75, but this is probably due to deficient experimental methods.I n van der Waals’ equation, the cohesion pressure is eqlial to a/v2, and the correction for the molecular volume is a constant b ; in these circumstances, the ratio wJvk (ideal volume : critical volume) has the value 2.67. This want of correspondence between experiment and van der Waals’ equation remains, even when b is regarded as a function of v. If the equation ( p + T)(V - b) = BY’ be accepted, and the cohesion pressure rr=a/vs/3 instead of a/v2, the ratio vo/vk is equal t o 3.75.This purely empirical law regarding the cohesion pressure, although it brings van der Waals’ equation into agreement with the critical phenomena, is without theoretical basis. 0 t her theoretical considerations lead t o the equation p=RT/(u - b) . e-A/ziT, where A is a function of v, and represents the work to be done by a molecule against the forces of cohesion, O K ~ the supposition that A = C/w, the ratio vJvk is equal t o 3.695, a value agreeing closely with that given by experiment. By HEINRICH LEY (Zeit.physikaZ. Chew,., 1899,30,193-%7).-1n a salt solution, besides the electrolytic dissociation, hydrolysis may occur with the formation of acid and base which further undergo electrolytic dissociation. The concentrations of the various molecular groupings present in the solu- tion are determined by the equilibrium constants for the hydrolytic dissociation and for the electrolytic dissociation of salt, acid, base, and water.The author first investigates theoretically the necessary equations for the cases where (1) either base or acid is weak ; (2) both acid and base are weak. For the determination of the hydrolysis, the method of sugar inversion was found suitable, and the author obtains the value 16.8 for the inversion constant a t looo, which is thus intermediate between the values 17.9 found by Trevor (Abstr., 1893, ii, 62) and 16.0 found by Smith (Abstr., 1898, ii, 155). The variation of the constant with temperature was also deter- mined and found to be given by the expression K T ~ = K T ~ e.A(T1- To)lTITo, where A is a constant.Some salts were found t o cause an irregular increase of inversion, apparently not due to hydrolysis, as, for example, lanthanum chloride. Lithium and magnesium salts have no effect, but beryllium and aluminium cause considerable inversion, and for these the hydrolytic constant was calculated a t dilutions from 32 to J. C. P. The Critical State. J. C. P. Hydrolytic Dissociation in Salt Solutions.68 ABSTRACTS OF CHEXJCAL PAPERS, 512. The values do not remain constant, but the author considers the agreement to be satisfactory, owing to the complicated equations and the fact that they are rigorously valid for only binary electrolytes. From the values of the dissociation, the basicity of the hydroxides may be compared, and it is thus found that beryllium hydroxide is about eleven times as strong a base as aluminium hydroxide.Salts of cerium, copper, and zinc are only very slightly hydrolysed ; lead causes greater inversion, but still far less than the alumiuiurn salts. The hydrolysis of methyl acetate was also employed for the deter- minations, and the values for the hydrolysis of aluminium chloride by this process agree well with those obtained by the inversion method. Conductivity determinations may also serve for the calculation of hydrolysis ; the acetates of manganese, cobalt, zinc, and nickel exhibit a perfectly normal change of conductivity with dilution, and are hence not hydrolysed. With acetate of lanthanum, cerium, and lithium, this is not the case, whilst acetates of lead, beryllium, aluminium, and mercury give very abnormal results, indicating considerable hydrolysis.Where quantitative results were obtained, the values of percentage hydrolysis a t v = 1024 and 25' are : beryllium sulphste, 5 per cent. ; aluminium chloride, 4% per cent.; lead chloride, 4.4 per cent. ; uranium nitrate, 5.9 per cent. ; mercuric perchlorate (v= 512), 37 per cent. (Abstr., 1898, ii, 66). Determination of Solubility Coefficients of Liquids. By A. A~GNAN and E. DUGAS (Compt. rend., 1899, 129, 643-645).-When aniline and water are mixed, there is no alteration of total volume consequelit on the reciprocal solubility of the liquids, and in this case i t is possible to determine the solubilities by observation of the volumes of the two layers before and after agitation? in two different experi- ments.The values so obtained in C.C. per cubic centimetre are : (1) aniline in water, 0-036 ; (2) water in aniline, 0.042. I n the case of water and fermentation amyl alcohol, however, the total volume does not remain constant, and very diverse values for the solubilities, sometimes even negative, are obtained, so that in this case the author considers the case is not one of simple solubility, and the results may be due to the fact that one of thealcohols present in the fermentation amyl alcohol is capable of combining with water. By W. HERZ (Zeit. ccnorg. Chem., 1899, 22, 279-284).--The results previously obtained (Abstr., 1899, ii, 752) were not in harmony with the law of mass action, but it is now found that a t lower concentra- tions the equation K= [Mn**][NH,]~//CNH4*l2 gives fairly constant values of K : in this equation, the symbols in square brackets indicate the concentrations of the respective molecules or ions.With the mean value of K = 1.6 x and the dissociation constant of am- monia = 0*000023, the solubility of manganous hydroxide is calculated t o be 0.6 x a value of the same order as that obtained by Bodlander feom other considerations. Fusion of Sodium Thiosulphate. Hydrates. By FRIEDRTCH WILHELM KUSTER and A. THIEL (Zeit. anovg. Chem., 1899, 21, 401--404).--Fueed sodium thiosulphate might be regarded either as L. M. J. I;. M. J. - Equilibrium between Manganous Salts and Ammonia. J. C. P.GENERAT, ANT) PHYSICAT, CHEMISTRY.69 a definite liquid compound, or as a reciprocal solution of t h e decom- position products of the crystallised salt. I n the first case, excess of water or anhydrous thiosulphate in the fused hydrate would give two distinct series of solutions, the properties of which might be repre- sented by two curves, cutting each other at the point corresponding with the composition Na2S,O,,5H,O. If, on the other hand, the fused hydrate is merely a reciprocal solution of water and anhydrous salt, its properties ought to be intermediate between those of solutions with excess of water and anhydrous salt respectively. The latter behaviour has been observed in the case of the conductivity. As the number of water molecules to one molecule of anhydrous salt rises from 4.69 t o 6.65, the conductivity increases proportionally, and there is no dis- continuity whatever corresponding with the composition Na2S,0,,,5H20.J. C. P. Molecular State of Ammonia and of Amines in Aqueous Solutions. By ARTHUR HANTZSCH and F. SEIZALDT (Zeit. yl~ysikccl. Chem., 1899, 30, 25S-299).-1n the hope of solving this ques- tion, the author determined the partition ratio of ammonia and amines between water and other solvents. Ammonia in water and chloroform mas first examined ; if i t exists as hydroxide, the scheme of dissociation is NH,HOSNH, + H,OZNH’, + HO’, and as ammonia is but a weak base, thelntter dissociation is very slight. The calcula- tion of the partition ratio is made on the assumption that the hydr- oxide itself is insoluble in chloroform, and as the concentration of the gaseous ammonia in the aqueous phase is proportional to that of the hydroxide, the total conceutration may be, and is, employed instead of that of the gaseous ammonia only.The value for the partition ratio, water/chloroform a t 2 5 O , is about 25, and remains constant for varying concentrations, but i t increases with fall of temperature. The values were not affected by the addition of ammonium chloride, a result the authors consider t o be surprising, although, in view of the slight electrolytic dissociation of ammonium hydroxide, i t might have been expected. The partition of piperidine between benzene and water and the effect of addition of piperidine hydrochloride, were next examined; the addition of sodium hydroxide was found to cause con- siderable decrease in t h e partition ratio, which was also found t o decrease with increase of temperature.The partition at various temperatures was also determined €or trimethylamine and triethyl- amine between water and toluene ; acetic acid, pyridine, hydrogen cyanide, and cyanacetic acid between water and benzene; and for acetic acid, cyanacetic acid, ferric thiocyannte, and mercurous chloride between water and ether. With the amines, in every case the partition ratio decreases with rise of temperature ; this was also the case in a few other systems, but in most the converse obtained. This seems t o indicate the existence of hydroxides and a n increase of molecular dis- sociation at higher temperatures, but the authors consider it more probable that hydrates, and not hydroxides, exist in the solutions.In ammonia solutions, the temperature coefficient is very small, and here especially the quantity of hydroxide must be very sinall. L. M. J.7 0 ABSTRACTS OF CHEMICAL PAPERS. Conversion of Mixed Crystals into a, Compound. By H. W. BAKHUIS ROOZEBOOM ( PYOC. K. Akad. Tetensch. Amsterdam, 1899, 2, 74-77).-No difference is observable in the melting points of dextro- Iawo-, and inactive camphoroxime, or of mixtures in any proportions ; the solid mass is further perfectly homogeneous, sa that the existence of mixed crystals is confirmed (Forster and Pope, Trans., 1897,71,1049), and the melting point CUITB for the mixture is hence a horizontal lint., The transitidn point to monoclinic crystaIs varies from 112.6' for 100 per cent. of either compound to 109.4' for t h e inactive mixture, and the curve is quite symmetrical, and here also mixed crystals are again formed.By cooling still more, a further change takes place, and this occurs at 103" for the inactive mixture, but the t'emperature is con- siderably reduced by excess of either component, and could not be observed at all when t h e percentage rose above 75. I n this case, therefore, the mixed crvstals become converted into a comDound. and the views' of Pope (Zoc.'cit.) are confirmed (see Abstr., 1896, ii, 401). L. M. J. Mixed Crystals of Mercuric Iodide and Bromide. By W. REINDERS (Proc. K. Akccd. Vetensch. Amsterdam, 1899, 2, 146- 148).- The melting point curve of mixed crystals of mercuric iodide and bromide is continuous between the temperatures 236 5' and 255*4O, the melting points of the bromide and iodide respectively. It passes through a minimum at 216.1', corresponding with a mixture containing 59 per cent.of mols. of the bromide, and at this temperature the crystals deposited have the same composition as the molten mixture; if the latter contains more (or less) bromide than the above-named quantity, the crystals deposited are richer (or poorer) in bromide than the mixture. Below 216", mixed crystals in all proportions can exist. At l27', yellow mercuric iodide is converted into the red modi- fication. By admixture of the bromide, this transition point is lowered and also widened out into a transition-interval determined by two limiting curves, one for the yellow, and the other for the red, cryst#als. The former of these runs from 127' when no bromide is present t o a point on the Oo abscissa corresponding with 33 per cent.of mols. of the bromide; whilst t h a t for the red crystals proceeds from the same starting point and cuts the 0' abscissa in a point indicating the pres- ence of 8.6 per cent. of the bromide molecules. The transition interval was determined partly by observation of the colour change, as this made i t possible to determine the composition of red crystals which a t a definite temperature change completely into the yellow variety ; further, solutions were found by trial, each of which deposits at a particular temperature, both red and yellow mixed crystals. These curves could not be continued below,OO, but their direction shows that, if there is a transition point for mercuric bromide, it must be at a very low temperature; at - 83", no indications of such transition could be found.Solid mercuric bromide and iodide diffuse into one another at ordinary temperatures, and more so when heated, and the transition temperature of a finely-powdered mixture of them agrees very nearly with that of the mixed crystals of the same composition. T. H. P.INOltGANIC CHEMISTRY, 71 Properties of Flames. By NICOLA TECLU (J. pr. Clmn., 1899, [ii], go, 396-399).-I. A stream of coal gas is allowed to issue from a platinum tube about 12 mm. in length and 2 mm. in diameter, so as to afford a flame of definite dimensions, the pressure of the gas at the point where i t enters the tube being registered by means of an alcohol manometer.It is found that on heating the platinum tube by means of a flat flame bunsen burner, if the gas supply is taken directly from the main, the flame suffers a contraction of about 70 per cent., whilst the manometer registers only R small increase in pressure (about 40 mm.). If, on the other hand, the gas is supplied from a small laboratory gas-holder, the flame suffers no appreciable contraction when the tube is heated, but the manometer registers an increase in pressure nearly three times as large as in the former case (about 110 mm.). The explanation offered is that the disturbances, set up by the sudden increase in bulk which the gas undergoes in coming into contact with the heated tube, are propagated backwards with the velocity of compression waves, and suffer reflection in the small laboratory apparatus, producing pressure in the mass of gas and thus affecting the manometer and serving to maintain the size of the flame ; where the enormous technical gasometers are involved, the energy of the waves is minimised or dissipated. 11. An apparatus is described which consists of a modification of that used in the ordinary lecture experiment for demonstratiiig the reciprocal nature of combustion. By ARTHUR JOHN HOPICIKS (Amer. Chem. J., 1899, 22, 407-410).-1n this apparatus, a glass tube passing through a doubly-bored indiarubber stopper, fitted to a tall glass cylinder, is con- nected near the bottom of the latter with one limb of a Y-tube, the lower limb of which is open, whilst the third is connected to a vertical glass tube which reaches up nearly to the stopper, and is there curved downwards. Through the second hole in the stopper passes a tube connected with a filter pump which serves to draw a current of air through the apparatus, the rate of this being regulated by a stop- cock on the tube open to the air. The crystals to be dissolved are placed a t the bottom of the cylinder ; the saturated solution formed there is withdrawn continuously by the suction in the Y-tube and discharged upon the less saturated solvent a t the top, fresh solvent thus being brought continuously in contact with the substance to be dissolved. W. A. I?. A. L. A Dissolver.

ISSN:0368-1769    

DOI:10.1039/CA9007805061

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

INOltGANIC CHEMISTRY, Inorganic Chemistry. Biological and Chemical Purification of Water. By A. TIXIER (J. Plzawn., 1899, [vi], 10, 297--300).-1n order t o avoid the liberation of free alkali which OCCU~S when potassium permanganate or calcium permanganate is used for the purification r>f water, the72 ABSTRACTS OP Crf EM1CAL PAPERS. author uses a solution containing aluminium permanganate and barium permanganate. The solution employed has a specific gravity of 35" B., and contains 290 grams of permangnnic acid per litre, and 7 per cent. of alumina. It is added to the water to be purified until a persistent pink coloration is produced ; the water is allowed to remain for 24 hours, and after filtration through a carbon or other filter is fit for consumption, By Nrcor,A TECLU (S.p. Chem., 1899, [ ii], 60, 402--403).-Several new forms of apparatus for exhibiting the phenomenon of ozone production during electric discharge are figured. By JOSEF M. EDER and EDUARD VALENTA (Chenz. Centr., 1899, ii, 358).-The spectrum of chlorine was ex- amined a t pressures varying from 10 to 100 mm., a concave grating being employed. The authors confirm Ciamicinn's observation of the broadening of many lines and increase of brightness of the continuous spectrum by increase of pressure, but no band spectrum was obtained. Very characteristic lines were those of wave-length 4132 in the violet and 3860 in the ultra-violet, and the wave-length of many lines are given which a t low pressures are seen to be doubled or trebled ; a line a t 3750 does not become broader by increased pressure.By E. H. SARLES (J. Amer. Chenz. Xoc., 1899,21, 1038).-When chlorine is passed into ethyl alcohol, the liquid finally separates into a lower yellow layer and an upper layer having a grass-green colour. The green solution has bleaching proper- ties which it, however, loses when uncombined chlorine is removed by a current of air or carbon dioxide. The solvent, which gives a green solution of chlorine, has not been isolated ; it is either easily decom- posed or very volatile, since when the liquid has been fractionated several times, the green colour is completely lost and cannot be re- gained by passing fresh chlorine into the liquid. Theory of the Electrolytic Formation of Hypochlorite and Chlorate. By FRITZ FOERSTER (Zeit.anorg. Chem., 1899, 22, 1-32).-1nvestigation of the formation of hypochlorite and chlorate as a purely chemical process (Abstr., 1899, ii, 278) has prepared the way for a theory of the electrolytic preparation of these substances. A review of the work dealing with the electrolysis of alkali chlorides (compare Oettel, Abstr., 1896, ii, 517; Haber and Grinberg, Abstr., 1898, ii, 215 and 365; Wohlwill, Abstr., 1899, ii, 213) shows that the following conclusions may be regarded as established. Hypo- chlorite is formed chiefly by the interaction of the chlorine liberated at the anode with the alkali produced during the electrolysis or previously present : in alkaline solution, hypochlorite can be oxidised t o chlorate by a primary anode process ; the formation of chloric acid in the electrolysis of dilute hydrochloric acid is due to the direct oxidation of C1 ions a t the anode.A theory of the secondary electrolytic formation of chlorate is discussed, based on two suppositions ; (1) that in the electrolysis of H. R. LE S. New Ozone Apparatus. A. L. Spectrum of Chlorine. L. M. J. Colour of Chlorine Soh tions. J. J. 8. -INOKGANIC! CHEMISTRY. 73 neutral alkali chloride solutions, chlorine is continually being liberated at the anode, (2) that the hypochlorite takes part in the electrolysis, and that its ions are discharged at the anode with evolution of oxygen. The known facts regarding the influence of current density, temperature, acidity, and alkalinity, on the formation of chlorate, are largely in harmony with the theory ; further experiments to determine the exact nature of the process have been made by Muller (see fol- 1 owing abstract).Formation of Hypochlorite and Chlorate in the Electrolysis of AIkaIi Chlorides. By ERICH MULLER (Zed. anorg. Chem., 1899, 22, 33-90. Comp:we Abstr., 1899, ii, 742).-The supposition that in the electrolysis of neutral alkali chloride solutions the formation of hypochlorite and chlorate depends on the same purely chemical process as in the non-electrolytic formation of these compounds, has several consequences. Experiment on the whole confirms these consequences, and shows that the electrolytic formation of chlorate in neutral alkali chloride solutions consists in the following processes ; chlorine is discharged at the anode, and unites with the alkali from the cathode to form hypochlorite ; even while the hypochlorite con- centration is still small, ClO ions are discharged a t the anode, forming hypochlorous acid, which in its turn oxidises hypochlorite and chloride t o chlorate; a t low temperatures, hypochlorite is to a small extent oxidised by anode oxygen.Experiments in acid and alkaline solutions of the alkali chlorides lead t o the conclusion that the electrolytic process in these does not differ essentially from that in neutral solution. The electrolytic formation of chlorate may thus be referred in general to four equa- tions : (1) 6 + 3HC10 = 610, + 3 H + 3El; (2) 610 + 2HC10 = 610, + 2 H + 2C1; (3) C1+ 3 0 = C10, ; (4) C10 + 2 0 = C10,. I n dilute hydro- chloric acid, the existence of C10 ions is excluded, and in this case the formation of chlorate must take place according to equation (3).I n other cases, the processes may be represented in varying degree; thus, when there is no appreciable evolution of oxygen, the chief pro- cesses are those indicated by equations (1) and (2); when the evolu- tion of oxygen is considernbls, as i n strongly alkaline solutions, the formation of chlorate will take place chiefly according t o equations (3) and (4). Molecular Weights of some Elements and their Derivatives. By GIUSEPPE ODDO and E. SERRA (Gccxzetta;, 1899, 29, ii, 343-353).- The molecular weight of iodine has been determined by the boiling point method, the solvents employed being tetrachloromethane, carbon disulphide, benzene, and ethyl alcohol.The numbers obtained with the first two solvents are sensibly the same as those of Beckmann and Stock (Abstr., 1895, ii, 382). Benzene and ethyl alcohol yielded the respective values 273-279 and 265-327, Beckmann and Stock's numbers being 335-360 and 330-342; the latter results, being corrected for the volatility of iodine, give the values 233-255 and J. C. P. -_ + - - - - + - - J. C. P.74 A4 13 Y T B ACTS 0 P C k1 EM IC A L P APE H S . 233-241 respectively. The authors' object to this very large correction being applied, as with slow boiling, the amount of iodine volatilised is very small and scarcely sufficient to colour the vapour of the solvent. I n boiling tetrachloromethnne, the sulphur molecule contains 8 atoms up to concentrations of about 3 per cent.; beyond that strength of solution, the results obtained are not concordant. Phosphorus pentachloride has the normal molecular weight in boiling tetrachloromethane. Solutions of iodine mono- or tri-chloride in tetrnchloromethane give lower boiling points than that of the pure solvent, I n the case of the trichloride, this is due to the fact that it sublimes a t 70-75". With the monochloride, dissociation takes place according to the equation 9ICl= I, + I, + 3IC1,, and the effect of the trichloride in lowering the boiling point is greater than that of the iodine in raising it. Action of Arsenious and Antimonious Oxides on Sulphur Monochloride. By GIUSEPPE ODDO and E. SERRA (Gaxxetta, 1899, 29, ii, 355).-When arsenious oxide and sulphur monochloride are heated together in a reflux apparatus, they react according to the equation : As,06 + 6S2C12= 4AsC1, + 3S0, + 9s.The reaction is complete in about an hour, and on cooling, nearly ail the sulphur formed crystallises out and the arsenic trichloride can be separated by decantation. Analogous reactions take place when antimony or bismuth sesquioxide is substituted for the arsenic compound. Hydrates of Sulphuric Acid. By EUGEN VON BIRON (Chem. Centr., 1899, ii, 467-468 ; from J. Russ. C'hem. Xoc., 31, 517-522).- The author has succeeded in crystallising the hydrate H,S04,2H20, predicted by Mendel6eff. A solution of the composition H,S0,,2H20, cooled with liquid air, solidifies to an amorphous mass. This mass, if rubbed a t rather a higher temperature with a glass rod, becomes crystalline, the thermometer rising a t the same time to - 35".The crystals thus obtained may be used to start crystallisation in a solution of the composition H2S0,,2H,0 cooled merely to - 75" with solid carbon dioxide and ether. Cooling with liquid air is detrimental t o the formation of the crystals. The freezing point of the hydrate was determined in a Beckmann's apparatus of small size, well protected by surrounding tubes, and cooled in a mixture of carbon dioxide and ether. During solidification, the thermometer remained steady for about 10 minutes, until practically no liquid was left, showing that the separation of the solid did not alter the freezing point of the remaining liquid. I n solutions which deviated from the composition H,S04,2H20, the thermometer was steady for only 1-2 minutes.The freezing point of the hydrate is - 38.9'; with the same apparatus, the hydrate N,S0,,4H2O solidified a t - 69". Polymerisation of Inorganic Chloro- Anhydrides. I. By GIUSEPPE ODDO and E. SERRA (Gazxetta, 1899, 29, ii, 318- -329. Corn- pare this vol., i, 92),-Determined by the boiling point method, the T. H. P. T. H. P. J. C. P.IN ORGAN I C C H E MIST R Y. 95 molecular weight of phosphorus oxychloride in various solvents is as follows : I n tetra,chloromethane, 325-362 ; benzene, 283-309 ; carbon disulphide, 214-244; chloroform, 159-164 ; ether, 147-157. The cryoscopic method gives a value 149-152 in benzene. The number corresponding with the formula POCI, is 153.5. The molecular weight of thionyl chloride in boiling chloroform is 229-235 and in freezing benzene 108-120; the formula SOC1, requires 11 9.Phosphorus oxybromide has a molecular weight of 287-310 in boiling tetrachloromethane and 334-352 in boiling benzene ; the cryoscopic method gives a value 293-308 in benzene. The calculated value for POBr, is 287. Phosphorus thiochloride gives the following molecular weights. I n boiling tetrachloromethane, 209 ; in boiling benzene, 236-247 ; in freezing benzene, 158-161. The calculated number is 169.5. For sulphur monochloride, the values obtained are, in boiling tetra- chloromethane, 169-173, and in boiling benzene, 180-193 ; the formula S2CI2 requires 135. Chromyl chloride in boiling tetrachloromethane gives the molecular weight 225-243 ; in boiling benzene, 441-528 ; and in freezing benzene, 165-175, The formula CrO,Cl, corresponds with st value 155.5.The cryoscopic method gives for the molecular weight of sulphuryl chloride in benzene the number 131, the value for S02C1, being 135. T. H. P. Properties of Solutions of Sodium Nitrite. By JOSSIF JURI BOGUSKI (Chem. Centr., 1899, ii, 470 ; from J. IZuss. Chem. Xoc., 1899, 31, 543 -551).-Sodium nitrite, prepared from the commercial article by crystallising from solutions saturated at 1 2 5 O , has a yellowish tinge which disappears, however, when the salt is dried over sulphuric acid or washed with alcohol, but even then the colourless salt still forms yellowish solutions. This coloration is dne to the presence of a foreign substance, The variation of the sp. gr. with the concentration of solutions of the nitrite is represented by a curve which is very nearly a straight line. The specific refractive index of solutions a t 20' may be calculated from the formula [nID = 1.33336 + 0*0011559 P, where P= percentage of nitrite dissolved. The original paper con- tains copious data and many tables.NOTE.-AS to the colour of sodium nitrite and its solutions, compare Divers (Trans., 1899, 75, 16), Groves (Proc., 1898, 222).-EDIToRs. By EDMUND GRAEFE and MORITZ ECKARDT (Zait. ccnoq. Chem., 1899, 22, 158-1 60).-A repetition of Winkler's experiments (Abstr., 1890, 331) on the reduction of alkaline carbonates proves Beketoff's assertion that the reduction to metal takes place more easily as the atomic weight increases. The preparation of ctmium is effected at a lower temperature than that of rubidium or potassium.A mixture in the proportion R,CO,: 3Mg is heated in an iron tube, free from rust, in a slow current of dry hydrogen and the metal, which distils E. W. W. Preparation of Cesium from the . Carbonate.76 BUSTRACTS OF CHEMICAL PAPEltS. collected under petroleum ; a theoretical yield is obtained. Metallic czsium is silver-white with B yellow tinge, retains its lustre under petroleum, oxidises with development of heat on exposure t o the air, then melts and explodes, swims on water, and burns with a reddish- violet flame with liberation of hydrogen. Calcium and its Compounds. By HENRI MOISSAN (Ann. Chim. Phys., 1899, [vii], 18, 2€?3-343).-A detailed account of work already published (compare Abstr., 1894, i, 313; 1898, ii, 116, 161, 578; 1899, ii, 25, 152, 153, 155, 219, 241, and 418).By KARL ZULKOWSKI (Chem. Centr., 1899, ii, 602-603; from Chem. Ind., 22, 349--352).-The setting of the ordinary roasted gypsum is due to the formation of the calcium salt, S(OH),:O,Ca, of hexabasic sulphuric acid by the action of water (2 mols.). Gypsum which has been roasted at a moderate red heat is also capable of taking up water, but ou account of its greater density i t only combines with 1 mol. of water, forming the calcium salt, SO(OH)2:0,Ca, of tetrabasic sulphuric acid. The water has a twofold action, first dissolving the more soluble calcium compound, and then combining with i t to form a less soluble compound which separates in a crystalline form and sets t o a compact mass.Preparation and Properties of Crystallised Barium and Strontium Phosphides. By A. JAROIN (Compt. rend., 1899, 129, 762-765).