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J O U R N A L OF THE CHEMICAL SOCIETY. ABSTR*ACTS OF CHEMICAL PAPEFLS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. PART I. Organic Chemistry. Elementary Composition of the Mfneral Oils. By CAnrl ENGLER and L. JEZIORANSKI (Bey., 1895, 28, 2501-2505) .-The fiuthors have mado analyses of samples of oil from Galicia, Sumatra, Baku (Bibi-Eibat), Alsace (Pechel bronn), and Pennsylvania, and also of the various fractions obtained from these oils, namely, below 150c, 150-20@', residue. From the analyses, arid from the amount of each fraction absorbed by concentrated sulphuric acid, the aut'liors con- clude that the lower fractions consist mainly of saturated hydrocar- bons of the paraffin series, except in the case of the Baku oil, whereas the portion boiling above 200' consists, in all cases, mainly of uiisatu- rated hydrocarbons of the olefine series.Fractional Distillation applied to American Petroleum and Russian Kerosene. By J. ALFRED WANKLTN and Wrrmm J. COOPER (Phil. .Mug., 1895, [ 5 ] , 40, 225--228).--'i'he paper contains the re- sults of the authors' experiments on the fractional distillatioil of American petroleum, and the vapour density, specific gravity, and composition of the various fractions, the results being compared with those obtained by the authors in the case of Russian kerosene. They consider that each of these petroleums contains a homologous series of hydrocarbons with st common increment of 7, instead of 14, a result that would require the accepted atomic weight of carbon to be halved. For a like carbon contents, the hydrocmbons of trhe Russia11 series, which contain '2 atoms of hydrogen less per molecule, always show a slightly greater specific gravity, the increment varying from 0.025 to 0.035.L. M. J . J. J. S. VOL, LXX. i. b2 ABSTRACTS OF OHEMICAL PAPERS. Russian Kerosene. By 5. ALFRED WAXKLYN and WILT,IAM J. COOPER (Cheiiz. A7e1c.9, 1895, 72, 7).-A tabular whume' is giren of the work done on the hydrocarbons existing in comnlercial Russian kerosene (Abstr,, 1895, i, 77 and 437). Hexylene and Hexylic Hydride derived from. Mannitol by Reduction with Hydriodic acid. By J. ALFRED WANKLTN (Chem. News, 1895, 72, 75j.-The specific gravity of hexylene at Oo is given :IS O.iO17, and of hexylic b-ydride a t OOas 0.6759, differing by 0.0258. A similar difference, of 0.025 to 0.035, is observed between the densi- t'ies of the hjdrocarbons of the same carbon condensation obtained from Russian and American petroleums respectively, the former being the denser.Unsaturated Hydrocarbons. By AL EXANDRE DESGREZ (Ann. Chim. Ph?ys., 1894, [7], 3, 209--246).-Berthelot (Ann. Chim Phys., [3], 43, 385, and [5], 23, 184) has shown that unsaturated hydro- carbons can be made to combine with the elements of water in- directly by means of sulphuric acid; and B6bal and Desgrez (Abstr., 1892, 1162) have shown that unsaturated hydrocarbons also mite with the elements of acetic acid at a fairly high temperature tlo form ethei*eal saJts. The author now demonstrates that the ele- ments of vater can be directly added to the hydrocarbons of the acetylene series.For this purpose, the hydrocarbon is placed with water in iron tubes, enamelled inside, and heated in a bath of sodium and potassium nitrates. Instead of acetylene, the author has used acetylenedicarboxylic acid, and finds that, when the acid and water arc heated at 315O for 20 minutes, a quantity of paraldehyde is formed. Tetrolic acid, when heated with water in a similar manner, gives rise to acetone. CEhanthylidene, with water at 3 2 5 O , yields methyl amyl ketone. Caprylidene, when heated with water for three hours at 320-330°, yields methjl hexyl ketone. Pheiiylacetylene, under similar condi- tions, gives ncetophenone ; methylbutylacetylene yields a mixture of equal quantities of niethyl amyl ketone and ethyl bulyl ketone. The ketone distils at 146-147", and does not unite with sodium hydrogeii sulphite.A number of experiments were made with rnethylan~~.lacet3-lene and water, from which the author concludes that the yield of ketone increases with the period of heating: that a maxininni is rcttcheci with a period of three hours, from which point t,he yield again decreases, and, further, t h a t the yield increases with the temperatiire, reaching a maximum of 75 per cent. of the theo- retical at 360". The product consists of n mixture of methylamyl- acekone and ethyl butyl ketone. Dip11 oiylrtcetylene (tolane), under similatr conditions, yields deoxy- benzo'in, w-liicli c u i be separated from the unaltered tolane by means of alcohol. It is finally sho:i.n that the above hydrocarbons contained no trace of hydrogcn c,liloricte, which might act as a condensing agent, and, t.hereforc, tlici general reaction given above shows a direct synthesis of ketones fivm thc ~ ~ ~ ~ s i L t u ~ a t e d hydrocarbons of the acetylene series.D. A. L. D. A. L. J. J . S .ORGANIC OHENISTRY. Compounds of Mercuric Cyanide with Metallic Chlorides. By RAOUL VXRET (Compf. rend., 1895, 121, 348-351).-Experiments vere made with the view of ascertaining whethtr compounds of the type 2Hp(CN),,bI"C12 + nH,O have really this constitution, or are compounds of a double cyanide and mercuric chloride, Hg (C N) ,M" ( CN) 2, Hg C I,. The first column contains the heat of dissolutioii of ihe crystallised salt; the secoiid column the heat developed by mixing dilute solu- tions of mercuric cyanide and the metallic chloride ; the third column the heat of formation of the solid double salt from solid mercuric cyanide, the solid metallic chloride and liquid water.2Hg(CK),.2NaCl + 2$H,O . . . . , . . 2Hg(CN),,2NH4C1 + 1$H20.. . . . . 2Hg(CN)2,BaC12 + 5H,O.. . . . . . . . 2Hg(CN)2,SrC12 + 6H,O . . . . . . . . . ZHg(CN)?,MgCi, + GH,O.. . , . . . . . 2Hg(CN),,ZnCl, + 7H,O.. . . . , . . . Hg(CN),,CdCI, + 2H,O ... .... .. ~H~(CN)~,C:LCI? + GHZO .. .. .. . .. 'I. 1 11. 1 1x1. I -16.20 Cal. I + 0 33 Cal. -14'80 ,, +0*38 ,, -17.1 ,, \ +O*46 ,, -15.80 ,, +O'45 ,, -14.20 ,, +O.GO ,, -13'30 ,, +O'60 9, - 9.30 ,, 1 +0'38 9, - ,, j +0.50 ,, + 7.95 Cal. + 3. '18 ,, +13-55 ,, +21 -25 ,, +26*1 ,, +404 ,, +23% )., + 6-48 ,, These results ifidicate that the whole of the cyanogen remains in direct combination with the mercury, and this view is supported by the fact that the cold solutions of the double salts are not alkaline t o litmus, and, if heated a t 30' wit11 a soluble picrate, no isopurpurate is formed.If, howerer, the solutions are boiled, they become slightly alkaline, and give the isopurpurate reaction, from which i t follows that, a t the higher temperature, there is a migration of atoms, and part of the cyanogen becomes combined with the alkali or alkaline- earth metal. C. H. B. Copper Ferrocyanide. By GTTSTAV RAUTER (Zed. mzgw. Chc117 ., 1895, 315--3316).-This is an investigation of the nature of the pre- cipitate formed, under varying conditions, by the interaction of copper sulphate and potassium ferrocyanide. Tile upshot is that the precipitate always retains potassium ferro- cyanide, but that this must not be looked onas a chemical constituerit but only as an impurity.Owing to thegreat difficulty experienced i n completely washing the roluminous deposit, a8 certain amount of potash is obstinately retained. L. DE K. Sulphur as a Preservative of Chloroform. By L. ALrATN ( J . Plzarm., 1895, [6], 2,252-255).-Chloroform, saturated with sul- phur in the cold, may be kept in direct sunlight for months, without iindergoing change ; in particular, no carbonyl chloride is formed. This stability is not due to any change produced by the sulphur, for the redistilled liquid rapidly decomposes when exposed to the mrne b 24 ABSTRACTS OF CEEMIOAL PAPERS. conditions. As the anadhetic properties of the chloroform are not modified by the presence of' tbe sulphur, the asddition of this pre- servative is to be recommended. JN.W. Nitro-alcohols. By LOUIS HENRY (Conzpt. r e d . , 1895. 121, 210 -213) .-Nitromethane and formaldehyde, in presence of a small yixantity of potsssiuni carbonate, react quantitatively with production of tertiitry nitrotrihydroxybdans, NO,*C(CH,*OH),, a white, solid compound, which cr-j-stallises in needles or in large prisms melting at 1.58-159', and soluble in watep, alcohols, and acetone, but less soluble in ether. Attempts to obtain products of the interaction of one molecule of nitromethane and one and two molecules respectively of formaldehyde were unsuccessful. Nitroetliane and formaldehyde, in presence of potassium carbonate, yield the compound N02*CMe( CH,*OH),, which is teTtias.y nitrodi- 'hydrozybzrtane or tertiary ?Litroisob.zctylenic glycol.It crystallises very readily, melts at 139-140°, and is soluble in water, alcohols, and acetone, but less soluble in ether. Secondary nitropropane and form- aldehyde, under similar conditions, yield the nitroisobntylic alcohol, NO,*CMe,*CH,*OH, which melts at 82", crystallises very readily, ifi very soluble in alcohols and acetone, but less soluble in water, and more soluble in ether than the two preceding compounds. From these results i t follows that the reaction capacities of the three nitroparaffins with respect to formaldehyde are proportional to the number of hydrogen atoms attached to the group C*N02, and there is little doubt that tertiary nitrobntane, N02*CMe3, would have no action on formaldehyde or the other aldehydes of the same series.Glucoseacetone. By EMIL FISCHER (Ber., 1895, 28, 2496-2497). -The author has previously shown (Abstr., 1895, i, 440) that &glucose, arabinose, and fructose react with two molecules of acetone, and rhamnose with only one ; it is now shown that glucose can also form a condensation product with one molecale of acetone. Thin substance has the composit,ion C6HlOo6:CMe2, and the author terms it, glucose-acetone. It diil'ers from the alcoholic glucosides in the fact that it is riot acted on by emidsin or by the enzyme of yeast; i t forms small, felted needles, melts a t 160-161O (corr.), is soluble in water, and is IEvorotatory. It has a bitter taste, does not snblirne a t loo", but may be distilled in small quantities without undergoing decom- position ; it is readily decomposed by dilute acids, but has no action on Fehling's solution.C. H. B. J. J. S. Inversion of Maltose and Isomaltose by means of Yeast. By CARL J. LINTNER (Chem. Centr., 1895, i, 271-272 ; from Z e d . Ges. Brauu.., 17,414-415).-Referring to the investigations of E. Fischer on the influence of the configurat,ion of the molecule on the action of enzymes, the author has observed t)hat the hydrolysis of maltose pro- ceeds most rapidly with yeast powder, the aqueous extract is less active, and precipitated invertin least,. Isomaltose is more readily attacked than maltose. The enzyme is less soluble than invertin, and appearsORGANIC CBlUllSTRY. 5 to be more closely allied to the glycolytic ferments.The presence of dextrose in small quant'ity in Munich lager beer, is due to the action of yeast on isomaltose. J. B. T. The Inulin of Garlic, Hyacinth, Narcissus, and Tuberose. By R. CHEVASTELOK ( J . €'harm., 1895, [6], 2, 83-86 ; from Inaug. Diss., Paris, 1894) .-The reserve material of the bulbs and other underground parts of certain monocotyledons is a kind of inulin. To separate this substance, the bulbs, he., are cut into small fragments, and digested with ether, to cause the expulsion of the sap from t8he cells ; the sap collecting a t the bottom of the vessel, together with a further amount remaining in the fragments, and liberated by pressure, is puritied with basic lead acetate and aninial charcoal, and the inulin precipitated by baryta water.The insoluble barytn compound of the carbohydrate is decomposed by carbonic anhydride, and the inulin precipibated with alcohol-ether as a syrup. Finally, this is dried in succession by washing with alcohol and ether, and then under diminished pressuye, and a t 100'. The inulin of garlic, CGHI0O5, is a white, inodorous, amorphous powder, distinct from the inidin of the Jerusalem artichoke. Its taste is insipid, and it is very deliquescent. It melts at 175-176', and is soluble in water and dilute alcohol, but only sparingly in strong alcohol. It does not reduce alkaline copper tartrate, and is completely hydroljsed by acids to levulcse. I t is precipitated neibher by normal nor by basic lead acetat,e, except in presence af ammonia. It is not hydrolysed by amylase (malt diastase), but is resolved into levulose by an enzyme inulase, which is secreted by Aspergillus niyer, and is similar to the enzyme of the inulin of the Jerusalem artichoke, and of Atracty7is. The inulin of garlic is not fermented either by hydrolytic or non-hydrolytic yeasts. The sap from the offshoots of the garlic bulbs contains only traces of reducing sugars, and yields nothing but levulose on hydrolysis, so that i t contnixis no reserve material but inulin.The inulin of the sap of the bulbs of various species of hyacinth is identical with that from garlic. The bulbs also contain a small amount of levulose, and a large amount of starch, so that here the reserve material is stored in both soluble and insoluble forms.The inulin from the bnlbs of the narcissus and tuberose is also identical with that from garlic ; neither. OE these contains starch, but the nsrcissus sap contains both glucose and levulose, whilst that of thc tuberose contains glucose only. Various other bulbous monocotyledons were examined, such as thc onion, tulip, and iris. Glyoxylic acid and its Behaviour towards Carbohydrates. By CARL BOE'rTIXGER (Arch. Phas.na., 1895, 233, 287-394) .-Gly- oxylic acid acts as a hydrolSsing agent towards starch and cane sugar, and i t prevents the fermentation of the products formed, for it acts on yeast as a poison. From gljoxylic acid and glucose, a syrup is obtained, which is asserted to have the constant compositioii The rotatory power is [ a ] ~ = -39'.JN. W.(-i ABSTRACTS OF CHEMICAL PAPXRS. CGHI2O6,C2H2O3 + H20 ; with galactose n sirsilar compound nzay have been obtained, and with levulose a. compound C6HI2O6,.2C2H3O2. C. F. B. Preparation of Glycogen. S y D. Huizisas (PJluger's AYC~L~V, . d95, 61, 32--38).--On account of the opalescence of glycogen solu- tions, the presence of albumoses in small quantity can only be ascer- tained by mean3 of the biuret reaction or hy Millon's reagent, ; with the former, not less than 0.5 per cent. can be detected; with the latter, a distinct orange colour is obtained when the solution contains 0.1 per cent. ; if the albumose is precipitated by means of a solution containing sodium tungstate (100 parts), phosphoric acid (50 parts), concentrated hydrochloric acid (10 parts), and water (500 parts), and the dried precipitate treated with 114illon's reagent, the presence of 0.02 per cent. of slbumose may be distinctly recoguised.The above experiments were made with nlbuiiiose prepared t'rom egg albumin ; the presence of glycogen is withuut effect on the reactions. The boiling water usually employed €or the preparation of glycogen extracts albumoses in considerable quantity, and their subsequent separation is attended with considerable ditEcnltJy ; triclilorscetic acid, which Frankel used instead of water, also dissolves dbuinoses, as do sulphosalicylic acid and formaldehyde solutions ; satui*ated solution of mercuric chloride extracts pure gl-jcogen, but the resulting liquid is often unsuitable for filtration ; the best resulcs were obtained by the use of equal parts of saturatbd solution of mercuric chloride and Esbach's reagent, made by dissolving picric acid (10 grams) and citric acid ( 2 ~ grams) in water (1 litre).The glycogen, after wash- ing with alcohol and ether-alcohol, was free from albumoses, and contained 0.62-0.80 per cent. of ash. This method, although good for the preparation of glycogen, is not adapted for its quantitative esti- mation, as i t yielded only 78-89 per cent. of the total glycogen determined by Kiilz's method. J. B. T. Oxycellulose. By R. W. TROMP DE HAAS and BERNHARD TOLLENS (Annulen, 1895, 286, 296-300; compare Abstr., 1893, i, 295).- The authors have hydrolysed, with sulphuric acid, oxycellulose obtained by treating fir saw-dust with nitric acid. Twent.y grams of oxycellulose was added slowly to 100 grams of concentrated sulphuric acid mixed wit,h 20 grams of water, SO grams of water being added after an hour ; on the following mornizig, 2.5 litres of water were added to the liquid, which was heated in a reflux apparatus for five hours i n boiling water.After neutralising the pale pellow liquid with calcium carbonate, the filtered solution yielded 3 grams oE dextrose, having the specific rotatory power [alD = -+ 51.2". Determination of cellulose by Lange's method indicated the presence of about 20 per cent., whilst 3 per cent. of furfuraldehyde was obtained from the oxycellu- lose by distillation with hydrochloric acid. From these results, the authors conclude that the oxyccllnlose obtained from fir-wood is not identical with the oxycelluloses investi- gated by Cross and Revan, Witz, and NastjulcoE.M. 0. F.ORGAN10 OHEMISTRY. 7 Remarks on the Foregoing Paper. By BERSIIIRO TOLLENS (Annulen, 1895, 286, 301-:302).--Many substances wliich yield furfuraldehyde when distilled with hydrochloric acid aye fourid to contain, in some form, pentoses or glycuronic acid. This is not the case with the oxycellulose described in the foregoing abstract, and the author suggests glycoson, CsH,,Os, as a possible source of the production of furf uraldehyde from this substance. Constitution of Pectin Substances. By B ERXKLI: n TOLLENS (Annulex, 286, 292-295) .-From a consideration of the properties O E these substances and the products of their hydrolysis, the author regards them as carbohydrates combined chemically with acids, this view having been already advanced by O'Sullivan regarding the vegetable gums.31. 0. F. 31. 0. F. Pectin Substances. By R. W. TROJIP DE HAAS and ELRNEARD TOLLENS (Annulen, 1895, 280, 278-292) . - S h y attempts have been made to establish a relationship between pectins and vegetable gums (carbohydrates). Accurate determinations of composition are essen- tial t o generalisations of this character, and the authors have accord- ingly prepared and analysed pectin substances from various sources, the proportion between hjdrogen and oxygen being indicated in each case. The. pectins were precipitated by alcohol in the juice espressed from the fruits, and, after being washed with ether, were dried over sulphuric acid. The analytical results are einbodied in the following table.Pectin. 1 Percentage of C. 1 R:itio of 11 to 0. Percentage of Ash. --_____ -_-] __-__.___ I_---- I Apple A ............... Apple U ............... Cherry ............... Rhubarb A.. .......... Rhubarb B.. Currant.. ............. J 1 Plum ' Swede A .............. Swede B . . ............ .......... I ................ 4.3 *35 43 '46 4.2 '42 43 '31 42 -89 46 *S7 42 a 9 2 41 *08 42 -33 From this it is clear hhat the pectins are allied in composition to the carbohydrates, and that the low proportion of bycicogen to oxygen (1 : 10-12) recorded by previous observers is not confirmed. Hydi.olysis of these pectins leads to the formation of liexoses or pentoses. 11. 0. F. Preparation of Methylamine. By AND R 6 B KOCH ET and It.CAMBIER ( J . Pham., 1895, [6], 2, 172-173 ; from Rcc. Chim. Itdustr., June, 1895 ; compare Abstr., 1805, i, 642).-Formaldehyde (90 kilos. of 40 per cent.) is distilled with ammonium chloride (10 kilos.). The action commences at 40°, whcn methylal passes over, and the distii- late up to 95' contains 60--79 per cent. of that snbstance. TheS ABSTRACTS OF OHENICAL PAPERS. residue is evaporaked down until ammonium chloride commences to crystallise ont, and, oii cooling, the whole excess of that substance separates. The liquid remaining is a nearly pure solution of methyl- amine hydrochloi~ide, from which the pnre substance is obtained by evaporation under low pyessure and recrystallisation from alcohol. The yield of 93 per cent. methylamine hydrochloride, melting a t 210°, is 8.5 kilos.with the above quantities, and, a t the same time, 3.8 kilos. of methylal and 2.2 kilos. of carbonic anhydride are formed, and 3.5 kilos. of ammonium chloride recovered unchanged. Jx. W. Chloro-derivatives of Amines. By ARMAXD BERG (Ann. Chim. Phys., 1895, [7 3, 3? 2E9--3Gl).