-Crystallised strontium phosphide is obtained by heating a mixture of lampblack and strontium phosphate for 3 or 4 minutes in an electric furnace with a current of 45 volts and 950 ampbres, and the barium compound is obtained in a similar way. StrontiulrL phosphide, Sr3P2, burns in fluorine a t the ordinary temperature, in chlorine a t about 30°, in bromine at 170-175', in iodine at it red heat, in oxygen above 300°, and in sulphur vapour at a higher temperature. It is decomposed by carbon at a high'temperature, but not by sodium a t a red heat ; by dilute acids and gaseous hydracids, but not by concentrated acids, nor by hydrogen sulphide or ammonia, nor by organic solvents.It alters rapidly i n moist air, is decomposed by water with liberation of hydrogen phosphide, and is violently attacked by oxidising agents. Its sp. gr. is 2.68 and it melts only in the electric furnace. Bccrium phosphide, Ba3P2, has similar properties, but is not so readily attacked; it burns in chlorine a t 90' and in bromine at 260-300". I t s sp. gr. is 3.183. Formation of Oceanic Salt Deposits, Particularly of the Stassfurt Beds. XIV. Influence of Pressure on the Forma- tion of Tachyhydrite. By JACOBUS H. VAN'T HOFF and H. M. DAWSON (Chem. Centr., 1899, ii, 401-402; from Sitxungsbey. Akccd. Viss. Uerlin, 1899, 557-562. Compare Abstr., 1899, 759).-The effect of increase of temperature and pressure on the evaporation of sea-water is to cause the separation of new compounds, for when the change of the solubilities of the various compounds affected by the alteration clf conditions exceeds certain limits, supersaturation with new compounds is rendered possible.Increase of temperature and pressure results in the formation of kieserite, liiweite, kainite, and lnngbeiuite, none of E. C. R. G. T. M. Setting of Gypsum. E. 177. W. C. H. B.I N 0 HG A N Ic' C H E M 1 YTR Y , 77 these compounds being formed when sea water is evaporated at 25' under the ordinary pressure. The salt basins of Besangon have a temperature of 62" a t a depth of 1.35 metres, and reckoning on this basis the variations of temperature and pressure in the case of the Stassfurt beds which have a maximum depth of 1500 metres amount t o 40 and 180 atmospheres respectively. The effect of changes of temperature and pressure has been investi- gated in the case of the formation of tachyhydrite (MgCl,),Ca,l 2H20, which easily separates from mixed solutions of the hexahgdrates oE magnesium and calcium chlorides a t 22".Experiments with the manocryometer and Beckmann's thermometer show that an extra pressure of one atmosphere only raises the temperature of the forma- tion of tachyhydrite by 0 . 0 1 7 O . This effect is comparable with that of pressure on melting points ; i t lies between the raising of the melting point of ice by 0.0073° and that of paraffin by 0.035" caused by a pressure of one atmosphere. Hence, since a n increase of pressure of 180 atmospheres would only raise the temperature of formation by 3', the effect 3f increase of temperature must be of much greater import- ance.E. w. w. By ALEXANDER P. LIDOFF (Chem. C'erdv., 1899, ii, 471 ; from J. Rum. C'hem. SOC., 1899, 31, 571--.572).-From the results of experiments oc the action of copper salts on alkaline eolutions of albumin, it appears that the biuret reaction really depends on the dissolution of copper, the copper salt being reduced t o soluble colloidal copper. An alkaline solution of gelatin in which copper gauze was placed had acquired a violet coloration after remaining a day, and after 48 days 3-54 per cent. of the copper was found to have been dissolved. By RICHARD Jos. MEYER and HANS BEST (Zeit. anorg. Chem., 1899, 22, 169-151).- The dark green solution of oxides of manganese in hydrochloric acid contains manganese trichloride. Xach of the oxides, Mn203, Mn304, or Mn02, when dissolved in absolute alcohol or ether saturated wlth hydrogen chloride, yields a solution of manganese trichloride which is decomposed by water and also by evaporation in a vacuum over sulphuric acid, and consequently the trichloride cannot be isolated.I t , however, yields very characteristic double salts with pyridine and quinoline hydrochlorides which crystallise in lustrous needles. The action of hydrogen bromide on the oxides of manganese results in the formation of the dibromide which yields a crystalline double salt with pyridine hydrobromide. When potassium permanganate is boiled with acetic acid, carbon dioxide is evolved and a brown solution obtained, which on cooling deposits the salt, 3Mn02,Mn2(C2H30,)G + 2C,H,02, and if a small quantity of water is added t o the mother liquor, Christensen's tri- acetate, Mn,(C2H30,), + 4H20, crystallises out.The solution obtained by reducing potassium permaaganate with acetic acid with the addition of 1 mol. of potassium acetate, when saturated with hydrogen chloride yields the double salt MnC13,BKC1 (Rice, Trans., 1898, 75, 258). If, however, the solution is only partially saturated with Solution of Copper in Gelatin Solutions. E. W. W. Manganese Trichloride and Tetrachloride. VOL. LXXVIII. ii. 678 ABSTRACTS OF CHEMICAL PAPERS, hydrogen chloride, the salt MnCl,,MnCI3,5KCl is obtained. When the acetic acid solution of potassium permanganate, without the addition of potassium acetate, is saturated with hydrogen chloride, a small qnantity of the salt MnCl4,2KC1 is obtained as a black, crystal- line precipitate, and the mother liquors contain large quantities of manganese trichloride.The corresponding ammonium salts could not be isolated, although the reaction proceeds apparently in a similar manner. Caesium permanganate, under similar conditions, yields the salt MnC13,2CsCl. Thallium permanganate does not yield a double salt . The double sulphate, Xn,(S0,),,K,S04, is precipitated quantitatively by adding sulphuric acid to the solution of potassium permanganate in acetic acid. The higher chlorides of iron, cobalt, and nickel are not obtained by the above method. Lead dioxide, when dissolved in cold alcohol saturated with hydrogen chloride, is converted into the tetrachloride, which yields crystalline double salts with pyridine, di- and tri-methyl- amine hydrochloride, and tetramethylammonium chloride.FhdZ&a permanganate, TlMnO,, jorms large, nearly black prisms. E. C. R. Atomic Weight of Cobalt. 111. Analysis of Cobaltous Chloride and Cobaltous Oxide. By THEODORE W. RICHARDS and GREGORY P. BAXTER (Zeit. anorg. Chem., 1899, 22,221-234. Compare Abstr., 1895, ii, 377, and 1899, ii, 753).-The authors have determined the weight of the cobalt obtained from a known weight of cobaltous chloride by reducing it in a current of hydrogen. The methods em- ployed are essentially the same as those previously described. The mean of the two experiments gives for the atomic weight Co = 59.045.The cobaltous chloride was prepared by decomposing purpureo-cobalt chloride at 200' and eliminating the remaining ammonium chloride by heating in a current of nitrogen and hydrogen chloride. The cobalt- ous chloride was found to contain small quantities of ammonium chloride, alkali salts, and silica. Cobaltous oxide is prepared by precipitating a solution of pure cobalt in nitric acid with ammonia, and after heating the precipitate over a spirit burner, decomposing the resulting black oxide at a red heat in a vacuum. The reduction of the cobaltous oxide by means of hydrogen gave for the atomic weight Co = 58.954 (mean of three experi- ments), An examination of the cobaltous oxide shows that it contains a small quantity of a higher oxide; also, by heating the oxide in a vacuum at 800°, a partial reduction takes place into metal and oxygen, and since a perfectly constant oxide could not be obtained, the authors have abandoned the experiments.The results of all the experiments show that the atomic weight of cobalt lies between 58-93 and 59-06 and the most probable value is Co = 58.995 when 0 = 16. Occlusion of Hydrogen by Cobalt and other Metals. By GREGORY P. BAXTER (Anzer. Chem. J., 1899, 22,351-364).-Although cobalt in the forffi of ingots, which therefore presents a minimum amount of surface, is known to occlude practically no hydrogen, it is E. C . R.INORGANIC CHEMISTRY. 79 found that when reduced from the oxide, and therefore in a very finely divided condition, it occludes relatively large amounts of this gas.Electrolytic foil, which although somewhat porous lies between the two modifications in relative surface, falls between them also in its occluding power. The volume of occluded hydrogen varies, in the case of metal reduced from the oxide, with its purity and the temperature of reduction ; it is remarkable that the metal reduced from cobalt bromide occludes practically no hydrogen ; this appears to bedue to its being deposited in a more compact form than that reduced from the oxide, as the presence of sodium bromide has no perceptible effect on the amount of occluded gas. Since the occlusion of hydrogen progresses very slowly at the ordinary temperature and is practically negligible at the temperature of reduction (400 -500°), it must be a maximum a t some intermediate temperature; the time during which the metal is in contact with hydrogen determines largely the amount of gas taken up.Although practically none of the hydrogen occluded is given off in a vacuum at the ordinary temper- ature, yet. on heating in a vacuum nearly the whole is evolved. The occlusion of hydrogen by nickel appears to be governed by similar conditions to those dealt with in t,he case of cobalt ; with pure copper and silver, the occlusion is practically nil. Chromyl Chloride, Chlorochromic Acid, and Aminochromic Acid. By RICHARD Jos. MEYER and HANS BEST (Zeit. anwg. Chem., 1899, 22, 192--199).-Chromyl chloride is obtained by the action of hydrogen chloride on a solution of chromic acid in acetic acid, but cannot be separated from the acetic acid solution.When pyridine, dissolved in acetic acid, is added to the solution, chlorine is evolved, and the pyridine salt of hexachlorotrichrompl chloride, Cr3O,C1,,3PyHC1, is obtained, which crystallises in brownish-gold leaflets. The same salt is also obtained by adding pyridine hydrochloride to a solution of pure chromyl chloride in acetic acid. Pyridine and quinoline, when added to a solution of potassium chlorochromate in acetic acid, yield pyridine and quinvline chloro- chromates respectively, which separate in yellowish-red crystals, are stable, and can be recrystallised from dilute hydrochloric acid. No evidence of the formation of aminochromic acid was obtained by the action of ammonia on a solution of potassium chlorochromate in dry acetone.E. C. R. Recovery of Chromic Acid from Chromium Residues. By FRIEDRICH REGELSBERGER (Zeit. angew. Chew,., 1899, 1123-1 la€!).- Various methods have been suggested for recovering chromic acid (compare Haussermann, DingZ., 288,163 ; Lorenz, Abstr., 1896,ii, 265 ; Heibling, French Pat. 275274 ; Fitzgerald, Eng. Pat. 1896, 5542 ; Dercum, Eng. Pat. 18'38, 3801 ; Meister, Lucius, and Briining, German Pat. 103860). Two different electrolytic methods are de- scribed in the paper. The one consists in oxidation in alkaline solution: a current is passed through a saturated solution of an alkaline chloride containing an amount of chromic oxide or chromium salt equivalent to the current in unit time. When potassium chloride is employed, potassium dichromate crystallises from the hot solution W.A. D. 6-280 ABSTBACTS OF CIIEMICAJ, PAPERS. after some time, and chlorine is liberated. The metal vessel in which the electrolysis was conducted served as the cathode, and platinum gauze as the anode, and, t o ensure complete admixture, a i r was blown through. The method may be of practical use when the chromium liquors contain considerable amounts of organic matter, or when solid chromium residues hare t o be dealt with. The second method consists in the use of lead anodes in acid solu- tion, either with or without a diaphragm ; the lead is first converted into peroxide, which then oxidises the chromium compounds. The electrolysis proceeds best in hot solution, and almost any metal may be employed as cathode. Iron salts must not be present in the liquid.Preparation of Molybdenum and Uranium with the Aid of Liquid Air. By ALFRED STAIENHAGEN (Bey., 1899, 32, 3065. Com- pare next abstract but one).-The yield of molybdenum from a mixture of molybdic acid, aluminium, and liquid air is poor, owing to the vola- tility of molybdic oxide. A mixture of uranic acid and aluminium explodes with great difficulty, but when liquid a i r is added, the reaction is very violent, and a thoroughly fused uranium regulus is obtained. G. T. M. J. J. S. Molybdenum Dioxide. By MARCEL GUICHARD (Compt. rend., 1899, 129, 722-785).--Various oxides of molybdenum, intermediate in composition between MOO, and MOO,, have been described by former observers as being produced by heating molybdenum trioxide with ammonium molybdate and by the electrolysis of fused molybdenum trioxide.Both these reactions have bean studied by the author, who finds that the sole product, after excess of molybdenum trioxide has been removed by successive washing with soda and hydrochloric acid, is in each case molybdenum dioxide, which was obtained in a pure, By ALFRED STAVENHAGEN (Bey., 1899,32, 3064-3065).--The addition of liquid air t o the mixture of aluminium and tungstic acid employed in the preparation of tungsten (Abstr., 1899, ii, 489), produces, on explosion, so great a rise of temperature that a completelyfusedregulus of tungsten is obtained which contains only traces of aluminium. The author was unable t o obtain t h e element by Hallopeau's electrolytic method (Abstr., 1899, ii, 158). When molten lithium paratungstnte is electro- lysed with a current of 3.5 amperes and a n E.M.P. of 12 volts, bluish- black crystals of lithium-tungsten bronze are produced. By EDGAR F.SMITH (J. Amer. Chern. Xoc., 1899,21, 1007--1008).-An introductory paper, referring t o those treated in the following abstracts and in this vol., i, 76, 89. Atomic Weight of Tungsten. By EDGAR F. SMITH and WILLETT L. HARDIN (J. Amer. Chem. Soc., 1899, 21, 1017-1037. Compare Abstr., 1898, ii, 336).-Recent experiments prove t h a t practically no hydrogen is occluded when metallic tungsten is allowed to cool in a n atmosphere of this gas (compare Waddell, Abstr., 1887,112 j Derenbach, crystal1 ine state. N. L. Preparation of Tungsten with the Aid of Liquid Air. G. T. M. Tungsten. J. J. S.INORGANIC CHEMISTRY.81 fnaug. Diss. FVu~xbu~y, 1892). It has been proved that tungsten tri- oxide exists in two varieties, crystalline and amorphous. These differ in specific gravity and also in their solubility in sulphur mono- chloride; they may be converted into one another. If the insolu- ble oxide is converted i r t o ammonium tungstate and then ignited, the oxide which is formed dissolves in sulphur chloride a t 145O, and when the metal obtained from the oxychloride is heated in a current of oxygen, the oxide formed is insoluble in sulphur chloride a t 145'. The authors conclude that, so far, there is no trustwortby method for the determinationof the atomic weight of tungsten. The methods they have employed are (1) heating pure tungsten in air or in pure oxygen ; (2) precipitating metallic silver from silver nitrate solution by the aid of metallic tungsten (compare Smith, hbstr., 1893, ii, 170) ; (3) estimating the water of crystallisation in barium metatungstate (compare Scheibler, J.prakt. Chem., 1861, 83, 324). I n no case were concordant results obtained. Action of Sulphur Monochloride on Tungsten Trioxide. By EDGAR F. SMITH and HERMAKN FLECK ( J . Amer. Chem. Xoc., 1899, 21, 1008--1013).-When tungsten tricixide, the dioxide, or the mineral wolframite or scheelite is heated with sulphur monochloride, a red solution of tungsten oxychloride, WOCl,, is obtained, together with a small amount of a brown, insoluble substance. The trioxide obtained by heating ammonium tungstate, or the trioxide which has been heated for some time in the aiy, is not completely acted on by sulphur chloride, whereas the trioxide obtained by beating the oxychloride is practically all dissolved by it.This difference is not due to the presence of a nitride or oxynitride. Tungsten itself is not acted on by pure sulphur monochloride, but if free chlorine is present, tungsten hexachloride is formed. By SKLODOWSKA CURIE (Compt. rend., 1898, 126, 1101-1 10S).-The electrical conductivity of air, when induced by the Becquerel rays emitted by uranium compounds, varies directly with the amount of this element present in the active substance. All uranium compounds are active, and the metal itself more so than any of its derivatives, except pitchblende and native chalcolite (copper uranylphosphate) ; the latter substance, however, when prepared artificially, is less active than the metal; these results seem to indicate that the two minerals con- tain an element far more active than uranium. Thorium compounds are very active, the action of thoria being more pronounced than that of metallic uranium ; cerium, niobium, and tantalum compounds are slightly active.Yellow phosphorus is extremely active, but its action is probably of a nature different from that of uranium and thorium ; iE the allotropic form and in the phosphates, it is quite inert ; the com- pounds of all other elements do not appreciably influence the electrical conductivity of air. The effects produced by the rays vary directly with the thickness of the layer of active substance ; the rays traverse thin sheets of glass, ebonite, paper, and the metals.The rays emitted by thoria are more penetrating than those from uranium, and the penetrative power is augmented by increasing the layer of the oxide. J. J. S. J. J. S. Rays Emitted by Uranium and Thorium Compounds.82 ABSTRACTS OF CHEMICAL PAPERS. Distinct photographic impressions are obtained in the case of uranium, uranous oxide, pitchblende, chalcolite, and thoria, but those produced by thorium sulphate and potassium fluoroxytantalate are very faint. When uranium and thorium compounds are subjected t o the influence of Rontgen rays, they emit secondary rays, which produce a more intense effect than those emitted by lead under similar conditions. New Radio-active Substance contained in Pitchblende, By P.CURIE and SKLODOWSKA CUR~E (Compt. rend., 1898, 127, 175-178. Compare preceding a bstract).-A specimen of pitchblende, having 2 i times the emissive power of uranium, was examined chemically wlth a view of isolating the radio-active principle which produces the abnormal activity. The mineral was dissolved in acids and treated with hydrogen sulphide, the thorium and uranium remain in solution, whilst the active substance is precipitated with the sulphides insoluble in ammonium sulphide; after separating these in the usual manner, i t is found that the substance in question remains with the bismuth. When the sulphides are treated with nitric acid, the less active por- tion dissolves more readily ; and when the solution of the nitrates is diluted with water the more active portion is first precipitated; the progress of the separation is controlled by determining the electrical conductivity of air induced by the various fractions.An extremely active product can be isolated from pitchblende by sublimation, and when the sulphides of bismuth and the active substance are heated in a vacuum a t 700°, a sublimate is obtained, the activity of which is 400 times t h a t of uranium. It is believed that the extremely active substance obtained from pitchblende contains an unknown metal to which the name polonium is given. Spectroscopic examination of the substance, however, has not revealed the existence of any characteristic lines indicating the presence of a new element. An extremely Radio-active Substance contained in Pitch- blende.By P. CURIE, SKLODOWSKA CURIE, and GUSTAVE B~MONT (Compt. rend., 1898,127, 1215-1217. Compare preceding abstracts). -In the course of their researches on radio-active substances, the authors have obtained a product having all the properties of barium chloride, and, in fact, consisting mainly of this compound, but differ- ing from the ordinary chloride in being extremely active. By repeated fractional precipitation of the active chloride from its aqueous solu- tion by alcohol, a product is obtained which is 900 times more active than uranium. Ordinary barium salts are never radio-active, and, moreover, spectroscopic examination of the active substance has revealed the presence of a well-defined line not belonging to any known element (compare following abstract) ; the distinctness of the line increases with the radio-activity of the fraction under inspection.For these reasons, it is supposed that the active barium chloride con- tains another radio-active element for which the name radium is proposed. The atomic weight of barium in the active salt is not markedly different from that of the element in its inactive compounds. The compounds of uranium, thorium, polonium, and radium all give photographic effects on sensitive plates, and in this respect G. T. M. G. T. M.INOHGANIC CHEMISTRY. 83 polonium and radium are far more active than the other two; the rays emitted by the new elements render barium platinocganide fluorescent, but the effect is less marked than with Rontgen rays. G. T. M. Spectrum of a Radio-active Substance [in Barium Chloride].By EUQBNE DEMAR~AY (Compt. rend,, 1898, 127, 1218. Compare pre- ceding abstract).-The spectrum of the radio-active barium chloride, together with distinct indications of barium and faint lines due to lead, calcium, and platinum (from electrodes), contains a well-defined line of wave-length 3814.8 (Rowland's scale) which appears bet ween the platinum lines 3819.9 and 3801.5; this line has not been noticed in the spectra of any of the known elements. Spectrum of Radium. By E U ~ N E DEMARCAY (Compt. rend., 1899, 129, 716-71 7).-The following lines characteristic of radium were obtained from the photographed spectrum of a specimen of barium chloride containing that element. The numbers 1 to 16 indicate the order of intensity. A, 4826.3, (10) ; 4726.9, (5) ; 4699.8, (3) ; 4692.1, (7) ; 4683.0, (14) ; 4641.9, (4) ; 4627.4, (4), the centre of a nebulous band ; 4600.3, (3) ; 4533.5, (9) ; 4458.0, (3), the centre of a nebulous band ; 4436.1, (8); 4364.2, (8) ; 4340.6, (12); 3814-7, (16); 3649.6, (12).A number of feeble lines of uncertain origin were also observed. Atomic Weight of the Metal in Radio-active Barium Chloride. By SKLODOWSKA CURIE (Compt. rend., 1899,129,760-762). -Radio-active barium chloride obtained from a large quantity of uranium residues was fractionally crystallised, and the radio-active constituent was found t o accumulate in the less soluble portions; when the latter were dissolved in water and fractionally precipitated by alcohol, the active substance was concentrated in the first precipi- tates.The atomic weight of the radio-active barium increases with the intensity of the radiation ; with an intensity 3000 times as great as that of uranium, the atomic weight is 140.0; 4700 times as great, 140.9, and 7500 as great, 145.8. The radio-activity of the crystallised or precipitated compounds increases in a marked manner for several weeks after their preparation, but eventually attains a limiting value which may be five or six times as great as the value imfnediately after their preparation (compare Giesel, Ann. Phys. Chem., 1899, [ii], 69, 91). C. H. B. By ERNST COHEN and C. VAN EYCK (PYOC. K. Akad. Wetensch. Amsterdum, 1899,2, 77).-It is well known that at low temperatures tin becomes converted into a grey powder, but the change has been but little investigated, and various reasons have been assigned for it, The authors find that at - 83' the change occurred in about 24 hours, and the reverse transition could not be observed below 30°.At temperatures between these limits, the velocity of the change becomes so small as to be incapable of measurement. By the addition of a few drops of a 10 per cent. solution of ammonium stannic chloride, however, the reaction is considerably accelerated, and dilatometric observations employing this liquid for measurement purposes indicated G. T. M. N. L. Enantiotropy of Tin.84 ALTSTKhCIT8 OF CHEMICAL PAPERS. a temperature of between 10' and 20' for the transition. Detormina- tions of the E.M.F. of the cell : white tin/l0 per cent ammonium stannic chloride/grey tin, gave 20' for the temperature of transition.It hence appears that all tin exists, save in exceptionally warm weather, in the metastable condition. L. M. J. Thio- and Seleno-antimonites. By ISIDORE POUGET (Ann. Chim. Phys., 1899, [vii], 18, 508-571. Compare Abstr., 1897, ii, 499).- The following salts are described for the first time. Lithium orbhothio- antimonite, Li,SbS, + 3H20, forms white, deliquescent crystals ; the para-salt Li2Sb,S7 + 3H,O, is a dark red, gelatinous precipitate which has not been obtained crystalline. Ammonium orthothioantimonite, (NH,),SbS,, is precipitated as a white, crystalline powder on adding alcohol to the mother liquor from the meta-salt ; it readily decomposes and is only stable in the presence of ammonium sulpbide. Barium metathioccntipmonite, Ba(SbS,& + 44H,O, is an amorphous, brown precipitate.Triargentic thioantimonite, Ag,SbS,, is obtained as an amorphous, black precipitate by the addition of silver nitrate to a dilute solution of potassium orthothioantimonite ; the double salt, Ag,KSbS,, is a yellow, crystalline precipitate produced by the action of silver nitrate on concentrated solutions of the potassium ortho- o r pyro-salt (Somrnerlad, Abstr., 1897, ii, 500). A series of double salts of the formula RAg,SbS, is obtained from sodium, lithium, and ammonium thio- antimonites; these compounds are all decomposed by water into triargentic thioantimonite and the corresponding alkali salt. Zinc orthothioantimonite, Zn,( SbS,),, forms a yellow, crystalline precipitate, produced by the action of zinc salts on dilute solutions of potassium thioantimonite ; the double salt, ZnKSbS,, is obtained when concentrated solutions are employed.The correspocding manganese salts, Mn,(SbS,), and MnKSbS,, are produced in a similar manner ; they form pale red, crystalline pre- cipitates. The Zeud salts, Pb,(SbS,), and PbKSbS,, are brown precipitates. The reaction between potassium orthothioantimonite and cadmium, nickel, cobalt, and ferrous salts, follows the same course as in the preceding examples, but the products are very unstable. Cuprouspotassium od't,othioantirnontite, Cu,KSbS, + 3H,O, is a yellow, crystalline precipitate obtained by treating a cupric salt with excess of a concentrated solution of potassium orthothioantimonite ; cuprous orthoantimonite, Cu3SbS,, is produced by treating the precediug double salt with water ; it is a red, crystalline precipitate. A black precipi- tate of cupric thioantimonite is formed when cupric salts are treated with a dilute solution of potassium orthothioantimonite ; if, however, the latter reagent is in excess, i b gradually reduces the cupric salt and the precipitate then consists of a mixture of this compound with the cuprous salt.When mercurous salts are added t o solutions of the alkali ortho- thioantimonites, the yellow precipitate at first produced is rapidly converted into a black deposit of mercury ; mercurous salts react in aINORGANIC CHEMISTRY. 8 5 similar manner. Gold chloride, when mixed with a concentrated solution of thioantimonite, produces a brown precipitato ; t h i s redis- solves on agitation, and the solution, when warmed, deposits metallic gold.Potassium ort?~oselen.oa?ztimonite, K,SbSe,, is obtained in the form of orange crystals on evaporating a solution of antimony selenide in potassium selenide in a current of hydrogen ; the salt is extremely unstable and its solution rapidly deposits selenium. The para-salt K,Sb4Se7 + 3H,O, separates as a gelatinous, brown precipitate on cooling a saturated solution of its generators. Sodium orthoselenoantirnonite, Na,SbSe, + 9H,O, crystallises in yel- low needles from a solution of antimony selenide in sodium selenide ; it is even more oxidisable than its potassium analogue, and its solution deposits red, tetrahedric crystals of sodium selenoantimonate, Na,SbSe, By the joint action OF selenium and antimony dissolved in potassium sulphide, the mixed salt, K,,Sb,S,Se, + 4H,O, is produced ; it separates from the concentrated solution in small, yellow crystals. When a solution of sodium selenide is employed as the medium, two compounds are produced ; the less soluble is a complex salt having the composition Na,SbS1.,Se2.5 + 9H,O, which corresponds with the thioantimonate, Na,SbS4 + 9H20 ; the more soluble salt, Na,SbS,.,Se,., + 9H,O, forms yellow needles and is analogous to the orthoantimonite, Na,SbS, + 9H,O.Tellurium derivatives, analogous to the preceding compounds, could not be prepared; antimony telluride does not dissolve in a hot solu- tion of potassium telluride, K,Te, or potassium hydrotelluride, KHTe, and tellurium itself is insoluble in alkali sulphides. 4- 9H20. G. T. M. Derivatives and Atomic Weight of Palladium. By WILLETT LEPLEY HARDIN (J. Amer. Chem. Xoc., 1899, 21, 943-955. Compare Rosenheim and Maass, Abstr., 1899, i, 163). -Palladobis-phenyl- ammonium chloride, Pd(NH,PhCl),, is obtained as a voluminous yellow precipitate when a slight excess of aniline is added to a hydro- chloric acid solution of palladious chloride, i t is insoluble in hydro- chloric acid, but dissolves in ammonium hydroxide solution ; the bromide, Pd(NH,PhBr),, resembles the chloride. Palladodiquinolin- ium cldoi*ide, Pd(C',NH,Cl),, the corresponding bromide and pallado- clipiljeridium cl~Zoi*ide, Pd(C5NHi,Cl),, all form pale yellow precipi- tates. They are not acted on by hydrogen at the ordinary tempera- ture, but are readily reduced to metallic palladium when heated in hydrogen and the product allowed to cool in a current of air. A com- pound, PdC1,,2NH2Et,2HCl, crystallising in brownish-red scales has also been prepared. The atomic weight of palladium has been determined by various authorities (Berzeliw, 1828 ; Keiser, Abstr., 1890, 17 ; Keller and Smith, ibid., 1893, ii, 73; Bailey and Lamb, Trans., 1892, 61, 745 ; Joly and Leidie, Abstr., 1893, ii, 284 ; Keiser and Breed, ibid., 1894, ii, 141) and has now been determined by analysing diphenyl- palladodiamnionium chloride (seven experiments) and bromide (five experiments), and also ammonium palladium bromide (four experi-86 ABSTRACTS OF CHEMICAL PAPERS. ments), all of which were prepared from carefully purified palladium. The mean result obtained was 107.014 (0= 16), which is somewhat above that given by other authorities. J. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9007805071

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

7 3 Organic Chemistry. The Wax of Bacillariacee and its Connection with Petroleum. By GUSTAV KRAMER and ADOLF SPILKEE (Bey., 1899, 32, 2940--2959).-Bacillariace~! (diatoms) are known to contain drops of oil distributed i n the plasma, and from peat, in which diatoms occur largely, 1.5-4 per cent. of a wax can be extracted which contains 10-11 per cent. of sulphur. I n the Uckermark, to the west of Stettin, the bed, some 23 feet in thickness, of a lake, which was drained long ago, consists chiefly of diatoms, and from i t a wax can be extracted. This melts at 50-70°, resembles ozokerite in appearance, contains C, '73.5 ; H, 11.2 ; S, 1.0, and ash, 2.4 per cent., from which it may be concluded that the wax contains oxygen and consists of esters of organic acids. Fuming nitric acid does not attack the wax in the cold, but dissolves 38 per cent.on heating ; from the residue, lekene, which occurs in ozokerite (Beilstein and Wiegand, Abstr., 1883, 1073), can be isolated. The latter contains only 0.15 per cent. of sulphur, however ; only traces of i t are hydrolysed by alcoholic potash, and when it is distilled no water is formed and the gas evolved contains no oxides of carbon and but little hydrogen sulphide. Of the wax from the lake silt, on the other hand, about 10 per cent. undergoes hydrolysis ; and on distillation of the peat-wax, water is formed and the gas evolved contains 10 per cent. of hydrogen sulphide together with carbon dioxide and monoxide. When ozokerite is distilled under a pressure of 20-25 atmos., the gas evolved consists of methane and olefines, along with traces of hydrogen sulphide and carbon dioxide; the gas obtained from the silt-wax in similar circumstances contains hydrogen sulphide and carbon dioxide and mon- oxide, and that from carnauba- and Japan-wax contains both oxides of carbon.I n all cases, a large part of the distillate boils a t 130-290°, and this fraction has the character of the paraffins ; its composition is C, 84-4-85.0, and H, 15.1 per cent., and its molecular weight is 149-169 determined cryoscopically in benzene solution (C,,H,, requires C, 84.7; H, 15.3; molecular weight, 156). A similar fraction from petroleum (from the Tegernsee) had a like composition. It is further found that the composition of the strata overlying the ozokerite deposits of Eastern Galicia and the petroleum beds of the Tegernsee contain the same mineral constituents as the lake silt.The following theory of the origin of petroleum is then developed. Lakes became filled up in the process of time with a growth of diatoms ; over this growth other deposits were formed subsequently. The decay of the diatoms (which takes place very slowly) gave rise to ammonium carbonate, which hydrolysed the wax present ; from the resulting acids, carbon dioxide and monoxide and water were eliminated, and ozokerite formed. Where the pressure was small and the temperature low, this was converted further into a comparatively low boiling petroleum ; under greater pressure and higher temperature, the sulphur present These waxes much resemble ozokerite. VOL.LXXVIII. i. 9744 ABSTRACTS OF CHEMICAL PAPERS. also exerting an influence, a petroleum was formed which contained a large proportion OE viscid, high-boiling substances (probably formed by polymerisation of olefines); more extended action of the sulphur, and of atmospheric oxygen, gave rise to a petroleum containing much asphalt. Generally speaking, the petroleum would be absorbed by the sandy bed of the lake; occasionally it might be absorbed by a calcareous bed, a deposit of asphalt being thus formed. C. F. B. Heptane contained in Grosny Naphtha. By K. W. CHARIT- SCHKOFF (Chern. Centr., 1899, ii, 474; from J. RUN. Chern. Soc., 1899, 31, 552-!554).-The benzene boiling a t 84-100°, obtained from the naphtha of Grosny, contains an isoheptane, C7H,,, which boils at 90.5-91*5", and has a sp.gr. 0.1158 a t 15". This naphtha only con- tains a very small amount of normal heptane. The interpretation of the curves representing relationships of boiling point and specific gravity is discussed in the original paper, the author inclining t o Aschan's, rather than to Markownikoff's, views. E. W. W. Action of Acetylene on Oxides of Copper. By FRANK A. G o o c ~ and DE FOREST BALDWIN (Amer. J. Xci., 1899, [ iv], 8, 354-358). Compare Erdmann and Kothner, Abstr., 1899, i, 21).-Several errors in calculation are pointed out in Erdmann and Kothner's communica- tion. The experiments have been repeated, and the conclusion arrived at is that Erdmann and Kothner's '' Kupferacetylen " is nothing lass than a hydrocarbon or hydrocarbons mixed with copper or an oxide of copper. The amount of copper found varies considerably (1.54 to 24.21 per cent,) with the conditions of the experiment.When cuprous oxide is employed, a temperature of 225" is the most favourable; similar results may be obtained with cupric oxide, but copper itself is not acted on until much higher temperatures are reached, Oxide of silver is acted on at the ordinary temperature, and, as a rule, an explosion occurs. NoTE.-The same conclusion as t o the nature of Erdmann and Kothner's compound has been arrived at by Alexander (Abstr., 1899, i, 843). J. J. S. J. J. S. Preparation of Tetrachloromethane. By E. SERRA (Gaxxetta, 1899, 29, ii, 353--354).--Details are given of the method employed for the preparation of tetrachloromethane free from carbon disulphide and from chloroform, which are very difficult to entirely remove.T. H. P. Isomeric Compounds, C,H804N,, from Acetylmethylnitrolic Acid. By CARL STEFFENS (Annalen, 1899, 309, 241-253).-Acetyl- methylnitrolic acid, COMe*C(NOH)*NO,, obtained by oxidising acetone with nitric acid, yields two compounds having the empirical formula C,H,04N, ; one melts at 191", and is produced by converting acetyl- methylnitrolic acid into nitromethylglyoxime, and heating the latter with sodium hydrogen carbonate (Behrend and Schmitz, Abstr., 1894, i, log), whilst the other, melting at 140°, is derived by the agency of hydroxylamine from the product of heating acetylmet hylnitrolic acidORGANIC CHEMISTRY. 75 (Behrend and Tryller, Abstr., 1895, i, 201). The author has attempted to establish the constitution of these two substances.The derivative melting at 191', referred to as Schmitz's com- pound, probably has the constitution represented by the formula N O H : C M e * C ~ ~ : ~ ~ C * C M e : N O H . The hydrochloride is decomposed by hot water, yielding the original substance, which dissolves in hot hydrochloric acid, liberating carbon dioxide ; the remaining products are a-isonitrosopropionic acid, ammonia, hydroxylamine, and acetic acid. The diacetyl derivative crystallises from alcohol in needles and melts at 141" ; the dibenxoyl derivative becomes brown at 200' and melts at 220-225O, when it decomposes. The compound dissolves in alkali (2 mols.), and is reprecipitated by acids from a freshly prepared solution, but after an interval, acids do not, yield a precipitate; it immediately reduces potassium permanganate.The isomeride called Tryller's compound may have the constitution g-% . The hydrochloride readily yields N*O*O*N the original substance, which gives rise to carbon dioxide, oxalic acid, ammonia, hydroxylamine, and acetic acid when treated with boiling acids; there is produced also a small quantity of a volatile ketone, probably the ketone of which Tryller's compound is the dioxime. The dibsnxoyl derivative crystallises in slender, white needles and melts at 1555-156.5". The anhydyide, C,H,O,N,, obtained by acidifying a solution in caustic soda which has been boiled for some time, crystallises from alcohol in lustrous, yellowish leaflets and melts at 188--290", becoming brown a t 150'.M. 0. F. Phosphoric Esters. By JACQUES CAVALIER (Ann. Chiin. Phys., 1899, [vii], 18, 449-507. Compare Abstr., 1894, i, 484; 1895, i, 638; 1896, ii, 590; 1597, i, 310; 1898, i, 616, ii, 499; 1899, i, 558, ii, 13,55).-A detailed account of work already published. G. T. M. Manufacture of Glycerophosphate. By MARCEL GU~DRAS (Clzem. Centr., 1899, ii, 626 ; from Mon. Xci., [iv], 13, 11,577-580). -Commercial glycerophosphate, CaPO,. O*C,H,(OH)2, prepared by heating phosphoric acid with glycerol for a day at 150" and then for 3 days at 115-1 25", and treating the glycerophosphoric acid with milk of lime, is alkaline towards litmus, but neutral to phenolphthalein, dissolves in about 25 parts of water, leaving a small quantity of in- soluble calcium phosphate, and is precipitated from its aqueous solu- tion by heating.Boiling alcohol usually extracts some glycerol and phosphoric acid. Sodium and potassium glycerophosphates are syrupy liquids. The magnesium salt is a powder, and has properties similar to those of the calcium salt. The iron salt, prepared by digesting crude glyceropbosphoric acid with iron dust below 60°, crystallises in leaflets which have a golden lustre. Quinine glycerophosphate, C8H7O2* 0 *PO(OH),,(C2,H,,0,N,), + 4H20, is slightly soluble in water, more so in alcohol, and may be used as a substitute for quinine sulphate. E. W. W. 9 276 AI3STRACTS OF CHEMICAL PAPERS. Esters of Tungstic Acid. By EDGAR F. SMITH and CLAUDE DUGAN (J. Amer. Chem. Soc., 1899, 21, 1016-1017. Compare Goessmann, Annalen, 1857, 101, 218 ; Maly, ibid., 1866, 139, 240).- When Maly's method is employed forthe preparation of estersof tungstic acid, the products obtained consist of a mixture of hydrated tungstic acid and an incompletely esterified product : for example, with tungsten oxy- chloride and isobutyl alcohol, a product, 3 WO,, 2H,O + WOCl,(OC,H,),, was obtained, which was suluble in dry ether, but was reprecipitated on the addition of pure ethyl alcohol. J.J. S. Action of Water on certain Fatty Acids. By EDWIN DE BARR (Amer. Chem. J., 1899, 22, 333--349).-The author has studied the rate of interaction of water with certain halogenated fatty acids at 150°, 3 mols. of water being used for each halogen atom present. Tables of values are given and curves plotted, which show the rate of displacement of the halogen atoms from y-chlorobutyric, P-chloropropionic, trichloroacetic, P-chlorobutyric, chloroacetic, di- chloroacetic, a-chloropropionic, a-bromopropionic, a-bromobutyric, and a-chlorobutyric acids; the relative ease with which the halogen is removed from the various acids is given by the order in which these are named.This order is, except in the cases of mono-, di-, and tri- chloroacetic acids, not the same as that of the affinity constauts. Most of the acids begin to undergo secondary change before the dis- placement of the halogen is complete ; the relative stability of the compounds at 150' under pressure and in presence of hydrogen chloride appears to be in the order, a-bromopropionic (7.06), a-chlorobutyric (7.50), a-brornobutyric (9.25), a-chloropropionic (1 1*41), dichloro- acetic (1 7*!'6), P-chlorobutyric (37.38), chloroacetic (47.1 l), P-chloro- propionic (50*49), trichloroacetic (1 OO*OO), and y-chlorobutyric acids (lOO.OO), the numbers attached to each acid showing the percentage of halogen displaced befure decomposition begins.On comparing this list with the foregoing, it appears that those acids which are most stable react the most rapidly with water, whilst those which are least stable react most slowly. It appears, moreover, that with the a-acids containing the same halogen, the rate of displacement of the latter diminishes in passing from acetic acid t o its higher homologues ; the same holds true with the @-acids, and a similar law regulates the total amount of transformation occurring before decomposition begins.It is especially noteworthy t h a t the further a halogen atom is removed from the carboxyl group i n the same acid, the more easily is i t displaced under the influence of water; thus, the amount of halogen replaced after half a n hour is 4.42 per cent. of the total in the case of a-chloro-, and 41.5 per cent, in the case of P-chloro-propionic acid. P-Chloropropionic acid is best prepared by the action of chlorine on P-iodopropionic acid, and melts at 61", not at 35.5" to 58" a s has formerly been stated; it boils a t 204". P-Chlorobutyric acid, pre- pared by saturating a n ethereal solution of crotonic acid with hydrogen chloride at 0", and subsequently leaving it in a sealed tube for 24 hours at t h e ordinary temperature, melts at 16-16*5", boils at 116" under 22 mm.pressure, and is entirely free from a-acid. y-Chloro-ORGANIC CHEMISTRY. 77 butyric acid, prepared similarly from trimethylenecarboxylic acid, melts at 12" and boils a t 196" under 22 mm. pressure. Electrolytic Oxidation of Succinic Acid. By CHARLES H. CLARKE and EDUAR F. SMITE (L Arne?.. Chem. ~ o c . , 1899,21,967-972). -The electrolytic oxidation of succinic acid in solutions containing known quantities of sodium hydroxide and of alcohol, has been studied. A divided cell was employed and a current density of from 0.034 to 1.55 amperes per 100 sq cm. of anode surface. The products found were tartaric, oxalic, and carbonic acids, oxygen, carbon monoxide, ethylene, and methane, together with some aromatic substances. A colouring matter, soluble in ether and melting a t 17S0, has also been isolated. J.J. S. By OTTO RUFF and GERHARD OLLENDORFF (Rer., 1899, 32, 3234-3237).-Phenylbenzyl- hydrazine is better adapted for the isolation of sugars than phenyl- hydrazine itself, because of the ready formation and insoluble character of the hydrazones produced, and this substance has already been em- ployed by Lobry de Bruyn and Alberda van Ekenstein (Abstr., 1896, i , 588 ; 1897, i, 41). l-Xylosep~ienylbenx~Z~y~?~c~x~nd melts a t 99' (corr.), and dissolves in about 1000 parts of water. d-Arabinose- plzenyZbenxylhyd.r*axone me1 t s at 174" (corr.), and is almost insoluble in water. The corresponding hydrazone of dextrose melts a t 165" (corr.), and not a t 150" as st:ited by these authors. The sugars are best regenerated from these hydrazones by treatment with form- aldehyde, removal of the formaldehydephenylbenzylhydrazone by ether, and repeated evaporation of the solution to remove the excess of formaldehyde.Fo~mu Zdeh y d eplt eny 1 benxy lhhy d m x o n e cry s t alli ses in white needles melting a t 41". A. H. Isomaltose. By HENRI POTTEVIN (Ann. de I'Inst. Pasteur, 1899, 13, 796--800).--From a solution of pure maltose and a non-reducing dextrin, the author has prepared an osazone which melts at 154" and crystallises in tufts of very slender needles. From this fact, and a consideration of previous work, he concludes that Lintner's iso- maltose is a mixture of maltose and a dextrin (compare Ling and Baker, Trans., 1895,67, 704,739 ; 1897,71,511 ; Brown and Morris, Trans., 1895,67, 709).By ARMINIUS BAU (Cliern. Centr., 1899, ii, 526 ; from Woch. Bmuerei, 16, 397-400).--Melibiose was prepared by fermenting a solution of melitriose by means of a pure culture of a top-fermenting yeast. After decolorising the solution of the pro- duct with animal charcoal, i t was evaporated and the melibiose precipitated from the residual syrup after filtering, by means of ether and purified by conversion into the barium compound, &c. Melibiose forms triclinic crystals containing 2H,O! is not hygroscopic, and is not changed by exposure to the air; it is easily soluble in water or methyl alcohol, and, like its aqueous solution, decomposes at 80'. It sinters a t 82-83', partially melts at 84-85', and has a specific rota- tory power [ aID + 129.38' a t 20' ; freshly prepared solutions give a W.A. D. Separation and Purification of Sugars. H. R. LE 8. Crystallised Melibiose.7s ABSTRACTS OF CREMTCAL PAPERS. slightly lower value for the last constant. Its power of reducing Fehling's solution, calculated on the dry substance, is only 92-95 per cent. as much as that of maltose, and it is neither hydrolysed nor fermented by top-yeasts, but is decomposed by bottom-yeasts, forming dextrose and d-galactose, which are completely fermented. E. w. w. Rhamninose. By CHARLES TANRET and GEORGES TANRET (Compt. rend., 1899, 129, 725-738).--Tt has been previously shown that xanthorhamnin, the glucoside of Rhamnus infectoria, is converted by the action of dilute acids into a mixture of rhamnetin, rhamnose, and galactose, the las t-named compounds being themselves the products of hydrolysis of a n intermediate saccharose, for which the name &am- ninose is now proposed. Rhamninose, which is best obtained by the action of the ferment rhamnase, or, as i t is more properly termed, rhamninase, on xanthorhamnin a t 70°, is slowly hydrolysed by dilute acids into two mols.of rhamnose and one of galactose. It has a slightly sweet taste, and is soluble in all proportions in water, and very soluble in strong alcohol. It has a rotatory power [a], -41°, and melts and slowly decomposes a t 140'; it has not been obtained crystalline. Rharnninose has one-third the reducing power of dex- trose. Ordinary yeast, invertase, emulsin, and the ferments of Aspergillus have no action on it.No insoluble osazone or phenylhydr- azone could be obtained from it. When treated with sodium amalgam in the cold, rhamninose takes up two atoms of hydrogen and is con- verted into a new sugar, rhamninite, C,,H,,O,,, which has a rotatory power [a], - 57", and yields rhamnose and dulcitol on hydrolysis. Rhamninose is oxidised by nitric acid to mucic and galactonic acids, and by bromine to rhamninot~ionic acid, ClsH32015. This acid is monobasic and bears the same relation to rhamninose that lactobionic acid does to lactose. It has a rotatory power [a], - 94O, but does not reduce Fehling's solution ; both it and its salts are amorphous. On hydrolysis, it yields two mols. of rhamnose and one of gslac- tonic acid.N. L. By WIKTOR SYNIEWSKI (Alznalen, lE99, 309, 282-315. Compare Abst,r., 1898, i, 551).-From experiments with potato starch, the author draws the following conclusions : 1. Potato starch granules consist of an individual substance having the empirical formula C,H,,O,. 2. Hydrolysis of potato starch can proceed in two wags, namely, carbinol-hydrolysis, in which addition of water t o the anhydride of two carbinol groups takes place, and carbon yl-hydrolysis, in which at least one of the two groups forming the anhydride is a carbonyl radicle. 3. The compound obtained from potato starch by the action of boiling water under atmospheric or increased pressures, caustic potash, or sodium peroxide, is the result of carbinol-hydrolysis; it does not reduce Fehling's solution. 4.The simplest product of carbinol-hydrolysis is amylogen, C,,H,,04,. The molecules of starch, and of all products of carbinol-hydrolysis standing between starch and arnylogen, consist of a number of amyl- Constitution of Starch,0 Ra AN I C C E l EM I S T R 1'. 79 agen molecules associated in the form of anhydrides by elimination of water from carbinol groups. 5. The composition of all such compounds may be expressed by the general formula (C54H96048)n -(3n - x)H20, in which n is unknown, and 2 is variable from 0 to 3n. 6. Amylogen consists of three maltose residues, combined with a dextrin containing 18 atoms of carbon. The dextrin is composed of three glucose residues, of which two are in the form of an isomaltose residue. 7. The first stage in the hydrolysis of amylogen is the separation of the maltose molecules from one another and from the dextrin; further action of malt extract on the latter resolves it into glucose and isomaltose, which finally yields a further quantity of glucose, 8.Diastatic hydrolysis of amylogen gives rise to intermediate pro- ducts, the changes being represented by the following equations : C18H,7012i 03(~12H231311)3 + 2H20 = Am ylogen. C18H30014: 02(c12H23011)2 + C12H22011 + H'2°' Dextrin-residue I. Maltose. C18H30014: 02(c12H23011)2 + H2° = C18H31015* 0(C12H23011) + C12H22011 -k H2°' Dextrin-residue 11. Maltose. C18H31015* O ( C l , H 2 , O , l ) + H 2 O = Cl8H32O1, + C12H2201, + H2O. Dextrin- Maltose. residue 111. C18H32016 + H2° = C12H22011 + C6H120,' Isomaltose. Pextrose.C,,H2,011 + H20 = 2C6HI2O6. Dextrose. 9. Diastatic decomposition of those products of carbinol-hydrolysis of starch which contain many amylogen molecules yields a large number of dextrinous compounds, of which those containing the dextrin-residues I, 11, and 111 are typical. The author uses the name dextrin for all products of starch hydro- lysis excepting sugars, and indicates as amylodextrins those which proceed from starch by carbinol-hydro1 ysis, and are therefore in- different towards Fehling's solution, and develop the familiar starch blue with a solution of iodine in potassium iodide ; the residual dex- trin produced from arnylodextrin by eliminating all the maltose is called '' Grenzdextrin." Dextrins between the latter and amylo- dextrins are called maltodextrins, and those derived from (' Grenx- dextrin " by withdrawing dextrose residues are called glucodextrins. M.0. F. Preparation of Starch Solutions and Separation of Starch Granules froin such Solutions. By HERMANN RODEWALD and A. KATTEIN (Chern. Centr., 1899, ii, 419 ; from Sitzungsbes*. Akad. FViss. Berlin, 24, 628--630).--When a solution of iodine in potassium iodideSO AESTRACTS OF CHEMICAL PAPERS. is poured over potato, wheat, or rice starch and the mixture (which should contain 15 parts of iodine and 200-300 of water for every 100 of starch) heated for 15 minutes a t 130°, a greenish-brown liquid is formed which consists mainly of excess of iodine solution with very small quantities of starch iodide and some sugar. The starch iodide grains, when examined under the microscope, appear to have been changed, and are soluble in water.The starch iodide may be separated by dialysing, and the blue solution so obtained forms a clear fi1- trate. This solution contains about 2 per cent. of the iodide and an amount of iodine corresponding with 14.3-14.85 per cent. of iodine in the iodide. When the solution is evaporated over a naked flame, the starch iodide separates and iodine is liberated ; the latter may be removed by treatment with steam, and a clear or very slightly turbid solution of starch is then obtained. When the solution is slowly cooled, a white precipitate is formed, and this, when examined under the microscope, appears t o consist of almost spherical starch granules. A similar precipitate is formed by all varieties of starch.The filtrate contains starch and gives an intense blue coloration with iodine; the blue compound may be separated by adding potassium iodide, The starch granules which separate from the solution also give a blue coloration with iodine, and after drying are insoluble in cold water, and are only gelatinised with difficulty by boiling ma ter. Potass- ium hydroxide also reduces the granules to paste. E. W. W. Saccharification of Starch, By HENRI POTTEVIN (Ann. de Z’lnst. Pasteur, 13, 1899, 665-688).-The dextrins obtained from starch by the action of amylase may be divided into three groups. (1) Achroo- dextrins, (2) amylodextrins, and (3) erythrodextrins. With the first, starch produces no coloration, but with the second, a blue, and with the third a red coloration is obbained.No red coloration is produced when starch is added to a mixture of achroodextrin and amylodextrin, so that Solomon’s statement that erythrodextrins do not exist, but are mixtures of achroodextrins and amylodextrins is erroneous. Musculus’ statement that amylodextrins in concentrated solutions give a blue coloration with starch and a red coloration in dilute solutions is also erroneous, because, whatever the dilution, a blue colour is always produced. Amylodextrin itself is not a single substance, for by careful precipitation with alcohol two dextrins have been obtained from it. The first, a-amylodextrin, gives opalescent solutions, which on warming become somewhat viscous, but on cooling again become opalescent. Its blue compound with iodine is readily precipitated by a 1 per cent.solution of sodium chloride. The second, or /3-amylodextrin, gives solutions which are viscous in the cold, and i t s compound with iodine is not precipitated by even a 20 per cent. solution of sodium chloride. The formation of dextrin from starch by the action of amylase is quite independent and distinct from the formation of maltose from the dextrin, for a solution may be prepared in which the formation of dextrin is still going on whilst that of maltose has completely stopped. When amylase acts on starch, the rate of saccharification rapidlyORGANIC CHEMISTRY 81 decreases. This is due to the fact that the starch granules are not all of the same size, the larger ones being readily attacked by amylase, whereas the smaller are only attacked with difficulty. H.R. LE S. Maltodextrin. By H.ENRI POTTEVIN (Ann. de I'lnst. Pastew, 1899, 13, 728-734).-The method of fermentation adopted by Brown and Morris to show that maltodextrin is not fermentable with yeast, is here objected to, since no precautions were taken to render the fer- menting liquid aseptic, or to prevent the subsequent introduction of microbes during the fermentation. Using carefully sterilised and aseptic solutions, the author confirms the statement of Brown and Morris that maltodextrin is not fermentable, but points out that this is no evidence that maltodextrin is not a mixture, because a mixture can be made of pure maltose and a suitable dextrin, which, like malto- dextrin, is not fermentable with yeast.Dextrins soluble in 70 per cent. alcohol retard the fermentation of maltose much more than those which are soluble in more dilute alcohol solutions. By careful frac- tional precipitation of a solution of maltodextrin by means of alcoholic solutions of varying strengths, precipitates of different composition are obtained, those obtained by precipitation with 58 per cent. alcohol consisting of 20 per cent. of maltose and 80 per cent. of dextrin, whereas with 94 per cent. alcohol the precipitate contains 70 per cent. of maltose and 30 per cent. of dextrin. A mixture of pure maltose and a dextrin (soluble in 70 per cent. alcohol) dialyses in exactly the same way as a solution of maltodextrin. The mere fact that maltodextrin dialyses as a whole is therefore no proof that i t is a single substance.Those dextrins soluble in dilute alcohol dialyse more quickly than Preparation and Estimation of Glycogen. By ARMAND GAUTIER (Compt. rend., 1899, 129, 701 -705).