-The normal butylamines hare been prepared according t o Hofmann's method by the action of butylic chloride on a dilute alcoholic solution of ammonia. The bases are first separated by means of their hydrochlorides, and then the primary base is purified by conversion into dibutyloxainide, C202(NHC,H,)2. which melts a t 153O, and is but sparingly soluble in water. The mother liquor contains butylamine butyloxamate, C4He'NH*C0.COO*hTH3.C~H~, which, when heated in aqueous solu- tion with calcium chloride, yields calcium butyloxamate, (C4H,.NHGO-COO),Ca + 2H,O.B u t y h n i ? t e oxdate, Cz02( ONH,*C4Hg),, is deposited on evaporating the mother liquid of the oxaniate. Dibuty lamiiie hyld~.ochlode is made use of in the separation of the secondary base. The azwocldoride, NH2( C4HS)2A~Clr, is precipitated when coiicentrated solutions of gold chloride and dibntylamine hydro- chloride are mixed ; it crystallises in long, golden needles, and melts at 170@. The sfai~izichZo?-ide, 2NH2(C4Hg)2Cl,SnC14 + H20, crystal- lises in long. colourless needles. Dibutylamine hydrogen oxalate, C O O H * C O ~ . ~ H , ( C , I ~ ~ ~ ~ , is much more readily soluble in water than the correspondiui diisobutylamine salt. a t 59.5'. Dibutylarniiae picrate melts The tributjlamin e hydrochloride is extremely deliquescent .The picrnte melts a t 100*5@, and is very sparingly soluble in water. The isobutylamiiies have been prepared by tt similar method ; the author finds that when a mixture of isobutylic chloride (1 inol.) and aqueous ami~ionia (1 mol.), to which j u s t sufficient alcohol for solution has been added, is heated at 110--115O, the primary base is the chief product. It may be purified by conversion into the oxamide (Malbot, Abstr., 1891, 817). The pure base boils a t 67-9-68', (Reimer gives 62-65@, and Perkin 68-49'.) The secondary and tertiary bases are best separated bj- coilversion into the acid oxalates. Diisobutylamine boils at 140*6-140.8". (Reimer gives 122-125', RIalbot 137', and Perkin 139-14r)O.) The amylamiiies have been prepared and separated by similar methods.Anrylamiiie amy Eoxumate, C5H,I.~H*CO*C00.NH3.C5H,1 + HzO, cr-j-stallises in colonrless needles, and is readily soluble in hot water. C'irIciwn umjZorca?)aate, ( C5H,,*NH*C0.COO)4Ca + HzO, is sparingly soluble in cold water, readily in boiling, and crystallises in slender, colouriess needles.ORGANIC CHEMISTRY. 9 Most of the chloramines have been described before (Abstr., 1690, 952; 1892, 804 and 1172; 1893, i, 296 and 497). The inonochlor- amines were prepared by the action of a concentrated solution of scdium hypochloi*ite on an aqueous solution of the hydrochloride of the amine. ButyZchZorarnine, C,Hg*NHC1, is a faintly yellowish oil, has a sharp odour, is insolnble in water, decomposes on heating, and has a sp..pr. of 0.992 at 0". Butyldichloramine, C4Hg*NC1,, is a yellow liquid, with a sp. gr. = 1.112 at 0". It boils a t 71" under a pressure of SO mm. Dibutylchlornrnine, (C,H,),NCI, is an oily liquid with a sp. gr. of 0.906 at 0", and boils a t 99" under a, pressure of 52 mm. ; it slowly decom- poses when kept. These chloramines undergo decompositions similar t o those given f o r the chloramines which ha,ve bee11 previously described; thus when acted on by reducing agents they are con- verted into the hydrochlorides of the corresponding bases. Quinol, pyrognllol, and gallic acid give colorations with the chloramines. Sulphuric acid acts on the monochloramines, converting them into thc base and the corresponding dichloramines.Aniylchloramine nntl silver nitrite act in the presence of alcohol, forming the silver deriva- tive of arnylnitramine, whicli crystallises in fine tablets. The reactions with potassium iodide and potassium cya1:ide arc' similar to those previously described. Constitution of the Isonitramines. By WILHELM TRAWL (Bcr., The dichloramines were prepared by Tcherniak's method. J. J. S. 1895, 28, 2297-2302 ; compare hbstr., 1895, i, 592).-The isoni- traminic acids are convei-ted, by boiling with dilute hydrochloric acid, into the corresponding amidoxylic acids, which may be reconverted into the isonitrnminic acids hy the action of iiitrous acid. Hydrowyl- atrznidoucetic acid, HO*NH.CH,*COOB, crgstallises in lusti-ous, rhombic tablets melting at 135", and reduces Fehiing's solut,ion at the ordinary temperat ure.Hydroxylnniidophenylpropio7tic acid, CH,.P h* CH ( NH-OH ) C 0 OH, crystallises in prisms melting a t 157-158". When this acid is treated with nitrous acid, it yields isonitraminephenylpropionic acid, identical with that' prepared from ethylic benzylacetoacetate and nitric oxide, along with another substance which has the formula C,H,NO. This second compound does not reduce Fehling's solution, and explodes when heated. XOH The isonitrttmink acids probably have the constitution RON< I 0 ' since they are formed by the action of nitroas acid on tlie amidoxylic acids. A. H. Existence of Imido-ethers derived from Hydrocyanic acid. By ADOLF PINNER (Ber., 1895, 28, 2454-2458).-A reply to the crihi- cisms of J. U. Nef ( A n u a l e n , 1695, 287, 328).Nef has stated t h a t the substance, previously described by the author as the hydrochloride of the ethylic ether of' forniimide, NH:CH.OEt,HCl, is a mixture of five different compounds. I n this paper remons ars given whv it should still be considered a homogeneous substance. J. J. S .10 ABSTRACTS OF CHEMICAL PA4PERS. Condensation of Isovaleraldehyde. By L. KOHN (Compt. rend., 1895, 121, 259-26O) .-Isovaleraldeliyde and potassium hydroxide do not yield secondar,y glycols analogous to those obtained by Fossek from isobutaldehyde, but two products are formed. One boils at 82' under a pressnro of 15 mm., or 187' uiider 746 mm., and oxidises very easilywith formation of an acid, CloH,,02. The other Foils at 140' under a pressure.of 18 mm., and seems to be a polymeride of valeral. C. H. R. Action of finely divided Silver on Halogen Derivatives of Aliphatic acids. By CARL HELL (Bey., 1895, 28, 2439-2445; compare J. Wislicenus, Annalen, 149, 215 ; Hell, Ber., 6,28 ; 7 , 319 ; 10, 2229 ; 13, 473 ; 22, 48).-The author considers that tlhe general equations previously given by him to represent the action of finely divided silver on the halogen derivatives of the fatty acids do not, account for the formation of many of the compounds obtained in the reaction. It is now suggested that in the formation of dicarhoxylic acids from a-halogen (e.g. bromine) derivatives of the fatty acids, two reactions occur : (1) the bromine atoms are removed by the silver, and the ta-o residues then unite to form a dicarboxylic acid ; (2) hydrogen bromide is removed by the union of the bromine of 1 mol.with a hydrogen atom in the a-position to tbe bromine of R second molecule. The author considers that this accounts for the formation of tetra- methylnuccinic and trimethylglutaric acids from bromisobutyric acid, and that it, also accounts for the formation of both stereoisomeric dialkylsuccinic acids by siinilar methods. Thus by reaction (1) we obtain one modification, R*~H*CooH + 2AgBr, COOH*CH*R 2R*CHBr*COOH + Ag2 = and by reaction (2) we obtain tlhe second modification- R*FBr* C 0 OH R*CH.COOH ' 2R-CBrH*COOH = HBr + t 28gBr. R. 7 H* C 0 0 H R.CH*C 0 OH + HBr + Ag2 = R*yBr*COOH R*C€I*CQOH A third reaction, which often occurs simultaneously, is the removal of hydrogen bromide from 1 mol., and t,he formation of an unsaturated acid cf the acrylic se:*ies. The formation of pyrocinchonic acid from a-brornopropionic acid and silver is probab!y due to a similar reaction.J. J. S. Electrolytic Synthesis of Nonocarboxylic acids of the Fatty Series. By WILHELN VON MILLER and HANS HOFER (Ber., 1893, 28, 2427-2439 ; cornpare Abst,r., 1894, i, 228) .-The authors have made electrol-ytic experiments with mixtures of potassium acet)ate and potassium etliylic succinate iii Hofer's apparatus (Ber., 27, 464). They show t h a t when a so1ut)ion of potassium ethylic succinate isORGANIC CHEMISTRY. I1 used as the positive electrolyte, and a concentrated solution of potas- sium carbonate (kept neuti'al by passing in carbonic anliydride) as the negative, theoretical Fields of ethylic adipate may bc obtained ; whereas C~um-Brow-11 and Walker by their method obtained a yield of only 35 per cent.(Abstr., 1891, 1192; 1893, i, 394). If a mixture of potassium acetate and potassium ethylic succinate is used as the positive electrolyte, and the negative is the same as in the previous case, a yield of 40-69 per cent. of ethylic butyrate can be obtained. A small quantity of the adipate is formed a t the same time, this amount varying with the cornpsition of the original iiiixture used. By replacing the potassium acetate by potassium propionatc, butyrate, and isobutyrate respectively, the authors have succeeded ill synthesising ethjlic valcrate, caproate, and isobutylacetate. The gases evolved during the electrolysis were examined in each case.They contain carbonic anhydride (73-62 peia cent.), oxygen (0*3-0*4 per cent.), carbonic oxide (1-3 per cent.). It has also been found possible to obtain ethylic iodide, togethe]. with iodof'orm and sodium iodate, by the electrolysis of a solutiou containing sodium propionate as the positive eiectrolyte and potas- sium iodidc as the negative. With potassium succiiiste as the posi- tive, ,G-iodopropionic acid is obtained. When sodiuni piaopionate ant1 potassium nitrite mere used a s the two electrolytes, a sninll quantity of nitroethnnc was obtained ; and when potassium acetate and potassium glycollatc were used, the authors obtained formaldehyde a t the negative pole and ethylic alcohol at tlie positive. Similar experiments with a mixture of potassium ethylic malonate and potassium acetate a t the positive pole, and potassium carbonate at tlie negative, gave e t h ~ l i c rropionate as the chief product; but with a mix kure of potassium ethylic mnlonate and potassium pro- pionate a t the positive pole, ethylic valerate was f'orrned, and simi- larly with a mixture of the mdonate nud potassium butyrate, ethylic valerate was tlie chief product. J.J. S. p-Hydroxy-x-dimethylisocaproic acid and Diisopropylgly- COlliC acid. Ijy ALEXANDER BARYLOWITSCH (Be?-., 1895, 28, A%;&- 2466) .-Re forma tsky has obtained ~3-h!tds.omy-a-dii,z ethyl iso:aproic wid. CHMe,*CH (i)H)*CMe,*COOH, bp the action of zinc a n d ethylic bromisobutjrate on isobutaldehyde. This acid melts a t 9A0, wliereas the acid described by Wohlbriick and Hantzsch under the same name melts a'; 111--119".The author has further investigated the acid of ~~olilbrucl;-Haiitzsch (Abstr., lSS7, 10'39), and finds that it is not p-hydroxy-a-dimetllylisocaproic acid, but is identical with the diisopropylgl~collic acid, OH*C( CHMe,),*COOH, previously described by hlarkovni koff. 2. J. S . Glucic acid (?). By HEINRICH TYIs'rER (Chem. C e ~ t r . , 1895, i, 371 -372 ; from Z. V e r . h'iibenzuck, 1894, 104C3-lO.jl) .-Invert sugar solution (1 per cent.), heated with lime water (0.5 per cent.) tit 66.50 , gives a white, volnmiuous, flocculent precipitate which prob- ably consists of basic calcium gIucate; it clissoIves when further12 ABSTRACTS OF CHEMICAL PAPERS. heated, becomes dark brown on exposure to air, and is sparingly soluble in water.TI:e precipitate cannot be removed by filtration; it was mashed six times with lime water by decantation, treated with dilute sulphuric acid, and extracted with ether ; this extract, when evaporated, left, a syrup, together with needle-shaped crystals, probably consisting of glucic acid ; after remaining for some time in a, desiccator, the neeciles disappeared, and crystals resembling those of cane sugar were produced (apoglucic acid ?) ; finally, tbese dissolved, the syrup darkened, gas was evolved, and a black resin was formed which yielded carbonic anhydride and formic acid when distilled with steam. The acid could not be recrystallised. J. B. T. New Synthesis of Uric acid and of its Methyl Derivatives. By EMIL FISCHER and LORESZ ACH (Ber., 1895, 28, 2473-2480; compare Liebig and Wohler, AnnaZen, 24, 284; Schlieper and Baeyer, Annalen, 127, 3 ; Horbaczewski, Abstr., 1885, 105U ; 1887, 918 ; Behrend and Rooseii, Abstr., lSSi, %l).-When Schlieper and Baeyer's pseudo-uric acid is fused with a large excess of oxalic acid at a temperature of 145-185' for 10 minutes, it loses a molecule of water, acd yields uric acid.The dimethylpseudouric acid of Techom (Abstr., 1895, i, 84), when treated i n a similar manner, yields a dimethyluric acid, which melts at 370"; it is moderately soluble in hot water, sparingly in cold water, in alcohol, and in acetone, but, readily dissolves in ammonia, forming an antnaonium salt, which can be obtained in a crystalline form by concentrating the solution.The siZner salt is a gelatinous precipitate, which decomposes slowly at ordinary temperatures, but much more readily when warmed. Another compound, which is formed in small quantity by the action of oxalic acid on dimethylpseudouric acid is E. Fischer and Reese's deoxyamalic acid (Abstr., 1884, 466) ; this forms a sparingly soluble sodium sali-,, and readily yields murexoin when treated with bromine and then with ammonia. If dimethylpseudo- uric acid is added to n mixture of acetic anhydride and zinc chloride, a, yield of 25 per cent. of ppdimethyluric acid is ob- tained. When the lead salt of this acid is heated, at lfLO0, with methylic iodide and ether, a new P-trimefhyZunk acid is formed. This @-acid melts between 313' and 32V, at the same time undergoing decomposition ; it is readily soluble in dilute alkalis, moderately in hot alcohol, and only sparingly in cold water and in alcohol.It gives the murexide reaction, is not readily acted on by phosphorus pentachloride, and, when heated with concentrated hydrochloric acid a t 150°, yields carbonk anhydride, methplamine, arid glycocine. When the lead saIt of /%crimeth~luric acid is further methylated, it yields the same tetrameth7luric acid as is obtained from the a-tri- metbyl acid. J . J. S. Formation of Methyluric Acids from Theobromine. By EMIL FIXHER (Ber., 1S115, 28, 24S0---2495).-When bromotheo- bromine is heated with normal potassium hydroxide solution for eightORGANIC CHEMISTRT. 13 Iiours on the water bath, the chief product is 8-dimetTayZzwic ~Me*Co*f?NMe>CO, accompanied by a small quantity of a bromine Clerivative, which can be removed by reduction with hydriodic acid.The acid is decomposed at a higher temperature, when it evolves unpleasant smelling gases ; it is only sparingly soluble in cold water, and crystallises from boiling water in prismatic plates, and readily gives the murexide reaction. The ammonium, sodium, and potassiunt salts are readily soluble in water, the silrer suit forms a colourless, amoyphous powder soluble in ammonia. When the lead salt is treated with methylic iodide and ether a t 165-170', i t yields the trimethyluric acid previously described b.y the author (Abstr., 1884, 13091, to which the formula I Chlorocaffe'ine, when heated with alcoholic potash, readily yields ethoxycaffeine ; aqueous potash reacts in a more complicated manner, and even with very dilute alkali only a small quantity of hyclroxy- caffejine is formed. Bromoxanthine is very stable, and the greater part remains unaltered, even when heated for six hours at 135-14V' with normal potassium hydroxide.ChZo.rodiox~dimethy~p~6rin, C7H7N40,CI, is obtained when &dimethyl- uric acid (1.5 parts) is heated with pbosphorus pentachloride (2 parts) and oxychloride (4 parts) at 140-145". It forms small, colourless needles, and melts at 290' (corr,), at the same time undergoing decomposition. When reduced with hydriodic acid and phospho- nium iodide, it give5 13-dioxydimethylpuriii, which is entirely decom- posed at 370'; this is readily soluble in dilute alkalis and mineral acids, gives an amorphous silver salt, an aus.ochZoride which crystal- lises in fine, yellow needles, and also a yellow pZatinocTaZo?-ide.The base, in conti-adistinction to the xanthine bases, does not give the murexide reaction. p-TrichZos.omethyZ~~rin, is the final product of the action of phos- phorus pentachloride on &dimet h yluric acid, on theobromine or on caffe'ine, the yield is much better when chlordioxydirnetl~ylpurin is first formed, and this is then treated with an excess of phosphorus pentachloride. It is readily soluble i n hot alcohol and in benzene, sparingly in hot water, crystallises in fine, colourless needles, melts at ls9-161" (corr.1, and map be distilled in small quantities. p- Dichloyoxytnetlz y Zpuriia, CCl.N.C-NH /CO, is formed when /3- trichloromethylpurin is boiled with 40 times its weight of 20 per cent.hydrochloric acid for 10-15 minutes. It crystallises in small, colourless needles, melts and evolves gas a t 278" (corr.), and is readily soluble in hot acetone bnt only sparingly in chloroform. It bas acid properties, readily dissolves in cold alkalis, and yields a silver deri- uatice which crystallises in slender needles; when the silver or lead salt is methylated, i t yields dichl~roxydimet~hylpurin (Abstr., 1884, 996). g- OxymefhyZpurin, C,H6N40, is obtained by the reduction of 6-dichloroxymethylpurin with hydriodic acid and phosphoniuni CO-NH*C-NH ?JMe*CO*$*NMe>CO is given. C 0 -NHORMe C C 1: $ *N Me ,14 ABSTRACTS OF CEEMICAII PAPERS. iodide ; it crystallises in fine, colourless needles, melts a t 266-267" (con.), and is readily soluble in hot, water, hut only sparingly in cold.It forms salts with both acids and alkalis, the platinochlon2e forms large, yellow crystals, and the aurochloride, C6H6N10,HAuC14, large, yellow plates. When heated a t 130" with hydrochloric acid (sp. gr. 1-19>, tri- chloromethylpurin is converted into y-methylzcric acid, THO C 0.g *NMe> o, C0.NH.C-NH This acid crystallises with lH,O, which it loses a t 140°, decomposes :tt 370-330" without melting, and readily gives the murexide test. The sodium and ammonium salts are readily soluble in water, the silver calt is obtained quite colourless on the addition of a small quantity of siIver nitrate to a solution of the ammoninm salt ; i€ too much silver nitrate is used, the salt becomes black.When heated with fuming hydrochloric acid at 170°, it is decomposed into carbonic mhydride, ammonia, and sarcosine ; and when oxidised with potas- sium chlorate and hydrochloric acid, it. yields allosan and mono- ineth ylurea. When trimethyluric acid is treated with phosphoms pentachloride and oxychloricle a t 130-150°, the dichloroxydimethylpurin previously described is formed. J. J. S. Action of Sulphurous Acid on Potassium Cyanide : Diazo- methanedisulphonic acid. By HANS VON PECHBIASB and PHILIPP MANCK (Rer., 1895, 28, 2374-2383 ; compare ibid., Ref., 522).- Hydrogen potassium anzidomethanedisulpkonate, HS 03*CH ( NH2)*S03K, is obtained by dissolving 100 grams of 99 per cent. potassium cyanide in a solution of hydrogen potassium sulphite, prepared bey saturatin: a solution of 150 grams of caustic potash in 600 grams of water with sulphurous anhydride ; the acid liquid is heated on the water hath, and becomes alkaline after 30-40 minutes.The solution is then carefully acidified with hydrochloric acid, and again warmed, addi- tion of acid being repented until the acidity is permanent, this being usually the case after 14-2 hours. On adding concentrated hydro- chloric acid to the cold liquid, about 200-250 grams of the hydrogen potassium salt crystallises out. It is a suowvy powder, which dissolves but sparingly i n water, yielding an acid solution ; boiling water resolves i t into the components. Uipotassirinz nrrricZomt.thanedisulphonnfe is prepared by dlowing the mixed solution of potassium cyanide and hydrogen potassium sulphite to remain for several days a t thc ordinary temperature without previous treatment with acid; i t crystallises from the liquid in rhombohedra, or in nodules of slender needles.It is more cou- veniently prepared by neutralising a solution of the foregoing salt with potassium carbonate. Recrystallised from h9t water rendered feebly nll~aline, i t contains 1H20, which is removed a t 105'; it dissolves very readily in water, undergoing decomposition when the solution is boiled, yielding the components. Formic acid, ammonia, potns s'lu ni tlii osulp h at c, and potassium t h iocyaiizte are also produced,ORGANIC OHEMIS rRY. 15 the two Iast-named being secondary products due to the action of potassium snlphi te on formic acid and of potassium thiosulphate on potassium cyanide respectively .Dipotassimn diazontethn nedisulpho?iala, C ( S O,K), < #H20, is pre- pared in the following manner. Hydrogen potassium amidomethane- disulphonate (23 grams) is mixed with water (34 grams) and treated with a 66 per cent. solution of potassium nit,rite (15 grams) at 15-16’ ; as the salt passes into solution, the temperature gradually rises to 40-45’, and, after 10-15 minutes, the orange-yellow liquid, which effervesces slightly, is 1-enderecl alkaline with caustic potash, and allowed to cool. The salt, recrystallised from 2 parts of boiling water containing a small quantity of potash, is obtained in orange- yellow needles or prisms containing lB20, which is removed in a vacuum at 60-!30°.At higher temperatures, water and sulphurous anhydride are liberated, the salt becoming colourless ; in dealing with a small quantity, this change occurs a t 210°, and the residue consists of potassium sulpbate, thiosulphate, and formate. The salt is readily soluble in water, forming a neutral solution which gradu- ally becomes acid and evolves gas, eneygetic liberation of nitrogen taking place in the boiling liquid; this gas is evolved quantita- tirely on treating the salt with acids. Dipotassium iodowtethanedklphonate, CHI ( S O,K),, 2 H20, is pre- pared by adding 30 per cent, hydriodic acid (12 grams) to a solution of the diazo-salt (10 grams) in water (100 grams) ; after 10 hours, the solution is treated with alcohol, and the precipitate thus obtained redissolved in a small quantity of warm water to which acetone is then added, the salt being obtained in aggregates of long needles.It contains 2H,O which is eliminated at 105’; the boiling solutiou yields silver iodide when treated with silver nitrate. Dipotassium diodomethaneJisiLl~1~o~~ate, C I?