-The process described, which serves for both the preparation and estimation of glycogen, is based on the fact that the nitrogenous substances with which glycogen is associated are completely precipitated by mercuric acetate in neutral solution. The well-bruised liver, muscle, or other material is thoroughly extracted with boiling water (addition of acid or alkali serves no useful purpose) and the liquid concentrated by evaporation, mixed with a little potassium acetate and a slight excess of mercuric acetate, filtered, and poured into an equal volume of 85 per cent. alcohol.The precipitated glycogen is purified by repeated solution in water and reprecipitation with alcohol, washed with a mixture of alcohol and ether, and finally dried a t 110-120°. Glycogen is thus obtained as a perfectly homogeneous substance having the composi- tion (C6Hlo05)n, It is not truly soluble in water, since it is more or less completely separated from the liquid by filtration. I n the presence of a trace of salts, it is wholly insoluble in 36 per cent. alcohol. Glycogen is not hydrolysed by heating a t looo with 3 per cent. potassium hydroxide solution or with 5 per cent. acetic acid, but when heated with 5-6 per cent. mineral acid a t 115-120", it is converted into a mixture of sugars having a reducing power slightly those which are only soluble in strong alcohol.H. R. L E S.82 ARSTRACTS OF CHEMICAL PAPERS. greater than that of dextrose. Glycogen from t h e human liver yields products having a notably higher reducing power than those obtained from rabbit’s liver, and from this and other considerations i t is concluded that different varieties of glycogen are contained in the different organs of the same animal and also in the same organs of different animals. N. L. Composition of the Gum of Grevillea Robusta. By REBER and PUAUX (J. Pharm., 1899, [vi], 10, 398--400).-The fresh gum is soft, and of a whitish colour, but on keeping it becomes hard, and of a yellowish, and often of a reddish, colour. It is odourless and pos- sesses a n astringent taste, It entirely dissolves in water, from which it is precipitated by 95 per cent.alcohol, and by basic lead acetate, after the addition of ammonia, until slightly alkaline. Its aqueous solution reduces Fehling’s solution, and when warmed with ferric chloride, its colour deepens, but no precipitate is produced. When the gum is treated with mineral acids, galact,ose and arabinose are pro- duced. A complete analysis of the gum is given. H. R. LE s. Nitroacetone. By AD. LUCAS (Bey., 1899, 32, 3179-3182. Compare Abstr., 1899, i, 401 and 433).-When silver nitrite is agitated for 24 hours with a dilute ethereal solution of iodoacetone, the nitroacetone produced remains insoluble, whilst the impurities dissolve ; the nitroacetone, separated and dissolved in a larger quantity of ether, crystallises from the concentrated solution in well defined plates, melts at 49O, is soluble in water and alcohol, and crystallises from benzene in needles.Cry oscopic determinations of its molecular weight show that this corresponds with the simple formula C,H,?,N. When dissolved in water, it reacts as a monobasic acid, and determina- tions of its electrical conductivity indicate that its strength is half that of acetic acid, the value of K for nitroacetone being 0.001026. Aminoacetone (Abstr., 1 S93,734) is obtained by reducing nitroacetone, and this result indicates t h a t the latter is a nitro-compound and not a nitrite. In aqueous solutions, both nitroacetophenone and nitroacetone behave like isonitroso-derivatives (Hantzsch and Veit, Abstr., 1899, i, 401), but the latter substauce does not appear to have any close con- nection with the compound described as a nitroacetone by Henry (Abstr., 1899, i, 475).When treated with phenylhydrazine, nitro- acetone yields a n oily phenyllkydyuxone. G. T. M. y-Amino-PP-dimethylbutane. By WASSILY SOLONINA (Chem. Centr., 1899, ii, 474; from J. Russ. CJzem. Xoc., 1899, 31, 541-542). --y-Aniino-~,&dimetJ~yZbutc~,ne, prepared by reducing a boiling alcoholic solution of pinacoline oxime, CMe,*CMe:NOH, with sodium, is a mobile liquid, has the odour of ammonia, boils at 103-104°, and is very slightly soluble in water. At - 20°, it forms a crystalline mass. The hydrochloride forms long needles, and the plutinichloride is prys- talline ; the aurichloride cryst’allises from dilute alcohol in long, pale yellow needles, and melts at 1 7 8 O .By the action of benzenesulphonic chloride on aminodimethylbutane dissolved in ether, the compound C,N,,*NH+3O2l’h is formed which cryst:tllises from aqueous alcoholORGANIC CHEMISTRY. 83 in thick plates, melts a t 96.5", and is insoluble in water, but easily SO in alcohol, ether, or benzene. By THOMAS CLARKE (J. Amey. Chem. Soc., 1899, 21, 1027-1031. Compare Cahours and Pelouse, Jahwsber., 1863,528 ; Schorlemmer, AnnaZen, 1863, 12'7, 318)-When P-heptyl bromide (Abstr., 1881, 82) is heated: with an excess of alcoholic ammonia a t 1 00", the products are primary P-heptylamine hydrobromide, heptylene, and ammonium bromide. The hydrobyomide, CH3*[CH,j4*CHMe*NH,HBr, crystallises from a mixture of benzene and light petroleum in slender, silky needles melting a t 163', and dissolves readily in alcohol, water, or benzene, and also in large quantities of dry ether.The amine is a slightly brown liquid boiling at 142-144' under atmospheric pressure, and of sp. gr. 0.7667 a t 24O/24". It dissolves readily in alcohol, ether, or light petroleum, is extremely hygroscopic, and has strongly alkaline properties, The Icydrocldoride crystallises in colourless, silky, somewhat deliquescent needles melting at 133' ; the pZatinichZoi*ide crystallises from warm water in large, *yellow plates decomposing a t 195" ; the ccurichlos-ide also crystallises in large, yellow plates melting a t 63-64', and the oxdate, (C7H,7N)2,H,C,04, in colourless plates which melt and decompose a t 204--205", and also decompose when boiled with water.Behaviour of Diamines on Neutralisation. By MARCELLIN P. E. BERTHELOT (Compt. rend., l899,129,694--70O).-The differences observed i n the heats of neutralisation for successive equivalents of acid afford a method of distinguishing betwoen monoacid and polyacid bases, and of fixing their molecular weight. The same end is more quickly attained by titrating the base with standard acid and ob- serving the behaviour of different indicators ; ethylenediamine and diethylenediamine are thus shown to be monoacid towards phenol- phthalein, and diacid towards methyl-orange. Both these bases may be estimated alkalimetricdly with considerable accuracy, but the end points are not so delicate with diethylenediamine as with ethylene- diamine, a fact which is in harmony with the lower heat of neutral- isation of the former base.Diarnines. Diethylenediarnine (Piperazine). By MARCELLIN P. E. BERTHELOT (Compt. rend., 1899, 129, 687-694).-Diethylene- diamine hydrate, C,Hl0K2 + 6H20, melts at 44' ; when distilled, a mixure of water and diethylenediamine passes over, the proportion of the latter gradually increasing as the temperature rises until, above 135O, the anhydrous base is obtained. This is a crystslline, tenacious, waxy substance which melts at 104" and dissolves very slowly in water, but is nevertheless very hygroscopic. The heat of dissolution of the base is +5.16 Cal. at 14', and of the hydrate - 9.15 Cal. a t 16'. The heat of hydration is therefore +14.31 Cal. (liquid water) or 4.9 Cal. (solid water). No evidence was found for the existence of more than one hydrate.The heat of combustion of diethylenediamine hydrate is 69 1.14 Cal. a t constant volume, and 691.3 Cul. at constant pressure. The heat of formation of the base E. W. W. P-Heptylamine. J. J. S. N. L.84 ABSTRACTS OF CHEMICAL PSPERS. from its elements is 16.6 CaI., and its heat of combustion is calculated as 705.6 Cal. Comparison of the heat of formation of diethylenediamine with that of ethylenediamine (8.8 Gal.) shows t h a t the conversion of the latter compound into the former, by the fixation of a C2H2 group, is accom- panied by the development of + 7.8 Cal., whereas this transformation, instances of which are cited, is always accompanied by the absorption of heat when the general function of the compound remains un- altered.These facts are in harmony with the view that diethylene- diamine is a cyclic compound. The heat of neutralisation of diethylenediamine is 10.36 Cal. for the first, and 7.05 Cd. for the second, equivalent of hydrochloric acid, all the substances being in solution ; diethylenediamine is therefore a weaker base than ethylenediamine, the corresponding figures for which are 12.52 and 11.0 respectively. The heat of dissolution of the hydrated dihydrochloride, C,H,oN2,2HC1 + H,O, is + 6.0 Cal., and of the anhy- drous salt, - 4.09 Cal. ; the heat of hydration is therefore + 1.91 Gal. (liquid water) and +0.3 Cal. (solid water). The heat of formation of the solid anhydrous dihydrochloride from the solid base and the gaseous acid is + 61.4 Cal. I n the activity of i t s basic function, diethylene- diarnine is inferior t o ammonia, ethylamine, and methylamine, but superior t o aniline.N. L. Amic Acids and Irnides of Aliphatic Dicarboxylic Acids. By KARL AUWERS [FRITZ MAYER, and F. SCHLEICHER] (Annoden, 1899, 309, 31 6-347).-The author’s method for identifying di- Larboxylic acids of the aliphatic series (Abstr., 1895, i, 504) meets with certain difficulties (compare Abstr., 1896, i, 639, and 1898, i, 126) which are discussed in the present paper, particularly with regard t o the struetarally isomeric amic acids of monoalkylsuccinic acids, CO,H*CHR*CH,-CONHR and CONHR*CHR*CH,*CO,H, of as-dialkylsuccinic acids, and t o those s-dialkylsuccinic acids which occur in two stereoisomeric forms. It is found that the imides obtained from the structurally isomeric amic acids of monoalkyl- succinic acids by heating them alone, or with acetyl chloride, are identical, and the same remark applies to the amic acids of ns-di- alkylsuccinic acids ; when the imides are hydrolysed with alkali, the amic acids produced are either the original ones, their structural isomerides, or mixtures of the two.The following facts in con- nection with s-dialkylsuccinic acids have been ascertained : 1. The fumaroid acid is converted into the fumaroid imide by heating it with a base during a short period, or by heating the fumaroid anilic acid above its melting point ; this does not apply to the anil, tolil, and P-naphthil of fumaroid diethylsuccinic acid, because these imides are very labile, and thus become converted into the corresponding maleoid derivatives.2. Hot acetyl chloride converts the fumaroid anilic acids into the maleoid compounds. 3. Boiling dilute acids con- vert the fumaroid and maleoid imides into the corresponding fumaroid and maleoid dicarboxylic acids, with a small proportion of the stereo- isomeric modifications. 4. Boiling, dilute, aqueous alkalis resolve the nnils into t h e corresponding anilic acids. The p-tolil of maleoidOKCIANIC CHEMISTRY. 85 dimethylsuccinic acid yields the maleoid p-tolilic acid with aqueous caustic soda, and t h e fumaroid p-tolilic acid witb baryta. 5. Alcoholic soda and potash also convert imides into amic acids, but at the same time change t h e fumaroid compound into the maleoid, the converse taking place to only a slight extent; in some cases, however, the rearrangement does not occur.6. On the other hand, hot, concen- trated aqueous alkalis invariably convert the maleoid amic acids into the fumaric modification ; this action is nut reversible. The following melting points a r e recorded : Methylsuccinic acid ptolilic acid, 164', p-tolil, 109-1 lo", P-naphthilic acid, 154*5", P-uaphthil, 160.5'. Isopropylsuccinic acid anilic acid, 143O, and, 9 1-92', p-tolilic acid, 143-144', p-tolil, 139-140', P-naphthilic acid, 198", P-naphthil, 132-1 32.5'. as-Dimethylsuccinic acid anilic acid, 84-86", p-tolil, 1 I 3'. Fuma.roid s-dimethylsuccinic acid p-tolilic wid, 194', p-tolil, 120-121", P-naphthilic acid, 209" ; maleoid s-dimethylsuccinic acid p-tolilic acid, 164", p-tolil, 153', P-naphthilic acid, 140°, P-naphthil, 220".Fumaroid s-methylethylsuccinic acid snilic acid, 164-165', anil, 76-77", p-tolilic acid, 175', p-tolil, 87-88*5', P-naphthilic acid, 191-192", P-naphthil, 148-150" ; inaleoid s-methylethylsuccinic acid anilic acids, 1 39-140', and 100-102°, anil, 103-1043,p-tolilic acid, 147-1 48', p-tolil 109--110', P-naphthil 159-160". Fumaroid s-diethylsuccinic acid anilic acid, 183-184', p-tolilic acid, 189-190', P-naphthilic acid, 202--203', maleoid s-diethylsuccinic acid anilic acid, 124-1 25', anil, 84-85", p-tolilic acid, 148- 149', p-tolil, 92-93', P-naphthilic acid, 145-146", P-naphthil, 118-1 19'. d-Camphornnilic acid, 203--1"04', d-cam- ptioranil, 117-1 18' ; I-iso-camphoranilic acid, 183-183.5'. Succinic acid p-tolilic acid, 1 79-1803, p-tolylsmide, 207' (compare Auwera and YHBr-CO Harger, Abstr., 1896, i, 640) ; dibromosuccinanil, CHBr.CO >NPh, prepared from bromine and the anil of maleic acid, 171" (compare Auwers and &nghof, Abstr., 1896, i, 644), chlorosuccinanil, - YH2-C0 CHCl*CO >NPlr, 1 17-1 1 So.1%. 0. F. Methyleneasparagine and Allied Compounds. By HUGO SCHIFF (G'ccxaettcc, 1899, 29, ii, 285-303. Compare Abstr., 1899, i, 870).-When exposed t o the air, dimethyleneasparagine gives up formaldehjde, the residual substance having a composition correspond- ing to a se,squinzet~~~yleneas~~aragi~e, CH,(C,H,0,N,:CH2)2 ; its copper compound has the composition C,,H,,O,N,Cu + H,O. Methyleneasparagine acts as a monobasic acid ; at 14', it dissolves in water t o the extent of 2.38 per cent., but i t is scarcely soluble in alcohol.On allowing its solution in alcoholic hydrochloric acid t o evaporate over sulphuric acid, i t deposits colourless needles of the hydrochloride of rnonoethyl aspartate. I n aqueous solution, [a], has a mean value - 47.58" ; a solution containing methyleneasparagine and potassium hydroxide in molecular proportion gives for potassium methyleneasparaginate [a], - 69.01'. The presence of a large quantity of water hinders the formaticn of methyleneasparagine ;86 ABSTRACTS OF CHFKMICAL PAPEIIS. on diluting a solution of methyleneasparagine, however, it is not decomposed. A solution of a-asparagine required for neutralisation 0.63 mol. of potash per mol. of the asparagine, whilst after adding formaldehyde the quantity of potash necessary mas increased t o 0.95 mol.The author prefers Piutti’s formula, NH,*CO*CH2*CMe(NH2)*C02H, for homoasparagine, since it resembles /3-asparagine in having a feeble acid reaction and in giving an azure-violet biuret reaction. Metl~yZenel~on~oc~s~~~~~g~ne,NH2*CO~CH2~CMe(*N:CH2)~CO2H + H20, is a colourless, crystalline compound which dissolves readily in water, but only slightly in alcohol, and does not give the biuret reaction. It behaves as a monobasic acid and forms a copper compound, Methyl-a-ssparagine gives a reddish-violet biuret reaction, but if formaldehyde is present, no coloration is obtained; it acts as a monobasic acid. Dimethyl-a-asparagine, however, has much feebler acid properties ; a concentrated solution neutralises 0.2 mol.of potash per mol. The addition of formaldehyde makes the solution strongly acid again, so that a further 0.6 mol. of potash is required for neutral- isation; in the course of an hour, further addition of 0.2 mol. of potash is necessary, the total amount of potash added being 1 mol. for each mol. of the dimethylasparagine. A solution of 1 mol. of di- methylasparagine in 1320 mols. .of water, is, however, neutral, but on adding formaldehyde neutralises a t once 0.6 mol. of potash, and in the course of the day the remaining 0.4 mol. must be added to keep the solution neutral. I n concentrated aqueous solution, 1 mol. of glutamine neutralises @l to 0.15 mol. of potash ; on adding formaldehyde, methyleneglutamine is formed, and acts as a monobasic acid, neutralising a molecular propor- tion of potash. Methyleneglutamine is a colourless, crystalline mass which dissolves readily in water and decomposes carbonates ; with copper hydroxide, it forms a dark azure-blue compound apparently very soluble in water.(C,H903N,),Cu. T. H. P. Nitrosoalkylurethanes. By ARTHUR HANTZSCR (Ber., 189 9, 32, 314S-3149).-A reply to Briihl (Abstr., 1899, i, 871). T. M. L. Constitution of Inorganic Compounds. XX. Thiocyanocobalt Salts and Structural Isomerides. By ALFRED WERNER, HERBERT MULLER, R. KLIEN, and F. BRAUNLICH (Zeit. unorg. Chem., 1899, 22, 91 --157).-lsothiocyanopentunamine salts, [Co(NH,),NCS] X,, are ob- tained by the action of potassium thiocyanate on concentrated hot solutions of aquopentammine salts, the slilphate being most advan- tageously employed ; blackish-green additive products of thiocyanic acid and the isothiocyano-salt are formed, but are decomposed on addition of water.The thiocyano-group in these compounds is not dissociated even in dilute aqueous solution, and the characteristic reaction with ferric chloride does not take place. The thiocyano-group is also un- altered by the action of mineral acids, whereby the other acid groups undergo substitution. With silver nitrate, additive compounds of the formula Co(NH,),(N03),SCNAg are formed, which, when treated withORGANIC CHEMISTRY. 87 hydrochloric acid, do not give a precipitate of silver chloride, but are converted into the corresponding chloride of the formula Co( NH3)SCl,SCNAg. IsothiocpanopentamminecobaZt sulphate, [Co(NH,),NCS]SO, + 2H,O, crystallises in four-sided, thin, yellow plates, and is conGerted into the hexammin e chloride when oxidised with chlorine.The nitrate, chloride, bromide, iodide, platinichloride, platinosochloride, thiocyanate, and nityite, obtained by treating the sulphate with the corresponding acids, are also described. Nitritotl~iocyccnotet~~am~inesalts, [CON O,(NH,),SCN]X .-The cldop-ide is obtained by the action of potassium thiocyanate on a hot solution of chloronitritotetramminecobalt chloride and subsequent treatment with hydrochloric acid. The thiocyano-group in these compounds is not so firmly combined as in the preceding series, and is gradually completely dissociated in dilute solution ; with silver nitrate, similar additive products of the formula [CoN0,(NH3),SCNAg]C1N03 are oh- tained, which, however, when boiled with water, are decomposed into silver chloride and nitritothiocyanotetramminecobalt nitrate ; when shaken with silver oxide, the corresponding base is not obtained, but decomposition takes place with the formation of silver chloride and thiocyanate and the base of the nitritoaquotetrammine series. Nitp.itothiocyanotetramminecobaZt c?doyide crystallises in lustrous leaflets when precipitated from aqueous solution by hydrochloric acid, and in needles and tabular prisms from neutral aqueoiis solution, is soluble in 33 parts of water, and when oxidised with chlorine yields chloronitritotetrammine chloride. The bromide, iodide, thiocyccnate, and nitrate are a h described.Dithiocya.nodiethylenediami~ecobccZt sults, [Co(C2H,N,),(SCN),]X.- By the action of potassium thiocyanate on dichlorodiethylenediamine- cobalt chloride and subsequent evaporation with hydrochloric acid, the chlorides of two isomeric dithiocyanodiethylenedjaminecobalt salts are obtained.This isomerism is determined by the isomerism of the dichlorodiethylenediamine salts, since the 1 : 2-dichlorodiethylene- diamine salts (violeo-salts) yield only one dithiocyano-series, the easily soluble salts containing iso-thiocyano-groups, whereas 1 : 6-di- chlorodietbylenediamine salts (praseo-series) yield both series of salts and more of the sparingly soluble series, containing thiocyano-groups, as the concentration of the solution to which the potassium thiocyanate is added increases. The easily soluble dithiocyanochloride, when oxidised with chlorine, is converted into diamminediethylenediamine- cobalt chloride, that is, the nitrogen atom of the thiocyano-group in direct combination with the cobalt atom is converted into ammonia.The sparingly soluble isomeric chloride, however, when oxidised with chlorine, yields dichlorodiethylenediaminecobalt chloride, in which the thiocyano-group is completely oxidised. As regards the thiocyano- groups, the isomerism is evidently similar to that between the thio- carbimides and the thiocyano-est ers. DiisothiocyanodiethyZenediamine- cobalt chloride crystallises, with 1H,O, in thin, triclinic, ruby-red tablets of rhomboidal habit, and, with l&H,O, i n thick, rhomboidal t'ablets which appear black in reflected light, 1s easily soluble in cold water,88 ABSTRACTS OF CHEMICAL PAPERS. yielding a bright ruby-red solution.The thiocyanate, hydjsogen sulphate, nityate, bromide, and iodide are also described. A normal sulphate cannot be prepared, and this forms a marked distinction between this series and the sparingly solitble series from which only the normal sulphate is obtained. Dithiocy~nodiethylened~u~in~cobult chloride crystallises, with 1H20, in thin, yellowish-red needles or prisms hrtving a bronze lustre, and in 5at, rhomboidal prisms which appear almost black in reflected light, is practically insoluble in cold water, fairly soluble in hot water, and gives a yellowish-red solution. The thiocyanate, sulphate, nitrute, bromide, and iodide are also described.Diumminediethylenediam~necobcclt chloride, [CO( NH,),( C,H,~,),]Cl, + H,O, obtained by oxidising the above diisothiocyanochlorlde with chlorine, cry stallises in triclinic, many-sided tablets, and in four-sided, yellow pyramids. The aqueous solution is completely precipitated by alcohol, and gives the typical luteo-salt reactions. With cobaltous chloride, similarly to the triethylenediaminecobnlt chloride, it yields a double salt which crystallises, with 2H20, in thin, four-sided plates. The thiocyano-group is generally combined in the normal manner. I n the four series of compounds, thiocyanopentammine salts, nitrothio- cyanotetrammine salts, chlorothiocyanodiethylenediamine salts, and oxalothiocyanotriammine salts, only the first series are derivatives of isocyanic acid, since, when oxidised with chlorine, they yield hexammine salts.The remaining salts, when oxidised with chlorine, yield respectively chloronitritotetrammine salts, trichlorodiethylenediamine salts, and oxaloaquotriammine salts. Further, the thiocyano- residues in Reinecke’s salt, Cr(NH,),(SCN)4K, and in potassium platinithiocyanate, are completely oxidised and eliminated by chlorine. The conversion of isothiocyano-group into the ammonia group which remains in direct combination with the cobalt atom, shows that the ammonia molecules in the complex radicle are combined with the metal atom in the same manner as acid groups which are in direct combination with the metal atom. The direct substitution of ammonia by acid groups and the converse substitution cannot be effected, as a rule, in the cobaltammonia compounds.When, how- ever, chloroarnminediethylenediaminecobalt chloride is treated with potassium thiocyanate, the ammonia group is replaced by the thio- cyano-group, and chlorothiocyanodiethylenediaminecobalt thiocyanate is formed. Dichloi~ocliethylenediuminecobalt thiocyccnate, [Co(C,N,H,)CI,]CNS, obtained by adding potassium thiocyanate to an aqueous solution of the diethylenediaminepraseo-chloride, crystallises in small, lustrous, green, six-sided prisms. Cl~lorot~iocyanodietl~ylenediuminecobcclt thiocyanate, [CO( C,N,H,)Cl*SCN]SCN, obtained by boiling dichlorodiethylenediaminecobalt chloride with potassium thiocyanate, is a brownish-violet, crystalline powder which, when heated with water, decomposes into the isomeric dithio- cyanochlorides, and when evaporated with hydrochloric acid yields the salt [ Co( C,N,H,)ClSCN 3 C1.E. C. R.Organo-mercuric Compounds. By GEORGES DENIC~S ( A m . Chirn. Plqs., 1899, [ vii], 18, 382-432. Compare Abstr., 1895, i, 411 ; 1898, i, 546, 549, 618; 1899, i, 22, 414, ii, 256).-Citric acid, even when in dilute solution, is readily oxidised by potassium permanganate t o acetonedicarboxylic acid ; the latter combines readily with mercuric sulphate, forming an insoluble compound (Abstr., 1899, ii, 454); this reaction may be utilised in detecting small quantities of the former acid in the juices of plants, wines, milk, &c. Glycerol, gum, dextrose, sucrose, and acetic, tartaric, malic, succinic, and lactic acids do not interfere with the reaction, but oxalic acid must be removed either by a preliminary oxidation with excess of permanganate or by precipitation as mercuric oxalate.G. T. M. Tungsten Alkyls. By EDGAR F. SMITH, E. A. BARNETT, and CLARENCE HALL (J. A,mer. Chem. Xoc., 1899, 21, 1013--1016).-1t has not been found possible to obtain the compound, WMe,T, described by Riche (Compt. rend., 1856, 42, 303) and by Cahours (Annalen, 1862, 122, 70) ; the authors obtained a black substance, containing over 94 per cent. of tungsten, together with small quantities of carbon and iodine. No tungsten alkyl i s obtained when tungsten hexa- chloride is treated with mercuric ethyl or zinc methyl, nor yet by the action of methyl iodide on tungsten prepared by varioixs methods. J.J. S. Cyclic Compounds, Ethylhexanaphthene and Mercuro- heptanaphthene Iodide. By N. KURSANOFF (Chenz. Centr., 1899, ii, 477; from J. Buss. Chem Soc., 1899, 31, 534--535).-By the action of zinc ethyl on chloro- or iodo-naphthene, about 30 per cent. of ethylnaphthene is obtained ; i t boils a t 132-133' and has a sp. gr. 0.7913 a t O"/O' and 0.7772 at 2Oo/O0. A vapour density determina- tion gave 4.04. Naphthylene (cyclohexene), ethylene, ethane, and saturated condensation products boiling a t 242-243' under 755 mm. pressure are also formed. '< Mercixro-heptanaphthene iodide," C6H,,HgI, prepared. by the action of sodium amalgam on iodohexamethylene, crystallises from hot alcohol in lustrous, white scales, melts a t 142', and is decomposed by prolonged heating with liberation of mercuric iodide.Derivatives of Nitroic Acids. Reactions of Nitro-com- pounds. By ARTHUR HANTZSCH and HERMANN KISSEL (Bey., 1899, 32, 3137-3148. Compare Abstr., 1899, i, 404).-The names ' nitroic acid ' and ' nitroic ester-acid ' are given t o the acids R*NO(OH), and R*NO(OR')*OH, formed by the addition of water and alcohols t o cer- tain nitro-compounds. Trinitrotoluene potnssiuna met?Loxide (potassium nrethgl dirzit~otoluene- nitroute), C,H,Me(NO,),*NO(OMe)*OK + H,O, is a dark violet salt, which explodes when heated; pG4 96.0 and plOz4 113.0, at 25', showing that the salt is hydrolysed t o a considerable extent. The ester-acid, hydrogen methyl dinitrotoluenenitroate, is a dark red sub- stance which dissolves only slightly in water or in organic solvents, except acetic acid, in which i t has a normal molecular weight ; it is st E.W. W. VOL. LXXVIII. i. h90 ABSTRACTS OF CHEMICAL PAPERS. feebke acid, plaza 15 at 25O, and is stable in aqueous solution, but evolves nitrous acid when boiled with dilute acids, and gives trinitro- toluene and methyl alcohol when dissolved in concentrated sulphuric acid ; i t is not attacked by phosphorus pentachloride, and crystallises unchanged from acetic acid, but acetyl chloride converts it into acetyl methyl diniti-otoluenenitroccte, a microcrystalline substance which ex- plodes o n gentle warming, and is hydrolysed by alkalis. Potassium methyl dinitrobenzenenitroate (trinitrobenzene potassium methoxide) and potassium methyl dinitroxylenenitroccte (trinitroxylene potassium methoxide) are immediately decolorised by acids, and do not give nitroic ester-acids.CGH,!N02)3*C02K,MeOK,MeOH, gives an unstable n.ztTozc ester-acid, from which trinitrobenzoic acid is regenerated on evaporating the solution. p-Xitrobenzylnitramine (Hantzsch and Hilland, Ber., 31, 2068) interacts with 2 mols. sodium ethoxide to form the sodium ethyl nitroate, N,O,Na*CH,* C6H;NO(OEt)*ONa, a deep-red, soluble salt which de- composes in moist air, cannot be recrystallised, and sometimes inflames spontaneously in the desiccator. The ester-acid is also extremely unstable, and changes quickly into a yellow resin, from which p-nitro- benzoic acid was obtained. Sodium trinitrobenzoate combines, at least partially, in solution with another molecule OF sodium hydroxide t o form a sodium nitroate, which could not be isolated, but was shown to be present by the con- ductivity and colour of the solution.Barium dinitrobenxonitroate, [ Ba<~>NO.C,H,(NO,),* CO, Ba, prepared by the action of barium hydroxide on trinitrobenzoic acid, is a dark, brownish-red salt, very slightly soluble in water, and very explosive ; the nitroic acid is un- stable. Trinitrobenzene and trinitrotoluene dissolve in caustic alkalis, giving deep red solutions, but the formation of nitroates appears t o be only very partial; on acidifying the alkaline solutions at Oo, red solutions are obtained which appear to contain the nitroic acids, but these are unstable at the ordinary temperature. Hepp's trinitrobenzene potassium cyanide (Anncclen, 1 SS3,215, 360), t o which the formula C,H,(NO,),*NO(CN)*OK is assigned, is a deep- violet, crystalline, explosive salt ; dinitrobenxeqzecyanonitroic acid (trinitrobenxene cynnhydrin), which is precipitated by mineral acids from a solution of the potassium salt, crystallises from ether or benzene in red needles, and decomposes at 175O; it is not acted on by phos- phorus pentachloride or acetyl chloride.The characteristic reactions of the nitro-paraffins are shown t o be really those of the isonitro-compounds. Nitroethane is scarcely attacked by bromine in aqueous solution, but a solution of isonitro- ethane, freshly prepared at 0' by the action of hydrochloric acid on the sodium salt, brominates completely and smoothly. A solution of nitro- ethane gives no nitrolic acid with nitrous acid, but isonitroethane- interacts readily with it.Isonitroethane and diazonium hydroxide interact immediately at Oo, whilst t r u e nitroethane is inactive ; simi- larly, phenylisonitromethane interacts readily with diazonium hydroxide and isonitroethane with p-bromodiazonium hydroxide, The conclu- Lobrg de Bruyn's salt, 1 2O#GANIC CHEMISTRY. 9 1 sion is drawn that the true nitro-compounds are, of themselves, no more active than the corresponding halogen compounds, and owe their apparent chemical activity entirely to the formation of the labile isonitro-compounds, and not to the negative character of the -NO2 group. T. M. L. Transformation of Styrene into Metastyrene under the Influence of Light, By GEORGES LEMOINE (Compt. rend., 1899,129, 719-722.Compare Abstr., 1898, i, 70).-The polymerisstion of styrene is effected by the action of heat in the dark, and also under the influence of sunlight a t the ordinary temperature ; in the latter case, the action is slower, 1-3 per cent. of the substance being trans- formed in an hour. In this change, the blue and ultra-violet rays are principally concerned ; their activity does not extend much below 5t depth of 4 mm., and is greatly decreased by cooling the insolated liquid; the action does not continue after removal from the influence of light, or only to a very small extent. The velocity of transforma- tion in the light is approximately equal t o that observed in the dark at a temperature 50" higher. The general conclusion arrived a t is that, in the conversion of styrene into metastyrene, light exerts an accelerating action on an exothermic transformation which takes place in the dark at the same temperature, although more slowly.N. L. Naphthalene-1 : 3 : 5-trisulphonic Acid. By HUGO ERDMANN (Bey., 1899, 32, 3186-3191. Compare Armstrong and Wynne, Proc,, 1887, 146, and 1893, 166).-Polysulphonic acids containing two or three sulphonic groups in P-positions are obtained when naphthalene is sulphoiiated with fuming sulphuric acid at high temperatures ; of these, the 1 : 3 : 6-trisulphonic acid, recognised by its sodium and lead salts and its chloride, is the chief product (Proc., 1587, 146). Naphthalene-1 : 3 : 5-trisulphonic acid, the original product of sulphon- ation, is only obtained when the whole of the reaction is carried out below 90".Sodium naphthalene-1 : 5-disulphonate is mixed with fum- ing sulphuric acid a t 50°, and the reaction completed a t 90'; the 1 : 3 :5-acid which is thus produced is separated in the form of its sodium salt; this compound is converted into the sulphonic chloride (m. p. 145-148'), which is then boiled with methyl alcohol, and the solution evaporated to dryness; in this way, the acid is obtained as a colourless syrup. Naphthalene-1 : 3 : 5-trisulphonic acid resembles the non-volatile mineral acids ; it is very hygroscopic, destroys cellulose with liberation of carbon, and decomposes sodium chloride. The aniline salt, C,,H,(SO,H),,SNH,Ph, produced by adding aniline to an aqueous solution of the acid, or by double decomposition from aniline hydrochloride and sodium naphthalenetrisulphonate, crystaldises from water in aggregates of white, silky needles.The salt is not hygroscopic, and is readily soluble in water, but less so in brine solution. The p-toluidine salt is more soluble than the aniline compound ; the benzidine salt, 2Cl,H,(80,H),,3Cl,H,(NH,),, crystal- h 292 ABSTRAC2S OF CHEMICAL PAPERS, lises with 4H20, and the dianisidine salt separates slowly from its solution in glacial acetic acid in short, hard needles. G. T. M. Polymerisation of Inorganic Chloroanhydrides. 11. By GIUSEPPE ODDO (Gctxxetta, 1899, 29, ii, 330-343. Compare also this vol., ii, 74).-The products obtained on heating phosphorus penta- chloride and oxychloride, in a reflux apparatus, with varying quanti- ties of water are as follows : With 2PC1, + H,O, half of the penta- chloride is converted into oxychloride, the rest being unchanged ; 2PC1, + 2H20 yields the theoretical amount of oxychloride ; 2PC1, + 3H20 or (POCI,), + H,O gives mainly oxychloride accompanied by a little pyrophosphoryl chloride, P,O,Cl,, and phosphoric oxide ; with the proportions 2PC1, + 4H,O or (POCl,), + 2H,O, the same products as in the previous case are obtained, the amount of oxychloride being considerably diminished, and that of phosphoric oxide correspondingly increased.The interaction of phosphorus pentachloride (3 mols.) on phosphoric oxide (1 mol.), yields a little oxychloride and a considerable quantity of pyrophosphoryl chloride, and is recommended as a good method for preparing the latter.Potassium chlorate reacts with phosphorus oxychloride according to the equation (POCl,), + KC10, = P,O, + KC1 + 3c1,. This reaction offers a convenient method of chlorination where a definite quantity of chlorine is required. By heating together phosphorus oxychloride and aniline hydro- chloride in molecular proportions in a reflux apparatus, hydrogen chloride is evolved and dichlorophosphoxymonoanilide, NHPh*POCI,, obtained. The molecular weight of the latter in boiling benzene varies from 215 with a concentration 0.7944 to 276 when the concen- tration is 5,2183; using the same solvent, the numbers given by the cryoscopic method are 221 (concentration 0.9676) and 252 (concentra- tion 1.8323). The calculated value is 210. Michaelis and Schulze (Abstr., 1894, i, 128) state that this compound distils in a vacuum with partial decomposition; the author finds, however, that a t 90' evolution of hydrogen chloride commences, and at 180" continues until 1 mol.HC1 is lost per molecule of the substance, the residue being a new compound to be described later. Using three mols. of aniline hydrochloride to one of phosphorus oxychloride, two products are obtained. The first, monochlorophos- phoxydianilide, POCl(PhNH),, gives, in boiling alcohol, a molecular weight varying from 270 with a concentration of 1.3856 to 184 when the concentration is 3.6192 ; the molecular weight falls if t h e boiling be prolonged. These observations are at variance with those of Michaelis and Schulxe (Abstr., 1894, i, 588). The other product is oxyphosphoazobenzeneanilide, melting at 320--325O, and not at 357' as stated by Michaelis and Silberstein (Abstr., 1896, i, 344).I f six molecular proportions of a benzene solution of aniline be treated with one of phosphorus oxychloride, the trianilide of ortho- phosphoric acid, PO(PhNH),, is obtained ; its molecular weight in boiling alcohol is 358-359, the calculated value being 323.OItGANIC CHEMISTRY. 03 The action of phosphorus oxychloride on phenol yields the compound POCl,* OPh, which gives the normal molecular weight in boiling benzene, a little of the chloride POCl(OPh),, triphenyl phosphate, which in boiling benzene has the normal molecular weight, and a little diphenylphosphinic acid. Salicylanilinoacetic Acid [o-Carboxyphenylglycollic Acid Monanilide] and its Derivatives.By GEORG COHN (J. pr. Chem., 1899, [ ii], 60,404-406).-The monoanilide of o-curboxyphenglglycollic acid, NHPh*CO*C,H,* O*CH,* CO,H, prepared by the action of chloro- acetic acid on salicylaniline, separates from alcohol, in which it is readily soluble, in white needles melting at 159'. The corresponding phelzetidide crystallises from me thy1 alcohol, in which it is sparingly soluble, in rhombic leaflets melting a t The anisidine compound, OMe*C,H,* NH*CO*C,H,* O*CH,* CO,H, crystallises from methyl alcohol in bundles of long needles and melts indefinitely a t 174'. A. L. Diphenylamine Derivatives, especially Sulphonic Acids. By ROBERT GNEHM and H. WEBDEKBERG (Zeit. angew. Chern., 1899, 1027-1030, 1051-1055, and 1128. Compare Merz and Weith, this Journ., 1873, 74).-Sulphuric acid of 66" B6.does not react with diphenylamine in the cold, and even on warming a t 100-150" the chief sulphonation product is the disulphonic acid, although a con- siderable quantity of the base remains unaltered ; the chief and, in some cases, the only product formed when concentrated sulphuric acid is employed, a t temperatures between 105' and 140', is the disulphonic acid. Fuming sulphuric acid of different strengths at 50' yields a mixture of mono- and di-sulphonic acids which i t is impossible to separate. I n all the experiments made, the unaltered diphenylamine was found to contain a substance soluble in ether and melting a t Diphenylaminesulphonic acid is most readily obtained by sulphon- ating acetyldiphenyIamine with fuming sulphuric acid (10-25 per cent.anhydride) and subsequently hydrolysing. I n the sulphonation, it is advisable to add phosphoric oxide in order to hinder hydrolysis by the water formed. Bariuni acetyldiphenylamine sui'phonute, C,,H2,?,N,8,Ba, is ex- tremely hygroscopic, and could not be obtained in a crystalline condition, For the preparation of diphenylaminesulphonic acid, it is not necessary to isolate the pure acetyl derivative ; the crude sulphonic mixture may be boiled with water for some 3 hours and then treated with barium carbonate. Barium clil3l~enylaminssuZphon~te, C,,H,,O,N,S,Ba, is very sparingly soluble in cold water, and crystal- lises in snow-white, anhydrous, glistening plates which do not decom- pose at 170". The copper salt, with 2H?O, and the sodium salt were also prepared.Diphenylaininesulphonlc acid condenses with form- aldehyde in a.queous acid solution, *yielding triccrnilinotri~~~en~llmetlzccne- sulphonic acid, C19H3109NSSS, which dissolves in water or alcohol, readily undergoes oxidation in solution, and turns pale blue on exposure to the air. T. H. P. 175-1 78'. 246-248'.98 ABSTRACTS OF CHEMICAL PAPERS. Diphenylaminesulphonic acid is best prepared from the copper salt ; it crystallises in colourless plates, is readily soluble in alcohol or water, and condenses with diazonium solutions, yielding acid dyes. Sodium p-sulphobenxeneaxodipheny Zcminesulphonate, C18H1306N3S2Na2, crystallises from hot water in violet plates and dyes silk or wool orange- y ello w. hydyox yd initvo benxeneccixodipheny laminesu I- phonate, Cl,H120,N,SNa, forms glistening, brown plates.Diphenyl- aminesulphonic acid (2 mols.) forms a salt with picramic acid (1 mol.), Acetyldi-p-nitrodiphenylamine, NAc( C,H,* NO,),, obtained when acetyldiphenylamine is treated with a mixture of sulphuric and nitric acids at 8--15O, crystallises from hot alcohol in pale yellow, glistening plates melting a t 164" and readily soluble in most organic solvents ; when warmed with concentrated hydrochloric acid, it yields di-pnitrodi phen ylamine. When barium acetyldiphenylaminesulphonate is nitrated with a mixture of fuming sulphuric (5 per cent. anhydride) and fuming nitric acids, first a t 15" and then a t 30-35", a nitro-derivative is formed the barium salt of which could not be obtained in acrystalline condition, but when hydrolysed with sulphuric acid (37 per cent.), rtitrodiphen~lamiesulphonic acid was obtained, the bccrium salt of which is readily soluble in water and forms dark red crystals.The acid has not been obtained in a pure form and is probably a mixture of ortho- and para-nitro-compounds. Barium diphenylaminesulphonate is much more readily nitrated than its acetyl derivative, the most suitable reagent being a mixture of concentrated nitric and sulphuric acids at 0'. The product is a mononits.o.derivative. Barium diphenyZaminedisuZphonate separates from water in crystal- line masses containing 2H,O ; the potassium salt contains 1iH20 and the copper salt 4H,O; the acid is readily soluble in water or alcohol, and bas only been obtained in the form of a syrup.When the barium salt is nitrated with a mixture of nitric acid of sp. gr. 1.4 and concentrated sulphuric acid, the product is a mononitro-derivative, the bccs.ium salt of which, C,,H,O,N,S,Ba + 2H,O, forms indefinite, orange-red crystals readily soluble in warm water ; the potassium salt contains l+H,O. When reduced by Claisen's method (Ber.,' 1879, 12, 1946), aminodi- phenyZaminedisulphonic acid is obtained, the burium salt of which, C,,H,,O,N,S,Ba, forms a reddish-coloured mass, readily soluble in water, but insoluble in alcohol. Sodium J. J. 8. Characterisation of Weak Acids and Pseudo-acids. By ARTHUR HANTZSCH (Be?.., 1899, 32, 3066-3088. Compare Abstr., 1899, i, 399)-It is well known that the molecular conductivity, p, of the sodium salt of a comparatively strong acid increases with the dilution,and that the increase consequent on a doubling of the dilution has a diminishing value, tending towards 0 ; further, that the in- crease consequent upon a change of dilution from 32 to 1024 litres per gram-mol.(A1026-32) has a value of 10-12 ; also, the sodium salts of such acids are neutral to litmus (or to a solution of potassium iodide and iodate), and are not hydrolysed appreciably in aqueous sol u-ORGANIC CHEMISTRY. 95 tion. Strong acids, moreover, combine with dry ammonia, both directly and when dissolved in non-dissociating media, such as benzene. I n the case of very weak acids, the sodium salts are more or less hydro- lysed; a certain amount of sodium hydroxide is present in the aqueous solution, which then has an alkaline reaction to litmus, and exhibits an increasing, instead of a decreasing, rate of increase of conductivity with dilution, and a resulting abnormally high value of Alo,4-32 (regard must be had to the fact that the alkalinity may be due, as in the case of diazotates, to a little alkali from which it is practicably impossible to free the salt).These regularities mere in- vestigated in the case of some weak, or very weak, acids, and the results are tabulated below: K is the value of the dissociation constant of the acid; and the percentage of the sodium salt hydro- lysed in an aqueous solution containing 1 gram-mol. in 32 litres (V32) was determined approximately by measuring the hydrolysing effect upon methyl acetats (compare Shields, Abstr., 1893, ii, 448) : Sodinm salt.Per cent. hydro- K at 25". 4 o a 4 - 32' lysed ( &2)' Phenol .................... 5 10-7 28.0 6 2 : 4-Dichlorophenol ...... 31 7, 11.9 0.52 ........... 11.7 0.52 - 0.37 2 : 4 : 6-Trichlorophenol .. . 1000 ,, It is noticeable that, although nitrophenol, OH*C,H,*NO,, is 10 times as weak an acid as trichlorophenol, yet its sodium salt IS less hydrolysed; this salt must therefore be derived from an acid stronger than trichlorophenol, such as O:C,H,:NO*OH, and nitrophenol must be regarded in consequence as a pseudo-acid. The following rules are given for use in the diagnosis of pseudo-acids. I. The substance is neutwd. (1) The salt is neutral (therefore not hydrolysed, and so the salt of a strong acid) : the substance is a pseudo-acid ; for instance, phenylnitromethane, CH,Ph*N02 4 CHPh:NO*ONa. (2) The salt is alkaline: if A1024-32 is not greater than 12-13 (or if the hydrolysis is small) : the substance is a pseudo- acid ; for instance, quinonehydrazone, NHPh *N:CGH,:O - NPh:N*C,H,* ONa, and isonitrosoacetone, NOH:CH*CMeO 4 NO*CH:CMe*ONa(?).11. The su6stance i s feebly, or very feebly acid. (1) The salt is neutral : the substance is a pseudo-acid ; for instance, nitrophenylnitrosnmine, o-Chlorophenol ............ - 16.7 2.1 p-Cyanophenol 61 9 7 p-Nitrophenol .............. 96 ,> 11.9 0.28 - - NO,* C,H,*NH*NO - NO,. C,H,*N:N*ONa(anti), ethylnitrolic acid, NO - C M e < Z G > O , and dinitro- ethane, NO,*CHMe*NO, -+ NO,*CMe:NO*O~Na. ' (2) The salt is alkaline: if Alo2z-32 is but slightly greater than the normal value, the substance is a pseudo-acid ; for instance, p-bromophenylnitros- amine, C,H,Br*NH*NO -, C,H,Br*N:N*ONa ; if Ah,,,,-,, is de- cidedly greater than the normal value, the percentage of hydrolysis must be determined: if this is much less than that of sodium96 ABSTRACTS OF CHEMICAL PAPERS.phenoxide, the substance is a pseudo-acid; in the opposite case, nothing can be predicated, and other properties must be taken into account. 111. The substance is a pronounced acid with a dissociation constant readily susceptible of measurement ; the salt is not perceptibly hydrolysed: the substance, at any rate the ionised part of it, has the same constitution as the ionised s a l t ; it is possible that the undissocinted substance may have a different constitution, when the case would be one of ' ionisation isomerism.' C.F. B. Bromophenols Insoluble in Alkalis. By KARL AUWERS (Ber., 1899, 32, 2978--2987. Compare Abstr., 1898, i, 70 and 646).-A further discussion of the formuls of these bromophenols. At mesent. i t is imDossible to decide whether a comDound insoluble in ilkalis of this tip., for example, C7H70Br, is repGesenhed by the CH:CH>~~, or formula CBr *CH,* O*CH, CH,Br* CH<CH: CH \ ,CH:CH \ / R. H. P. Bromophenols from as-o-Xylenol and as-m-Xylenol. Eg KARL AUWERS (Be?-., 1899,32, 2987-3005).-A comparison of the properties of the compounds described in the following three abstracts. R. H. P. Pentabromide from [Pentabromo-derivative of ] as-nz-Xylenol. By KARL AUWERS and W.HAMPE (Ber., 1899, 32, 3005-3016. Compare Abstr., 1896, i, 424, and 1897, i, 33).-The acetyl deriva- tive of ww : 2 : 5 : 6-pentabromo-1 : 3 : 4-xylenol, C6Br,(CH,Br),~OAc (Zincke, Abstr., 1898, i, 70), forms colourless needles melting at 180', and is easily reduced t o the acetyl derivative of tribromo-1 : 3 : 4- xylenol, which crystallises from glacial acetic acid in lustrous prisms melting at 115-116'. ~~-l)iiodot~ibrorno-l : 3 : $-xyZenot, C,Br,(CH,T),* OH, prepared from the corresponding diacetate (m, p. 172', loc. cit.) by treatment with hydrogen iodide, crystallises from glacial acetic acid in rosettes of small needles which melt at 182-183', and undergo gradual decom?osition without previous solution when treated with aqueous alkalis. The same diacetnte, on treatment with a n excess of alkali, yields an in- soluble, amorphous powder, the constitution OF which could not be determined ; on treatment with acetone, i t yields a substance which melts at 230-232O, and is probably the acetyl derivative of tribromo- 4-hydroxy-m-xylylene glycol, OH* C,Br,( CH,*OH)*CH,*OAc.The glycol, obtained by treating the dibromide with acetone and water, crystallises from benzene in slender needles melting a t 145-146', and yields a trimethyl ether melting at 95-96', which, when treated with hydrogen bromide, yields pentabronzo-l : 3 : 4-xylend methyl ether, G1,Br,(CH2Br),~OMe, melting at 165-1 68'. Pentabromo-1 : 3 : 4-xylenol, when treated with aniline in benzene solution, yields a QO dianilide, which is a yellow, crystalline powderORGANIC CHEMISTRY. 97 melting at 118-121".If the acetyl derivative of the pentabromo- compound is used, a monoucetyl derivative of the dianilide is obtained ; i t melts at 209", is soluble i n alkalis, and when boiled with acetic anhydride yields a diacetate insoluble in alkalis and melting at 116-115°. The dipiperidide, obtained in a similar manner, is a colourless, crystalline powder melting at 115-1 1 To, and yields bromanil on oxidation with nitric acid, The diacetate (m. p. 172O), when oxidised in similar manner, yields a tetmbromotoluquinone, C B r < ~ ~ ~ ~ ~ ~ > C * CH,* Br, which crystallises in yellow, lustrous leaflets melting at 258-259", and on reduction yields the corre- sponding puinol, which forms brownish needles melting at 226-227".R. H. P. Pentabromo-derivative of as-o-Xylenol. By KARL AUWERS and R. VON ERGGELET [and in part H. VAN DE ROVAART and W. WOLFF] (Bey., 1899, 32, 3016-3033).--0-0 : 3 : 5 : 6-Pentabronzo- 1 : 2 : 4-xylenol, C,Br,(CH,Br),*OH, obtained by heating tribromo-1 : 2 : 4- xylenol with a n excess of bromine in a sealed tube at 130°, crystallises from glacial acetic acid in lustrous needles melting at 149-150°, and is insoluble in alkalis. The acetyl derivative melts at 127-128", and is only slowly decomposed by boiling alkalis ; on reduction, i t yields the acetyl derivative of tribromo-1 : 2 : 4-xylenol (m. p. 111--212°). : 3 : 5 : 6-Tetrab~onao-1 : 2 : 4-xylenol-o-methyl ether, OH* C6Br3(CH2Br)*CH2* OMe, formed when the pentabromo-compound is boiled with methyl alcohol, melts a t 132-133') and is soluble in caustic soda solution.The monoacetyl derivative melts indefinitely between 80" and 90' and, if treated with sodium acetate and acetic anhy- dride, yields the diacetate, OAc*C,Br,(CH,* OAc)* CH,* OMe, melting at 101-102". The corresponding ethyl ether forms sharp-angled prisms melting at 124-125", and yields a similar diucetate melting at 105-107". OH* C,Br,(CH,Br)* CH2* OH, prepared by treating the pentabromo-compound with acetone and water, crystallises from benzene in needles melting at 166-167", and is soluble in alkalis. A poor yield of the corresponding glycol melt- ing at 185" is obtained after further treatment with acetone. Its dimethyl ether, OH* C,Br,( CH,. OMe),, is a colourless, crystalline powder melting at 157".The diethyl etliev, obtained by treating the mono- ethyl ether of the tetrabromo-xylenol with alcohol, crystallises in the form of compact prisms and cubes melting at 94". The triethgl ether is a thick oil, which, on treatment with hydrogen bromide, yields penlabyorno-1 : 2 : 4-xylenol ethyl ether, C,Br,(CH,kh.')2*OEt, in the form of needles melting at 108-1 14'. The pentabromo-compound, on treatment with sodium acetate and acetic acid, yields the monoacetyl derivative, OH* C6Br,(CH2Br)* CH,* O h , which crystallises in needles melting at 154-155", forms a phenylurethans melting at 193", and when boiled with alcohol yields an ethyl ether, OH* C,Brs(CH2Br)* CH,* OEt, melting at 124-125'. The diacetyll derivative of t h e tetrabromo- compound forms small needles melting at 116", and on treatment with w : 2 : 5 : 6-F&c~bromo-L : 2 : 4-xylenol,98 ABSTRACTS OF CHEMICAL PAPERS, acetic anhydride yields the t~iacetyl derivative, OAce C,Br,(CH,* OAc),, melting at 133-1 34".On treatment with o-toluidine, the pentabromo-compound is converted into the di-o-toluidicle which melts at 153' and forms an ethyl ether melting at 121-123'. The tetrabromo-compound, when treated with aniline in benzene solution, yields the compound OH* C6Br3(CH2* OH). CH,*NHPh, which melts at 171" and forms a triacetyl derivative melting and decompos- ing at 179-181". ww-Diiodotribromo-1 : 2 : 4-xylenoZ, prepared by treating the tetra- bromo-compound previously described with hydrogen iodide, forms yellowish, compact crystals melting at 165-166*, and yields a monoacetgl derivative melting at 142'.On treatment with acetone, this diiodo-compound forms a monoiodo-derivative melting at 193", the diet?t,yZ ether of which melts at 110-11 1". The diiodo-compound, when treated with. glacial acetic acid and sodium acetate, yields the nzonoacetgZ derivative of the monoiodo-compound which melts at 185-1 90". On reduction, the tetrabromo-xylenol yields the alcohol, OH* CH,*C,MeBr,* OH { = 1 : 2 : 41. This crystallises from benzene as silky needles melting a t 170-180°, and yields a diacetate melting at 135-1 37". The monoucetyl derivative, OH- C,&IeBr,* CH,O Ac, melts at 140-142". On oxidation of the alcohol with nitric acid, tribromo- toluquinone is obtained in the form of yellowish leaflets melting at 23 3-2 35".R. H. P. Heptabromo-derivative of as-o-Xylenol. By KARL AUWERS and HARRY BURROWS [and in part H. VAN DE ROVAART] (Bey., 1899, 32, 3034--3045).-wowo : 3 : 4 : 6-1re;l)tabrorno-1 : 2 : 4.xglenol, OH- CoBr,(CHBr2)2, prepared by heating tribromo-1 : 2 : 4-xylenol in a sealed tube at 190" with an excess of bromine, forms light, silver-grey crystals melting at 199", and is insoluble in alkalis. The acetyll deriva- tive melts at 193", and is easily reduced to acetyltribromo-1 : 2 : 4- xylenol. On boiling the heptabromo-derivative with methyl alcohol, the clirrzethylucetul, CH(OMe)2*C,Er,(CHBr2)*OH [ = 1 : 2 : 41, melting at 116-1 1 8 O , is formed. The corresponding diethyl acetccl melts at 143". The corresponding diacetate, formed by treating the heptabromo- xylenol with glacial acetic acid and sodium acetate, crystallises in colourless plates melting at 155", and when boiled with acetic anhy- dride yields the triacetyl compound, OAc* C,Br,(CHBr,)*CH(OAc),, melting at 132-133'.Wher, the acetals just described are warmed with glacial acetic acid, w o : 3 : 4 : 6-pentabromo-5-hydroxy-o-toluabdehyde is obtained ; it crystallises in small needles melting at 168", is soluble in alkalis, and forms an acetyl derivative melting a t 150'. On oxida- tion with nitric acid, it yields pentabyonaotoluqucirtone, CHBr,* CBr,?,, which crystallises from glacial acetic acid in yellow prisms melting at 160". 3 : 4 : 6-T~*ib~~omo-5-hydroxy-o-tolualdehyde, obtained by the reduction of the pentabromo-compound, forms small needles melting at lS7--!8So, and yields a benxoyl derivative melting at 167-168" and a n oxime melting at 207"; on oxidation, it yields tribomotolu- quinone melting a t 234". Attempts were made to synthesise this aldehyde by brominating p-hydroxy-o-tolualdehyde, In this way,OR(3ANLC CHEMISTRY, 99 4 : 6-dibromo-3-hyd~~oxy-o-to~uuldehyds is obtained ; it forms small needles melting at 161-162', yields an oxime melting at 197', and is oxidised to 4 : 6-dibromo-3-hydroxy-o-toluic acid, which forms small, white needles melting at 232'.On further treatment with bromine, this aldehyde is converted into tetrabromo-m-cresol. This can also be prepared by the direct bromination of m-cresol or of us-0- xylenol ; it forms long, thin needles melting at 194O, is easily soluble in alkalis, and forms a n acetyl derivative melting at 165-166", and a benxoyl derivative melting at 15S-154O ; when treated with nitric acid, it yields tribrornotoluquinone and an unstable mononitro-derivative melting at 88'.~?.ibromo-p-hydroxy~~~~~~uZuZdeiLyde, OH* C,Br,( COH),, prepared by treating pentabromohydroxytolualdehyde with lime water, crystal- lises from dilute alcohol in the form of colourless needles and prisms melting at 202', and yields a n acetyl derivative melting at 205-209'. An isomeric substance melting at 245-247", and forming an acetyl derivative melting at 218-220°, is obtained in small quantity in the By CHARLES MOUREU (Ann. Chint. Phys., 1899, [ vii], 18, 76--139).-An account of work already published. (Compare Abstr., 1896, i, 215, 426, 477, 646; 1897, i, 336, 403; 1898, i, 411, 518, 644, 660; 1899, i, 30, 125, 433, 494, 679, 700.) preparation of this hydroxyphthalaldehyde.R. H. r. Catechol Derivatives. G. T. &I. Hydrogenised Derivatives of Diphenylmethane and By DANIEL VORL~NDER (Annnlen, 1899, 309, Triphenylmethane. 348-355).-An introductory paper (see following abstracts). 31. 0. F. Formaldehyde Derivative of Dihydroresorcinol. By DANTEL VORL~NDER and FRITZ KALKOW (Aiznalen, 1899, 309, 356-374. Compare Merling, Abstr., 1894, i, 177, and Vorliinder and Kalkow, Abstr., 1897, i, 513). - The sodium derivative of methylenebisd-ihydroresorcinol crystallises in prisms and contains 2H,O. The anhydride (octohydroxantheizedionej forms the oxime, C,3H,y0,N3, which is microcrystalline, and melts at about 300'.Alcoholic ammonia converts methylenebisdihydroresorcinol into deca- hydroacridinedione, which has been described already. Nitrous acid transforms this substance into octol~yd.l.oacridinedio?~e, ~H,-CO-~:CH*~*CO~qH, CH,*CH,.C:N-C*CH,* CH,) which crystallises in white needles melting at 140--142", and yields acridine when distilled with zinc dust ; the oxime becomes brown above 200°, and melts and decomposes at 250". A similar ketonic base, C,,H,,O,N, obtained by distilling decahydroacridinedione, crystallises in flat needies and melts at 144'; the hydrociilo~~ide crystallises from water in colourless needles, and the oxinze melts and decomposes at about 2 8 0 O . The ketonic acid, CI3Hl8O5, obtained from methylenebisdi- hydroresorcinol and caustic alkali, forms anhydrous bccrizcm, silver, and100 ACSTRACTS OF CHIEMICAL PAPERS.lead salts ; the oxime and sernicarbaxone melt a t 159' and 218' respec- tively, and the diethyl ester boils at 235-240'under 24 mm. pressure. Methylenebismethyldihydroresorcinol, C,,H,,O,, and methylenebisdi- methylaihyldroresorcinol, C17H2,0,, melt at 152' and 187-188' respectively ; the latter yields tetyanzethyloctohydyoxanthenedione, C17H2203, which melts at 171' and, with alcoholic ammonia, forms tetramethyldecah ydroucridinedione. Met~ylenebis~~henyldiJLydroresorcinoZ, C,,H,,O,, melts at 2 12' ; diphenyloctohydroxanthenedione, C25H220S, melts at 225-226'. Pentarnethyloctohydroxunthenedione, C,,H,,O,, from dimethyldi- hydroresorcinol and acetaldehyde, melts at 174'. Etlqltetramethylocto- hydrorcanthenedione, C,,H,,O,, melts at 139'.Wexamethyloctohydyo- xanthenedione, C,,H,,O,, melts at 245'. Compounds of Dihydroresorcinol with Aromatic Aldehydes. By DANIEL TORLANDER and 0. STRAUSS (Annalen, 1899, 309, 37~-383).