( SOsK),, is obtained by adding iodine (15 grams) in small quantities to a solution of tho diazo-salt (30 grams in I20 grams of water), mixed with a solution of potassium hydrogen carbonate (22 grams in 88 grams of water) ; it crystallises from boiling water in lustrous, rectangulay leaflek, and becomes yellow when exposed to light. Silver nitrate precipitates silver iodide from the hoiling solution, but no change is produced in qolutions of this or the foregoing salt by salts of other metals.Sodium amalgam converts both ioclomethanedisulphonates into di- potassium methanedisulphonate. N Basic po tass t t c m szdp h o h yd m z i r n e t 1~ y 1 euediszi lphonat e , NK c (S03K)z<~.so,K’H?O’ is obtained by gently heating the diazo-salt (30 parts) witli a solu- tion of potassium sulpliite, prepared by neutrnlisiug with potassium carbonate (9-10 parts) a solution of hydrogen potassium sulpliite (45 parts), formed by satuyating a solution of caustic potash (I : 5 ) with sulphurous anhydride. It is very soluble in water, forming an alkali tie solution which yields a precipitate with barium chloride ; this is dissolved by h~droclilo~~ic mid, and on heating the liquid,16 ABSTRAOTS OF CHEMICAL PAPERS. barium sulphate is thrown down, this being due to the quantitative elimination of the snlphonic group attached to nitrogen.When the salt is decomposed with sulphuric acid, hydrazine sulphate is formed, cai*bonict and sulphurous anhydrides being eliminated (compare Absty., 1895, i, 647). 1 4 ~ ~ 0 , crystallises in small, lustrous prisms from a concentrated solution of the basic salt which has been saturated with glacial acetic acid. It is readily soluble in water, and the solution gives no precipitate with barium chloride. Hydro,~y~nefIianetriszilphho?zic acid, C( S03H)3*OE, is obtained, in the form of its potassium salt, when the hydrazi-compound or the diazo- salt is treated with boiling water; the yield is more satisfactory when the latter is heated with a solution of hydrogen potassium sulphite.The potassium salt is identical with the compound described by Albrecht (Annalen, 1872, 161, 139). The barium salt vrystsllises in lustrous leaflets, and contains 4Hz0. The ?iovrnaZ salt, C(SOBK)z< NH I N*SO3Ko M. 0. F. Chloro-derivatives of ax-Dithienyl. By OTTO ERERHARD (Bey., 1895, 28, 2:38%2$86) .-Monochlorodit~hienyI, obtained by thc action of concentrated sulphuric acid on monochlorothiopben (Abstr.. 1894, i, 117) is converted by excess of sulphuryl chloride into tetrachloro-aa-dithienyl, CaH,C1,S2 ; this crystallises in small, yellowish-brown needles, melting at 126.5-127O (corr.).’ When i t is heated with two molecular proportions of sulphuryl chloride at POO”, it yields perchlorodithierzy E, C8C1&, which forms long, reddish-yellow needles, melting a t 211*5-212*5° (corr.).Tetra- chlorodi thienyl is converted by bromine into tetrachlorodihromo- (lithien#, C8Brz*CI,Sz, which crystalliseu i n hard yellowish needles, and melts a t 189*5-190° (corr.). All these products can also be pre- pared from the synthetical acr-dithienyl, and this fact proves that the dithieiiyl derivatives previously described by the author belong to the same series. A. H. Synthesis of Aromatic Hydrocarbons. Ry ALBERT TOHL (Bw.. 1895, 28, 24.59-24G3; compare Abstr., 1891, 1022; Tohl and Geyger, Abstr., 1892, 968 ; T6hl and Karchowski, Abstr., 1892, 990, and Jmnasch and Wigner, Abstr., 1895, i, 655). In preparing para- propyltoluene by Fittig’s method of synthesis, the author observed t h a t propylic bromide gave a much better yield than the iodide.The author in conjunction with Tripke now shows that a fairly good yield of propylmesitylene may be obtained by the action of propylic bromide on mesitylic iodide, or still bettcr on inesitylic bromide in the presence of sodium and ether. Ethylmesitylene has been obtained in a similar manner, but the yield is not so good as that obtained by Jannasch when working with ,z xylene solution. Cymene lias also been syrithesised in a similar manaer by the action of sodium on ieopropylic bromide and parabromotolaene. P~opylrnesitylene boils a t 220 -22l0, does iiot solidi€y at -20°, has a sp. gr. = 0.8773 at No, and when oxidised yields mesitylenecarboxjlic acid (Jannasch and Weiler, Abstr., 1895, i, 283).0 R GA N LO C HEBIIST RP. 1': Dibronzopropylmesity leizc crystallises from alcohol in slender, long needles and melts at 56".Barium prop1jlmesitylenesiclpho?zate, (C12H1,S03)2Bn -f- 2H20, crystal- lises from water in small, glistening plates. The sodium salt, C1,H1,*S03Na + 2H20, is readiiy soluble in water. The cnlcium salt crystallises with lHzO, and the maguesizm salt with 2H20, but the copper salt is anhydrous. Propylmesitylenesulphonamide crystallises from concentrated solutions in small needles, which melt at 93-99". Dinitropropylmesitylene, obtained by dissolving the hydrocarbon in cold, fuming nitric acid, crystadlises in small colourless needles, and melts a t 93-94". A substance, which melts at 135O, is also formed, but the constitution of this product has not yet been determined. NitropropylntssityZene, obtained by slowly dropping double the theoretical quantity of fuming nitric acid into the hydrocarbon, is an oily product, and on reduction yields amidopi.opyE/7zesifyZene, which is also an oil.The amido-compound yields a sulphate, which is readily soluble in water, crystallises in small needles and melts at 117", and an acetyE derivative which me1 ts a t 161". Ethylmesitylene boils at 207-209" (uncorr.) whereas Jannasch gives 212-214" as the boiling point. Dibromethylmesitylene, C6Br,Me3FX, melts at 219", and the dinitm-derizatiue, C,Me,Et(NO,),, at 1 2 3 O . The sulphonic acid yields a barium salt which is very readily soluble in water, and also a sodium salt, CIIHl,-SO,Na + HzO, which loses its water of crystallisation when kept over sulphuric acid.J. J. S. Action of the Monobromo-derivatives of the Aromatic Hydrocarbons on the Lead Salts of the Thiophenols. By ED. BOURGEOIS (Ber., 1895, 28, 2312--2330).-When an aromatic monobromo-derivative is heated with the lead salt of an aromatic thiophenol, the latter dissolves at a temperature which is usually below 175'. When the solution is heated, action takes place in two stages; in the first between 180' and 190°, 2(RS),Pb + 4R'Br = (RS),Pb,PbBr, + RSH' + 2R'Br, the double compound of the lead salt and lead bromide separate in the solid form, a t a higher tem- perature, 225-230", the reaction is completed i n accordance with the equation (RS),Pb,PbBr, + 2R'Br = RSR' + BPbBr,. The author proposes to measure the velocity of the reaction during the first stage, which is undisturbed by secondary rlctions, and thus to obtain some idea as to the effect of the nature of the aromatic group on the power of the bromine atom to enter into reaction.'l'he following new snlphides have been obtained by the above method i n the course of the preliminary experiments. All the snlphides when pure have a faint and not unpleasant odour, but acquire the usual smell of garlic whendistilled. Phenylic metatolylic sulphide boils at 309*5O, and has the sp. gr. 1.1058 at 0"/4". Yhenylic paratolylic sulphide melts at 15*7", boils at 31 P5', and has the sp. gr. 1.09 at its melting point. as-Phenylic orthoxylylir, sulphide, (file2 : S = 1 : 2 : 4), boils at 181.5O (pressure = 11 mm.) and has the sp. gr. 1.0962 a t 0°/40. as-Phenylic metaxylylic szclphide, [Me2 : S = 1 : 3 : 41, VOL. LXX.i. C18 ABSTHAOTS OF OHEMIOAL PAPERS. boils at 172.5" (pressure = 11 mm.) and has the sp. gr. 1.0935 a t 0°/4'. PIJenylic parnzylylic sulphide [Me2 : S = 1 : 4 : 21 boils aii 171' (pressure = 11 mm.) and has the sp. gr. 1.0913 at 0°/4". Phenylic mesitylic s d p h i d e boils at 180" (pressure = 11 mm.) and has the sp. gr. 1.081 7 at 0°/4". U ? - t l ~ ~ p a ~ a d i t ~ l ~ l i ~ sdphide boils at 173' (pressure = 11 mm.) and has the sp. gr. 1.0889 at 0°/4'. Metapara- ditolylic d p h i d e crystallises in lustrous needles, melts at 27.8", and boils at 179" (pressure = 11 mm.). Paratolylic orthozylylic sulphide [Me2 : S = 1 : 2 : 41 forms crystalline granules melting at 28.6". It, boils at 193*7' (pressure = 11 mni.).Pdmtolylic rnetaxylylic szd- phide [Me, : S = 1 : 3 : 41 boils at 188" (pressare = 11 mm.) and has the sp. pr. 1.0716 atl 0"/4'. Paratolylic: paraxylylic szclphide, [Me2 : S = 1 : 4 21 melts at 6' and boils at 185" (pressure = 11 rnrn.). Ptrmtolylic mesitylic suZphide crystallises in sma11, lustrous needles, melts a t 89-6", and boils at 190" (pressure= 11 mm.). Ortho-zylylic a-naphthylic sulphide is ayellocv liquid which boils at 2413' (pressure=ll mm.), and has the ~ p . gr. 1.1346 at 15"/4". Ortho-xylylic P-naphthylic subhide melts at, 68" and boils at 2-51-5' (pressure = 11 mm.). dletaxylylic a-naphthylic sulphide is a yellowish liquid, which boils st 259.5' (pressure = 11 mm.) and has the sp. gr. 1.1355 at 15'/4O. Jfetazylylic @inphthylic sulphide crystallises in lustrous needles, me1 ts at 39.6' and boils at 244.5" ( pressnre = 11 mm.).Paraxyl!/lic a-naphthylic sulplzide forms needles, melts at 36.2' and boils at 235' (pressure = 11 mm.). Paruxylylic 0-naphthylic sulphide also forms needles, melts at 36.7s and boils at 240' (pressure = 11 rnrn.). Afesifylic a-naphthylic sulphide crystallises in large, lustrous tablets, melts a t 120.6" and boils at 24.5' (pressure = 1 1 mm.). Mesitylic p-napldhylzc szdphide crystal- lises in prisms melting at 87*5', and boils at 245" (pressure = 11 mm.). The temperatures given are corrected. A. H. potassium Derivatives of Quinone and Quinol. By CHARLES ASTRE (Compt. Tend., 1895, 121, 326--328).-When an ethereal solu- tion of quinone is boiled with potassium, hydrogen is liberated, and the compound CaH,KO(OH) + Et,O is obtained as a deep green compoui~d, which oxidises very rapidly Then exposed t o air, and becomes incandescent when heated at 100" or brought in contsct with a mineral acid.In presence of benzene, the action of potassium on quinone yields quinhydrone and tt brownish-green crystallii b com- poiind which oxidises with great rapidity, becomes iricatidescent in moist air, and takes fire if rubbed i n presence of air. In contact with water, it is converted into a blue compound, which rapidly becomes brown ; in contact with iriorgsnic acids, it becomes incmdescent. It seems to have the composition Cl2H,OdK3. The action of potassium on quinol in presence of ether, yields a white, crystalline compound, OH*C6H4*OK,CJ14(OIr),, wliich rapidly oxidises, and becomes first blue, then greyish-white, and finally very dark brown, in presence of moist air or oxygen.The formation of these conipounda supports the view that quinone is R diketone. C. H. B. The liquid has the sp. gr. 1.072 at 6"/4'.ORGANIC CHEMISTRY, 19 Action of Sodium Alkyloxides on Chloranil. Acetals derived from Substituted Quinones. By C. LOKING JACKSON and H. S. GRTSDLEY (Amer. Chena. J., 1895, 17, 579-607).-DichZoro- diphenozyquinone, C,Cl,O,( 0 P h),, is prepared by heating chloranil (25 grams) with an aqueous solution of phenol (25 grams) and potas- sium hydroxide (12 grams) on the water bath, and recrystallising the separated solid from benzene. It crystallises in aggregates of rcd needles, melts at 2 4 3 O , and dissolves sparingly in alcohol, benzene, and chloroform, freely in hotJ glacial acetic acid, and not at all in water, ether, light petroleum, carbon bisulphide, or acetone.Caustic soda hyclrolyses it, forming chloranilic acid. It is not reduced by flulphurous acid at loo3, but hydriodic acid converts it into dichloro- diphewoxypinol. C6C1,(O~I),(OPh),, which crystallises in large colourless prisms and in arborescent needies, melts a t 1 97-19g0, and dissolves in most solvents except water, benzene, and light p etro 1 e u ui. When warmed with aniline, dichlorodiphenoxyquinone yields dic hlo rodiani lido y ninon e. Tetrethylic dic;hloroquinonedimalmate, c6c120,[ CH(COOE t)2]2, is prepared by mixing dichlorodiphenoxyquinone with alcohol and ethylic sodiomalonate, when a dark blue precipitate separates ; this is washed with alcohol, dissolved in water, and the solution treated with acid.The new compound crystallises in long, slender, stellate needles, melts at 132O, and dissolves in alcohol, b u t not in water. By reduc- tion, it yields the corresponding quinol, already described by Stieglitz (Abstr., 1891, 455). A s already indicated, the sodio-derivative C6C1,0,[CNa(COOEt),],, has a blue colour, and is soluble i n water, but not in alcohol. When the quinone is boiled with sodium car- bonate in absolute alcohol, trtrethylic diethoxyquinonedimaionate, C,O,(OEt),[ CH(COOEt),],, is obtained ; this forms nearly white crjstals, melts at 115O, and dissolves i n alcohol and ether, but not in water. Dichlorodirnet h oxyquinone dim eth y 1 h emiacetal, C6C1, (OH) (OMe),, is prepared by warming dichlorodiphenoxyquinone (10 grams) with a methylic alcohol solution of sodiuni (6.5 grams) methoxide ; the white crystalline compound which separates, is dissolved in water and treated with dilute sulphuric acid, when the new compound is precipitated.The same compound is formed when chloranil is treated with a solu- tion of scidium methoxide in methylic alcohol, It is a wbde, amorphous solid, insoluble in all common solvents, and is easily convertpd into dichlorodimethoxyquinone (methylic chloranilate, Abstr., 1890, 136) either by heat or by dilute acids ; i t is a feeble acid, forming a white crystalline compound with sodium methoxide. Dzchiorodiethoxyyui- none diethylhemiacetal, C6C1,( OH),(OEt),, is similarly prepared, sodium ethoxide and ethylic alcohol being substituted for the meth- oxide and rnethylic alcohol respectively; i t is a white, amorphous solid, which dissolves slightly in alcohol, but is partially decomposed thereby ; i t is insoluble in all other conimon solvents.A t 140-143° it is converted into dichlorodiethoxyquinone (106. cit.), and melts ; dilute acids effect the same change. Dichlorodimthoxyquinone diethyl- hemincetal, C~C12(OMe)2(OH)2(OEt)2, was prepared from diclilorodi- C f l20 ABSTRAOTS OF CHEMICIAL PAPERS. methoxyqninone and sodium ethoxide i n alcoholic solution ; it is similar in properties to the two preceding compounds. The authors discuss the constitution of these hemiacetals in some detail. They find them to be incapable of redaction to quinols or of forming oximes with hydroxylaniine hydrochloride, so that the ketonic character of the parent quinones has been lost; from this i t is concluded that the sodium salt of dichlorodimethoxyquinone dimethylhemiacetal, for instance, has the constitution OMe C(0Me):CCl ONa OKa>C<CCl:C(OMe)>C<OMe It is suggested that the constitution of phenoquinone and quin- hydrone is similar to that of these hemiacetals.A. G. B. Hydrolysis and Synthesis of Dihydroresorcinol. By DAXIE L VORLAKDEE (Ber., 1895, 28, 2348-2349 ; compare Abstr., 1894, i, 528)-It has been already shown (Zoc. cit.) that phenyldihydrores- orcinol is converted into phenylacetylbutyric acid when treated with hydrolytic q e n t s . The autlior finds that di hydroresorcinol behaves i n the same way on fiubjection to similar treatment, yielding y-acetlyl- butyric acid when heated with a concentrated solution of barium hydroxide during several hours a t 150-160' ; the semiembarone dis- solves with di5culty in water, and crystallises in lustrous leaflets melting a t 164-166'.The reaction by which dihydroresorcinol is converted into y-acetyl- butyric acid is reversible, dihydroresorcinol being produced when ethylic Ppacetylbutyrate is treated with sodium ethoxide ; this is tho simplest case of passing between the aromatic and aliphatic series. Dihydroresorcinol is not formed by the action of ethylic sodaceto- acetate on ethylic acrylate, the product being ethjlic a-acetylgluta- rate. M. 0. F. Action of Bromine on Anetho'il.B.y CARL HELL and 0. vos Gijh'THERT (J. pr. Chem., 1893, [2], 52, 193-210 ; compare Abstr., 1895, i, 341).-In the preparation of bromanethoyl dibromide, the use of hot alcohol must be avoided, since, when hot, this solvent reacts with the dibromide, removing 1 mol. HBr, and forming a conzpoulld which crystallises in long prisms and melts at 62'. A study of the behaviour of the dibromide with hot water led to no definite conclusion. When bromanethoil dibromide is dissolved in aniline, aniline hydrobromide separates, and the filtrate from t h i s yields a yellow powder, ClaHlsOBrN (m. p. "So), when decomposed by hydrochloric acid ; this compound yields bromanisic acid when oxidised with potassium pe rmangan ate. The dibromo- ke ton e obtained by ox idisi ng bromanethoYl dibromide (Abstr., 1895, i, 341) also yields an amline derivative, C,,H,,@,BrN, when heated witch aniline ; this crystallises in small aggregates of needles, melts at 119', and dissolves easily in ether, alcohol, benzene, and chloroform, but only sparingly in light petroleum ; it dissolves in strong snlphuric acid, and is precipitated unchanged therefrom by water ; the compoiind appears to bare beenORQANIO OREMISTRY.21 formed by the substitution of the aniline residue for the bromine atom of the side chain. Anetho'il dibromide also yields a ketone, CIOH11Br02, when oxidised with chromic acid in an acetic acid solution (compare Zoc. cit.) ; t<his forms large, strongly refractive crystals, melts a t 65-47', and dig- solves in alcohol, ether, and light petroleum; the compound has a pungent odour, and burns the skin.When heated with alcoholic ammonia on t,he water bath, the ketone dissolves, and the solution ieaves, when evaporated, a compound, which is probably an isoindole- like compound of the form N< I * this is a yellow, C3fe CH(CGH4.0Me) ' crystalline powder, melts at 1 7 6 O , andhissolves easily in ether, but only sparingly in alcohol, and not at all in light petroleum. Oxidation with potassium permanganate converts the ketone into anisic acid. Two dibromanethozl dibronzides, CloHIoBrrO, weye obtained I)y heat- ing bromanethoil dibromide with bromine (1 mol.) in a sealed tube; the one crystallises when the ethereal solution of the product of the action is evaporated, and forms slender needles which melt at 113--ll.Po; the other remains as a syrup when the ether has been evaporated, and crystallises from this after a time ; it melts at 89", and is much more soluble in light petroleum than its isomeride.Reduction with zinc dust convel'ts the dibromide inta dibromanethoil. The dibromide reacts with aniline to form the co~upoui~d CI,H150Br2N, which melts at 82'. Oxidation with chromic acid in acetic acid soln- tion, converts the dibromide into a ketone, C,,H,Br,O,, which contains two nucleal bromine atoms ; it is a yellow powder, melts at 135O, and dissolves easily in ether, benzene, aud chloroform. Two acids were extracted by sodium carbonate from the crude product of the oxidation of the dibromide ; one of these melts at 85", and is also formed when the ketone is oxidised by potassium permanganate ; but neither has been identified. The compound CloH,Br2N0, which is obtained by the action of alcoholic ammonia at 180° on the ketone, is insoluble in most organic solvents, and sublimes, without melting, at a high tem- perature.The behaviour of the ketone with aniline is also described. The Cholesterols of Cryptogams. By ERXEST G ~ R A R D (J. Pharm., 1895, [ 6 ] , 1,601-608 ; compare Abst8r., 1892,1d!X).-The author has extracted cholesterol fyom orclinary brewer's yeast, from a common mould (Mzccor mucedo), and from a, lichen (Lobaria pulrnonacea). The processes adopted in the three cases were similar. Yeast (30 kilos.) containing 25-30 per cent. of solid matter is extracted with a large quantity of 96 per cent. alcohol. The 1-esidne, dried at 40-50", and the aqueous solution left on distilling off the alcohol, are extracted with ether, and the combined ethereal extracts, which contain the cholesterol, together with the fatty matter and other substances, are evaporated to dryness ; the cholesterol and €ats are then extracted from this residue Tvith light petroleum, and, after the removal of the solvent, are boiled with alcoholic potash to liberate the cholesterol.The alcohol having been removed, the cholesterol is extracted with ether from the aqueous alkaline soap solution, and A. G. B.22 ABSTRACTS OF CHEMICAL PAPERS. the crystals thus obtained are washed with alcohol, and recrydallised from ether or benzene. The cholesterol of yeast crgstallises in rectangular plates or slender needles melting at 135--136O, and has a specific: rotatory power, [a], = -105'.It is very sparingly solnblc, even in boiling alcohol, but readily in the usual organic solvents. Tbe benzoate could not be prepared in a pure state. The mould was cultivated i n a 6 per cent. solution of milk sugar containing the usual inorganic salts. Owing to the comparatively small amount of material available, the amount o€ cholesterol obtained was very minute, but i t crptallised in plates, and a.ppeared from its reactions to be identical with Tanret's ergosterine. The product obtained from the lichen also crystnllised in needles and plates, and exhibited siniilar reactions. The cholesterol from cryptogams differs from animal cholesterol in its colour reactions with sulphuric acid. The latter gives a yellosrish colour with the concentrated acid, which blackens on the addition of water, whilst under the same conditions the former gires a red colour, changing to blue.Similar colorations are yielded by carbon tetrachloride solutions of the chulesterol, with the excep- tion that the yellow solution turns white instead of Black; the chloro- form solutions also exhibit analogous colour changes, Js. W. Electrolytic Reduction of Paranitro- compounds dissolved in Sulphuric acid. By ARTHUR A. NOYES and JOHN J. DOREANCE (Ber., 1895, 28, 2349-2352 ; compare Abstr., 1893, i, 406 ; also 1894, i, 503).-A large platinum electrode is fitted closely to. the side of a small beaker, in which is placed a porous cylinder containing a small platinum electrode ; 20-30 grams of t-he nitro-compound is dissolved in two to three times its weight of concentrated sulphurie acid, and transferred to the beaker, whilst the porous cell, originally filled with concentrated sulphuric acid, is replenished from time to time with dilute acid.A current of 1 or 2 amperes is employed during 40-50 hours. Paranitraniline yields paradinmidobenzene sulphate, paranitro- phenol giving rise to paramidophenolsulphonic acid, which is also formed when parachloronitrobenzene is reduced. The paper contains a short summary of the result,s hitherto obtained. Action of Aniline on Mercurous Iodide. By MAURICE FRAN~OIS (Compt. rend., 1895, 121, 253--256).-When mercurous iodide is mixed with excess of aniline in the cold, metallic mercury separates, and diphenyldimercurammonium iodide, HgI,,'LNH,Ph, is formed and dissolves.At the boiling point of the aniline, the change takes place verj rapidly. With aniline in smaller proportion, but still in excess, some of the mercurous iodide remains unchanged, and if mercuric iodide is dissohed in its own weight of warm aniline, and mercury is added, a small quantity of mercurous iodide forms on the surface of the metal. Itl follows that the action is, to a certain extent, rever- sible, and the author finds that when equilibrium is established a t the boiling point of aniline, there are 26.35 parts of mercuric iodide No analysis is given. M. 0. F.0 ROAN10 CHENISTRY. 23 in every 100 parts of the solution. The result is the same, whether the original substances are aniline and mercurous iodide, or aniline, mercuric iodide, and mercury.The quantity of mercuric iodide in solution when equilibrium is established varies with the temperature, but an exact determination was only made at the boiling point of the aniline. A solution of mercuric iodide in aniline containing 26 parts of the salt in 100 parts of solution, does not decompose mercurous iodide at 182O, but dissolves it in considerable quantity, and the mei-curous salt separates in crystals when thc liquid is cooled, whilst the undissolved mercurous iodide, if the latter is in excess, is also €ound to hare become crystalliue. C. H. B. Halogen Additive Products of the Anilides. By HEKRY L. WHEELER (Amer. Chem. J., l895,17,612--619).-Meta~iitracetaniZide dibromide, C8HRNZOSBr2, is prepared by acting on metanitracetanilide in nitrobenzene with bromine, washing with light petroleum, and crystallisiDg from chloroform.It forms stellate, yellow prisms, and melts and effervesces a t 143'. Water removes hydrogen bromide from it, yielding pcirabromometanitracetanilide, which crystallises in yellow needles, and melts at 1 4 3 O . Bromonitraniline, [NH, : NOz: Br = 1 : 3 : 41, is obtained ..:hen parabromometanitracetanilide is boiled with alcohol and strong hydrochloric acid. It crystallises in slender, yellow needles, and melts at 131'. The author shows that in the above dibromide the bromine atoms are probably attached to the benzene nucleus, not to the nitrogen of the aiiilide group. Its hydrocltloride and sulphate are described.A. G. B. Behaviour of Ethers of Azophenol on Reduction with Stannous Chloride and Hydrochloric acid. By PAUL JACOBSON (Annnlen, 1895, 287, 97-147; compare Abstr., 1893, i, 327; and 1894, i, 26).-The paper forms an introduction to the matter brought forward in the following abstracts ; it is divided into three portions, dealing respectively with the results of the investigation, their theo- retical bearing, and the methods which have been adopted in the course of the work. 'l'he changes involved when ethers of azophenol are reduced, folIow three alternative courses, resulting in the formation of orthosemidine bases, parasemidine bases, a i d scission bases, the quantity in which bases of each class is produced being influenced by the nature of tho azophenol derivative erriployed, a n d by the position in the molecuio occupied by the substituent.The author has, therefore, collected in 8 table the quantitative results obtained on reducing various deriva- tives of benzeneazopheneto'il. M. 0. 1'. Reduction of Ben zeneazo-orth ocresetoil and Ben zene azo- metacresetoil. By PAUL JACOBSOX, F. K. FmrrscH, FRED. MARSDEN, and G. SCHKOLSIK (Annalen, 1895, 287, 147--160).-Benzeneazo- orthocresetoll yields the orthosemidine base, 2 : 4 : 5-amidoethoxy-24 ABSTRACTS OF CHEMIOAL PAPERS. rnefhyldiphenyZamine, NH2*C6H2Me( OE t,).NHPh, which crystallises in lustrous leaflets, and melts at 94-95' ; the hydroc7doride is crystal- line. The aziinide, C,,H,,N,O, is obtained by the action of nitrous acid on the base, and crystallises in colourless needles melting at 118' ; the methenyl derivative, C16H16N20, formed on treating the base with boiling formic acid, crystallises from petroleum, and melts ah 102", whilst the nitrate and hydrochloride crystallise in needles.The thiocar- benyl-compound, C16H16N20S, is obtained by heating the base with carbon bisulphide and alcohol ; i t crystallises in small needles, softens at 225', and melts a t 238-240'. The stiZba.zoniu~n base, C,,H,,N,O,, is obtained by condensation with benzile ; it. forms lustrous, lemon- yellow leaflets, and melts at 136'. Monaizilidotoluquinone is obtained by oxidising the orthosendine base with ferric chloride, and is also formed in preparing the azimide by treatment with uitrous acid ; i t crystallises from alcohol i n lustrous, violet-red needles, and melts at 148".Dianilidotoluquinone is produced when the foregoing substance is treated with aniline in alcoholic solution ; it separates from glacial acetic acid in the form of a crystalline powder, and does not melt below 300'. The orthosemidine base is not the sole product of reduction of benzeneazo-orthocreseto'il, a small quantity of a parasemidine base, 4-amido-4' : 3'-ethoxyrnethyldiphenylamine, NH2*C,H,*NH*C6H,~~e*O~;t, which crystallises from petroleum in lustrous, colourless needles, and melts at 110-111' being obtained ; the acetyl derivative crystallises in rosettes of needles, and melts at 173'. From 10 grams of benzene- azo-orthocresetoil, 4.95 grams of the orthosemidine base were obtained, the yield of the parasemidine base amounting to 2.1 grams, whilst 2 grams of scission bases were also formed.Benzeneazometacresetoil, 0 E t-C,H,Me*N,P h, crys tallises in ornnge- red needles, and melts at 51.5" ; the chief product of its reduction is the parasemidine base, 4-anzido-4 : 2'-ethoxymethyldiphenylamine, which crystallises from petroleum in pink prisms, and melts at 61'. The nzonacetyl derivative of this base melts at 97-98' ; the diacetyl derivative at 153'. The thiocarbamide crystallises in nacreous leaflets, and melts at 181.5'. 4.7 grams of the parasemidine base were obtained from 10 grams of benzeneazometacresetoyl, 4.1 grams of mixed aniline and metacresetidine being formed at the same time. 31. 0. F. Reduction of Ethers of Tolueaeazophenols. By PAUL JACOB- SON, FR. D~~STERBEHN, J.KLEIN, and G. SCHKOLNIK (Annalen, 1895, 287, 161-183) .-Reduction of ort.hotolueneazopheneto'i1 gives rise t o the parasemidine base 4 : 3 : 4'-amidomethylethoxydiphenylamine (D. R. P., 75,292), which crystallises from petroleum i n colourless needles, and melts at 82' ; the hydrochloride dissolves in cold water with extreme difficulty, and crystallises in leaflets. The diazoiodide is formed when a solution of the diazochloride is poured into aqueous potassium iodide, and crystallises in reddish-yellow needlee. The monacetyl derivative melts at 15G0, and the diacetyl derivative at 180-181" ; the benzylidene derivative and orthohydroxybenzylidene derivative melt at 86-87" and 12k125' respectively. 4 : 4' : 3-Chlor-ORGAN10 OHESIISTRT. 25 et~x?l~?zethyEdi~he~2yEamine is obtained from the parasemidine base by Sandmeyer's reaction, and melts at 77-78' ; the nitrosamine melts at 49-50', From 10 grams of orthotolueneazophenetoyl, 5.1 grams of the parasemidine base were formed, 3.6 grams of a mixture of ortho- tolnidine and phenetidine being formed at the same time.Metatolueneazophenetozl, C,H4Me*N,*C6H4.0Et, crystallises from alcohol in orange-red prisms, and melts at 65O ; ou rediiction, i t yields approximately equal quantitiefi (26-28 per cent.) of orthosemidino and parasemidine bases. The hydrochloride of the former, 2 : 5 : 3'- arnidoethoxyinethyldi~he?zylami~ze, was isolated, but the base has not been obtained in the crystalline state; the azirnide forms colourless needles, and melts a t 110-111', and the stilbazoizium h s e crystallises in lustrous, yellow needles, and melts at 176".The methenyl com- pouud was obtained in the form of the nityafe, which crystallises in needles. The parasemidine base, 4 : 4' : 2-anzidoetho~ymethyldiphenyl- nmine, crystallises in long, colourless needles, which rapidly become blue when exposed to air, and melts at 92-93' ; the hydrochloritle ci*ystallises from hot water in colourleas leaflets, and the monacet:yZ derivative melts at 112-113O. An attempt has been made to obtain this base by synthetical means. 4' : i2-~thoxymeth?yldiphenylnmirze was prepared by the action of ethylic bromide and sodium ethoxide on hydroxymethjldiphenylamine ; it separates from petroleum in pale yellow crystals, and melts at 81-82", boiling under atmospheric pressure at 354' (uncorr.).The nitrosamine melts at 71-72', but the transformation of this derivative into the parasemidine base has not been effected in a satisfactory manner. Reduction of paratolueneazophenetojil, which is first converted into paratoluenehydrazophenetoyl, gives rise to an ortliosemidine base, which is either 2 : 5 : 4'-arnidoethoaymethylcliphenylamine, or 2 : 4' : 5-amidoethoaymethyld~phe~zylamine, in quantity amounting to 18 per cent., a mixture of paratoluidine and paraphenetidine being also produced to the extent of 69 per cent. Neither the hydro- chloride nor the base has been analysed; the azirnide, however, crystallises in colourless leaflets, and melts at 117-118", and tho stilbazonium base crystallises from alcohol in yellow needles, sinters at 141', and melts at 144-146'.When the isobntyl ether of paratolueneazophenol is reduced, 72 per cent. of the material employed, is obtained as a mixture of para- toluidine and the isobutjl ether of paramido phenol, the products of the semidine transformation not having been, in this case, examined. The benzyl ether of paratolueneazophenol yields paratoluidine and poramidopheqlic benzylic ether, which crystallises in silky leaflets, and melts at 56" (Abstr., 1893, i, 330); the acetyl derivative melts a t 139'. The mixture of these bases amounts t o 78.5 per cent. of the material employed. M. 0. F. Reduction of Tolueneazocresetoi'ls. By PAUL JACOBSON, E. HEBER, F. HENKICH, and c. SCHWARZ (Annulen, 1895, 287, 183- 211).-Orthotolueneazo-orthocreseto~l crystallises in red, transparent aggregates, and melts at 35-37" ; the difficulty with which i t solidi- fies accounts for the observation of Noelting and JVerner (Abstr.,26 ABSTRAOTS OF CHEMICAL PAPERS.1891, 214), who describe this substance as a red oil. On reduction, i t yields the orthosemidine base, 2 : 5-amidoethox~-2' : 4-dimetI~yEdi- ph,enylamine, which crystalhes in flat prisms, and melt8 at 78'; the hydro- chloride is an oil which rapidly solidifies. The thiocarbenyl-compound, C,,Hl8N2OS, melts at 2-53', and the stilbazonium base crystallises from alcohol in small, yellow iieedlea, and melts at 153'. Oxidation with ferric chloride converts the orthosemidine base into orthotolu- idotoluqinone, which crystallises in dark, lustrous leaflets, and melts a t 145-146'.The parasemidine base, 4 : 4' : 3 : 3'-amidoethoxydi- metjLZlldiphenylamine, is also formed on the reduction of orthotol uene- orthocresetoil ; it crystallises in colourless leaflets, becomes red when exposed to air, and melts at 86'. The snonacetyl derivative melts a t 1 4 3 O , the thiocarbaniide at 17Y--18O0, and the diformyl derivative at 146-147'. The ortho- and pam-semidine bases are obtained in quantities amounting to 29 and 36 per cent. respectively, the re- mainder of the product consisting of scission bases. Metntolueneazo-orthocresoZ, CsH~Me*N2*C,H,Me*OH [N : Me : OH = 1 : 3 : 41, is obtained by bringing together diazotoluene chloride and orthocrssol in molecular proportion ; it crystallises from benzene in lustrous, golden yellow needles, and melts at 115'.Metatolueneazo- orthocreseto21 crystallises in reddish-yellow plates, and melts at 4 6 4 7 ' . When this ether is reduced, the orthosemidine base, 2 : 5-amidoethoxy-3' : 4-dii)2ethyldipl~enylamine, is produced in quantity amounting to 43 per cent. of the material employed ; it crystallises from petroleum in aggregates of colonrless needles, and mclts a t 91-92-3". The azimide crystallises from petroleum in leaflets, and melts at 83--84* ; the stilbazonium base melts 137*5-140', and the solution in alcohol exhibits grecnish-yellow flu.orescence. Oxidation with ferric chloride converts the orcthosemidine base into metatohhido- tolupuinone, which forms purple-red needles, and melts at 142'. The parasemidine base, 4 : 4' : 2 : 3'-amidoethoaydimethyldiphenyl- amine, is also formed when metatolueneazo-ort hocresetoil is reduced, the yield amounting to rather more than 5 per cent. It crystallises from petroleum in long needles, and melts at 99-looo.Reduction of paratolueneazo-orthocresetoil gives rise to the ortho- semidine base, 2 : 5 : 4 : 4'-amidoethoxydimethyldiphenylamine, which crystallises from dilute alcohol in small, white needles, which become violet when exposed to light or air, and melt a t 76". The azimide crystallises in colourless leaflets, and melts at 131', the thiocarbenyl- cornpound at 205-206O, and tho stilbazonium base at 146-149'. The yield of the orthosemidine base amouuts to 50 per cent., 21 per cent. of mixed bases being also obtained. ~rthotol~ceneazometacresoE crystallises in orange-red plates, and melts at 112" ; the sodium derivative crystallises in lustrous, yellow leaflets.. ~Ietaci.esolbisazo-ol.t~iotoluelte, ( C6H4Me.N2),C6H,Me*OH, is formed during the preparation of t h e phenol, and melts a t 188'. 0rthotoZueneazu7,Letac?.esetoi'Z crystallises from alcohol in deep red, lustrous needles, and melts at 64" ; when this substance is reduced 4.3 per cent. of the parasemidine base, 4 : 4' : 3 : 2'-amidoethoxydi- methyldiphen!llnmilze, is formed, 53 per cent. of other bases being pmduced at the same time. The base crystallises in white leaflets,ORGAN10 OEEMISTRT. 27 and melts at 86'; the sdphate ci:yst.allises from alcohol in long, colourless needles, and the mmacetyl derivative and dictcetyl derivativo melt a t 144' and 115" refipectively.Met atoliieneazonzet awesol crys tall ises in orange- yello w, rh ombic plates, and melts at lOS-lOiO ; during its preparation metacresozbis- a.zo?netatolzhe?ze is formed, crystallising in long, reddish- brown needles, and melting at 1 0%--103'. lMetatolzceneazo~netaci-esetoi'l crystallises from alcohol in red prisms, and melts at 73' ; on reduction, it yields 44 per cent. of the payasemidine base, 4 : 4' : 2 : 2'-amidoethoxydimethyl- diphenylamine, which crystallises in co!ourless prisms from benzene to which petroleum has been added ; it melts at 95-96', the monacetyl derivative at 116", and the thiocndamide at 70-72'. Paratolueizeazoi~~etuc~~esol crystallises from benzene in orange-red prisms, and meits at 135" ; metacresolbisazoparutoluene is formed at the same time, and melts at 107".Paratolueneazometacresetoi'l cry- stallises from alcohol in orange-red, four-sided plates, and melts a t 64'; on reduction, it yields 24 per cent. of an orthosemidine base. The stilbazonium base crystallises in long, canary-yellow needles, and melts 178-179'. M. 0. F. Reduction of Metaxyleneazophenetoil. By PAUL JACOBSON and G. SCHKOLNIK (Annalen, 1895, 287, 212-212).-3~etaxyleneazo- phenol crystallises from benzene in brown prisms, and melts at 134'. 2lfetaxyleneazophenetoi:l crystallises in red needles, and me1 ts at 97". On reducing this substance, 74 per cent. of mixed bases is obtained, consisting of xylidine and phenetidine. Reduction of Azophenetoile. By PAUL JACOBSON and FRIEDRICH MEVER (Annalen, 1895, 207, 212-220).-Orthop?~eaetoi'lazopara- phenol, OEt*C,H,*N,.C,H,*OH, is obtained by adding a solution of diazotised phenetidine to a well-cooled solution of sodium phenoxide containing 1 gram of phenol to 25 grams of water ; i t crystallises from benzene in lustrous, reddish-brown leaflets, and melts at 151".Ortho- phenetoalazopara~henetoi'l crystallises from alcohol i n brown leaflets with a golden lustre, and melts at 77-78". When this substance is reduced, the parasemidine base, 4 : 3 : 4'-a?~ziaodiethozydiphien!/la,nine, is obtained ; this crystallises from petroleum in lustrous, feathery lerrflets, and melts at 84.5" ; the hydrochloride forms aggregates of colourless needles, which rapidly become blue. The thiocarbamide melts at 154.5-135'. The parasemidine base is obtained in quantity amounting to 5 1 per cent.of the material employed. ~Ietaphenetoi'lazopn~aphenol melts at 105-106', metaphe~ietoi'lpara- plzenetoil a t 70-7 Lo ; on reduction, the latter yields 69 per cent. of a, mixture consisting of ortho- and para-semidine bases. Paraphenetoilazoparaphenol melts at 125-126', and not at 204*5" as already stated (D. It. P., 48,543). On reducing the ethyl ether, 95 per cent. of paraphenetidine was obtained. M. 0. F. By WrLLrAnr NCPHERSOK (Ber., 1895, 28, 2414-2418).