-Benxylidene6isdiJ~ydro~esorcinol, C,,H,,O,, prepared from dihydroresorcinol and benzaldehyde, melts and decomposes at 208' , phenyloctohydyoxanthenedione, C,,H,,O,, melts a t 255', and the p-nitro-derivative, obtained fiom p-nitrobenzaldehyde, dihydroresor- cinol, and glacial acetic acid, melts at 246'. Phenyldecahydro- acridinedione, C1,Hl9O,N, produced on heating phenylhydroxanthene- dione with alcoholic ammonia, does not melt below 310°, and fosms, i n alcohol, a colourless solution which exhibits blue fluorescence ; distillation with zinc dust gives acridine.Benxy I idene bisdime t Ji y ldihydroresorcino I , C23H28041 obtained from dimethyldihydroresorcinol and benzaldehyde, melts at 193'; phenyltetva- methyloctohydvoxcanthenedio~ae, C2.7H2G03, melts at 200'. Cuminylidene- bisdimethyldiJnjdyoresorcinol, C26H3203, melts at 173'. Benxylidenebispheny ZdiJL ydroresorcinol, C31H2S04, me1 t s at 1 2 5', water being eliminated ; triphenyloctohydroxanthenedione, C,, K2603, is identical with '' benzylidenephenyldihydroresorcinol " (Vorlander and Erig, Abstr., 1897, i, 275), and melts at 230'. Triphenyldecahydro- acridinedione, C,,H270,N, forms red solutions having green fluorescence. By LEO MARCHLEWSKI (L pr. Chem., 1899, [ii], 60, 407-408. Compare Abstr., 1896, i, 96 and 235).- When isatin reacts with o-phenylenediamine acetate in acid solution, a mixture of indophenazine and o-aminophenimesatine is formed ; as the imesatine cannot be converted into the indophenazine under the conditions employed, i t is clear that the isatin acts as a mixture of lactam and lactim.Acids, such as acetic acid, appear t o be able t o cause the con- version of the lactim into lactam, as isatin when condensed with o-phenglenediamine in 50 per cent. acetic acid solution gives only a trace of imesatine, whilst the latter changes only excessively slowly into indophenasine when bailed with acetic acid of t h a t btrength. A . L. Optically Active truns-Hexahydrophthalic Acids. By ALFR~D WEIIKEH. and H. E. CONRAD (Bey., 1899, 32, 3046-3055)- k.ans-HexahSdrophthalic acid is a racemic compoupd apd is resolved M.0. F. M. 0. F. Tautomerism of Isatin.OltCANIC CHERIISTRY. 101 into its optically active components by fractional c r y s t a h a tion of its quinine salts in alcoholic solutions ; the neutral salt of the dextro- rotatory acid separates first, whilst the acid salt of the laxorotatory acid remains dissolved. The anhydrides of the optically active acids, prepared by heating these compounds with acetic chloride, crystallise in broad plates, whilst the corresponding racemic compound separates in needles. The dimethyl esters were produced by heating the acids with methyl alcohol containing hydrogen chloride ; the monomethyl esters were obtained by warming the anhydrides with methyl alcohol. The rnonoumide of the racemic acid was prepared by passing dry ammonia into an acetone solution of the inactive anhydride ; it melts a t 196".Active traiuhexahyd ro- phtlialiG acids and derivatives. d-truns-Acid ......... I- ,, ......... &Anhydride ......... L ,, ......... d-Dimethyl ester ... I- ... d-Monomet hyl ester. I- ,) 9 , 9 , E U l D . - 76.7 75.8 ] - 29-6 26.5 - 24.8 } M. p. of racemic M.p. compound. 17 8 -1 83" 215" 164" 140 below 0' 33 39" 96 cis-Hexahydrophthalic acid is not resolved into active components by the aid of quinine, cinchonine, o r coniine; this acid differs from its trans-isomeride in forming the ucid potussium salt, CyH,,04K c 3H20. Constitution of Santonic and Metasantonic Acids and of Metasantonin. By LUIGI FRANUESCONI (Gaxxstta, 1 S99, 29, ii, 181-257. Compare Abstr., 1898, i, 267).-A detailed account is given of the various transformations of santonic and metasantonic acids and of metasantonin.Xuntonic ucid dioxime, C,5H2204N2, is a white, friable substance which melts and decomposes a t 120-125" ; it dissolves readily in dilute halogen hydracids, alcohol, or ether. Its specific rotatory power is [a]. - 102.4". With excess of phenylhydrazine, santonic acid gives the phenyl- hydraxone of santonic acid phenylhydraxide, C27H3202N4, which is an orange-yellow powder melting and decomposing a t 95" ; it is readily soluble in alcohol, ether, or acetic acid. G. T. M. I t gives a barium salt, (C,,H,,O,N,),Ba. yO*~Me*QH-CO*~*OH Tviketosantonic acid, CMe. cH, c. CHMe. CO,H, obtained by the action of bromine on santonic acid, forms glistening, straw- yellow needles melting and decomposing at 234" ; it is readily soluble in ethyl acetate, alcohol, or water, the aqueous solution having an intense yellow colour, I t s specific rotatory power in alcohol is [ u ] ~ - 458.7'. The barium salt, C,,H120,Ba t 2H20, is a golden- yellow substance.The ethyl ester, C,,H,,0,*C02Et, forms glistening, pale yellow needles which melt a t 157-158" and dissolve readily in102 ABSTRACTS OF CHEMICAL PAPERS. ethyl acetate or alcohol; the specific rotation i n alcohol is [.ID - 394.1'. The dioxinze, C15H,,0,(NOH),, is a hard, friable substance of a straw-yellow colour and is readily soluble i n ether, alcohol, or w:rtter. The anhydride of the dioxime, C15H405<Z>0, is a hard, friable, orange-coloured mass which softens at about 1 30°, melts and decomposes at 140°, and dissolves in the ordinary solvents.~ribromo-a-santonin, C15H1503Br3, obtained by the action of bromine on santonic acid! melts a t 187-18S0 and dissolves in ethyl acetate and to a less extent in ether, but is insoluble in solutions of alkali car- bona tes. T. H. P. Action of Sodium Methoxide on Dibrornides of Propenyl Gompounds and of Unsaturated Ketones. By F. J. POND, 0. P. MAXWELL, and G. M. NORMAN (J. Amer. Chern. Xoc., 1899,21, 955-967. Compare Pond and Beers, Abstr,, 1898, i, 645).-When isoapiole dibromide (Ciamician and Silber, Abstr., 2890, 1294) is treated with sodium methoxide according t o the method previously described, a ketone, COEt* C6H(OBle),:0,:CHq is obtained which crystallises from alcohol in colourless prisms melting at 95.5' ; its oxime cryatallises from methyl alcohol in colourless needles melting at 124", and is readily reconverted into the ketone when heated with dilute sulphuric acid on the water-bath.The constitution of the ketone follows from the fact that it yields propionic acid when heated at 250" with concentrated sulphuric acid. Eugenol propyl ether, OYr* C,H,(OMe)*CH,* CH:CH,, is a colourless oil boiling a t 270.5'and having a sp. gr. 1.0032. Cahours (this Journ., 1877, i, 461) gives its boiling point as 263-265'; when boiled with alcoholic potash, it is converted into isoeugerml propyl ether, CHhlIe:CH* C,H,( OMe)*OPr, which distils at 280-281' and forms large, colourless prisms melting at 53-54'; it may also be obtained by the action of propyl bromide on the potassium salt of isoeugenol.I t s dibmmide melts at 53-54", is readily soluble in alcohol or ether, but cannot be recrystallised without decomposing ; when treated with sodium methoxide, it yields t h e ketone, COEt- C,H,(OMe)*OPr, which, after distillation under reduced pressure, crystallises from methyl alcohol in large prisms melting at 63-64', and boiling with slight decomposition at 284-287' under atmospheric pressure. The oxinze, Cl,Hl,O,N, forms large crystals melting at 114'. Benzylideneacetophenone (Claisen and Clapardde, Abstr., 1882,5 12) yields a dibwmide crystallising in small prisms and melting at 156O; this dibromide is converted by the action of sodium metboxide into dibenzoylmethane (Baeyer and Perkin, Abstr., 1884, 64 ; Claisen, ibid., 1887, 575).An unstable oil, probably the unsaturated ether OMe* CPh:CHBz, has been isolated as a n intermediate product; on treatment with dilute acids, it yields dibenzoylmethane. Anisylideneacetop~enone crystallises in fine, yellow needles melting at 77-7Soj its dibromide cryatallises in white prisms melting a t 140-141', and on treatment with sodium methoxide yields anisoyLORGANIC CHEMISTRPI 103 befixoylmethacne, ClsH1403, crystallising in plates and melting at 131-132'. Bromine converts the diketone into a bromine derivative melting at 127-128'. By R. C. FARNER and ARTHUR HANTZSCH (Ber., 1899, 32, 3101-3109)- The criteria enumerated in this vol., i, 95, are applied to the cases in question. Isonitrosoacetone, NOH:CH* CMeO, is neutral to litmus, is not appreciably dissociated, and does not form a compound with dry ammonia.But the sodium salt exhibits on dilution a n increase of conductivity, A1024;321 only a little greater than in the case of salts of strong acids, and it IS only slightly hydrolysed in aqueous solution. Consequently, isonitrosoacetone is a pseudo-acid, and its sodium salt has a different constitution, either NO*CH:CMe*ONa, CMe<ti>N*OEa, J. J, S. a-Oxirninoketones and Quinoneoximes as Pseudo-acids. or ONa CMe<$i>N. Quinonemonoxime, NOH:CGH,:O, does not unite with ammonia in benzene, and very slowly in ethereal, soIutions ; but its sodium salt exhibits the normal increase of conductivity on dilution, Alo24-32 ; it must therefore be the salt of a comparatively strong acid, and hence quinoneoxime is a pseudo-acid.Quinoneoxime, in aqueous solu- tion, has a decided acid reaction and a moderately large dissociation constant, and its very dilute solution has the same (greenish-yellow) colour as equivalent solutions of the red sodium (with 2&H20) and green potassium salts (with 1H,O) ; hence the oxime 'itself undergoes a partial transformation in aqueous solution and the case is one of ' ionisation isomerism.' Quinonedioxime, on the other hand, has no appreciable conductivity, and i t s sodium salt is a true oxime salt, for it is largely hydrolysed in aqueous solution, as the abnormally large increase in conductivity on dilution, A1024-32, shows ; indeed, the solution gradually deposits a n anhychicle, (CGH4<s>O) , a bright- red, amorphous, very stable substance. o-Toluquinoneoxinie resembles its lower homologue, and '' nitroso-orcinol " forms a very strongly acid solution.C. E. B. Space Isomerism of the Ethers of Toluquinoneoxime. By W. CONGER MORGAN (Amel.. Chem. J., 1899, 22, 402--407).-The benzoyl derivative of toluquinone-m-oxime melting at 139' (Bridge and Morgan, Abstr., 1899, i, 130) is completely converted into the stereoisomeride melting at 193' by heating with alcohol in a sealed tube for 3 hours at 120' ; the latter, under similar conditions, is not changed, but on raising the temperature t o 150°, is completely decom- posed. Caustic alkalis hydrolyse the compound of lower melting point to the corresponding oxime, which, however, on treatment with benzoyl chloride, yields ,the modification of higher melting point exclusively ; the latter appears from these experiments t o be the more stable form, The phenomena described by Bridge and Morgan have been repro- duced completely in the ethers formed by the interaction of acid chlorides with the sodium salt of the oxime prepared by the action of amyl nitrite on the sodium salt of o-cresol; since there is no104 AUSTRSCTS OF CHEMICAL PAPERS. possibility of a hitro-compound being formed under these conditiods, although this is not precluded in the action of nitrous acid on the cresols, the lower melting stereoisomerides cannot be considered as merely the higher melting compounds rendered impure by such ad- mixture.The benzoate, C,,H,,O,NBr, of bromotoluquinone-o-oxime, prepared by boiling the corresponding dibromide, Cl4HI1O3NBr2 (Bridge and Morgan, Zoc.cit.), with 75 per cent. alcohol, forms yellow crystals and melts a t 184". The dichloride, C,,H,,O,NCI,, of toluquinone-o-oxime benzoabe crystallises from glacial acetic acid in short, thick, colourless prisms and melts a t 149'; when boiled with dilute alcohol, it loses hydrogen chloride and yields cldorotoluquinone-o-oxime benzoate, C,,H,,O,NC1, which forms yellow crystals and melts and decomposes a t 185-133'. All these compounds appear t o exist in one form only. W. A. D. Isomerism in the Menthol Series. By IWAN L. KONDAKOFF and EUGEN LUTSCHININ (J. pr. Chem., 1899, [ii], 60, 257-279).- Menthyl iodide, prepared by the action of hydriodic acid on either menthol or menthomenthene, boils a t 124-126' under a pressure of 18 mm., and has a sp.gr. 1.3836 at 0' and 1,3155 at 16.5'. It acts very rapidly on moist silver oxide, yielding tertiary menthomenthol ; the passage from secondary menthol to tertiary menthomenthol is closely analogous to that from methylisopropylcarbinol to dimethyl- ethylcarbinol. Dihydrocarvone, prepared by oxidising the dihydrocarveol from I-carvone, boils a t 221-224', has a sp. gr. 0.9308 a t 16', a refrac- tive index n, 1.47243, the molecular refraction being 45.78; its specific rotation is [.ID + 17' 27.5'. The constants obtained for the product from d-carvone were as follows : boiling point, 221-222'; sp. gr. 0.9269 a t 22', refractive index nD =1*46998, molecular refraction 45.80, and specific rotatory power [a], - 19' 35'.This dihydrocarvone is readily reduced by sodium and alcohol to pure dihydrocarvol boiling at 224-225', and is readily converted into carvenone by Kondakoff and Gorbunoff's method (Abstr., 1898, i, 145); the latter substance boils for the most part a t 231-233' under 763 mm., and at 101-103° under 10 mm. pressure, but invariably leaves a residue which boils a t 233-240'. Klages' observation that carvenone may be obtained by treating dihydrocnrvone with formic acid (Abstr., 1899, i, 624) is the natural outcome of the work of Kondakoff and Gorbunoff ; it is not necessary, however, to use anhydrous formic acid or to prolong the action; the product obtained by this method boils a t 232' under 759 mm. pressure, and not a t 232-235" as stated by Klages. Carvomenthol, obtained by reducing carvenone by Wallach's pro- cess (Abstr., 1894, i, 44), boils at 220-221' under 762 mm.pressure, but contains a fraction boiling a t 240' ; i t has a sp. gr. 0.9070 at 20.2" ; its refractive index is nD 1,4672, its molecular refraction being 47.49. The foregoing carvomenthol was purified by conversion into tetra- hydrocarvone as recommended by Wallach, but much loss is ex- perienced in this process. The substance now boiled at 222", had aORGANIC CHEMISTRY. 105 ~ p . gr. 0.9010 at 23', a refractive index n, 1.4696, and a molecular refraction 47.58. Carvomenthol, prepared from specimens of active carone, varies considerably in opticzl activity, as do the derivatives prepared from it. Carvonzenthyl acetate, C,,H,,OAc, boils at 235-238' under 76 1 mm.pressure, and a t 105-107° under 11 mm.; it is a colourless, fairly mobile liquid having a faint odour of cherries; it has a sp. gr. 0.9250 at 22'/4', a refractive index n, 1.45079, a molecular refraction 57.42, its specific rotation being [ u ] D + 4'7'. Carvomenthyl chloride, C,,H,,CI, is colourless and has an odour resembling menthyl chloride; it boils at 90-95' under 15 mm. pressure, and at 82-55' under 11 mm., is optically inactive, has a sp. gr. 0.9450 a t 21°/4', and refractive index VZ, 1.46534 a t 21°, the molecular refraction being 50.48. The bi*omide, CloH19Br, is colour- less, boils a t 95-99' under 10 mm. pressure, has a sp. gr. 1,1870 at 21°, a refractive index nD 1.49060 a t 21"/21', and a molecular refrac- tion 53.39.Carvomenthene, prepared by heating carvomenthyl chloride or bromide with alcoholic potash, is divisible in two portions by fractional distillation, about 90 per cent. of the whole distilling a t 172-1745", and the rest a t 174°5-1780. It is a colourless, mobile liquid having an odour of menthene, is altered by exposure to air, and reacts readily with permanganate and with bromine. The portion of the carvomenthene of lower boiling point has a sp. gr. 0.8230 a t 16.5"/4', a refractive index n, 1,45979, molecular refraction 45.68, and a specific rotation [a], - 2'4'. The fraction of higher boiling point had a sp. gr. of 1.8230 a t 19'/4', a refractive index n, 1.46105, a molecular refraction 45.89, and a specific rotatory power [a], - 1'28. Carvc?;nlenthene hydrochloride boils at 90-98" under 18 mm., and a t 89-95' under 16 mm.pressure ; it has a sp. gr. 0.9390 at 19"/4', a re- fractive index ~YL, 1.464941, the molecular refraction being50-95, whilst its specific rotatory power is [ a ] , - 1'22'. I t s properties are thus identical with those of carvomenthyl chloride, with the exception of the rotatory power. Baeyer has shown (Abstr., 1893, i, 722) that carvomenthene combines with hydrogen bromide or iodide in the cold, yielding tertiary halogen derivatives, convertible through the intermediary of the corresponding acetates into a mixture of carvomenthene and tertiary carvomenthol. The authors have prepared the bromo-compound by heating the hydro- carbon with strong hydrobromic acid a t 160-170° ; it boils at 92-98' under 10 mm.pressure, has a sp. gr, 1.1620 at 20*5"/4', a refractive in- dex n, 1.48822 at 20*5", and a molecular refraction 54.27 ; it is opti- cally inactive. Its properties are almost identical with those of carvo- menthyl bromide, but it is highly probable that it consists of a mix- ture of the secondary and tertiary bromo-compounds, derived from two isomeric carvomenthenes in the parent hydrocarbon. The carvo- menthene regenerated from the hydrobromide boiled at 172-1 75', had a sp. gr. 0'8230 at 20'/4', a refractive index VZ, 1.45959, a mole- cular refraction 45.69, and a specific rotatory power [a], - 0'83'. Carvomenthyl chloride or bromide, on treatment with moist silver VOL. LXXVIII. i. 2106 dBSTRACTS OF CHEMICAL PAPERS. oxide, affords tertiary carvomenthol and a small auantitv of a sub- stance, C10H2203, whYich crystallises in slender neekes anh melts a t 1 0 1-1 0 2 O .It is not improbable that the behaviour of menthomenthol and carvomenthol illustrates a general law whereby hydro-aromatic alcohols containing the group *CHR*CH(OH)* are converted by halogen hydrides into tertiary halogen derivatives. The behaviour of fenchyl alcohol in this respect is being investigated. Solubility of Camphor in Hydrochloric Acid. By AL. J. ZAHARIA (Chem. Centr., 1899, ii, 308; from Bul. SOC. Sci. Bucuresci, 1899, 8, 53-61).--CTamphor is rather soluble in water and the aqueous solution becomes turbid on addition of sodium carbonate or sodium chloride solution. Camphor is very soluble in concentrated hydrochloric acid, and the more concentrated the acid and the lower the temperature the greater the quantity dissolved.On account of the volatility of camphor, the amount dissolved could not be determined. A saturated solution containing 35.74 per cent. of hydrochloric acid has a sp. gr. 1.1405. The acid solution of pure camphor is orange- yellow, and of impure camphor reddish-yellow, changing gradually to deep-red. Any excess of camphor is coloured light brown and may be dissolved with the exception of a small resinous residue by adding more hydrochloric acid. When a few drops of nitric acid are added t o the hydrochloric acid solution, an oil separates which, when distilled or treated with water, again forms camphor. By electrolysing the hydrochloric acid solution, hydrogen is liberated a t the cathode and a liquid is quickly formed a t the anode, which by exposure to the air or treatment with water regenerates camphor.The amount of camphor in solution could not be determined polarimetrically, for the rotatory power depends on the quantity of hydrochloric acid present. When chlorine is passed into a hydrochloric acid solution of camphor, an oil is very slowly formed. Camphor appears t o behave towards hydriodic acid in a similar way. E. W. W. Nitroso-derivatives of Caryophyllene and Cadinene and their bearing on the Characterisation and Classification of the Besquiterpenes. By OSWALD SCHREIR'ER and EDWARD KREMERS (Pharrn. Archives, 1899, 2, 273-300. Compare Abstr., 1899, i, 619). -A pure specimen of caryophyllene, boiled at 136-137" under 20 mm.pressure, had a sp. gr. 0.90301 at 20°/20", index of refrac- tion N~ 1.49976 a t 20°, and specific rotatory power [a], .- 8.959 a t 20°. The nitrosite is not polymerised, but has the simple formula C15H2403N2, as shown by cryoscopic determinations in benzene solu- tion ; it has a specific rotatory power [a],, of about + 103 in 1.6 per cent, benzene solution, and, with benzylarnine, it yields a product which melts a t 167'. When exposed t o sunlight in absolute alcoholic solution, it is transformed into a colourless (a) isomeride with the same mole- cular weight ; this melts a t 113-114', is soluble in alcohol and benzene, and has no appreciable optical activity. When the nitrosite is exposed to sunlight in benzene solution, another colourless (/I) substance is formed, which melts at 146-148', ,and is insoluble in benzene or A.L.0 R G AN I C C H E bl ISTR T, 10'9 alcohol j the yellow-orange rays are most active in effecting this change. The nitrosochloride can be obtained crystalline by mixing caryophyl- lene, alcohol, ethyl acetate, and ethyl nitrite, cooling in a freezing mixture, adding saturated alcoholic hydrogen chloride, leaving the whole in the cold for an hour, and then exposing it to sunlight ; it melts and decomposes a t 1 5 8 O , and has the bimolecular formula (C,,H,,ONCl), ; with benzylamine, i t forms two derivatives, u and /3, melting a t 167' and 12s' respectively ; the former is the less soluble in alcohol. The nitrosate is also bimolecular; with benzylamine, i t yields a product, melting a t 12S0, identical with the P-product obtained from the nitrosochloride. The hydrochloride of caryophyllene can be obtained crystalline by saturating an ethereal solution of the sesqui- terpene with hydrogen chloride, and exposing the solution to intense cold ; it melts a t 69-70'.When cadinene is mixed with glacial acetic acid, cooled with a freezing mixture, ethyl nitrate added, the mixture treated with strong nitric and glacial acetic acids, and diluted with alcohol, cadinene nityosate, melting and decomposing a t 105-1 lo", is precipit- ated. When a saturated solution of hydrogen chloride in glacial acetic acid is added, instead of the nitric and acetic acids, a nitrosocldoyide, melting and decomposing a t 93-94', is obtained. C. F. B. Oil and Terpenes from Aralia Nudicaulis.B~WILLIAM C. ALPERS (Chem. Centr., 1899, ii, 623 ; from Amer. P?m~nz., 71, 370-378).- The fresh root of Aralia nudiccculis contains 40-60 per cent. of water, and the dry drug yields on a n average 5.53 per cent, of ash, which contains about 1-38 per cent. of sodium and potassium chlorides and sulphates, The dark red, fatty oil, obtained by extraction, has a sp. gr. 0.921 a t 20', is soluble in light petroleum, benzene, ether, o r chloroform, slightly so in absolute alcohol, and insoluble in water ; i t solidifies at 3', has acid number 7.3, saponification number 192, iodine number 106, and molecular weight of about 900 ; it consists chiefly of triolein. About 0.12 per cent, of an oil is obtained by distilling finely powdered aralia with steam ; it has a pleasant, aromatic odour, and is composed mainly of a sesquiterpene, wwliene, CI5Hl4, which boils at 270", has a sp.gr. 0.9086 at 20', a specific rotatory power [aID - 7 to - So, and a refractive index nD 1.49936. It combines with bydrogen chloride t o form an oily hydrochloride, but does not yield a solid bromide by the action of bromine. With a solution of hydro- gen chloride in glacial acetic acid, it forms a bluish compound. The ethereal oil also contains a small quantity of a sesquiterpene alcohol, and a little azulin, U,,H,,O, which boils a t about 300". E. W. W. Liquorice Oil. By HEINRICH HAENBEL (Chenz. Centr., 1899, ii, 624 ; from Pharm. Centr.-H., 40, 533).--Sy distilling Spanish liquorice root (Glycyryhizu glubrcc), 0.03 per cent. of an ethereal oil is obtained ; the Russian roots yield 0.035 per cent.These oils have a feeble acid reaction, which is possibly due to glycyrrhizic acid, but their composition is not identical, for whilst the Russian oil is dextrorotatory, the Spanish is laevorotatory. E. W. W, i 2108 ABSTRACTS OQ CHEMICAL PAPERS. Ethereal Oil of Poplar Buds. By FRITZ FIcmxR and E. KATZ (Ber., 1899, 32, 3183-3285).--'lhe principal fraction obtained by distilling oil of poplar buds under diminished pressure is a terpene boiling a t 132-137' under 13 mm. pressure, and a t 263-269' under ordinary pressure; it has a sp, gr. 0.8926 a t 15O/4', and a specific rotatory power 10'48' at 22'; its vapour density corresponds with that of a sesquitierpene, C,,H,,. The nitrosochloride, C,,H,;KOCl, obtained from the sesquiterpene and amyl or ethyl nitrite, and hydrochloric acid, separates as a crys- talline powder from its solution in benzene or chloroform on the addition of methyl alcohol; it melts indefinitely, the range of tem- perature being 164-1 70".The nitrolpiperidine from the preceding compound and piperidine crystallises from alcohol and melts at 151-152" ; the nityolbenzyl- amine crystallises from alcohol in needlesand melts a t 132-133' ; the chlorides of these substances have the composition C,,H,,ON* C,NH,,, + HCl and C,,H,,ON*NH* CH,Ph -I- HCl respectively. The nitroso- or iso~itroso-sesp.2c~~rpene, C15H2,:NOH, is obtained as an oil on treating the nitrosochloride with sodium ethoxide ; on re- duction, this substance yields an aminosesquiterpene.The nitrosite, produced by the action of nitrous acid on the sesqui- terpene, separates a t first in blue needles melting at 127'; after crystallisation from alcohol, it becomes colourless and melts at 172'. The nitrosate from the sesquiterpene, amyl nitrite, and nitric acid, crystallises from benzene and melts at 162-163'. The sesquiterpene does not yield crystalline additive compounds with bromine, hydrogen bromide, or hydrogsn chloride, neither does it combine with elements of water (Wallach, A bstr., 1893, 101). The properties of the sesqui- terpene of poplar buds and its derivatives resemble those of t,he humulene in oil of hops (Chapman, Trans., 1895, 67, 57 and 780). On the other hand, the sesquiterpene, although it may contain humu- lene, cannot consist wholly of this hydrocarbon, for the former is optically active whilst the latter is inactive.The higher fractions of poplar oil coxltain a mixture of paraflins, stearoptenes," consisting of the hydrocarbon C,,H,, and its higher homologues ; the total amount of paraffin in the oil is only h per cent. G. T. M. Glucosides and Enzymes contained in the Root of some Spirmas. By MARTINUS W. BEYERINCK (Chenz. Centr., 1899, ii, 259 ; from C'entr. Bakt. Parusitenk., [ ii], 5, 425--429).-The roots, rhizomes, and lower portions of X p m m ulrnayia, X.3Jipendula, and 8. palrnata contain a glucoside, gaultherin, and an enzyme, gaultherase, and by the interaction of these compounds methyl salicylate is formed. The elder portions of the roots and rhizomes of 3.kamschatica also contain a second glucoside, spirzin, which is decomposed by gaultherase, forming salicylaldehyde. Gaultherin is prepared from the root nodules of X.$Zipendula by treating with boiling alcohol or boiling water, which dissolves the glucoside, but decomposes the enzyme. The glucoside could not be obtained in a crystalline form. Gaultherase, prepared from the same root by allowing the enzyme toORGANIC CHEMISTRY. 109 act on the glucoside and then extracting with alcohol, is soluble in water. It is not identical with emulsin, since it does not act on salicin or amygdalin, and gaultherin is not attacked by emulsin. By distilling the decomposition products formed in the production of gaultherase in steam, gaultheria oil is obtained. Hydrocyanic acid could not be detected in the products of the decomposition of gaultherin or of spirzein.The presence of even 0.1 per cent. of gaultheria oil prevents the growth of mould. The odoriferous substances contained in plants may serve to protect them from insects. The merest traces of Capuchin oil are sufficient to prevent the growth of Sacchammyces mycodevma, but this oil has very much less effect on the lactic acid ferment or on acetic acid bacteria. This preventive action may be due to the presence of a hydroxybenzylthiocarbimide. E. W. W. Derride and Pachyrhizide : Indian Fish Poisons. By H. E. TH. VAN SILLEVOLDT (Chem. Centr., 1899, ii, 588-589 ; from Ned. Tijd. Pharm., 11, 246-256; and Arch. Pharm., 1899, 237, 595).