-Two views have been held with regard to the constitution of the hydroxjazo-compounds ; N. 0. F. Constitution of the Hydroxyazo-compounds.28 ABSTRAOTS OF CHEMIOAL PAPERS. one that their constihtion is that denoted by the name, the other that they are in reality qiiinone-derivatives. Benzoquinone reacts with phenylhydrazine and its alkyl derivatives to form quinol, free nitro- gen, and other products.With /3-benzoylphenylhydrazine, however, it reacts like a ketone, yuinonemonophenylbenzoylhydrazone, C6H40:N*NPhBz, being formed. This substance ci*ystallises in yellowish needles, or in groups of flat prisms, which melt at 171’. It is quantitatively con- verted by zinc dust and acetic acid into benzanilide and paramido- phenol ; this reaction is exactly similar to that shown by many of the acetic and beiizoic derivatives of the orthohydroxyazo-compounds. Q uinonebenzoylhgdrazone explodes when i t is brought in contact with phenylhydrazine, aud even in alcoholic solution a vigorous ac- tion, accompanied by evohtion of nitrogen, takes place.Quinone- benzoylhydrazone, which from its properties and the method by which it is obtained, must have the formula given above, is entirely different in its properties from the benzoate of parahgdroxyazobenzene (Ber., 43, 56l), which is hydrolysed by concentrated sulphuric acid or alco- holic potash into benzoic acid and parahydroxyazobenzene, and there- fore appears to have the formula OBz*C6H4*N:NPh. This true hydroxyazo-compound is converted by zinc dust and acetic acid into a, dihydrogen derivative, which is probably the corresponding hydrazo- compound. Quinonebenzoylhydrazone, like the benzoate of parahydroxyazo- benzene, is converted by sulphuric acid or alcoholic potash into benzoic acid and parahydroxyazobenzene, so that the two isomeric benzoic derivatives yield, on hfdrolysis, only one compound (compare Nef, Annalen, 287, 354).These results seem to show that parahydroxyazobenzene really has the constitution indicated by its name, and is a true hydroxy-deriva- tive and not a quiiionc derivative. The research is being extended to the naphthalene derivatives. A. H. Rules controlling the Formation of Azo-colouring Matters. author points out that the formation of azo-colouring matters may be well compared with the bromination of aromatic hydroxy- aud amido- compounds. Such differences as are noticeable may be traced to the closer relationship of the amido-group t o the azo-group than to the hydroxyl-group, and to the smaller acidifying power of the azo-group as compared with that of the bromine atom, as well as iu the spacial relationship of the azo-group towards the bromine atom.It must further be noted that bromination takes place in acid solution, whilst the formation of azo-dyes is generally effected in alkaline or neut,ral solutiom, seldom in the presence of acids. WILHELM TTAIJBEL (J. pr. Chem., 1895, [el, 52, 284--288).--The A. G . B. Symmetrical Dibenzylhydrazine (Hydraziphenylmethane). By THEODOR CGRTIUS and E. QCEDENFELDT (Ber., 1895, 28, 2345- 2347 ; compare Abst>r., 1889, 393).-Syrnmetriral diteirz2/Ehyr~r.a,-ine, CH,Ph*NH*NH*CH,Ph, is obtained by reducing benzglideneazine inORQANIO OHEMISTRY. 29 alcoholic solution with sodium amalgam ; it crystallises in large, lustrous plates, and melts at 65'. On remaining exposed to the atmosphere, i t becomes converted into a colourless oil. The base is indifferent towards alcohol, water, acids, and alkalis, and does not reduce Fehliiig;'~ solution ; it reduces zl cold, ammoniacal silver solu- tion however.The ?nonohydrochloride is not decomposed on exposure t o air ; i t crystallises in colourless prisms, and melts a t 153'. The picrote is insoluble in water, but ci*ystallises from alcohol in long, golden-yellow prisms, and melts at 130'. The acetyl derivative crys- tallises in colourless needles, and melts at 78" ; the benzoyl derivative melts at 87", and the nitroso-derivative, which crystnllises from alcohol in large, yellow prisms, at 89". When the nitroso-derivative is treated with reducing agents, ammonia is formed, together with dibenzylhydr- nzine or benzylamine, according as reduction is mild or energctic.Oxidation of dibenzjlhydrazine in alcoholic solution with mercuric oxide, leads to the formation of a compoi~nd which crystnllises from alcohol in colourless prisms, and melts ah 152'; aJthough having the em- pirical formula of azobenzyl, its molecular weight is found to be twice CH2Ph*r*T*CH,Ph CH2Ph*N.N*CH,Ph' as great, and it prcjbably has the constitution Benzylideneazine tetrabroniide, CHBrPh*NBr*NBr*CHBrPh, is ob- tained by adding bromine to a chloroform solution of benzylideneazine ; it forms orange-red crystals, and melts a t 134'. On dissolving it in acetone, a colourless liquid is obtained, bromacetone and the dihydro - bromide of benzylideneazine being formed. Liberation of nitrogen takes place when benzylideneazine tetrabromide is dissolved in alcohol : the reaction proceeds quantitntivclg, mineral acids and boiling water producing the same effect.hi. 0. P. Tautomerism. By WILLY MARCBWALD (Annalen, 1895, 286, 343-368 ; compare Abstr., 1895, i, 347).-The author is of opinion that the amidines are tautolneric compounds, and that the hypothesis of pseudomerism cannot be applied t o them. Derivatives of this class would he expected to behave consistent,ly with having both the structures NHR'*CR:NR" and NR':CR.NHR" ; this is actually the case, and where contradictions have occurred in the apparent exis- tence of two isomerides, repetition of the experiments in question has established their inaccuracy. The author criticises von Pechmann's views regarding the constitution of formazyl-compounds (Abstr., 1894, i, 456), and discusses the subject of tautomerism at some length.In the formul3e given below i t is to be understood that the taiito- meric formula is also implied in each case. Orthopal.aditoEylcLcetamidi?ze, C6H4Me*N:CMe-NH*C6HJMe, is ob- tained from ethylisothioacetorthotoluidide and paratoluidine, or from ethylisothioacetoparatoluidide and orthotoluidine (Wallach and Wus- ten, Ber., 1883, 16, 148). It crystallises from alcohol i n needles, and melts a t 144-145'; the same product is obtained from both sources, and the previous investigators were mist,aken in recognising two modifications.30 ABSTRACTS OF OHEMIOAL PAPERS. Phenylparatolylbenzamidine (von Pechmaun, Abstr., 1895, i, 347) is obtained from benzauilide imidochloride and paratoluidine, or from benzoparatoluidide imidochloride and atdine; the two forms originally described by von Pechmann are identical, as he, himself, has since shown (Zoc.cit.), and both preparations, when recrystallised, melt at 1:31-132' t o a turbid liquid, which becomes clear a t 1:B'. The nitrate forms small, white crystals, and melts and decomposes at 144' ; the hydrochloride melts at 237O, and the picrate a t 195'. Diphenylparatolylguanidine, C6H4Me*N:C( NHPh),, is formed from aniline and phenyltolylcyananiide ; aniline, phenyltolylthiocarbamide, and lead oxide ; paratoluidine, diphenyl thiocnrbamide, and lead oxide, or from paratoluidine and diphenylcyanamide ; Huhn, by means of the first two methods, obtained products which he believed to be different from one another (Abstr., 1886,1036).Tho baQe separates from alcohol in white crystals, and melts at 128-129'; the hydrochloride melts at, 221-222', and the ylatinochEoride becomes brown at 230°, but does not melt at this temperature. Tetyap henglpara to1 y ldiguanide, NHPh-C (NPh)*N( C6H4Me)*C(NPh)*NHPh, is obtained as a bye-product in preparing the foregoing compound from diphenylcyanamide and paratoluidine ; it crystallises from absolute alcohol, and melts at 150'. It is prepared by allowing the latter substance to remain in alcoholic solution with the former (2 niols.) for one day. The hydrochloride melts and decomposes at 1 5 6 O , and the platinochlwide melts at 136'. Pentaphenyldiguanide, NHPh-C (NPh)*NPh*C (NPh) *NHPh, is a bye-product in the preparation of triphenylguanidine ; it is also pre- pared by allowing an alcoholic solution of aniline and diphenylcyan- amide to remain for one day a t the ordinary temperature.It melts at 160°, and when heated with aniline yields triphenylguanidine. The hydrochloride melts at 213O, and the ptatinochloride is amorphous. PhenSldiorthotolyl,uanidine, NPh:C(NH*C6H4Me),, was described by Huhn, who obtained a product melting at 102O from diorthotolyl- cyanamide and aniline, and from diorthotolylthiocarbamide, aniline, aiid lead oxide, whilst a preparation from phenylorthotolylcyanamide and orthotoluidine, or from phenylorthotolylthiocarbamide and ortho- toluidine by the action of lead oxide, melted at 112'. Making use of these four methods, the author has been able to isolate one form only of phenyldiorthotolylguanidine ; this separates from alcohol in we1 1- formed, colourless crystals, and melts at 97-98' ; the hydrochloride nielts a t 197', and the r7itl.de melts and decomposes at 183'; the piutinochloride forms minute orange-yellow crystals, and melts a t 213-214'. When the base is prepared by either of the methods irldicated, tritolylguanidine (m.p. 130-131O) is formed at the same time ; its hydrochloride melts above 250°, and the nitrate decomposes and melts at 204'. The action of carbon bisulphide on phenpldiortho- tolylguanidirie affords evidence of the tautomeric nature of this sab- stance; if its structure is to be represented by the tautomeric forrnultx NPh:C (NH*C6H4Me)*NH*C,U4Me and NHPh*C (NH*C6H4D/I e) :N*CsH,Me,ORGAN10 CHEMISTRY.31 a, mixture of diorthotolylthiocarhamide and phenylthiocnrbimide with phenylorthotolylthiocarbamide and ortliotolylthiocarbimide should be formed under the influence of carbon bisulphide, whilst a substance having a rigid strncture would yield only one thiocarbamide and one thiocarbimide. Experiment shows that the former alternative takes place, irrespective of the source from which the base is derived. Uiphenylorthotolylguanidine, C6H,Me*N:C (NHPh),, is the sole pro- duct of the action of orthotoluidine on diphenylcFanamide ; i t separates from alcohol in white crystals, and melts at 112'. The nitrate melts at 1 7 2 O , and the plutinochloride a t 210'. Tetraorthotolylphertyldiguanide, C6H4Me*NH*C ( N*C6H&fe) *NPli*C (N* C6HB,hle)*NH*CGH,Me, is obtained by the union of aniline with diorthotolylcyanamide (2 mols.) ; it ciytallises from alcohol in white needles, acd melts -at 111O.The hydrochloride and the platinochloride are sparingly soluble i n water. M. 0. F. Mixed Amidines and Tautomerism. By HANS VON PECHMANN (Bey., 1895, 28, 2362-2374 ; compare Abstr., 1895, i, 347).-Former cAxperiments have dealt with the tautomerism of the types NX:R*NHY and NHX*R:NY, in which X and Y represent chemically similar radicles ; i n the present series, the radicles are dissimilar, and it is found in consequence that tautornerism does not occur. N e t h y 1 benzaniide imidocNoride, C PhC 1 :NMe, is obtained by the action of phosphorus pentachloride on methylbenzamide ; i t is a, colourless, mobile liquid which has an irritating odour, and boils at 124O under a pressure of 60 mm., undergoing. slight decomposition.13- Napht h ylanzido5enzeii~~lmeth~l imidine, NMe:CPh*NH*C,,H7, is ob- tained by allowing p-naphthylamine to act on the foregoing sub- stance dissolved in ether, or from /3-benzonaphthalide imidochloride and methylamine. It separates from much boiling alcohol in lustrous crSstais, and niel ts at 204'. The crystalline form is monosymmetrio, a : b : c = 1.8456 : 1 : 0.70848 ; /3 = 81-39'. The picrate crystallises i n sulphur-jellow prisms, and melts at 166.5O. NMe:CPh*NMe*C,oH7, is obtained by mcthylnting the foregoing substance, and is identical with the amidine obtained from methylbenzamide imidochloride and p-methylnaphthylamine ; it is an oil which readily forms the picrate, crystallising in orange-yellow plates, melting at 155.5O.is formed when diniethylamine remains in contact with benzonapli- thalide iniidochloride ; the hydriodide crystallises from ether i n colourless prisms, and melts at 215O, whilst the picrate forms bright yellow prisms, and melts a t 150'. Phcnylumidobenzenylm ethy limidisze, MeN:CP h*NHPh, is obtained by the action of aniline on methylbenmmide imidochloride, and of methylamine 011 benzanilide imidochloride ; it crystallises from alco- hol in colourless needles, and melts at 234'. Thepicmte melts at 1 6 9 O , and the hydriodide at 190". p-Naphthylmethy lamidobeiizenylmetJ/ ybimidine, Dimet hylumido benzm y 1 - P-rLap ht h y h i d ine, SIe,N*C P h: NC I0H7,32 ABSTRACTS OF CHEMIOAL PAPERS.Met 1, y 111 hen y 1 amido benzeu y lm et 1, y l i n d ine, MeN : C P h*NMe PI], is produced on methylating the foregoing substance ; i t crystallises from petroleum, and melts a t 56". The hydriodide is colourless, and melts at 190' ; the picrate melts at 174". Dzmeth yZarnidobe?ue?a ylphen ylimid ine, Me,N*CPh :NPh, is o b tai D ed from henzanilide imidochloride and dimethylamine ; it melts at, 73-74". The hydriodidc forms lustrous prisms, and melts a t 196" ; tbe picrate melts a t 126". Pheiaylamidobenze~zyla.lailimidine. NHPh*CPh:N*NHPh, is obtained by heating a mixture of benzariilide imidochloride and phenylhydra- zine on the water bath ; it cr~-stallises in yellow prisms, and melts a t 119'. Ferric chloride develops a red coloi-ation in the alcoholic solution ; i n coucentrated sulphui*ic acid, the same coloration is developed by potassium dichromate, whilst ferric chloride produces no change.Pehling's solution is slowly reduced on boiling. The hydrocldoride is sparingly soluble, and crystallises in needles, and the picrate melts and decomposes a t 202". A~zilamidobenzen~lphe?z~limidir~e, PhN:CPh*NH*NHPh, is produced by heating a solution of benzophenylhydrazide imidochloride in ben- zene with aniline, and also in the preparation of the foregoing base ; it crystallises in lustrous needles, and melts at 174-175'. Ferric chloride develops a brown coloration i n the alcoholic solution, and a violet coloration in concentrated sulphuric acid solution ; E'ehling's golution is reduced on boiling.The hydrochloride is readily soluble, and crystallises in needles; the picrate melts and decomposes at 175". M. 0. F. Action of Phenylic Isocyanate on some Acids and Ethereal Salts. By ALBIN HALLER (Compt. reud., 1895, 121, 189-193).- Phenylic: isocyanate and cyanacetic acid, in molecular proportion, react at the ordinary teniperat ure, and jield cyanacetanilide, CN*CH,*CO*NHPb, which crystallises from alcohol in nacreous white plates melting a t 199O. Methylsalicylic acid and phenylic isocyanate at 120' yield methyE.salicyEaniZide, which melts a t 62O, and is not affected by water or by boiling aqueous potash. Anisic acid, on the other hand, at 120°, yields anisic anhydride, identical with that obtained by the action of phosphorus oxychloridc on sodium anisate ; a t 180-1903, however, it yields anisanilide.Anisic acid, therefore, behaves in the same manner as benzoic, toluic, phthnlic, camphoric, and other acids (Sbstr., 1895, i, 679). Phenylglycollic acid yields only phenylglycollamide, OHCHPh*CO*NHPh, melting at 145-146°. Benzoylbenzoic acid and p henylic isocyanate, in presence of ether or light petroleum, yield unstable crystals, which readily split up into their proximate constituents when dissolved in any hot neutral solvent. If, however, the two compounds are heated a t 100" i i i the absence of any solvent, symmetrical diphenylcarbamide and benzojlbenzoic acid are formed ; the latter crystallises from alcohol in transparent, lozenge-shaped crystals melting a t 140-141°, and is identical with the anhydride obtained by von Pechmann by heatingORGANIC CHEMISTRY.33 acetylbenzoj-lbenzoic anhpdride at 200'. this product rneltiug at 140-14l0, and not a t 120'. as stated by Pechmann. At 140-1.50", beuzoyl benzoic acid and phenylic isocyanate seem to yield be:ixoylbenzanilide, but the lattei. could not be isolated. It follows that benzoyl benzoic acid behaves both as a lactone-alcohol, CO<06~>CPh*OH, C H and as an acid ketone, COOH*CsH,*COPh. Ethylic tartrate and p henylic isocyanate, in presence of dry benzene, at 130" yield the compound CO OEt C (OH) (GO NHP h).C (OH) (C: 0 NHP h) *GO OE t , which crystallises from benzene in white needles melting at 164', and, when dissolved in chloroform, has a molecular rotatorF power [ajD = -61.56'. C. H. B.Action of Bensoic Chloride on Urethane. By HAKS VOK PESHMANN and LUDWIG VANISO (Bey., 1895, 28, 2383-2384).- Benzoyl~ret~haue is obtained by heating a mixture of urethane, benzoic chloride, and pyridine, in molecular proportion, for 10-12 hours in boiling water ; the mass is agitated with caustic soda and ether, and the alkaline liquid acidified. A solution of the product in alcohol deposits ethylic benzoyZaZZophanate, COPh*NH*CO*NH*COOEt, which crystallises in silky needles, and melts at 179" (compare Kretschmar, Bw., 1875, 8, lop), whiht benzoylurethane (m. p. 110") crystallises from the mother liquor. When ethylic benzoylallophanate is heated above its melting point, it solidifies at 200-205°, phenylic cyanide distilling over ; the residue crystallises from alcohol in lustrout; leaflets, and melts at 223".M. 0. F. Syntheses with Sodamide Derivatives. By CARL BLACHEK (Bey., 1895, 28, 2352-2360; compare Abst,r., 1895, i, 289).-The author has continued his study of sodamide derivatives, and included sodium succinimide and sodium phthalimide in the investigation. Sodium succinimide yields benzylsuccinimide when heated with excess of bcnzglic chloride for four hours in a reflux apparatus; sodium acetanilide gives rise to acetobenzylanilide. Benzoic anhy- dride and acetic anhydride yield with sodium benzamide, dibenz- nniide and acetylbenzamide respectively ; diacetanilide is formed =hen acetic anhydride acts on sodium acetanilide. The action of sodium or potassium ethylic sulphate on sodium benz- amide and sodium phthalimide leads to the formation of ethylbenz- amide and ethylphthalimide respectively.M. 0. F. Ethereal Imidocarbonates and the so-called Normal Ethereal Cyanates. By ARTHUR R. HANTZSCH and LGDRIG MAI (Ber., 1895, 28, 2466--2472).-The authors agree with Nef (d?znaZeii, 287, 310) in stating that the ethereal salts of cyanic acid described by Cloez (Annulen, 102, 355) have no existence. The products of the reac- tion between cyanogeii chloride and sodium alkyloxides consist mainly of the ethereal salts of imido-carbonic acid (as much as VOT,. LXY. i. d34 ABSTRAOTS OF CHEMICAL PAPERS. 92 pel- cent.), together wit.h small quantities of etheral salts of cyan- uric acid. Phen ylic imidocarbonate, NH:C( OPh),, is most readily obtained by the action of cyanogen bromide (1 rnol.) on a mixtuine of sodium phenoxide (1 mol.) and phenol (1 mol.), dissolved in ether.It forms a hard, white mass, melts at 54O, and readily undergoes decomposi- tion even a t the ordinary temperature, yielding phenylic cjanurate and phenol. The decomposition takes place much niore rapidly wlren the solution of the phenylic imidocarbonate in light petroleum is heated for several hours. By no alterations in the methods of pyocedure, were the authors enabled to obtain normal phenylic cyanate. Parabromop hen ylic irnidocarbonnte, NH:C ( O*C6H4Br)2, is readily ob- tained by the action of parabromophenol (2 mols.) on cjanugen bromide (1 mol.) ; it melts at 129O, is sparingly soluble in ether and cold alcohol, and is also more stable than the corresponding phenylic salt.Ethylic imidocarbonnte is very stable, and is only decomposed into alcohol and ethylic cyanurate when heated in sealed tiibes at 200' for several hours. Aqueous solutions OF the imido-ether, when treated with an alkaline solution of bromine, give a precipitate of ethylic brminzidocarbonnte, NBr:C(OEt4)2 ; this is readily soluble in ether, and crystallises in needles, which melt a t 4?. No trace of ethylic cyanate could be obtained by the action of cyanogen bromide on sodium ethoxide, nor yet of methylic: cyanate from sodium methoxide. The chief product was always the imido- ether, together with s.r)all quantities of the cyanurate. Sodium phenoxide and also sodium parabromophenoxide cause the condensation of phenylic isocjanate into phenylic isocyanurate.The polymeride of phenylic isocyanate obtained by Hofmann (Annalen, 1, 37) differs from this cyanurate, and is shown to be LZ &molecular iso- cyanate, whereas the isocyanurate is a tri-molecular compound. Benzazide (Benzoylazoimide). Acid Azides of the Fatty Series. By THEODOR CCRTICS (J. pr. Chen2., 1895, [el, 52, 210- 226 : compare Abstr., 1895, i, 32).-Benzoylazoimide (benzazide) (Abstr., 1891, 56) is best purified by dissolving it in acetone, from which i t crystallises in large, colourless tables melting a t 32'. Its behaviour with water, with alcohol, with bromine, and with aniline has been described (Abstr., 1894, i, 331 ; 1895, i, 32). Dimetanitro- diphenylcarbamide melts at 24i--250G, not at 233" as heretofore stated. When reduced by means of sodium amalgam in alcohol, benzoyl- azoirnide is converted into etliylic benzoate and sodium azoimide ; when alcoholic ammonium sulphide is the reduciug agent, benzamide and ammonium azoimide are the prociucts, hydrogen sulphide being liberated.When zinc dust and glacial acetic acid are used, benz- amide can alone be isolated ; but when caustic soda is substituted for acetic acid, sodium benzoate and sodium azoimide are formed, unless the solution is very dilute, when nitrogen is evolved and dibenzoyl- hydrazine (m. p. 233'), NHBz-NHBz, produced (compare Zoc. cit.). J. J. S .ORGANIC: CHEMISTRY. 35 Phenglazoimide, PhN3, can be similarly reduced to hydrazobenzene, SHPh-NHPh, by sodium amalgam in alcohol. dzccciny Inzoimide, C2H4( CO*N3)2, is prepared by graclually adding sodium nitrite (2 mols.) to a well cooled, concentrated aqueous solu- tion of auccinylbydrazine hydrochloride (Abstr., 1895, i, 264) , and shaking with ether.It crystallises in long prisms, and explodes when heated. It is easily soluble in alcohol, sparingly so in ether, and insoluble in water. Under water, it melts nt 30". Boiling water decomposes it with evolution of carbonic anhjdride and nitrogen, and formation of ethyleiiecarbaniide. Boiling alcohol decomposes it, with formation of ethylenediurethane (ni. p. 110'). Attempts to prepare oxalylazoimide, N3.CO*CO*N,, have not been successful ; treatmenc of oxalylhydrazide (Zoc. cit.) in the manner descrilwd in the preceding paragraph, yielded hydr*azioxnZyZ, ?o*NH*NH'?o which is a white solid, insoluble i n all solvents.CO*NH*NH*CO' JI&?zylaZoimide, CH2( CO*N3)r, prepared by diaaotising malonyl- hydrazine (Zoc. cit.) in the manner described for succinylhydrazide, is an explosive oil which is converted into a yellow oil when heated with alcohol ; the reactions of tlie yellow oil prove it to be methylenedi- urethane. GlycoZylazoirraitle, 0 tl*CH2*CO*N3, is easily obtained by diazotising glycol~lliydraziiie (Abstr., 1895, i, 331) hydrochloride ; it crystallises in double pyramids, and explodes feebly. Boiling alcohol coriverts it into the wethtme, OH*CH,*NH.COOEt, wliich melts at 189'. A. G. B. Azides (Azoimides) of Substituted Benzoic acids. By A. STRL-VE aiid RUDOLF RADENHAUSEN ( J . pr. Chem., 1895, [ a ] , 52, 227- ~ 4 2 ) . - ~ I e f a n ~ t ~ o b c ~ ~ z ~ y l a z o ~ m ~ d e , N0,*C6H4*CO*N,, is prepared by dis- solving metanitrobenzoylhydrazine in dilute nitric acid, and adding the calculated quantity of sodium nitrite.It crystallises in white lamince, melts at, 6S0, and dissolves e:tsily in ether, benzene, alcohol, and glacial acetic acid, but not in water. It is also the main product of the action between diazobenzene sulphate and metanitrobenzoyl- hydrazine. When heated with much water, it is converted into di- me tnnitrodiphenylcarbsmide melting at 234' (compare preceding abstract). Tef ~~nizit~~odiphenylca~ba~~zide crystallises in jellow needles. When metanitrobenzoylazoimide is boiled with alcohol, it yields meta- 12itroluhenyZuretha?ze, N02*C,H,*NH*COOE t, which crystallises in yellow needles, melts a t 56", and dissolves easily in alcohol and ether ; strong hydrochloric acid at 120' decomposes it into carbonic anhydride, alcohol, and me tan it raniline. 01.thonitrclheiizoyZazoirnide is similarly prepared ; it crystallises in y e h w prisms, melts at 36", and dissolves freely in ether, chloroform, aiid benzene, but only sparingly i n light petroleum.Parani~i.obeiizoyln~oi~~~ide crystallises in coloui~less laminae, melts at 69", and resembles the meta-derivative in solubility. Hot water con- verts it into d~p:pnralzitl.odiphenylcur.~a?nide, CO ( NH.C6H4.N02),, which ci*ystallises in lemon-yellow needles, melts above 260°, and is insoluble in water ; hydrochloric acid at, 130' decomposes i t x i t b formation of d 236 ABSTRACTS OF CHEMICAL PAPERS. paranitraniline, but the change is more difficult to accomplish than in the case of the meta-derivative.Hot alcohol converts paranitro- benzoylazoimide into paranitrophenylurethane (Abstr., 1885, 149). Orthobromobe?azoy Zhydraziize, C6H4Br*CO*NH*NH2, from ethylic orthobromobenzoate and hydraziiie hydrate, crystallises in colourless needles, melts at 153'. and is only sparingly soluble in water, but freely so in alcohol and hot benzene. Metnhydroxy benzoy Zh yd?*azine, OH*C,H,*C 0.NH*NH2, from et hylic metahydroxybenzoate and hydraziiie hydrate, forms white crystals, melts a t 150°, and dissolves in water and alcohol, but not in ether, chloroform, or benzene. When its aqueous solution is shaken with benzaldeh yde, benzylidenenzeta hydro~:?lbeizzoylhyd,.uziiae, separates ; it melts at 205'.Metahydroaybenzoylazoimide, OH*06H4*CO*N3, prepared by diazotis- i n g the hydrazine, forms small, nearly colourless crystals, melts a t 95O, and dissolves easily in alcohol, ether, and chloroform, but only sparingly in light petroleum ; when heated with water, it yields tli- metahydroxydiphe?iyZcarbamide, CO(NH-C,H,*OH),, which forms colourless crystals, and melts at 280". Parahydro~benzoylhydrnzi?ae, prepared like the meta-derivative, crjstallises in white laminae, melts at 260°, and dissolves in hot water and alcohol. The corresponding benzylidene derivative forms white crystals, and melts at 218'. Pnraltydroaybenzoylazoimide crys- tallises in white needles, melts a t 132", and dissolves in ether, alcohol, benzene, and chloroform, but not in water.When it is heated with alcohol, it yields a crystalline compound which melts at 105-l1Oc, and is converted by hot water into diparnhydroxydi- pheny Icnrbanzidc ; thi? crystallises in colourless ncedles, and decom- poses, without melting, at 230". Ortholi ydroxybenzoylh ydrazine, prepared from methyiic salicylate at id hydrazine hydrate, crystnllises in colourless lamine, and melts at, 145". The corresponding benzylidene derivative forms small, colourless crystals, and melts a t 230". Orthohydroxybenzoylazoinzide crystallises in large, colourles~, rhombic plates, melts at 2 7 O , and has a powerful, tear-exci ting odour. Diort hoh!/di*oxydipheu ylcnrb- nilside crjstallises in white needles, and melts at 125'. Meta??zic7obeizzoylhydl.uzine, NH,*C,H,CO-NH*NH,, is prepared from ethylic metamido benzoate and hydrazine hydrate.It forms colour- less crjstals, melts a t 77", and is 1-ery soluble in cold water and in alcohol ; the iLydrochloi*ide, ~H2.C6HJ*CO*N.IH3,2HCI, melts a t 265". The benzylidene derivative, PI'HI,.C,H,.CO*PITH*N:CHPh, melts a t 180". ~fetnniidobeirzoylazoinside, NH2*C6HI*CO*~\r3, is precipitated by adding sodi urn acetate to a mixture of metamidobenzoylhgdrazirie and diazo- benzene sulpliate in aqueons solution ; it ciytallises in yellow needles, melts a t 85", and dissolves in ether, benzenc, and light petroleum. OH* C,H,CO *NH *N: CH Ph , A. G. B. Hydrazide and Azoimide of Hippuric Acid. By THEODOR CCRTILS (J. p a . Cheric., 1895, [Z], 52, 243-2'il).-The author describes in detail the prepaiation of hippurplhydrazine (-4bstr.,ORQANIC CHE3IISTRY.37 1891, 56; 1802, 112; 189.5, %2) by the action of hydrazine hydrate on (1) ethylic hippurate, (2) hippuramide, (3) hippurylazoimide, (4) ethylic hippurylglycolats. Hippirylhydrazine hydrochlode, NHBz*CH,*CO*NH*NHz,HCI, forms colourless crystals. The pZafinosocILloride, ( NHBz*CHz*CO*NH*NH?),PtC I:, crystdlises in slender needles. Hippurylbeiizylidenehydrazone has pi-evionsly been described (Abstr., 1891, 56). H~~pziryZcinnn??aylidene- hydrazine, ?JHBz*C H,* C 0 *NH*N: C: H*CH: C H P h, cry st allises in y el- lowish pi*isrns, and melts a t 201.5". S?yminetrical acetytkippIiry2lLydra- zine, NHBz*CHz*CO*NH~NHAc, is formed by the iiiteraction of acetylbydrnzine (Abstr., 1895, 263) with hippurylazoimide in ethereal solution; it crystallises in colourless needles, melts at 18G0, and dissolves easily in alcohol.Syinmet&nl hippiIryZ~hen~l!Z7Lydraxine, NHBz*CH2*C0.NH*NHPh, from phenylhydrazine and hippuryhzo- imide, crystallises in si1ver.y lnmiiize or needles, melts at 182*5O, and can be distilled nearlF unclecomposed when quickly heated ; it dis- solves in hot alcohol, but not in water or in ether; it does not reduce hot Fehling's solution. 1~~L'tro.sohi~~'lC).l!lphenylhy~).atine, N BBz*CH2*C0.NH-NPh*N 0, prepared by treating the last-named compound in glacial acetic acid solution with sodium nitrite, forms a yellow, crystalline powder, me1 ts at 128-12Y0, and dissolves in alcohol, but not in water; hot water decomposes it into phenyl- azoimide and hippuric mid.Acetylhippurylphenylhydrazine, N HBz* CH2* CG*NH*NPhAc, prepared by digesting hippurylphenylhydrazine with acetic anhyd- ride, forms a white, crystalline powder, melts at 15.io, and dissolves in water and alcohol, but not in ether. l)i7Lippz~rylhydrazine, (NHBz*CH,*CO)~N,H,, can be prepared by heating a mixture of hippurylhydrazine and ethylic hippurate in molecular proportion ; it forms small, silvery crystals, melts at 268--f169", and is insoluble in boiling alcohol, boiling water, and etLer ; i t is a feeble acid. Hippii~ylazoimide, NHRz*CHz*CO*N3, the product of the aztion of sodiuni nitrite and acetic acid on an aqueous solution of hippuryl- hydrazine, has been previously described :IS a nitrosohippurylhydra- zine (Abstr., 1891, 571, and as diazohippurarnide (Abstr., 1892, 113) ; new analyses have now established its identity.It does not give Liebermann's reaction, as prsviously stated, neither does it give a p1.e- cipitate with silver nitrat.e in alcoholic solution until some time has elapsed, when silver azoimide sepamtes. With alkalis, hippurylazo- imide yields the alkali azoiniide and the alkali hippurate, but as an intermediate product R salt is obtained which has a blue fluorescence (compare Zoc. cit.). With acids, hippurylazoimide is hydrolysed into hippuric acid and azoimide, whilst with ammonia it yields ammo- nium azoimide and hippuraniide. This reaction with ammonia is typical of the behaviour of hippury lazoimide with aniline, para- toluidine, and metatoluylenediamine ; the following new compounds have been prepared by such reactions.Hippiimnilide cyystnllises in long, lustrous prisms, melts at 208*5O,3s ABSTRACTS OF CHEMICAL PAPERS. and dissolves easily in hot glacial acetic acid and hot alcohol, but only sparingly in cold alcohol or ether, and not at all in cold watei.. Nit,.osollippuraniZidc, XHBz*CB,*CO*NPh*NO, obtained by the actiou of nitrous acid on the anilide, is a yellowish, crystalline powder, 'which darkens below loo', and melts between 195" and 197". H~ppzLropal.atoZuicJz'de, N H Bs C B p*C O*NH*C6H4Me, cry s t all i ses i u colourless needles, and dissolves freely in hot alcohol and hot glacial acetic acid, biit only sparingly in water, cold alcohol, or ether. Hippur-oparatoluylenedinmide, NHBz~CH,*C0.NH~C6H,Rle~NH,, crystallises iii pale yellow, lustrous Inmine, melts a t 205'.and slloms a similar solubility t o that of hippuroparatoluidide. The behaviour of hippui-ylazoimide with hjdrazine and acid hjdra- zides has already been indicated (Abstr., 1895, 34), and the products of these reacticris will be described in n future communication. In discussing the behaviour of hippurazide with water, alcohol, and halogens (compare Abstr., 1894, i, 331 ; 1895, 32 ; this vol.! i, 34)) the author adopts the name hippenyl for the radicle NHBz.CH,-. Dih~~~enylcartamide, (KHBZ*CH,-KH)~CO, is obtained when liip- purylazoimide is boiled with water, carbonic anhydride and ni trogeii being eliminated. It forms microscopic, colourless crystals, melts at 246', and is nearly insoluble in water, but, dissolves to some extent in hot alcohol and gJacial acetic acid.Hydrochloric acid. at 120", coriverts it into benzoic acid, ammonium chloride, carbonic anhydride, and formaldehyde. When the hot filtrate from the dihippenylcarb- amide is cooled, a compound, probably iiippenylcndanil, R'HBz*C H,*N:C 0, or a polynieride thereof, separates in the form of colourless crystals, which melt at 233" ; dilute acids readily decompose it into beiizoic acid, ammonia, formaldehyde, and carbonic anhydride. A third compound, C9H6N20, is left as an oil when the mother liquor from the carbanil is evaporated; it is soluble in alcohol and in glacial acetic acid, from which it is precipitated in the form of crystals ; it melts a t 98'. The same substnnce is produced when hippurylazo- imide is heated either by itself 01% in an indifferent medium.Hippnrylazoimide reacts with alcohok at their boiling points to form the correspondiiig hippenylurethanes ; these are hydrolysed by hydrochloric acid, a t loo', iuto benzoic acid, ammonia, formaldehyde, carbonic anhydride, and the parent alcohol. Hippenylethy Zzcrethaue, NHBz*C HZ*NH-C 0 OE t, cry stallisea i n aggregates of colourless needles, melts a t 162', and dissolves easily in hot alcohol, benzene, and glacial acetic acid, but only sparingly in hot water. It behaves as a base, and can be distilled almost unchanged. Hippenylnzethyl- urethane, NHBz*CH2*NH*COOM e, crystallises like the ethyl com- pound, and melts at the same temperature (162'). HippenyZbeizzyl- urethane, NHBz*CHZ*NH.C00.CH,Ph, crystallises in felted needles, which become highly electrified by friction; i t also melts at 162'.Both the last-named compounds resemble the ethyl compound in properties. Alkylic haloyd salts react with moist hippurylazoiniide, when warmed therewith, to form the corresponding hippenylurethane, withORGANIC CHEMISTRY. 39 liberation of hydrogen halo'id. I n this reaction, the author sees evidence that moist hippurylazoimide has the constitution NH B z* C H2*C O N €3. IT2* 0 H. By treating hippurylazoimide with a halogen in ethereal solution, nitrogen is eliniinated, and a di'nalo'id hippenylcarbanil is formed. In this way, compounds which are assumed to be dib).onsoh.ippe,rylcai.b- anil, NHBz.CH2*NBr2:C0, and d i i o d o l i i p ~ e i ~ ~ l c ~ ~ ~ ~ b a n i l have been crys- t a1 li sed. Heactions of hippurylazoimide with hydrogen chloride, aldehyde, and acid amides, are briefly mentioned, but their elucidation will receive further attention. A.G. B. Appendix to recent Publications (Benzoylhydrazines). BJ- THEODOR CURTIUS ( J . pr. Chem., 1895, [2], 52, 272--276).--1n describing carbohydrazimine, Curtius and Dedichen (Abstr., 1895, i, 29) have overlooked the fact that Angeli (Abstr., 1894, i, 149) had previously prepared the same compound. The compounds described as hjdrazimines i n the same paper arc wroi~gly named ; they contain two fewer hydrogen atoms, and are identical with Pinner's isocli- hydrotetrazines (Bcr., 1889, 22, 3274). The author thinks Pnrgotti's claim for priority (Abstr., 1895, i, 27) cannot be allowed. Ethylic benzoylh~~rnzc)ilclacefoclcrtate, COPh-KH-N:CMe*CH2*COOEt (compare Struve, Abstr., 1895, i, 3 4 ) , has been prepared by heating benzoylhydrazine with ethylic acetoacetate ; the crude material melts at about 60°, but when its solution in alcohol is diluted, i t separates as an oil, which is still liquid at -15'.The preparation of ethylic metanitrobenzoylhydrazoneacetoacetate (Abstr., 1895, i, 276) is detailed. A. G. B. Metallic Bisulphite Compounds of Aldehydes. By A. FAGARD (J. Phawz., 1895, 6, [2] , 145-148).-Benzaldehyde lithium hydroge9L szclphite, CiH60,LiHS03 + *H20, is prepared by passing sulphurons anhydride into an aqueous suspension of lithium carbonate, into which benzaldehyde is slowly dropped. The product is evaporated to crystallisation, preferably under low pressure.The sulphate crys- talliaes i n small, colourless prisms, and appears to resemble the analogous sodiuni compound. Acetone bin~izirn h y d ~ o g a u szclyhite, 2C3'E-T60,Ba( S03H)z,Hz0, is made by passing sulphnrous anhydride into a mixture of barium hydroxide, water, and acetone. The baryta gradually dissolves, with evolution of heat, and the additive cornpound separates on cooling. It crystal- liscs in s111a11, brilliant plates, resembling those of boric acid. The corresponding strontium compound is anhydrous, and forms small needles, or twinned prisms. JN. w. Resolution of Benzaldehy dacyanhydrin by means of Alkalis. By CARL GLUCKSYASX (Chem. C'entr., 1895, i, 8i3-274, from Yhamz. Post., 27,573-574 and 585-588 ; compare E. Utescher, Abstr., 1893, i, 419) .-The fact that benzaldehyde combines with40 -4BSTRACTS OF CHEMICAL PAPERS.hydrocyanic acid in dilute solution has no bearing on the question of' the hydrolysis of benzaldehydecyanhydrin, since this is treated successively with alkali, acid, and silver nitrate. The action of magnesium hydroxide is, like that of potash, direct; it is not dependent on the formation of silver oxide, and the hydrolysis is completed more rapidly. Parahydroxybenzaldehyde. By CARL PAAL (Ber., lE'9.5, 28, 2407-2414) .-The monobromo- and moniodo-derivatives of para- hydroxybenzaldehyde described by Herzfeld (Ber., 10, 2196) are in reality disubstitution products. Bromine converts parahydroxy- benzaldehyde, when dissolved in dilute alcohol, directly into the dibromo-derivative, whilst if chloroform be used as the solvent, metnbromoparahydroxybenzaldehyde [CHO : Br : OH = 1 : 3 : 41 can readily be obtained.It crystallises from hot water in white plates, melts at 124', and decomposes when distilled. The sodium and silcer derivatives orystnllise in needles. JIetabyomoparahydroxybenz- aZdo.cime crystallises in druses of white needles, melting at 133". ,lIetabrornoparahydroxybenzylideneaniline forms flat needles, melting at 135'. Metabromoparahydroxjybenzoic acid is formed by the oxida- tion of the aldehyde with alkaline permanganate ; it crystallises in concentric groups of:white, flat, needles, melting at 148', and is soluble in hot water. Jletiodoparahydyoxybenzaldehyde is found in the mother liquors obtained in the preparation of the di-iodo-derivative.I t crystallises in white plates, biit has not yet been obtained quite pure. Metanitroparnhydroxybenzaldehyde can be readily prepared by dissolving the hydroxybenzaldehyde in acetic acid and adding nitric acid. A. H. By HEINRICH LIMPRICHT (Amden, 18'35, 288, 306- 342).-The ketones described in the following abstracts were pre- paTed by mixing the chloride employed with a slight excess of the hydrocarbon, adding several volumes of carbon bisulphide, and heating the liquid with alnminium chloride in a reflux apparatus for 8-12 hours. The ketone is obtained as a resinous cake, and, after being washed with water, is crystallised from alcohol. The carbonyl group in these ketones occupies the para-position with respect to the methyl of the tolyl residue.Metanitrophenyl Paratolyl Ketone. By HEINRICH LIIIPRICHT and M. LENZ (Annalen, 1895, 286, 307-321).-31etanitrophenyl paratolyl ketone crystallises in white leaflets, and melts at 111" ; in small quanti- ties, it may be distilled without undergoing decomposition. The ketone is readily soluble in organic solvents and hot alcohol, but is sparingly soluble in cold alcohol and 50 per cent. acetic acid. The dichlo7eide is obtained as a brown oil by heating i t with phosphorus penta- chloride ; the ketone is regenerated on treating this substance with alcoholic ammonia or aiiiliiie. The monochloro-derivative is formed when chlorine gas is led into the ketone at 150" ; it crystallises from alcohol in long, brittle needles, and melts at 96". The monobromo- derivative crystallises from alcohol in long, white needles, 2nd melts a t 116".~~~etanitrophenyl-par~tol~b-lteto~~es:zil~hoizic acid is obtained by J. B. T. Ketones. 31. 0. F.ORGANIC CHEllISTRY. 41 dissolving the ketone in several volumes of fuming sulphuric acid ; it crystallises from water in large, rhombic plates containing 3H20. The substance effloresces in the atmosphere, and melts a t 140" with effervescence, but if heated for eight hours in the vapour of boiling toluene it becomes anhydrous, and then melts at 215' ; the barizcrn salt crystallises from water in colourless prisms, and contains 3Hz0. Diniirophmyl paratolyl ketone formswhite scales, and melts at 125"; the tyinitm-derivative cry s t a k e s in minute, six-sided prisms, and melts at 165'.Azoxyphenyl paratolyl ketone is prepared by dissolving the nitroketone in alcoholic potash ; i t separates from alcohol in yellow crystals, and melts a t 145'. The ketozime, obtained by heating the alcoholic solution of the ketone with hydroxylainine hydrochloride and sodium carbonate, crystallises from alcohol in white, lustrous needles, melting at 111'; if caustic soda is employed, the kefozime of the azoxy-derivative is formed, occurring in two modifications which melt at 235' and 243' respectively. SIetanzidophe?tyl paratolyl ketone is obtained by reducing the nitro- ketone in alcoholic solution with stannous chloride ; i t crystallises from alcohol in amber-coloured prisms, melts at ill', and may be distilled in small quantities without undergoing decomposition. The hydrochloride crystallises in needles, and melts at 198'; the szdphate separates from water in aggregates of needles, and melts at 142O.The szclphonic acid of the amido-ketone forms small crystals which decrepitate when heated ; it melts at 300", and effervesces and blackens. The acetyl-derivative crystallises in small, white prisms, and melts at 139'. On adding sodium nitrite to an aqueous solution of the amidoketone sulphate, the diazo-compound is formed : gas is evolved when the diluted liquid is boiled, and the slender, white needles which the cold solution deposits melt a t 120°, and consist prob- ably of hydroxjphenyl pamtolyl ketone. Phenyl paratolyl ketone is obtained from the amido-ketone by adding a concentrat4ed aqueous solution of sodium nitrite to a solution of the hydrochloride in absolute alcohol, and treating the liquid with 6nely divided copper.The keloxiine of amidophenyl parat oyl ketone crystallises in minute, white prisms, and nielts R t 146' ; the amido-ketone is regenerated on heating i t with concentvated hydrochloric acid for four hours. Xetanitropnmbenzo yl beizzoic acid, N 02- CsH,* C 0- C,H,*CO OH, is ob- tained by oxidising the nitro-ketone, in glacial acetic acid solution, with chromic anhydride ; it crystallises in rhombic tables, melts a t 242', and sublimes a t higher teuiperatnres, forming white crystals. The potas- siziin salt crjstallises in white needles, and the barium salt, cmtain- ing lHzO, foiams leaflets ; the chloride melts at 94', and the nmide at 2 0 4 O . Jletaniidoparabemoylbenzoic acid is obtained by reducing the foregoing nitro-compound with stannous chloride ; it crystallises from alcohol, and contains 1H20, which is lost at 145", when the sub- stance melts ; the b a ~ i z m salt is anhydrous, the hydrochloride crys- tallises in long, slender needles, melting above 250", and the szdphnte contains 2H20.When the chloride of nitrobeiizoglbenzoic acid is heated with toluene and aluininium chloride, metanit~ophenyZpa~atoZyZ- phe?z!