-The stupefying fish poisons occur mainly in plants of the family of Papilionucece.Derride, C3,H3,01,, prepared from the root of Dewis elliptptica, Benth., by treatiag with water, extracting with alcohol, evaporating, and treating the residue with ether, is a pale yellow substance,melts a t 73", and is easily soluble in the usual organic solvents, slightly so in light petroleum, and insoluble in water. The alcoholic solution has a faintly acid reaction. Derride is dis- solved by sulphuric acid, forming a brownish-violet solution, from which it is reprecipitated by water, and it appears to combine with phenylhydrazine. By boiling with an alcoholic solution of hydrogen chloride, it forms an anhydro-derivative, C33H2809, wh:ch is also present in crude derride, and is nct dissolved by ether. This com- pound forms small needles, melts a t 214O, and when treated with hydriodic acid forms a compound, ~,oH190,(OH)3, which melts a t 2 4 0 O .The preparation of pachyrhizide, C,,H,,Olo, from the seeds of Pachy~hizzcs angulatus, Rich., is similar to that of derride. Pachy- rhizide melts at 81°, and closely resembles derride. A compound, C2,H2,09, which is insoluble in ether and melts a t 196" is also con- tained in the seeds. The anhydro-derivative of pachyrhizide, C,,H,,O,, obtained by warming it with an alcoholic solution of hydrogen chloride, is a crystalline substance, melts at 182O, combines with phenylhydrazine, and contains two methoxy-groups. Derride and pachyrhizide appear to belong to the same homologous series as Pfaff's timboin (Abstr., 1191, 938), for which the formula C,,H,,O,, may be calculated from his analyses.E. W. W. Chlorophyll. By G. BODE (J. p. Chem., 1899, [ii], 60, 385-3136). -A reply to lSlarchlewski (Abstr., 1899, i, 381). Phylloxanthin. By G. BODE (Chem. C'sntv., 1899, ii, 529; from Bot. Centr., 20, 227--239).-A continuation of the controversy with Marchlewski (Abstr., 1899, i, 381). The alcoholic plant extract which contains chlorophyll combined with a lecithin is named crude110 ABSTlElACTS OF CHEMICAL PAPERS. chlorophyll solution, By the action of weak acids, this compound undergoes an intramolecular change, being converted into the crystal- line, olive-green chlorophyllan, and by the action of alkalis or of strong acids is decomposed into the lecithin constituents and alkali or acid compounds of chlorophyll ; the latter (Marchlewski’s alkachlorophyll and phyllocyanin) are decomposed by water.The chlorophyll com- pounds have different colours, according to the nature of the solvent and the concentration, which determine whether the compound remains undecomposed or is resolved into ions (compare Ostwald and J. Wagner; Deussen). Marchlewski’s phylloxanthin is impure chlorophyllan and, like phyllotaonin, not really a chlorophyll derivative, whilst phyllo- porphyrin is a product formed from chlorophyll by an intramolecular change. E. W. W. Furfuraldehyde from Beetroot and Molasses. By KARL ANDRL~K (Chem. Cent?.., 1899, ii, 460 ; from Zeit. 2uck.-Ind. Bdhm., 23, 55 1-559).--The colour of the furf uraldehyde-phloroglucide obtained from molasses is not the same as that of the pure compound.I n an experiment in which large quantities were employed, about 7 per cent. of a substance which appeared to be methylfurfuraldehyde was found in the portion which distilled a t 162-168’. Constitution of Arginine. By ERNST SCHULZE and ERNST WINTER- STEIN (Ber., 1899, 32, 3191-3194. Compare Abstr., 1898, i, 281 ; 1899, i, 107).-The formula previously proposed by the authors for arginine is confirmed by the fact that this substance is formed when ornithine is treated in the cold with cyanamide. Ornithine itself is probably as-diaminovaleric acid, since the distillation of its hydro- chloride yields a small amount of a substance which gives the re- actions of pyrrolidine, but has not yet been analysed. By D. LAWROFF (Zeit, physiol. Chem., 1899, 28, 585--586).-A method is described of isolating the hexon bases by the use of benzoyl chloride and subse- quent extraction with various solvents such as light petroleum. E.W. W. A. H. Benzoyl Compounds of Hexon Bases. W. D. H. An Alkaloid contained in the Bark of the Pomegranate. By ANTONIO PTCCININI (Gaxxettcc, 1899, 29, ii, 311-318).--From the light petroleum mother liquors obtained in the preparation of methyl- granatonine from the pomegranate root, an oily substance may be separated from which the author has isolated a buse of the composition C,HIFON. On decomposing the picrate by means of potassium carbon- ate, it is obtained as a colourless oil which has a very faint basic odour and boils at 114-117O under 26 mm. pressure. It is soluble in water in all proportions, giving a strongly alkaline solution.The picrate, C1,H,,O,N,, forms a crystalline powder melting at 152-153’ and soluble in boiling alcohol. The aurichZoi*ide, C,H170N,HAuCI,, separates from dilute hydrochloric acid in orange-yellow rosettes and melts at 115-1 17”. The hydrochloride is a viscous mass soluble in water. ‘J.’he base forms a semicap6cczone, C10H200N4, which separates fromORGANIC CHEMISTRY, 111 water in large, colourless, lustrous crystals which melt a t 169' and dissolve in alcohol, but are insoluble in ether. The hydrochloride, C,,H2,0N,,HCl, crystallises from dilute alcohol in slender, colour. less needles which melt with decomposition and evolution of gas a t 208' and are very soluble in water but insoluble in absolute alcohol ; the aqueous solution of the hydrochloride gives a yellow, oily precipi- tate with a solution of gold chloride.T. H. I?. By GOTTFRIED FENNER and JULIUS TAFEL (Bey., 1899, 32, 3220-3228. Compare Abstr.i 1898, i, 446)-The normal aurichloride of piperidine is always formed when auric chloride acts on piperidine hydrochloride in aqueous solution, and is also produced by the action of water on the abnormal salt. The latter is formed when piperidine hydrochloride and auric chloride are brought together in alcoholic solution, or when the normal salt is treated in alcoholic solution with hydrogen chloride or piperidine hydrochloride. It appears to dissociate when heated, either alone or in alcoholic solution, into the normal salt and piperidine hydrochloride, Abnormal isopropglamine aurichloride, ( C,H,oN),AuCl,, is prepared in a similar manner to the piperidine compound, and is a golden-yellow, microcrystalline powder melting a t 159' ; water decomposes it with formation of the normal salt.Abnormal 1-methyl piperidine auricldoride, (C,H,,N),AuCl,, melts between SO and 88' and yields the normal salt when treated with water. I n aqueous solution, 2 : 5-dimethylpyrrolidine yields an oily normal aurichloride, but in alcoholic solution a n abnormal aurichloride, which crystallises in yellow plates melting at 102-104°. Abnormal guinoline uurichloride melts a t 180' and decomposes a t 260'. Methylamine, coniine, aniline, and pyridine do not appear to yield abnormal salts. A. H, Synthesis of Glutaric and Trimethylene Derivatives.By ICILIO GUARESCHI and ERNESTO GRANDE (Chem. Centr., 1899, ii, 439-440; from Atti. Real. Accad. T o r h o , 34. Compare ibid., Abnormal Aurichlorides of Organic Bases. 33)-3 ; 5-Dicyano-4methg 2-4-eth?/Ztrimet~~Z~nedicccrbonimide- (dicyano- homocaronimide), NH<Co.C(CN, co*F(C")>CMeEt, prepared from the di- bromide, N H < ~ ~ , " ~ ~ l ~ ~ { > C M e E t , by heating at 110' for a \ I short time, crystallises in hard, lustrous, rhombic prisms, melts a t 210°, and is slightly soluble in water. When heated with sodium hydroxide, the imide loses 1 mol. of ammonia, and the SOlUtiOR, after acidifying with acetic acid, forms a silver salt when treated with silver nitrate ; by the action of hydrogen sulphide on this salt, an acid is obtained which is soluble in water and melts a t lS4'.Unlike dicyano- 2 : 6-dioxy-4-methyl-4-ethylpiperidine, the dicarbonimide does not evolve ethane from neutral aqueous solutions, and even when heated to 240-245' gives only small quantities of carbon monoxide, methane, and ethane. The ammonium derivative of 3 : 5-dicyano-2 : 6-dioxy- 4-dimethy@iperidirte, prepared by the action of acetone on ethyl cyanoacetate in presence of alcoholic ammonia, forms a white, crystalline, easily soluble mass ; its aqueous solution does not evolve gas even if112 ABSTRACTS OF CHEMICAL PAPERS. in lustrous, colourless leaflets, melts a t 216-217', and is slightly soluble in cold water, more so in alcohol or acetic acid. With potass- ium nitrite and sulphuric acid, it gives a characteristic, yellow colora- tion, and when heated at 310-320' evolves methane. The silver derivative, C,H,O,N,Ag, forms a white, crystalline precipitate. The dibromo-derivative, C,H102N,Br2, melts a t 190-1 95", and when heated for a long time with a 40 per cent.solution of acetic acid yields 3 : 5-dicyano-4-dimethyZtrimethyZenedicnrbonimide, CgH70,N,, which crystallises in small, hard, lustrous, colourless prisms, melts and decom- poses at 242', is soluble in water, alcohol, or acetic acid, and forms a silver salt. 3 : 5-Dicyano-2 : 6-dioxy-4- methyl-4-lzexylp~eridine, pre- pared by the action of methyl hexyl ketone on ethyl cyanoacetate in presence of alcoholic ammonia, crystallises in broad, colourless leaflets, melts a t 156-157", is very slightly soluble in water, and decomposes i n aqueous solutions, forming hexane and dicyanomethylglutaconimide, C,H,02N3.The dibvomo-derivative, C,,H,70,N,Br2, forms small, lustrous crystals, melts at 135O, loses its bromine when heated for several hours with a 50 per cent. solution of acetic acid, forming 3 : 5-dicyccno-4-methyl-4-hex~~tvimet~~~~ened~cavboni~ide, C, 4H, 70,N3 ; this compound crystallises in nacreous leaflets, melts a t 154-155', and is very slightly soluble in water. Pinacoline does not react with ethyl cyanoacetate and ammonia. The following conclusions are drawn : (1) By the action of ethyl cyanoacetate and ammonia on ketones of the type CH,* CO*C,H2,+1, the glutarimides o r piperidine derivatives, \ I are formed. These compounds may also be regarded as derivatives of aa-dicyanoglutaric acids, CnHan+l* CMe[CH(CN)*CO,Et],.(2) These new saturated eompounds form dibromo-derivatives from which tri- CO*C(CN) methylene derivatives, NH<Co, b,C-,)>CMe(CnHZn+l), may be pre- pared, Unlike the compounds of the p;-eceding class, these substances, and the dibromo-derivatives from which they are prepared, do not give a yellow coloration with potassium nitrite and sulphuric acid. E. W. W. Action of Heat on Hydrogenised Compounds. By ICILIO GUARESCHI and ERNESTO GRANDE (Chem. Centr., 1899, ii, 440; from Atti Real. Accad. Y'ovino, 34. Compare this vol., i, 52).-(1) Cyano- trimethyldihydropyridone, C,H,,ON,, decomposes at 320-330°, forming mainly methane and cyanodimethylpyridone, which melts a t 288-289'. (2) Cyanotetramethyldihydropyridone, C,,H1,ON,, which melts at 142--143*5O, decomposes at 320-330°, forming methane and cyano-1 : (?)-dimethylpyridone, CgH,,0N2; the latter melts a t 203-204O.3 : 5-Dicyano-2 : 6-dioxy-4-dimethylpiperidine, and other compounds which contain the group *CH,*CMeEt* or the group *CH,*CMe,*, under similar conditions, y.ield methane or ethane. (3) Ethyl 2 : 4 : 6- trimethyldihydropyridinedicarboxylate, C,,H,,O,N, decomposes0 1tG A N I C C H EM I STR Y . 113 340-350°,forming carbon dioxide, carbon monoxide, methane, ethylene, and alcohol, together with ethyl 2 : 6-dimethylpyridine-5-carboxylate, C,,H1302N, and ethyl 2 : 6-dimethylpyridinedicarboxylate. Of these two esters, the former (compare Weiss, Abstr., 1886, '719) is a colour- less base and boils at 255--257", and the latter crystallises in long, colourless needles, melts a t 7 3 O , and boils a t 300-305°. (4) Ethyl phenyldimethyldihydropyridinedicarboxylate, C,,H,,O,N, prepared by the action of benzaldehyde on ethyl acetoacetate in presence of alcoholic ammonia, forms crystaIs and melts a t 157'.On dry distillation, it decomposes into carbon dioxide, ethylene, hydrogen, and ethyl phenyl- dimethylpyridinecarboxylate, Cl6HI7O2N, which boils a t 315--320'. Alcohol, benzene, carbon monoxide, and ethyl trimethylpyridinedi- carboxylate are also formed by secondary reactions. ( 5 ) Ethyl dimethyldihydropyridinedicarboxylate, C1,Hl,O,N, prepared by the action of formaldehyde on ethyl acetoacetate in presence of aIcoholic ammonia, crystallises in fluorescent needles, melts at 183', and, on dry distillation under the ordinary pressure yields carbon monoxide, carbon dioxide, ethylene, ethane (?), ethyl dimethylpyridinecarboxylate, and ethyl dimethylpyridinedicarboxylate. The last compound melts at 73", and is the principal product of the decomposition.The results of these experiments shorn that the esters of dihydro- acids decompose on distillation, liberating 1 mol. of hydrogen, which often takes part in secondary reducing actions, and that the carboxy- ethyl group of the original compound, or of the est,er derived from it, also decomposes, forming carbon dioxide and ethylene, E. W. W. Pseudo-ammonium Bases. By ARTHUR HANTZSCH and M. KALB (Bey., 1899, 32, 3109-3131. Compare Abstr., 1899, i, 400).- Pseudo-bases are neutral substances isomeric with true ammonium hydroxide bases, aod correspond with the pseudo-acids previously described (Abstr., 1899, i, 399 ; this vol., i, 94, 103).Their existence may be discovered (1) by the phenomenon of gradual neutralisation, when the conductivity of a mixture of the ammonium chloride with sodium hydroxide gradually decreases to that of the sodium chloride produced, as the true base changes to the pseudo-base; (2) by 'abnormal neutralisation phenomena,' even where the velocity of change in (1) is too great t o be observed, the neutral ammonium chloride giving a neutral solution with a n equivalent of alkali, and the neutral pseudo- base giving a neutral salt when mixed with an equivalent of acid; (3) by the reluctance of the dry pseudo-base to combine with a dry acid or anhydride (CO,,HCN); (4) by the formation of abnormal anhydrides and ethers.The ammonium cyanides resemble the hydroxides, and frequently pass into pseudo-salts which are insoluble in water, soluble i n organic solvents, undissociated, and stable towards acids. Methylpyridinium hydroxide, C,NH,Me(OH), gave p32 = 21 3 and p25s=219 at 25'; i t is almost completely dissociated a t moderate dilution and shows no tendency to pass into a pseudo-base. 1-Methylquinolinium 1-hydroxide, C,NH,Me*OH, gave pZ2 = 20'7.5,114 ABSTRACTS OF CHEMICAL PAPERS. but is much less stable than the pyridine base, and passes into 1-methyl-1 : 2-dihydroquinoline oxide, O(CyNH7Me)2, th'e anhydride of the pseudo-base ; this separates in minute, white needles. Methylisoquinolinium hydroxide gave pZa = 206.9, and, like the preceding base, rapidly undergoes change.Phenylmethylacridinium hydroxide, CPh' 'NMe* OH, gave pzs6= 117.5 a t Oo, falling to 57.4 in 10 minutes, 14.1 in 1 hour, and becoming zero in about 15 hours. For the chloride, pIz8 = 45.6 a t Oo, and pm is calculated to be 50.0; whence p a for the base=127.2, showing that it is as highly dissociated as the caustic alkalis. A t 25", the isomeric change proceeds very rapidly, especially during the first few seconds, and is complete within 6 hours. Phenylmethylacridol, OH* CPh<CGH4>NMe, C H the pseudo-base, is completely insoluble in water, to which it imparts not the slightest conductivity, and does not combine with carbon dioxide or hydrogen cyanide, although with strong acids i t gives true acridinium salts; it is stable towards oxidising and reducing agents, and cannot therefore be represented by the formula CHPh<E:%>NMe:O.C6H4 \c,H,/ 6 4 When liberated from ;he= iodide by sodium hydroxide, dimethyl- /C,H*\ acridinium hydroxide, CMe' 'NMeeOH, is completely converted into the pseudo-base in 3 hours a t 0' in N/512 solution and methyl- acridinium hydroxide within 20 minutes in N/256 solution. At 25", ' gradual neutralisation ' can no longer be observed, but ' abnormal neutralisation ' occurs, the neutral iodides giving a neutral solution on adding an equivalent of caustic soda, whilst the pseudo-base is precipitated immediately, a separation which only takes place very slowly in the case of the phenylmethylacridinium base.Phenglmethylacridine ctjanide, NMe<C6H4>CPh*CN, CH separates gradually from a mixture of potassium cyanide and phenylmethyl- acridinium iodide as a white, crystalline substance, which melts a t 176". dissolves in organic solvents but not in water. and \C,H,/ 6 4 is not attacked by a d s . The first product is the true cianide, CPh /c"4\NiNe*CN, --___ which is stable at Oo, but is gradually con- \(?,HA/ verted [nt; the ' pseudo-salt ' a t 25O, the conductivity reaching a minimum within 16 hours. The pseudo-base does not combine with hydrogen cyanide. The azonium bases are regarded as pseudo-bases and shorn ' abnormal neutralisation ' lshenomena : thus the neutral salt I N-C H f;lph,$i>NPhC1 a t once gives a neutral solution with anORGANIC CHEMISTRY.11s equivalent of caustic soda and is converted into the pseudo-base y*C,H,.rYh - CPh-CPh,OK, which is quite insoluble in water, but dissolves in organic solvents. Aqueous solutions of cotarnine give evidence of the presence of a pseudo-base in the high temperature coefficient of the dissociation- constant and the formula C , H , O , < ~ ~ ~ . ~ ~ ~ > H M e is suggested for pseudocotai*nine. By the action.of hydrogen cyanide on co tarnine, or of potassium cyanide on the hydrochloride, a cyanide is produced which is regarded as pseudocotarmhe c p n i d e , C , H , O , < ~ ~ ~ ~ ~ ~ Y Y ; i t melts a t 86O, dissolves readily in organic solvents but only slightly in cold water, crystallises unchanged from water, and, unlike the true cyanides, is neutral, undissociated, indifferent to hydrochloric acid, and gives no precipitate with silver nitrate, By RUDOLF CAM Ps (Be?., 1899, 32, 3228-3234).-o-Acetaminoacetophenone is readily converted by aqueous soda into a mixture of 2-hydroxy-4-methyl- quinoline and 4-hydroxy-2-me thylquinoline, the elements of water being eliminated.A similar reaction is given by other acylaminoacetophenones, 2- or 4-hydroxy-derivatives, or a mixture of these, being formed, ac- cording to the constitution of the acid residu-es. In addition to the two hydroxymethylquinolines, o-acetamino- acetophenone yields a small amount of o-aminoacetophenone and of o-flavaniline and its acetgl derivative. T. M. L. Synthesis of 2- and 4-Hydroxyquinolines. o-Flavaniline, which has already been obtained in t e r i smdl amount by Bischler (Abstr., 1893, i, 531), crystallises in yellow needles melting a t 83-84' ; the clcetyl derivative melts at 13s'.I n the preparation of o-aminoacetophenone by the reduction of the corresponding nitro-compound, an oil boiling at 127-128" under 16 mm. pressure is obtained, which yields indigo when heated in the air, I t s constitution has not yet been ascertained. A. H. Carbamide and Thiocarbamide Derivatives of Diacetone- amine. By WILHELM TRAUBE and H. W. F. LORENZ (Bey., 1899,32, 3156-3163. Compare Abstr., 1894, i, 170).-Anhydrodiacetone- phenylthiocarbamide may be represented by one or other of the follow- ing formuh : CH<Eg'f>C-NHPh or CHqCafelN CMe*NPh>C.sH. in accordance with the former, it should, as a derivative of penthi- azoline, have a basic character, mhereas it reacts as a feeble acid forming metallic derivatives, the silver compound, C,,H,,N,SAg, being described ; the chemical behaviour of the substance is therefore more closely indicated by the second formula.The basic character of the pyrimidine ring is rendered manifest when the compound is alkylated, the methyl derivative being a stropg base.116 AlPSTltACTS OF CHEMICAL PAPERS. The oxime, C, 3H,0N,S, of diace t on ep hen yl t h iocar bamide, obtained by treating this compound with alcoholic hydroxylamine, melts at 152-1 5 3 O ; the corresponding phenylhydraxone, C,,H,,N,S, separates from alcohol in colourless crystals and melts at 169". hydriodide, C,,H,,N,S,HI, produced by mixing together alcoholic solutions of anhydrothiodiacetonephenyl thiocarbamide and methyl iodide, separates from water in lustrous crystals.Diacetoneullylthiocal.bamide, C,,H,,ON,S, crystallises from alcohol and melts at 138' ; its phenylhydraxone melts at 122O. The anhydro- compound is obtained either by heating the thiocarbamide above its melting point, or by treating i t with warm dilute sulphuric acid ; it crys- tallises from alcohol and melts at 130" ; its silver derivative is produced by treating the substance with a n alcoholic solution of ammonia and silver nitrate. ~-Methothiogl-p~~enyl-4 : 4 : 6-trimethyldihydropyrimidine 2-Methothio-d : 4 : 6-trimet?~yFl-aZlyZdihydrop~~imi~irne, CMe*N (C,H,)>c SMe, CHqCBze,- N obtained as a n oily base by treating anhydrodiacetoneallylthiocarb- amidewith an alcoholic solution of methyl iodide and sodium meth- oxide, boils at 159' under a pressure of 580 mm.; its platinichloride, (C1~I3~,N2S),, HgPtCIG, forms orange-yellow crystals. Anhydrodiacetonecarbamide (Abstr., Zoc. cit.) resembles the pre- ceding anhydrothiocarbamides, and by analogy its formula should CMe-NH>co be CH%Me2*NH ~rinitroccnh?/drodiucetonecccr6anzide, C7H,0N2(N0,),, cry stallises from methyl alcohol in colourless, silky needles which, when heated, take fire like guncotton. The substance is a dibasic acid dissolving in alkalis and ammonia to form dark yellow solutions. The barium salt, C7H7N2(N0,),Ba + 3H,O, crystalliees in reddish-yellow needles ; when heated, it explodes violently, and is decomposed by prolonged boiling with water. The silver salt, obtained i n brown needles, is even more explosive.The free acid, when boiled for some time with water, is converted into the compozsnd CGH,O,N,; this substance, which is obtained by concentrating the solution under diminished pressure, crystallises i n obliquely truncated prisms and melts at 214'; it is a monobasic acid, and is not explosive ; its bayium salt, (C,H,O,N,),Ba + 2H20, is sparingly soluble in water. G. T. M. Action of Amidines on Mesityl Oxide and Phorone. By WILHELM TRAUBE and RUDOLF SCHWARZ (Bey., 3163-31 74. Compare Abstr., 1887, 932; 1894, i, 170; 1898, i, 121 ; and preceding ab- s trac t >.- 2 -Anzino-4 ; 4 : 6-trimeth yldihydropyrimidine, CMe=N>cj .NH,, CH,<CMe, * N prepared by heating a mixture of guanidine and mesityl oxide on the water-bath, crystallises from hot water in white, rhombic plates, melts at 145O, boils a t 210' under a pressure of 10 mm., and sublimes in a vacuum, forming fern-like aggregates of slender needles.ItORGANIC CHEMISTRY. 117 dissolves in Tvater, alcohol, or benzene, and rapidly absorbs carbon dioxide from the a i r ; it is a strong monoacidic base, its salts being decomposed by caustic alkalis but not by ammonia. The hydrochloride is very hygroscopic, the oxdate forms colourless crystals and melts at 238', the picrate crystallises i n needles and melts a t 246', and the platinichloyide, (C,H,,N,),,H,FtCI,, and mercuricldoride melt at 176-177' and 184' respectively. The base takes up six atoms of bromine when treated with this reagent in glacial acetic acid solution ; the product, when crpstallised from warm water, forms reddish-purple, four-sided prisms which sinter together a t 108' and melt at 113'; when separating from boiling solutions, i t appears as yellow needles, these sinter together a t 108' but only melt a t 137' ; the purple prisms appear t o be a n impure form (containing free bromine) of the yellow compound, C7H1,N,Br6 ; the latter compound is decomposed on pro- longed boiling with water.When aminotrimethyldihydropyrimidine is heated with acetic anhydride, it yields an oily acet3Z derivative which has basic characters ; its platinicldovide, (C,H,,ON,),,H,PtCl,, crystallises in yellow leaflets and melts a t lSl-182'. Diacetoneguccnidine, NH:C( NH,)*NH* CMe,* CH,Ac, prepared by heating a mixture of guanidine thiocyanate, mesityl oxide, and sodium ethoxide at 120°, crystallises from hot water in needles melting at 163' ; it was only obtained crystalline in one experiment, the product at other times being amorphous.The acet?yl derivative, C,H,702.N,, produced by heating the crude base with acetic anhydride, crystallises from hot water in long needles and melts at 157'. 2-Phenyl-4 : 4 : 6-trinzet~yZdil~ydyo~yri~idine (anhydrodiacetonebenz- amidine), CH2<CMei. N>CPh, obtained by heating benzamide and mesityl oxide on the water-bath, separates from methyl alcohol in colourless, acicular prisms and melts a t 91'; i t is readily soluble in the ordinary organic solvents. The Iydrr-ocldoride, C,,H,,N2,HC1+ 2H20, crystallises from alcohol in well-defined cubes and melts a t 74' ; the platinichboride, ( C13H,6N,)2,H,PtC16 + 2H,O, crystallises in aggre- gates of rhombic plates and melts at 193'; the mercurichloride, C,,Hl6N2,HHgC1, + 2H20, crystallises in flattened needles melting at 179'; the oxalate crystallises in rosettes of leaflets and melts a t 210-21 1'.Anhydrotriacetonediguccnidine, C,,H,,N,, result,s from the condensation of guanidine (2 mols.) with phorone (1 mol.), the reaction being assisted by heating on the water-bath ; the product, a diacidic base, crystallises from water in long needles melting a t 1'74-175'. The hydrochloride, C,,H,,N6,ZHC1, crystallises in lustrous, rhombic plates and melts at 269' ; the plcctinichloride, C,lH,,N,,H,PtC1, + H,O, crystallises in yellow leaflets and decomposes a t 246'.Tricccetonedi- benxcLmid ine, CO( CH, CMe,*NH* CPh N H),, obtained by heat in g together phorone and benzamidine and extracting the product with cold alcohol, crystallises from the alcoholic solution on the addition of light petroleum; it melts a t 160'. The nitvate crystallises in prisms or six-sided plates ; when separated slowly from warm water, it melts a t 134', but when repeatedly crystallised from rapidly cooled solutions, it meltsat 218'. Theplc~tinicl~loi.ide, C,,H,,ON,,H,PtCl, + H20 CMe * N118 ABSTRACTS OF CHEMICAL PAPERS. crystallises from hot water in four-sided leaflets and decomposes at 263-265' ; the mercurichloride melts a t 269'. L formed as a bge-product in the preceding condensation, is obtained in larger quantity when the reaction is carried out at 160-110°, or when tha preceding base is heated to the same temperature ; it crystal- lises from alcohol in four-sided, acicular prisms, and melts a t 212", sintering at 201'.The hydvocldoride, C,,H,7N,0,HC1 + H,O, crystal- lises from hot water in six-sided prisms, sinters a t 150°, and melts a t 165'. G. T. M. Carbamide and Guanidine Delaivatives of Diacetoneamine. By WILHELM TRAUBE and MAX. SCHALL (Ber., 1899, 32, 3174-3176. Compare preceding abstracts).-The cyclic anhydrodiacetonephenyl- thiocarbamide does not exchange its sulphur for oxygen, but the open chain diacetonephenylthiocarbarnide, when boiled with yellow mercuric oxide and alcohol, yields an oil which is probably diacetonephenyl- carbamide, for on further treatment with acetic acid 2-hydroxy-l- phenyl-4 : 4 : 6-trimetJt?/ldiJqdropyrimidine (anhydrodiacetonephenyl- carbamide), CH<CMez-N>C*OH, CMe-NPh is produced ; this substance crystaliises from dilute alcohol in lizstrous leaflets, melts a t 161°, and dissolves in concentrated, but not in dilute, acids.results when the removal of sulphur is effected by mercuric oxide in alcoholic ammonia; it melts at 161' and is a strong base, but its salts are ill- defined ; the platiniclhloride, however, is crystalline. Diucetonetolylthiocurbamide melts a t 168' ; when treated in succession with mercuric oxide and acetic acid, i t yields 2-hylroxy-l-tolyl-4 : 4 : 6- trz'rnethyldihydro~yrin~i~ine, which crystallises from dilute alcohol in needles melting a t 151'. Similar compounds are obtained with xylylcarbimide.Additive Products of the Carbodiirnides. By WILHELM TRAUBE and A. EYNE (Ber., 1899, 32, 3176-3178. Compare Abstr., 1898, i, 241, and 1899, i, 192).--The carbodiimides readily combine with ethyl malonate, ethyl acetoacetate, and similar substances in the presence of a trace of sodium ethoxide, yielding additive products having the general formula NR : C: NHRoCHXY. NPh:C(NHPh)*CH(CO,Et),, produced from carbodiphenylimide and ethyl malonate, crystallises in colourless needles and melts a t 16'7'. The corresponding ditolyl com- pound from carboditolylimide melts a t 135'. G. T. M. Ethyl diphenyletJ~enyZ~c~idinedic~?.bonate, Ethyl acetyZdipl~emyZetJ~engZarnidi?zecarbonate, NPh: C(NHPh) CHAc* CO,Et, from ethyl acetoacetate and carbodiphenylimide, melts at logo; the ditolyl compound melts at 97'.ORGBNIC CHEMISTRY, 2i9 biacetyldiphen ylethen y lamidine, NP h : C( NH P h) CH A c2, from ace t yl- acetone and carbodiphenylimide, melts a t 150' ; the ditolyl compound meltsat 149'.The combination does not take place unless sodium ethoxide is present ; all the compounds produced are readily soluble in the ordinary organic solvents. Preparation of Phenylindoxyl. By MARTIN HENZE (Ber., 1899, 32, 3055-3060. Compare Abstr., 1895, i, 371, and 1896, i, 696).