/Zene diketone, N0,*C6H4*C0.C6H,*Co*c6H~~~e, is formed ; it crystallises in colourless leaflets, and melts at 210". When oxidised42 ABSTRACTS OF CHEJnCXL PAPERF. with chromic anhydride in glacial acetic acid solution, i t yields a2etn- nitro~nl.nbenzoylpa,.abcnzoyEbenzoic acid, which melts at 276' ; the sodiicm salt crystallises i n nacreom scales.M. 0. F. N02*CGH~*CO*CGH11CO*C~H~*COOH, Paranitrophenyl Paratolyl Ketone. By HEIXRICH LTJI PR IC HT and E. SAMreirz (Annulen, 1895, 286, ;3'21-332).-Yal.aizit,.oyhelzyl paratolyl ketone crystallises in white needles, and melts a t 122-124". I n small quantities, it may be sublimed without undergoing decom- position ; the ketone is soluble in organic solrents and in concentrated sulphuric acid. Dinitrophenyl paratolyl ketone melts at 127', and tri- nitrophenyl paratolyl ketone at 159'; both these compounds have been obtained by Milne (Ber., 1874, 7, 983), and they appear to be icien- tical with the dinitro- and trinitro-ketones described in the foregoiug abstract. P(rz.a?nidophe?zyl paratolyl ketone is obtained by reducing an alcoholic solution of the nitro-compound with stannous chloride ; it separates from benzene in well-formed crystals, and melts a t 179'.The szdphate forms nacreous leaflets, and melts and decomposes at 210-216' ; the ncetyl derivative melts a t 155'. On adding sulphuric acid and sodium nitrite to an alcoholic solution, the amido-ketone becomes diazotised ; copper powder is then added, and on filtering the liquid into water, separation of pheiiyl paratolyl ketone (m. p. 52") takes place. Dinmidophenyl pnratolyl Jcetone is obtained by reducing the dinitro-compound, and melts a t 178" ; the s d p h a t e becomes dark, and decomposes above 240'. !l?rinrnidophenyl parcttolyl ketone crystallises from water i n white needles, which becotne brown on exposure to air ; it melts at 199".Parahytlroxy~henylpa?-atolyl ketone is obtained by boiling an aqueous solution of the diazotised amido-ketone ; it crystallises i l l long, white needles, and melts at 160O. Ilronzophenyl p n m t o l y l Eetoue is prepared by treating the diazo-compound with hydrogen bromide End copper powder; it crystallises in small, white needles, and melts at 139". The ketozime of paranitrophenyl paratolyl ketone crystallises in aggre- gates of needles, and melts a t 145' ; the phenyllqdrazone crystdlises in lustrous, scarlet needles, and melts a t 1.54". The phenyZlLydyazmJ of tho amido-ketone forms Iiistrous, brownish-red, rliombic ci*~stals, andmelts at 163". ParaIzityopa?.atrenzoylbenzoic acid is obtained by oxidising paranitro- phenyl paratolyl ketone with chromic anhydride in glacial acetic acid solution ; it melts at 255".The sodiu?72 salt crystallises in small, an- hydrous leaflets ; the chloride melts at 124". Pa?.n7,2iJopara~e?azo.~~- benzoic acid crjstallises i n bright yellow needles, and melts at 211' ; the sulphate is colourless and anhydrous. Paraiiitropheql para f olylph eiay lei1 e diketone, NO,*Cg H,* CO'C~HA'C O*C~HIMEL is obtained from toluene and the chloride of paranitropnrabenzoyl- benzoic acid by treatment with aluminium chloride ; it melts a t 236'. Paranitropnrabenzo yl~nrnbeiazoylbenz~ic acid crysta llises in 1 ust rous leafleh, aud melts a t 306-308" ; the S o d i u i i L salt dissalves sparingly in water. Jf. 0. F:ORGAN I C C HE M I ST K I-. 43 Metanitrophenylxylyl Ketones.By HEISRICH LIAIPKICHI and H. FaLKKsst; KG (Anualen, 1895, 286, 3~3--542).--7Ie~nrLilt.ophc-)zyl ?netuxylyl ketoue crystallises in lustrous yellow leaflets and melts at 64'. The ~1.initI.o-deri~-ative crystallises from alcohol in yellow needles and melts a t 138-139'. Xetamidopheti yl metazylyl ketone is obtained by reducing the nitro- conipound with stannous chloride ; it forms brownish crystals 2nd melts at Ll8'. The hydrochlo~ide crystallises in needles and the szblphcrte in lustrous nodules. The sulphoizic acid of metanitrophenyl metaxlyl ketone crystallises from water in long, white, lustrous needles; the barium salt contains 2H20, which is lost a t 13G'. Azox!lphenyl nzetaxylyl ketone is preFared by treating the nitro-ketone with boiling alcoholic potash ; it separates from petroleum in small, red needles and melt,s a t 134".The ketozime of metanitrophenyl met'axylyl ketone fornis small, white crystals, and melts between 131' and 149O. Two ~netaiaitrobenzoylmetatolzLic acids, N02.C6H4.C O*CsH3Me*COOH, are obtained by oxidisi ng the nitro-ketone with chromic anhydride i n glacial acetic acid solution, melting a t 173" and 152-153" respec- tively. The barium salt of the former is anhydrous, and crystallises in yellow needles and the silcw salt! forms minute white prisms, becoming violet when exposed in the moist state to light ; the chlo~ide is an oil, and the amide forms yellowish-brown crystals and melts a t 2 2 6 O . Xeta?zitrophe:Lyl orthnzylyl ketone crystallises in yellow plates belonging to the rhombic system, and melts a t 100'.Jletamidophcuyl orihoxylyl ketone is very soluble in alcohol and ether; the sdphate crystallises in pale-red nodules, and the lr ydTochZoride forms white needles. X e t unit 1.0 beizzo y lo~tlzo to l u i c acid forms small, ye1 lo wish crystals aucl melts at 191' ; the b a r i u m salt crystallises i n jellow needles, and the silrer salt is also crystalline, becoming violet when exposed t o light in the moist condition. illetanitriphenyl p a r a x y l y l ketone forms white, silky crystals, and melts a t 97-98'. ilIetall,idopheri y l pamxlyl 1;etone was not obtained in the crystalline state ; the sulphnte forms reddish crjstals, and t h e hydrochZoride crystallises in yellowish needles. b~eta~iitroph.e~zy1paratolz~ic acid crystallises from glacial acetic acid i n lustrous, brownish needles, and melts a t 189'; the bariunt salt fornis small, yellow crystals, and the moist silcei.salt is decomposed by light. M. 0. F. Resacetophenone. By GEOKG GREGOI{ (Monatsh., 1895, 16, 619-629 ; compare Nencki and Sicber, Abstr., 1881, 591 ; Wechsler, Abstr., 1894, i, 521, and Gliicksmaiin, Abstr., 1892, 38).--Wlieii diethylresacetophenone (1 mol.) is suspended in water and oxidised by the gradual addition of a solution containing potassium permanganate (1 mol. K2R/Inz08) and potassium hydroxide (2 mols.), 2 : 3-dietlzo.zy- benzoylformic acid, C6H3(OEt),-CO*COOH, is formed. It is insolxble in cold water but dissolves in hot water, and more readily in alcohol and ether ; from the solution in benzene, it separates in small crjstals44 ABSTRACTS OF CHEMICAL PAPERS.which melt at 1'27'. It forms an osime, C12H14@1:NOH, which crystal- lises from benzene and melts and decomposes at 130°, R silver salt, Cl2HI3AgO5, which is amorphous, cz sodiicnz salt, Cl2Hl3NaOS + 6H,O, which crystallises in scales, and a crysta.lline barium salt, (C12H1305)zBa + 8H2O. On reduction with sodium amalgam, the rtlcoholic acid, Cl2HI6O5, is formed. This crystallises from benzene, melts at 115', forms the silver salt, C12H15Ag05r and is oxidised by permanganate in dilute acid solution to an acid identical with the product of oxidation of Tiemann and Lewy's diethylresorcylaldehyde, which is therefore un- symmetrical diethoxybenzoic acid, OEt.C<cH- CHoC(oEt)\. C.COOH. -CH> The author therefore concludes that resa,cetophenone has the constitu- G: T.M. Constitution of Fisetin. By SmNtsrlbus VON KOSTANECKI and JOSEF TAYBOR (Be).., 1895, 28, 2302-2309 ; compare Abstr., 1894, j, 93) .-Two constitutional formulae are possible for fisetin, which is converted by fusion with potash into resorcinol, glycollic acid and pro- tocstechuic acid, C6H,(oH)<o-~*C6H3(oH)2 , [OH:O:CO=1:5:6 013 1 : 3 : 43. When tetraethylfisetia is boiled with alcoholic potash, i t yields diettiylprotocatechuic acid and diethyl fisetol ether, which, if fisetin have the second of the above formulae, must have the formula, O~;t*C6H3(OH).C0.CH,*oEt [ = 1 : 3 : 41, according to which it is an ethoxy-derivative of monethyl resacetophenone ether. On oxidation, diethyl fisetol ether is converted into ethyl-p-resorcylic acid (Herzig, Abstr., 1891, 1386).The authors have now shown that ethyl resacetophenone ether yields exactly the same product and have thus confirmed the accuracy of the view that the second of the above formula represents the constitution of fisetin. When resacetophenone is t.reated with alcoholic potash and ethjlic iodide, it yields a mixture of the two ethers. Diethyl resacetophenone ether crystallises in quadratic prisms melting at 74-75'. E t h y l res- acekphenoxe ether, OEt*C6tZ3(OH)C0.CH2*oEt, separates from dilute alcohol in white plates melting at 49'. On oxidation, the latter of these compounds is coiiverted into ethyl-S-resorcylic acid, ideiiticnl with that obtained by Herzig from diethyl fisetol ether, and with that prepared by the authors from p-resorcylic acid.Benzoylrcsorcinol differs from resacetophenone in its behaviour to wards alcoholic potash and meth ylic iodide, bemoylmet hy lresorcinol, C6H2XeBz(OH)2, being forrnecl. This substance crystallises in faintly yellow lustrous plates, melting at 176' ; i t does not contain a methoxyl group, and yields a diacetate, melting at 120', and a diben- zoate, melting at 149'. The benzoylmetliylresorcinol is accompanied byv bcnzoyZmrt7i ylresorciiiol methyl ethey, O&Ie*C6H2MeBz-OH, which crystallisea in rliombic tablets, melting at 125'. The ?nonacetate melts at 86". A. H. COOOHORGANIC CHEMISTRY. 45 Action of finely divided Silver on Ethglic Phenylbrom- acetate. By CARL HELL and S. WEISZWEIG (Bey., 1895, 28, 2445-- 2454) .-Phenylbromacetic bromide was prepared by the action of phos- phorus pentabromide (2 mols.) on mandelic acid (1 mol.), and was then converted into the ethylic salt by dissolving it in ethylic alcohol.The authors find t,hat the yield is just as good when one-half or eyen one-quarter of the theoretical quantity of pentabromide is used ; this is due to the fact that the hydrogen bromide which is formed duriny the reaction also acts on the mandelic acid. The ethylic salt boils at 175' under a pressure of 25 mm., and small quantities may be dis- tilled at ordinary atmospheric pressure mi tliont undergoing decom- position. Finely divided silver acts on the ethylic salt at the ordinary temperature, but the action is greatly accelerated by heating the two together in an oil bath at 170-180'. No product of low boiling point could be isolated, butl the ethereal extract yielded a mixture of u- and P-ethylic diphenylsuccinates(compare Reimer, Abstr., 1882,200 j, together with a small quantity of some oily ethylic salt which could not be obtained in a state of purity.Both a- and /3-salts, when hy drolysed with alcoholic potash, yield Reimer's a-diphenylsuccinic acid, whereas when hydrolysed with hydrobrornic acid they both yield the p-acid. The action of silver 011 ethylic phenylbromacetate is thus similar to its action on a-brominated fatty acids generally, and we may suppose the two isomeric ethereal salts to he formed according to the two general reactions previously given (see this vol., i, 10). J. J. S. Reduction of Phenolcarboxylic acids.By ALFRED EIXEIORN and JOHN S. LLXSDEK (AnizaZeiz, 1895,286, 257--277).-The authois' experiments shorn that whilst metaphenolcarboxylic acids are con- verted by reduction into yhydroxyhexamethylenecarboxylic acids, the ortho-derivatives generally yield dibnsic acids of the pimelic series. Pimelic acid is formed when salicylic acid is reduced with sodium and amylic alcohol (Abstia., 1894, i, 246). The quantity of this acid, which is formed on reducing ethylic salicylate 01- its ethyl ether, is extremely small, and probably arises from hydrolysis ; the main pro- duct of the action consists of hexnhydrobenzoic acid. By the action of sodium on ethylic pimelate moistened with alcohol, Dieck- mann obtained ethylic /3-ketohexamethylenecarboxylate (Abstr., 1894, i, 173), which is converted into ethylic liexahydrosalicylate on reduc- tion.The authors have treated ethylic P-ketohexsmethylenecarbosy- late dissolved in amylic alcohol with sodium, and obtained pimelic acid. This acid is also formed when guaiacolcarboxylic acid is reduced. Phen ylenuceticpopionic acid, C OOH*CH,*C,jH,*C Hz.CHz*C 0 0 EL, is obtained by reducing 2 : 3-hydroxpaphthoic acid (m. p. 216') in the manner indicated ; it is also formed when 2 : 1-hydroxyiiaphthoic acid (m. p. 156') is reduced, a mixture of ac- and ar-t,etrahydro- /&naphthol being prodnced a t the same time. It crystallises from water in colourless, hexagonal prisms, and melts at 159" ; it dissolves46 ABS'1'RACTS OF CIHEMICAL PAPERS, readily in ether and alcohol.The calcium and barium salts are anhy- drous, the silcer salt darkens slowly in daylight, and the copper salt is bright green ; the ethylic salt is a viscous oil, which has an agree- able odonr, and boils a t 210-212' under a pressure of 40 mm. ~iti.ophenylenacetic~l.opioizic acid crystallises from water in oolourless, lustrous leaflets,and melts a t 172"; i t is sparingly soluble in cold water, but dissolves more readily in hot water, and is very soluble in alcohol and ether. The calciunt salt is anhydrous, and the silver salt explodes readily when heated. When the calcium salt is submitted to dry distillation, p-ketotetrahydronxphthalene (Abstr., 1894, i, 419) is formed ; if the latter is slowly added to boiling dilutc nitric acid, phenylenediacetic acid is produced.31. 0. F. Isomeric Bromocinnamic acids and Cinnarnic acids. By Emr, ERLEMIEPER (,4.nnalen, 1895, 287, 1-25).-The author's experiments show that Glaser's a- and p-bromocinnamic acids are geometricallv isomeric modifications of a bromocinnamic acid having the halogen in the a-position. By the reduction of G laser's 13- bromocinnamic acid, in alcoholic solution, with zinc dust, an acid has been obtained which resembles Liebermam's isocinnamic acid in every respect except crystallo- graphic form; it belongs to the monoclinic system, a : b : c = 1.146 : 1 : '2.344 ; p = 79" 59'. On other c)cc:Lsions, reduction of this acid gaye rise to a mixture of cinnamic and allocinnamic acids, whilst the exclusive product of Glaser's cr-bromocinnamic acid was ordinary cinnamic acid.Transparent crystals of the new isociiinamic acid (m. p. 44') rapidly become opaque, and then melt, a t 68' ; this indicates the spontaneous transformation of the substance into allocinnamic acid. Aniline converts both modifications of isocinnamic acid into allocinnamic acid ; a n d the aniline salt, of isocinnamic acid (Liebermann, Abstr., 1890, 1417), when treated wiih alkali, yields allocinnamic acid. Treatment with concentrated sulphuric acid at 50' for 15 minutes converts allocinnamic acid and both modifications of isocinnamic acid into ordinary cinnamic acid. When allocinnamic acid (0.5 gram) is dissolved in alcohol (5 c.c.), treated with zinc bromide (0.7 girtrn), and allowed to remain for several days at the ordinary temperature, dilution with 20 C.C.of water causes the separation of an oil which solidifies to crystals, con- sisting of isocinnamic acid. It seems probable, therefore, that when Glaser's p-bromocinnamic ticid is reduced in alcoholic solution with zinc dust, a mixture of allocinnainic with ordinary cinnamic acid is first produced, the former being transformed into isocinnnmic acid under the influence of zinc bromide. Glaser has already shown that the cc-bromocinnamic acid of low melting point is converted into the other modification when heated ; the author's experiments prove that between the /?-bromo- cinnamic acids the converse change takes place. The author confirms the description already given by Xichael and Browne of the treatment of phenylpropiolic acid with hydrogen bromide (compare also Abstr , 1892, $49).ORGANIC CHESIISTRY.47 The discovery of a second isocinnamic acid introduces a fourth An attempt is made to explain t,he isonieric phenylacrylic acid. relatiollship which exists between these four modifications. Condensation of Glyoxylic acid with Amido-acids. By CARL B@ErrTIS(;ER ( A ~ c h . Phamz., 1895, 233, 199-209).-The amidobenzoic acids condense with glyoxylic acid in alcoholic solution to acids of the composition COOH*C6H~*XCHz*C00H These are yellow sub- stances ; they dissolve in alkaline carbonates, and form di-sil.z;er salts : the 1 : 2- and 1 : 3-compounds readily lose carbonic anhydride, but the 1 : 4-compound is more stable. No well-defined product was obtained by the action of glycocine on glyoxylic acid. The oxnlates of the three amidobenzoic acids are described.M. 0. F. C. F. B. Benzenesulphonamides and Mixed Secondary Amines. By OSCAR HINSBERG and A. STRUPLER (ilnnalen, 1895, 287, 220-230 ; compare Abstr., 1893, i, 168). - Diphen~ls.zc~honethyEelzedia~nine, C,H4(NH*S0,Ph),, is prepared by warming ou the water bath a mixture of benzenesulphonainide, concentrated aqueous potash, and ethylenic bromide ; it crystallises from alcohol in colourless needles, and melts at 168". D~hen.ylsulphcnediet~i ylethylenedianziiae is obtained from the fore- going compound on treating i t with potassiiini hydroxide and ethylic bromide or iodide ; it separates from alcohol in minute crystals, and melts a t 152.5'. Dietl~yZ~!t?Lylenediamine, CJJ,(NHEt),, is formed when the sulphonc derivative is he&ed with concentrated hydrochloric acid at 160° (Hof- niann, Juhresbericht, 1859, 386) ; the hydrochloride crystallises in colourless needles.Di~hen~~l.su~hoiaeo~~tl~op1~ e n y 1 enediamine, C,H, (NH* S 0,Ph ) ,, is ob- tained on agitating ortliophenylenedianiine with benzenesulphonic chloride and excess of potash ; i t crystallisee from glacial acetic acid i n slender needles, and melts a t 186'. Y e t rciphen,qldisulp 11 oti eort hopl~eny lenediamiir P , C6H,[ N( SO,Ph),],, is obtained from phenjlsulphoneortliophenylenediamiiie (LeIlmann, ,innale;z, 221, 17) by the protracted action of benxenesulphochloride and soda ; i t dissolves with difficulty in ordinary solvents, and melts a t l5O-15lo. Dipheu ylsdphoue~net h y leneo 1 s t hophenplen ediu nz ine, is preparLd by adding niethgleiiic iodide to a solution of diphenyl- sulphonephenylenediamine a d sodium ethoxide in alcohol, a n d heat- ing the mixture until it is neutral ; i t melts a t 147-148', and is ~011- verted by hydrochloric acid at 160" into phenylic bisulphide.Dipheny lsulph oneth yleneort1LopJi e q leizediamine separates €1.0 in gla- cial acetic acid in colourless crystals, and melts at 180'. EthyZenephe?ayle~ze~~um~~i~ (tetrahydroquinoxaline) is obtained from the foregoing derivative by ti-,?al,ment with concentrated hydro- chloric acid at 160-170" (ccmpaie Xei-z mid Ria, Abstr., 1887, 722).48 ABSTRACTS OF OHEMICAL PAPERS. The dinitroso-derivative cr-ystallises in minute, yellow needles, and melts and decomposes a t 168". ~ i p h e n y l s z ~ l ~ ~ o i z e t r i ~ a e t ~ ~ yleneplienyltzizedian~~ne, separates from glacial acetic acid in colourless crystals, and melts at 204-205".T~imethyZenephenyle?zediamine, CJ& < NH,C NH*CH2 H,> CH2, is obtained from the foregoing derivative by tieeatment with concentrated hydrochloric acid a t 170"; it melts a t 10So, boils a t 290-300°, and reduces an ammoniacal silver solution when heated with it. ' Ferric chloride develops a violet-red colour with the base. The diiiitroso- derivative melts at 120". Dipl~enylsuIpho~temetapheizyc!enediamine crystalliaes from alcohol or glacial acetic acid, and melts at 194'. When the sodium derivative is treated in aIcoholic solution with ethylenic bromide (1 mol.j, a compound of the formula C2,,H,,N2S20, is formed; it melts at 190-195".M. 0. F. Parabromanilinesulphonic acids : A New Method of Prepar- ing Benzoicsulphinide. By HARS KREIS (Annulen, 1895, 286, 377-388) .