-The following compounds were prepared in attempting to synthesise phenylindoxyl. Phen yliminodi~henykacetic acid, NPh (C HPh. C0,H) 2, produced either by melting together ethyl anilinophenylacetate and zmc chloride o r by warming a mixture of anilinophenylacetic an6 bromophenylacetic acids at looo, is a white, amorphous powder sintering a t 90" and melting a t 105-1 10'.G. T. 11. v TetraphenyZ-P6-diket opiper axine, CHP h < ~ ~ , ~ ~ ~ > C H P h , obtained by heating a solution of anilinophenylacetic acid in acetic anhydride a t 155', is a white powder decomposing at 260'; this reaction is reversed when the condensation product is boiled with sodium amyloxide. Ethyl CLnthrunilrphenylacetate, prepared by boiling an alcoholic solution of anthranilic acid, ethyl bromophenylacetate, and sodium acetate, crystallises in white needles and melts a t 175-176", the acid, CO,H*CGH,*NH.CHPh*CO,H, melts at 227". Neither this acid nor benzylanthranilic acid is affected by fusion with caust,ic alkalis at 2 0 9-300'. G. T.AT. Orthoquinonoid Structure of Saffranine, Oxazine, and Thiazine Colouring Matters. By ARTHUR G. GREEN (Bey., 1899, 32, 3155-3156. Compare Kehrmann, this vol., i , 62).-With reference t o Kehrmann's formulation of the azonium, oxazine, and thiazine colours as orthoquinonoid bases, it is pointed out t h a t the author had previously expressed similar views (Proc., 1892, 195, and 1896, 226), and had also given reasons for believing that oxygen and sulphur ar0 quadrivalent in the latter compounds. The following are suggested as alternative formula, C,H4< NR>C,H4 and NCl y c1 C,H4<$C,H,. These formuh differ from those proposed by Kehrmann, C,H,<T>C,H,, in containing the acidic radicle (chlorine in this case) attached t o nitrogen and not to oxygen (or sulphur); this seems more probable in view of the more basic character of the nitrogen atom.Another constitution for these substances is possible, namely, that in which both aromatic nuclei are represented as being quinonoid, In certain azonium compounds, it is found that both nuclei appear to be quinonoid, and react with amines; these formuh offer a simple explanation of this behaviour, it being otherwise necessary to assume a migrationof the CsH4gN NC1 R>C,H4 and C,H,<~!?>C,H,.120 ABSTRACTS OF CI-IEMICAL PAPERS. quinone linkings (Kehrmann, Abstr., 1898, i, 439). Moreover, the formulae suggested for the azonium bases render it possible to repre- sent saff ranones, rosindones, and similar anhydrides as p-anhgdro- their constitution being more probable than that based on Kehrmann's / 1.p- formula, which represents them as m-anhydrides, $JiNB>c6H, I C.T. M. Constitution of &Methyluric Acid, By ROBERT BEHREND and EMIL DIETRICH (Annalen, 1899, 309, 260--281).-Although uric acid contains only four replaceable atoms of hydrogen, five mekhyluric acids have been described (compare E. Fischer, Ber., 1899, 32, 461). Of these compounds, &methyluric acid, which certainly contains the methyl raaicle in the alloxan group, is regarded by Fischer as 4-methyl- acid, CO ."&.C .NH >CO, along with a-methyluric acid (Hill) YH-CO $*NH and c-methyluric acid (Fischer and Ach, this vol., i, 63). The authors' experiments, however, lead them to the conclusion that &methyluric ri\ile*CO*E*NH acid is 6-methyluric acid, c(, , NH, .NH>CO.If this is actually the case, it would become necessary to reconsider the accepted formultx of several purine derivatives. The results which have led to this con- clusion are as follows. Besides acetylcarbamide and oxalic acid, methyluracil yields oxaluric and acetic acids when oxidised with potassium permanganate. I n the same circumstances, P-dimethyl- uracil gives rise t o acetylmethylcarbamide, and acetic, oxalic, and methyloxaluric acids ; from a-dimethyluraci1,rnethyloxaluric acid only is obtained, showing that the isomerides, so far as concerns the position of the methyl group, have the constitution NMe<gE::g>CMe. Nitric acid converts a-dimethyluracil into nitromethyluracilcarboxylic acid, NMe<CO-N&>C*C02H, CO*C(NO ) which loses carbon dioxide, yield- ing methylnitrouracil ; the same methylnitrouracil is produced by methylating nitrouracil; it is the same substance from which von Loeben first prepared &methyluric acid.P-DirnethyluraciZ, NMe<CO CO*CH ,NH>CMe, occurring in the mother liquor of a-dimethyluracil (m. p. 219-220°), is produced when methyl- uracil, dissolved i n alcoholic potash, is heated with methyl iodide, a-dimethyluracil and trimethyluracil being formed at the same time ; it crystallises in serrated leaflets or long needles before precipitation, the purified substance forming lustrous prisms which melt at 260'. Methyloxaluric acid, NH,. CO *NMe*CO*CO,H, prepared by oxidising a-dimethyluracil, crystallises from water in prisms, and melts and decomposes at 1S0-l9O0, according to the rate a t which the tempera-ORGANIC CHEMISTRY.121 ture rises ; the potassium salt forms a gelatinous mass which becomes crystalline. Nitronzethyluracilcarbo~~lic acid, obtained hy the action of nitric and sulphuric acids on a-dimethyluracil, crystallises from water in needles or prisms containing the solvent, which is removed a t l05', the anhydrous substance melting at 255-256' ; the potctssium salt contains 1H,O, and forms a potussium nityate double salt. Isodialuric acid is readily converted into dialuric acid under certain conditions, and if the analogous change took place when methyliso- dialuric acid is condensed with carbamide, 3-methyluric acid would be produced ; the authors find, however, that dialuric acid itself yields no trace of uric acid, but merely undergoes, in part, oxidation to nlloxan.M. 0. F. Deoxytheobromine. By JULIUS TAFEL (Bey., 1899, 32, 3194-3206. Compare the following abstract).-When a solution of theobromine in 50 Der cent. sulDhuric acid is submitted t o electro- lytic reduction, deo&theobromini (5-0x9-1 : 4-dimetlql-6 : 7-dihydro- NH* CH,*#*NMe purine), &O.NMe.C-N>CH, is formed ; it crystallises from water in thin prisms containing 2K,O, which are sparingly soluble in cold, but very readily in boiling water ; the anhydrous base melts a t 215'. The hydrochloride forms large, very soluble prisms, the platinichlwide is a granular precipitate, the picrate decomposes at 205O, and the meycurichloride is a crystalline precipitate. Bromine in chloroform solution converts the base into a n unstable monobromo-compound, C7H90,NBr, which readily passes into the isomeric 5-oxy-1 : 4-dimethyl- purine hydrobromide.Deoxytheobromine is converted by oxidation with silver acetate. bromine, and acetic acid, or lead peroxide and F=CH-g-NMe acetic acid into 5-oxy-1 : 4-dirmethplpurie, CO *NMe*C--NaCHP which crystallises, with 2H,O, in colourless prisms, and melts, when anhydrous, at 256-257'. This compound is also formed by the methylation of 5-oxy-l-methylpurine, its constitution and that of deoxytheobromine being thus determined. The hydrochloride, hydro- bromide, hydrogen sdphute, picyate, and platinichloride 81-0 all crystal- line salts. A. H. Deoxycaffeine. By THOMAS B. BAILLIE and JULIUS TAFEL (Be?.., 1899, 32, 3306-3220.Compare Abstr., 1899, i, 268, and the pre- ceding abstract).-In addition to the salts of deoxycaffeine which have ahead y been described, the sulphate, nitrate, cupochZm*ide, and rnethiodide have been prepared. When boiled with baryta water, the base yields carbon dioxide, formic acid, a n amino-acid of unknown composition, ammonia (1 mol.), and methylamine (2 mols.). Bromine in absence of water converts deoxgcaffeine into a monobromo-corn- pound which is probably 5-oxy-1 -:Cdimethylpurine 6-methobromide, NMeBr:CH* C *NMe &-,-NMe-E-B>CH, whilst a yellow perbromide is formed when a n excess of bromine is employed. Oxidation with lead peroxide and VOL. LXXVIII. i. I;122 AUS’I’11ACTS OF CHEMICAL 1’AI’X:BS. acetic acid converts the base into oxydirnetlLylpwine suetlbocccetate, TMeAc: CH- C*NMe CO-NAfe-z-N>CH, which is converted by alkalis into 5-0x9- this decomposes and melts a t 160°, is stable in the air, and does not; absorb carbon dioxide, whilst the solution is strongly alkaline and behaves in every way like that of a strong ammonium base.It is therefore probable that the constitution of the dry salt is reDresented rMe*CH* (OH)*fi*Nlne by the formula CO--NMe &CH, and that of the basein solution by the alternative formula just given. The ciiboride, bromide, picrate, pldinichlovide, and aurichlode have all been prepared. The same base is formed when 5-oxy-1 : 4-dimethylpurine rnethiodide is converted into the acetate, and the latter decomposed by alkali. From this it follows that the methohydroxide has the constitution assigned to it above, whilst deoxycaffeine is 5-oxy-1 : 4 : 6-trimethyl- 6 : ’7-dihydropurine, O-NMe-c-N, >CH.When the metho- hydroxide is heated at 170-lSOc, caffeine and deoxycaffeine are formed along with decomposition products of the latter. Constitution of the so-called Oxyazo-compounds. By 3%. C. FAUMER and ARTHUR HANTZSCH (Bey., 1899,32, 3089-3101).- The criteria enumerated in this vol., i, 95, are applied to the case in question. Free quinonehydraxone (“ hydroxyazobenzene ”) is neutral to indicators, is not an electrolyte, and does not form a compound with ammonia in benzene solution ; its constitution is probably NHPh*N:C,H,:O (and that of its hydrochloride, NH2PhCl*N:C,H,:O). But it is a pseudo-acid, for its sodium salt, with 3H,O, is only hydro- lysed t o the extent of about 0.3 per cent.at dilution VS2, and therefore must be derived from a comparatively strong acid, probably having the formula NPh:N*C,H4*ONa ; moreover, the quinone- hydrazone dissolves in aqueous ammonia, probably having undergone a molecular transformation into the hydroxyazo-compound, which then united with ammonia, pQuinonephenylhydrazone forms alkali salts most easily ; the oquinonephenylhydrazones (from o-toluquinone and from pseudocumoquinone) do so less readily and the products are less stable ; the meta-isomeride could not be obtained. P-Naphthalene- 0-quinonephenylhydrazone will only form a salt when treated with the alkoxide ; the p-chloro- and p-nitro-phenylhydrazones form salts with concentrated aqueous potash, but the salts are decomposed by water.The abnormal hydrates, NHPh*N:C,H,(OH)2 (Hewitt, Abstr., 1895, 353), occupy a position intermediate bet ween the quinonehydrazones and hydroxyazo-compounds ; they are best prepared by treating the hydrochlorides of the quinonehydrazones with water or aqueoua sodium carbonate or acetate, and they contain 1, or more often +, H,O; a number were prepared, although not all for the first time. Some benzoates and acetates were prepared from the qninone- rHMe*CH,*fi *NMe A. H.ORGAKIC CHEMISTRY. 123 hydrazones or their hydrates, and methyl derivatives (azoanisolcs, NR:N*C6H,*OMe) were prepared from the sodium or silver salts, and also from the nitrosohydrocarbon and the anisidine ; in no case was a nitrogen-ether obtained.No hydrazone could be obtained from quinone and phenylhydrazine ; quinol, and an oxidation product of phenylhydrazine, diphenyltetrazone, being obtained instead. Derivatives of ( p - ) cluinone : m-chlorophenylhydrazone, the methyl derivative is yellow and melts at 53"; o-tolylhydrazone, the acetate melts a t 65", and the methyl derivative is brown and melts at 59" ; pseudocumenehydrazone, the hgdrocldoride melts at 162", and the methyl derivative is brown and melt,s at 89'. Derivatives of o-chloroquinone : the phenylhydrazone is yellow and melts a t 8 8 O , the hydrochloride melts at 150°, the hydrate, which is brick-red below 50" and yellow above, melts at 73"; o-tolylb ydrazone, the hydrochloyide melts a t 148". Derivatives of o-toluquinone : m-chlorophenylhydraxone is yellow and melts a t 104", the hydmte is red, melts a t 76", does not Iose water readily, and is not dissociated in benzene solution, as cryoscopic experiments show, the benzoate is pale yellow and melts at 101"; o-tolylhydrazone, t h e hydvocldoride melts at 157", another Aydyate is brick-red, effloresces readily, and melts a t 83".The following compounds are, perhaps, new. 0. F. B. Constitution of the Hydroxyazo-compounds. By WILLIAM MCPHERSON (Amer. Chem. S., 1899, 22, 364--383).-The early por- tion of this paper contains details of work already published in brief (Abstr., 1896, i, 27) ; that thep-hydroxyazo-compounds have the con- stitution denoted by their names, and are not, quinone derivatives of the type O:R:N*NHPh, is held to be established by the following facts. (1) p-Hydroxyazobenzene by direct acylation or alkylation, yields derivatives unquestionably of the type NPh:N.C,H,* OR (R = acyl o r alkyl), although o-hydroxyazo-compounds give by acyla- tion derivatives as unquestionably of the form O:R:N*NPhAc (Golclschmidt and others).(2) The free p-hydroxyazo-compounds do not interact with phenylhydrazine at loo", although all p-quinone- benzoylphenylhydrazones react explosively with this substance. (3) All p-hydroxyazo-compounds are readily soluble in dilute caustic alkalis, whilst the o-hydroxyazo-compounds derived from naphthalene, which are undoubtedly quinonephenylhydrazones, are insoluble. (4) The results obtained in the aryoscopic researches of Auwers and Orton (Abstr., 1897, i, 40, and ii, 11 2).The hydrazones described were prepared by the interaction of the quinones with salts of the respective hydrazines. QuipionencetyZpheny Zhp?raxone, 0: C,H4*N *N P h Ac, crystallises f rorn a mixture of benzene and light petroleum in flat, yellow needles, melts at 11 So, and i s not identical with p-acetoxyazobenzene, NPh:N*C,H,*OAc (Wallach and Kiepenhener, Ber., 1881, 14, 2617), which melts at S9*5', not 84-85'; when heated with alcoholic potash, however, i t yields p-hydroxyazobenzene. Toluquinonebenxoyl- phenylhydrcczone, O:C,H,Me: N*N Ph* COPh, cry st allises from benzene in small, square, y+ow plates, and melts at 151"; when reduced with zinc dust and acetic acid, it yields benzanilide, and is converted by124 ABSTRACTS OF CHEMICAL PAPERS.alcoholic potash into benzeneazo-0-cresol, although not identical with the benzoate of the latter (Noelting and Kohn, Abstr., 1884, 901 ; compare Goldschmidt and Pollak, Abstr., 1892, 974). Thyrnoquinone- benxoylphenylhydrcLxone, O:C,H,MePrB: N*NPh* COPh, crystallises from a mixture of benzene and light petroleum in yellow plates and melts at 132'; there is also formed a colourless, crystalline substance, Cl5HI4O2N2, melting nt 155'. The hydrazone, on reduction with zinc dust and acetic acid, yields benzeneazothymol, but is not identical with the benzoate of the latter, OBz* C6H2MePrs*N,Ph, prepared by Baumann's reaction, which crystallises from hot alcohol in reddish- yellow needles, melts at 115', and is converted by alcoholic potash into the parent substance.a Napht7~nquinonebenzoylphenyZhyd~*azone crystallises from a mixture of benzene and light petroleum in yellow, silky needles, and melts at 161.5' J i t is not identical with benzene- azo-a-naphthyl benzoate (Meldola, Trans., 1889, 55, 606). When benzoqninone and a-phenylmethylhydmzine hydrochloride are brought together in aqueous solution, nitrogen is evolved and diphenyl- dimethyltetrazone formed ; with toluquinone and thymoquinone, similar action occurs. Diphenyldibenxyltetyaxone, N2( NPh*C,H,),, ob- tained similarly from benzoquinone and a-phenylbenzylhydrazine sulphate, crystallises from a mixture of benzene and light petroleum in colourless rhombohedra, and melts and decomposes at 145'. a-Naphthaquinonephenylmetir.ylhydraxone, O:C',,H6:N*NMePh, crystal- lises in long, flat, amethyst-coloured crystals, melts at 118.5: and is not identical with 4-benzeneazo-a-naphthol-1-methyl ether, OMe*C,,H,* N2Ph (Zincke and Bindewald, Berm, 1884,17,3026).a-N'pht?~apuinonepli,enyl- benzylhyclrazone, O:C,,H,:N *NPh* C,H,, cryetallises f rorn a mixture of benzene and light petroleum in yellow, dichroic, flat needles aIid melts at 136'; the benzyl ether, C,H,* 0 *C,,H6*N2Ph, prepared by the action of benzyl chloride and caustic soda on benzeneazo-a-naphthol, forms ruby-red monoclinic crystals, and melts a t 1029 The benxoyl derivative, O:C,,H,:N*NPhBz, is obtained by the action of benzoyl chloride on an alcoholic solution of P-naphthaquinone- phenylhydrazone and sodium ethoxide, and also by the interaction of P-naphthaquinone and a-benzoylphenylhydrazine sulphate ; i t forms yellow needles, melts at 19l0, and on hydrolysis with alcoholic potash or concentrated sulphurie acid, yields benzoic acid and @-naphtha- yuinonephenylhydrazone.When the latter is heated with methyl iodide and alcoholic sodium methoxide, the methyl ether of %benzene- azo-a-naphthol is formed (compare Meldola and Hanes, Trans., 1894, 65, 834; Noelting and Grandmougin, Abstr., 1891, 1076), which crystallises from alcohol in reddish-yellow plates and melts at 95O ; P - n a p ~ t h a q u i n o n e p h e n y l ~ e t ? ~ ~ Z ~ y ~ r ~ z ~ e crystallises from alcohol in yellow needles and melts a t 1345O. W. A. D. Action of Benzoyl Chloride on the Phenylhydrazones of Benzoin. By PAUL C. FREER (Amer. Chem. J., 1899,22, 396-402. Compare Smith, Abstr., 1899, i, 909).-The product of the action of benzoyl chloride on benzoin-@-phenylhydrazone dissolved in absolute ether at winter temperature," consists principally of0 RG A S 1 C C H E 31 I ST 1i Y . 125 benzanilide and benzil, together with lophine, dibenzoylaniline, hydrogen chloride, ammonium chloride, and aniline hydrochloride, but a considerable amount of resin is also formed; tm-nitrobenzoyl chloride, under similar conditions, gives rise to m-nitrobenzoylaniline, but the action of benzoyl chloride on benzoin-P-phenylhydrazone methyl ether yields only an intractable resin.The author discusses the nature of these reactions at some length, on the assumption that CPh t h e compound, NH<Nph>CPh, is initially formed ; the formation of lophine from benzoin-P-phenylhydrazone is explained by assuming that the latter first dissociates into benzaldehyde and the group :CPh*NH*NHPh, the benzaldeh yde subsequently combining with the benzil and ammonia simultaneously formed.The author reiterates his statement (Abstr., 1899, i, 357) t h a t benzoin-a-phenylhydrazone is not affected by benzoyl chloride. W. A. D. Unsymmetrical Disubstituted Hydrazones. By HANS LABHARDT and K. vox ZEMBRZUSKI (Bey., 1899, 32, 3060-3063).- The phenylhydrazones of benzaldehyde, salicylaldehyde, and their homo- Zogues are white or pale yellow; the hydrazones containing nitro- groups and their sulphonic acids are either yellow or red, the latter compounds dyeing wool and silk from acid baths. The hydrazones derived from secondary hydrazines -and aromatic aldehydes have similar properties and the following compounds of this type are described : PlLenyl-p-nitvo benx ylidenemetltylhydraxine, NMePh N: CH * C6H;N0,, obtained by mixing equivalent amounts of p-nitrobenzaldehyde and a-phenylmethylhydrazine in alcoholic solution, melts a t 132O ; the m-nitro-compound melts a t 11 2' and the o-nitro- a t 77" ; these sub- stances form red crystals readily soluble in the ordinary organic solvents; the para-compound may also be produced by methylating phen yl-p-nitrobenzylideneh ydrazine.Phenyl-o-hydroxybenxylidenemthylhydvuzine crystallises in white needles and melts a t 71' ; its solution in alcoholic potash is yellow, Plhenyl-p-nit~obenzylidenetl~ylhydruzine melts a t 13 1' and the rn-nityo-compound at 114' ; these substances are red, whilst the o-nitro- derivative, which melts a t 44', crystallises in brownish-yellow needles.Dipl~enyl-p-nitrobe~zyZiden~T~ydrazine melts a t 13 lo, the m-nitro-com- pound at 119-120'; both these substances are brownish-yellow ; the o-nitro-compound melts at 146' and is yellowish-red ; the o-hydroxy- compound crystallises i n white needles and melts at 139O. p-~olyl-a-methylhydruxine, prepared by reducing p-tolylmethylnitros- amine, is a non-crystallisable oil, readily soluble in the ordinary organic solvents ; it is decomposed by concentrated mineral acids, its hydrochloride being most conveniently obtained by passing hydrogen chloride into its ethereal solution. p-Toly I- p-nitro benxylidenemetl~ylhydrazine melts at 1 4 3', the m-mho- compound at 150*5O, and the o-nitro-compound a t 90.5' ; these nitro- derivatives are red, whilst the p-hydroxy-compound melting a t $5--86", is pale yellow. G.T. M.126 ABSTRACTS OF CHEMICAL PAPERS. Normal Diazo-compounds as ‘‘ Pseudodiazonium Compounds.’ By ARTHUR KANTZSCH (Ber., 1899, 32, 3132-3136 j.-The relation of normal diazo-compounds (metallic salts, diazo-oxides, diazo-ethers, and normal diazo-cyanides) to d iazonium salts exactly corresponds with t h a t of the pseudo-bases (see this vol., i, 113) t o the ammonium salts. The non-existence of the isomeric diazonium compounds corre- sponds with the labile or unstable natnre of the ammonium bases, their cyanides and other derivatives, the velocity of change being here too great to be observed.v The latter part of the paper is a reply to Bamberger (Ahstr., 1899, i, 750). T. M. L. Decomposition of Proteids by Acids. By THOMAS BOKORXY (Zeit. angew. Chem., 1899, 1099--1100).-The action of 4 per cent. aqueous solutions of hydrochloric, hydrobromic, sulphuric, oxalic, an& acetic acids on purified egg-albumin has been studied. The action begins soonebt with hydrochloric acid, and the others follow in t h e order given. The albumoses and peptones formed were separately precipitated after the several mixtiires had been boiled for 2 hours. Moderately large quantities of peptone were obtained from t h e hydrochloric, hydrobromic and srilphuric acid solutions, none at all from the clxalic acid, and merely a trace from the acetic acid.Com- pare Wroblewbki on peptonisation (Abstr., 1895, ii, 516). J. J. S. Amount of Tyrosine from Proteids. By FELIX REACE (Vi~chow’s Archiv, 1899, 158, 288-296).--The amount of tyrosine obtained from the decomposition of various proteids is very differently given by different observers, and also differs considerably with differ- ent proteids (from 0.25 to 5 per cent.). In the present research, the proteid material was decomposed by pancreatic digestion, but in parallel experiments with the same proteid the results vary. Thus with fibrin, the amount of tyrosine varied from 0.6 t o 3.8 ; with egg-white from 0.1 t o 0.6 ; with muscle pro- teids, from 1.06 to 1.37 per cent. The one experiment quoted with casein gave a yield of 4.5 per cent. of tyrosine. W. D. H. Nomenclature of the Mbumins of White of Egg. By ALExEr A. PANORMOFF (Chem. Centr., 1899, ii, 480; from J. Buss. Chem. Xoc., 1899, 31, 555--556).-The eggs of different birds contain different kinds of albumin, and the author proposes t o name the albumin of hen’s egg, which is easily crystallised from ammonium sulphate solution, albumin, and the more soluble albumin, albuminin (compare Abstr., 1899, i, 655). I n other cases, to the albumin which is least solubIe in ammonium sulphate solution a name is given which is formed by attaching the termination “-in ” t o the zoological name of the bird, the more soluble albumins being similarly designated by words ending in “-inin” and “-inidin” in the ordex of increasingsoluhility. Thus the amorphous albumin of pigeon’s egg is columbin and the more soluble crystalline albumin is columbinin. E. W. W.Action of Heat, Dilute Acids, and Alcohol on Albumin. By ALEXEI A. PANORMOFF (Chem. Centy., 1899, ii, 480-481 ; from J. RIMS. Chem. Soc., 1899, 31, 556-560. Compare Abstr., 1899, i, G55).- When 0*05-0*5 per cent. solutions of albumin in hydrochloric, hydro- bromic, phosphoric, pyrophosphoric or metaphosphoric acid are dialysed at the ordinary temperature, acid solutious are obtained in all cases but the last, metaphosphoric acid alone forming a precipitate, The rotatory power of these acid solutions differs from those of the original solutions and is still further increased by heating a t 100'. I n both cases, compounds of albumin with the acids are formed, and the change of rotatory power must therefore be due to polymerisation or depolymerisation. These polymeric compounds have also n diff crent solubility in water. The compounds obtained by dialysing the cold solutions, when reduced, regenerate the original albumin, but the com- pounds prepared by heating at looo yield only amorphous compounds of the same composition. The formula Alb,5HC1, in which Alb = C,,,H42,0,,N6,S,, is ascribed to the hydrochloride and Alb,3HBr to the hydrobromide. Phosphoric acid forms compounds containing 2 H,P04, 3H,P04, and 4H,P04 respectively, according to the concentra- tion of the acid, and pyrophosphoric acid compounds containing 3 H4P,07 or 7H4P,07. By heating either of the two latter compounds with a 0 3 or a 0.5 per cent. solution of pyrophosphoric acid, the compounds Alb,4H,Y04 or Alb,3H,P04 are formed respectively. The albumin obtained by evaporating dialysed albumin in a vacuum or by coagulat- ing it at 1OOOand finally drying at looo in a stream of hydrogen, has properties which differ from those of the albumin prepared by pre- cipitating with alcohol and ether and drying in a similar manner, although both have the composition given above. Solubility of Serum-Globulin in Water. By EMIL MARCUS (Zeit. physiol. Chem., 1899, 028, 559-575).-Doubt is cast on the hitherto accepted fact that serum-globulin is insoluble in water. It was prepared by several methods from serum and subjected to dialysis ; only a small quantity of the globulin was precipitated. The globulin so precipitated and that which remains in solution do not, however, differ in elementary composition, coagulation-temperature, or specific rotatory power. W. D. H. By V. ARNOLD (CILem. Centv., 1899, ii, 344; from Centr. med. Wiss., 37, 465--468).-The rose-red solu- tion of haematoporphyrin in alcohol or chloroform turns violet on adding bromine water. On adding strong hydrochloric acid, the solution becomes steel-blue. When mixed with aqueous caustic potash, a brown colour is obtained; on adding excess of bromine water, the mixture turns a dirty green, and when hydrochloric acid is added in excess a pure green is obtained. Measurements are given of the bands contained in the absorption spectra of these various solutions, E. W. W. Spectroscopy of the Blood. L. DE K. Extractives of Muscle. By MAX SIEGFRIED (Zeit. physid. Chem., 1899, 28, 524-529).-The N : P ratio in various preparations of carniferrin varies considerably according t o the method of preparation.128 ABSTRACTS OF CHEMICAL PAPERS, This is due to varying amounts of impurity, of which the principar constituent is an albumose-like substance. W. D. H. By TH. RICHARD KRUGER (Zed. physiol. Chem., 1899, 28, 530-534).-By ‘ salting-out ’ solutions of muscle nucleon by sodium chloride or magnesium sulphate, the amount of nitrogen is diminished slightly. If ammonium sulphate is used, the phosphorus is lessened also, and the N : P ratio sinks. These results show that decomposition occurs, A corresponding effect is produced by peptic and tryptic digestion. Similar experiments with milk nucleon gave t h e same results, except that peptic digestion produces no change and ammonium sulphate causes little or no precipitation. Nucleons. W. D. H. Plasmic Acid. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1899, 28, 426--438).-This substance was originally prepared from yeast nuclein by Kossel (Abstr., 1893, i, 680), and differs in many of its characters from nucleic acid. It is now shown to be metaphosphoric acid. As prepared, however, it contains about 1 per cent. of iron,. although whether this is to be regarded as ‘ organic ’ or ‘ masked ’ iron is uncertain, the various colour reactions giving contradictory results. W. D. H. By CARL THORE MORNER (Zeit. physiol. Chem., 1899, 28, 471-523).-By treating gelatin in succession with water, dilute potash, dilute acetic acid, water, alcohol, and warm water, filtering, precipitating with alcohol, drying, powdering, ex- tracting with ether, &c., a product was obtained containing only from 0.25 to 0.75 per cent. of ash. It contains 0-2 per cent. of sulphur ; this is present in the gelatin, not in impurities ; the higher percentage of sulphur given by others is due to proteid admixture. With Millon’s reagent, it gives a reaction which, however, is transitory unless the reagent is considerably diluted with water. With sodium chloride, potassium ferrocyanide, and acetic acid, i t gives a precipi- tate when these reagents are present in suitable proportions. The idea that gelatinisation depends on the presence of mineral constituents was not confirmed ; neither was any support found for what Dastre calls the ‘ salt-digestion ’ of gelatin. Cystin, a Decomposition Product of Keratin. By KARL. A. H. MORNER (Zeit. physiol. Chem., 1899, 28,595-615).--Horn was treated on the water-bath with 25 per cent. hydrochloric acid for several days ; among the products of decomposition (tyrosine, &c.) separated out, most interest attaches t o the presence of cystin, 11 grams of which were obtained from 450 grams of dry keratin ;. cystein was also obtained. I n another experiment, more cystin was obtained in proportion, but no cystein. Properties of Gelatin. W. D. H. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9007800073

出版商:RSC    

年代:1900

数据来源: RSC