-Parabromanilinemetncsulphonic acid [ Br : HSOs : NH2 = 1 : 2 : 41 is prepared by dissolving parabromacetanilide (30 grams) in fuming sulphuric acid (200 grams) containing 15 per cent. of sul- phuric anhydride, and heating the liquid a t 140-150" in an oil bath ; effervescence takes place, and when this has ceased, the liquid is poured on to 600 grams of ice. The sulphonic acid crystallises from water in slender, white needles containing the solvent, which is eliini- uated on exposure to air ; the barium salt is anhydrous. When para- bromanilinemetasulphonic acid is reduced with caustic soda and zinc dust, anilinemetasulphonic acid is formed. Parabromanilineorthosulphonic acid is obtained by heating para- bromacetanilide (20 grams) with sulphuric acid (10 grams) at 170-180" for one hour ; it crystallises in anhydrous leaflets, and in needles containing 1H20.Parab?.o?izocyaizoEenz~ia~o~thosul~~o~a~c acid is obtained from the fore- going substance by means of Sandmeyer's reaction ; the sodium and potassium salts crystallise i n colourless, silky needles, and contaic 1+H20. The szdphonic chloride separates from a mixture of benzene and petroleum in lustrous crystals, and melts a t 90", and the szdphonamide is a white powder which melts above 250" ; it crystallises from pyri- dine in leaflets which contain the solvent. Parabromobenzoicsnlphinide is obtained by heating the sulphon- amide with aqueous caustic soda; it melts a t 227.5" (compare Remsen and Bayley, Bey., 1886, 19, 835).Anilineorthosulp honic acid is obtained by eliminating the bromine from parabromanilineorthosulphonic acid by means of caustic soda and zinc dust ; from this substance the author has prepared several com- pounds which hare been already described (Abstr., 1S93, i, 715), andORGANIC CHEJIISTRY. 49 records the production of benzoicsulphinide by heating orthocyano- benzenesulphonnmide dissolved in 25 parts of vater with one mole- cular proportion of sodium hydroxide. >I. 0. F. Formation of Indigo by the Action of Sunlight. BY CARL ENGLER and K. DORANT (Rer., 1895, 28, 2497-2501 ; compare Be?.., 3, 885, and Abstr.,l895, i, 231).-An alcoholic solution of orthonitro- acetophenone readily condenses with benzaldehyde, in the presence of dilute sodinm hydroxide solution, to form benzlllideneorthonitroaceto- pheizone, N0,*C6H,*CO*cH:CHPh ; this crystallises in long, colour- lees, silky needles? melts at 124', and forms a hydrazone which melts at 146-147O.When the ketone is spread on a shallow plate and exposed to bright sunlight, i t is rapidly decomposed into indigo ant1 benzoic acid, owing to the oxidising action of the nitro-group ou another part of the molecule. No action takes place i n the dark, and the rate at which the ketone is converted into indigo depends on the nature of the rays, being greatest when a blue glass plate is interposed between the substance and the sun. Similar intra- molecular oxidations have been previously observed by Baeyer (Abstr., 1881, 274 ; 1883, 341) and by Friedlaender (Abstr., 1895, i, 543).Bt.rLzylidelleol.thonnzidoacetop~~enone is formed when the nitro-ketone is reduced with stannous chloride. It crystallises in prisms which melt at 147", nnd its salts are deep red ; the ricetyl derivative melts a t 165*, the hydrnzoize at 154", and a bronzo-derizative at 159-160". Ferric chloride oxidises the nmido-ketone to a snbstance which melts at 214-216'; other products are also formed. When the nitro- ketone is reduced with zinc dust and boiling water, it substance melt- ing at 68" is formed together with the amido-compound. This pro- duct is being further examined, as i t does not give the reaction of the expected hydroxylamine derivative.J. J. S. Sulphonephthale'ins. By JOHN WHITE, jun. (Amer. Chem. J., 1895, 17, 54.5-556 ; compare Abstr., 1889, 7lO).-When sulphone- fluoresce'in is treated with bromine, a dibromo-substitu tion product is chiefly formed, and with phosphorus pentachloride a tetrachloro- derivative, which appears to he produced by the displacement of the two hydroxyl groups and the anhydride oxygen in the sulphone- fluoresce'in. It is not possible to prepare sulphonefluoresceh by the action of resorcinol on orthosulphobenzoic acid, but when an action between these compounds occurs, either four or six residues of resorcinol enter into combination according to the conditions of experimentation. No pure compounds are described in the paper. Sulphonephthalei'ns' from Orthosulphoparatoluic acid.B y WALTER JOXES (Amer. Chem. J., 1895, 17, 556-569) .-An~mon'i7~~n paranaet hyldih ydroa.ybenzoy1 benzenesulyhonate, A. G. B. VOL. LXX. i. eis prep are d by h eating am rn onium 11 y c3 rogen o rthosul pho paratolua te (Abstr., 1S91, 1225) with resorcinol ; it forms colourless crystals, and its aqueous solution yields an insoluble basic lead salt, with 12H20, when boiled with minium; t,he corresponding acid is obtained by decomposing the lead salt with hydi*ogen sulphide, and forms colour- less crystals, with 4H20. The barium salt (C,,H,,sO6),Ba + 5H20, the normal lead salt, with 7&0, the caZci?inr, salt, with 6H20, the zinc salt, with zH20, and the silzer salt, with 2H20, n w descrihed. Attempts to substitute other acid radiclcs for the phenolic hydroxjl groups i n paramethyldihydroxybenzoylbenzenesulphonic acid provetl unsuccessful.When the acid is heated at 170°, it yieldspnramethyl- szLZ~honeJluorescezti, O<C6H,(oH C,H,(OH) >>C<" C HMe 0" ->SO,, orthosulpho- paratoluic acid, and water ; treatment of this fluorescein with phospliorus pcntachloride, produces a tetravhloro-derivative, and treat- ment with excess of bromine, produces a dibromo-substitution product which fluoresces like eosin. Two other sulphonepb thale'ins can he derived from orthosulphopara- toluic acid, by treating it with resorcinol ; one containing four and t h e other six resorcinol residues. A. G. B. Allofluorescein. By BROSISLAW P ~ w r ~ ~ w s ~ r (Bey., 1895, 28, 2360-2362 ; compare Abstr., I &95, i, 219) .-AlZoJluorescei'?i, is obtained by heating resorcinol with phthnlic chloride alone or in solo- tion, on the water bath ; the red or yellow product is then treated with ncetic anhydride €or several hours at 3.50-1 SO", and, after evaporating the liquid, the residue is repeatedly extracted with glacial ncetic acirl and with alcohol.The colourless, amo~.phous substance melts at, 140". and is almost insoluble in the niajority of organic solvents ; it dis- t-olves to some extent in boilirig glacial acetic scid, and to a greater degree in acetic anhydride and ethylic acetate, separatiny frorii solution in the amorphous state. 'l'he freslily prepared substanccb dissolves readily in alkalis and alkali cai-borintes, the liquid exhibiting strong fluorescence ; the dried or fused substance, however-, dissolves in concentrated alkalis with great difficultj. The flaorescence 0:' solutions in ammonia o r barium hydroxide is green.The paper contains a detailed comparison of allofluorcscein witli the ordinary modification. Relation of the Indulines to the Safranines. By OTTO FISCEIKK and EDuARD HEPP (Ber., 1895, 28, 2283--2289).-Phenosafra- nine belongs to the samc group of compounds as the mauvejiiies, indulixies, arid indazines. On treatment with :ilkalis, i t yields safran~], Or l,Sdl.oxS"posah*anonc, which only contains one hydroxyl-g~*oup, su tlint phenosifranine must itself be free from Avitter, a t all events a t 100". Al)osafranine, which is obtained from phenosafrnnirie by the rcrtloval of the amido-group, therefore, is t o be looked on :is the &implest meso-pheiiJ1 derivative oE the series, corresponding with M.0. P.ORGANIC 0HER.IISTRT. 5 i YH :CH*y--”.$! :CH* EH The NH: C-CH : C *NP h* C : CH* C H’ rosinduline, its formula being f)lcts, which, previously, were apparently at variance with this view, heve now been more accurately investigated. The free .base itself is free from water, like phenosafranine (Abstr., 1895, i, SOS), and the beirzoyl derivative is also anhydrous. This substance crystallises from benzene i n dark violet plates, which contain 1 mol. of benzene; it is strongly basic, and forms yellow salts. The relation between apo- safranine and the simplest benzene-induline, appears to be precisely similar to that bet ween aposafranone and the simplest benzeneindone.When aposafranone is heated with aniline and aniline hydrochloride, i t is converted into the substance previously termed benzeneindone (A?rnaZen,, 1884, 226,254), and formulated as C,,H,,N,O. The forma- tion of this substance from aposafranoiie now shows that its true for- mula must be CZ1HliN30, and i t is, therefore, anilidoajposufr~?zo,ze. When it is boiled with 75 per cent. sulphuric acid, it is converted into 7~lldl.ozyaposafraiior~e, C18H14N202, which was previously described as benzeneindonehydrate. Hpdroxyaposafranone is also fsrmed when ;iposafranone is boiled with alcoholic potash. Anilidoaposafranone may be reconverted into aposafranone by boiling with 60 per cent. acetic acid and zinc dust. I n the same way, the simplest induline derived from aposafranine, which is known a s anilidoaposafranine (Kehrmann) may be reconverted into aposafrauine.l’henylinduline, which is derived from benzeneindone by the dis- placement of a single atom of hydrogen by the mil-group, must now receive the formula C30H22N0, instead of that previously assigned to it, and all the indulines must be classed as anilidosdranines, their formula being altered in accordance with this relationship. A. H. Action of Alkalis on Paranitrotoluenesulphonic acid. By OTTO FISCHER and EDUARD HEPP (Ber., 1895,28,2281-2283 ; compare Abstr., 1893, i. 697). The authors, in reply to Bender’s criti- cism (Abstr., 1895, i, 287), maintain the accuracy of the results obtained by them i n the reduction of parani trosostilbenedisulyhonic acid by means of ferrous sulphate, and its oxidation by chromic acid, new experiments having given the same results as the ones previously quoted.A. H. Synthesis of Bidiphenyl and its Identification as Benzery- threne. By ARTHC“: A. NOPES and ROLE’E M. ELLIS (Amer.Chem. J., 1895, 17, 620-622) .-ParabidiphenyZ, PhCGH1*C6H4Ph, was pre- pilred from parabromodiphenyl by boiling an ethereal solution of it with sodium ; the solid matter was separated, washed with water and henzene, and sublimed. I t forms large, crystaliiue lamina+ melts a t 31‘i0, and distils at 428’ (18 mm. pressure) ; i t is insoluble in boiling alcohol, ether, chloroform, and carbon bisulphide ; boiling benzene dissolves it sparingly. The compound termed benzerythrene, CZ4HJ8, by Schmidt and Schultz (Amden, 1880, 203, IS), and ob- tained by the action of heatt on benzene, melted a t 308O, and was iusoluble i n alcohol, but slightly soluble in boiling benzene.Tlie e 252 ABSTRACTS OF CHEMICAL PAPERS. author2 conclude t,hat beiizerythrene is identical with pambidi- phenyl. A. G. B. Reduction Product of Xanthone. By G. GUR(;ESJASZ and STAXISLAUS VON KOSTAN~XRI (Be?.., 1895, 28, 2310--231l).-When xanthone is boiled with acetic acid and zinc dust, i t is converted into dixanthylene (te trap henyleneet 11 ylenedioxidc) , This crystallises from benzene in long, thick, almost white needles, which melt at 315'. The solution i n benzene has a bluish-green fluorescence. 4 : 5-Dimethylxanthone is converted by similar treat- ment into 4 : 5 : 4' : 5'-teti-anzef7i?i?dixanthyZene, which does not melt below 360'.2 : 7-Dirnethylxanthone yields 2 : 7 : 2' : i"-tei~amethyL xn?athyEene which sublimes without decomposition at 275-277'. A. H. Benzylidene-p-dinaphthylic Oxide. By E. MERCB (Chew .. Centr., 1895, i, 431; from Ber. u. d. Ju~w., 1894, 21-22).-Thc. residue obtained dnring the preparation of henzoyl-&naphthol con- tains benzylidene-p-dinaphthyl oxide (m. p. 188-191') ; i t must have been formed from benzaldehyde or benzylidene chloride contained in the benzoic chloride employed. Synthesis of Phenanthridine. Ry AMB PICTET and A. HIJIXI~T (Chem. Cedr., 1895, 432-433 ; from Arch. sci. phys. Qenire, 1894: 32, 493-504) .--The method employed consists in the condensation, by means of zinc chloride, of acidyl orthoamidodiphenyl derivativrs, IrtNH*C6H4Ph.Orthoamidodiphenyl is most readily prepared by Graebe and Rateann's method (Abstr., 1894, i, 529). 2-FornaylamidorliphenyZ, COB.NH*C6HoPh, crptallises in colourless needlep, melts at 75', and, when heated with zinc chloride ( 5 parts) at 280-300', yields phennnthridine. Mesometkylpher~anthridine, C6H4<i6g>CMe, is formed in a similar manner a t 320' from acetyl- amidodiphenyl ; i t crystallises in small, colourless needles, and melts at 85'. The hydrochloride and mercwochloride are colourless, and melt at 285' and 247' respectively. The picrate and inethiodide are yellow, and melt at 233' and 263' respectively. The platinocldoride ;C,4H,2N)2PtCl6 4- 2H20 (m. p. 272') is flesh-coloured ; the dz'clzronzute is orange-yellow, and darkens at 150'; thc aurochloyide (tn.p. 163-164') is pale yellow. All these derivatives crystallise in needles. 2- Prcvpio.layln?nidodi~henyl crptallises in colonrless, lustrous needles ; it melts a t cis', and yields mesoethy Zphenanthridine, J. B. T. which is deposited from light petroleum in small, colourless needles melting a t 54-55'. The following derivativcs crystallise i n needles.URQASIC CHJCMISTRY. 53 The hydroch1o?.ide and mercwochloride, melting at 205" and 214" i-espectively; the dichromate is golden yellow; the picrnte is pale yellow, slowly decomposes when heated, and melts a t aboixt 2 1 0 O ; the pZatixochloride, ( C,,Hl3N)2,HJ'tCI, + 2H20, and the au~*ochZoride, are yellow, and melt at 241-242' and 149' respectively. a 2-Be?~zo~ZanaiJod~p~~~zyZ, NHBz*CsH,Ph, crystallises in pearly, lus- trous plates, melts at 85-86', and at 300-360' yields nzesophenylphen- anthridine, c6H4 <c6H4>CPh, which is also formed by heating st mix- ture of amidodiphenyl, benzoic aci2, and zinc chloride; it crystal- lises in iridescent, transparent, quadratic plates, melts at log', boils above 360°, is a feeble base, and dissolves in dilute mineral acids with a violet fluorescence.Its salts are only stable in presence of acid ; they are decomposed by water. --N The hydrochloride, CI9H,,N,HCl + E20, crystallises in yellow prisms melting at 95-96' ; the anhydroub: com- pound forms pale yellow needles, and melts at 220'. ThepZatino- chloyide crystallises with ZH20 in yellow needles, and decomposes :it about 300'. Orthodip hen y Zwethane, C6H4P h*NH*C 0 0 E t, prepared from orthamidodiphenyl and ethylic chlorocarbonate crystdlises in colourless needles, melts at 186', and, when heated with ziric chloride, yields phenanthridone.J. B. T. Orientation in the Terpene Series. By AUOLF vos BAEYEB and FMTZ BLAU (Be?.., 1895, 28, 2289-2297 ; compare Abstr., 1891, i, 252).-l-B~om0-A"~-ter~ene is formed when Wallach's terpene tri- bromide is dissolved in a mixture of alcohol and ether, and treateil with zinc-dust ; it forms compact rhombic prisms, iiielting at 34-- 350 . Hydrogen bromide converts it into dipentene dihydrobromide, along with a11 oily substance. When bromoterpene is treated with sodium nitrite and hydrobromic acid, the uitrosobromide is formed in blue crybtals, which melt at 44', but could.not be obtained quite pure.A'*8-Terpenol acetate also jields a ~titrosobromide, which crystallises iii blue needles, and melts a t 81-42'. The two nitroso-bromides just descrihcd yield the same prodnct when they are treated with a solution of hydrogen bromide in acetic acid, bromine being in both cases set free. This product crystal- lises in thin, quadratic plates, which melt at 182-184', its constitu- tion being most probably expressed by the formula, I t reduces silver salts and Fehling's solution. When this substance is dissolved in water, and potash or ammonia added, 2 mols. of hydrogen bromide are removed, and a base, CloH18NOBr, is obtained, which crystallises i n indefiuite forms, and melts at 100-106'. This base also reduces Behling's solution, aud probably has the constitution, C M e B i ~ < C , ~ : ~ ~ z ~ C * C M e z * ~ H * O5 4 ABSTRACTS OF OBEMICAL PAPERS.Kitrous acid converts it into a nitroso-compound, C10H17B~N202, which crystailises in serrated, rhombic t:) blets, melting a t 138-139". This substance may be obtained by ;L similar series of reactions fronl (lac11 of the three compounds, the nitrosobromide of brornoterpene, the nitrosobromide of terpcnol, and the nitrosochloride of terpeiiol wetate, a fact which confirms the f o r m u l ~ proposed. The product of the action of hydrogen bromide on the nitroso- chloride of terpenol acetate has the formula, CloHJ!TOClIlr2, and crystallises in almost rectangular tablets melting a t 179-180". The hydroxylamine derivative, CloHIJVOBr, which is formed from the nitrosobromide by the action of hydrogen bromide, is converted hy the action of bromine into the original nitrosobromide, so that t h e action is a reversible one.Trihydrozyterpane, ClOHPoO3, is formed by the action of dilute potassium permariganate solution on A*.'-terpenol. It forms crystals which contain 1 mol. water, arid melts a t 95-96'. The anbydrous substance melts at 110-112', and boils at 200' (pressure = 20 mm.) almost without decomposition. Hydrobrbmic acid converts it into TVallach's tribromide. A considerable amount of a substance which melts at 127-128', aud has the formiila of dipentene tetrabromide, is formed during the preparation of the tribromide from dipentene dihydrobromide. From Pinene to Carvacrol. By JOHN L. MEAD and EDWARD KREMERS (Anzer.Chem. J., 1895,17, 607-61l).-Urban and Kremers have already shown that " nitrosopinene " is really an oxime, and that i t yields an oil, ClaHlrO, on hydrolysis (Abstr., 1894, i, 468). It is now shown that this oil is carvacrol (compare von Baeyer, Abstr., 1895, i, 379). A. G. B. A . H. Ethereal Oils. By EDUARD GILDEMEISTER (A&. Phnrm., 1895, 233, 174--189).-The oil expressed from the xind of sweet limes (Citrus Linzettn Risso), growing in South Europe, was found to con- tain limonene with possibly :I little phellandrene ; aIso, in smaller amount, linalyl acetate, together with a little linalool ; it thus re- sembles oil of bergamot, which contains dipentene in addition. The sample exanlined was brownish-yellow, had the sp. gr. = 0.872 at 15', and [ajD = +66" 52'.Linalool was identified by oxidisiiig it wit,li chromic mixture to geranaldehyde, and converting this, by Doebner's method (Abstr., 1894, i, 261), into citryl-/3-naphthocinchoninic acid, melting at 197". Four samples of oil of origanum from Smyrna were examined: their exact botanical origin was unknown, perhaps they were ob- tained from Origanum sn~~i*naic~irn. The sp. gr. was 0.916-0-932 a t 15"; the rotation in a length of 100 mm. -7' 52' and -8' 44' in two of the samples ; the percentage of phenols (by shaking 10 C.C. of the oil with 50 C.C. of 5 per cent. soda, and noting the volume of t h e residual oil) 32.47 ; all the samples dissolved in 2$ parts of alcohol of 70 .per cent. strength by volume. The oil was found to consist mainly of linaliiol ; cymene is also present, and possibly an " olefinic rerpene " (compare Semmler, Abstr., 1591, 655, and Cliapltiau,ORGAN10 CHElllISTRT.5s Trans., 1895, .5%) ; the phenol present is rnninly carvncrol, but therc is a small quantity of a phenol that gives a violet coloui- with ferric chloride. C:wvacrol was identified b y means of its plienylic cyanate derivative (Goldschmidt, AbLti.., 1895, i , 723) ; cymene by oxidising it with potassium dichromnte and dilute sulphuric :icid 011 the water bath to hydroxyprop3lbenzoic acid, melting a t 15G--158", and con- verting this by boiling with fuming liydrocliloric acid into isopropenyl- benzoic acid, melting at 25.5 - 260" (\\';tllach, Annulen, 264, 10). c. F. B. Oil of Lignaloes. By PHILIPPE; DARIUER and Lours I~OUVEAUI;~~ (Compt.rend., 1895, 121, 168--170).--Oil of lignaloes coirtains, ilk 1000 parts, 1 part each of a biv;ilent terpene, a quadrivalent terpeuc, and methylheptcnone, 20 part,.; of licarhodol, 30 parts of a sesqui- terpene, and 900 parts of licsreol. The sesqniterpcne, C15H24, boils at 135-136' under a pressure of 10 m n . , has a faint, pleasnilt odour, and combines with 4 atoms of bromine ; its proportion w r i e s con- siderably in difFerent specimen? of the oil. The methyllieptenone is always present in the oil, and is identical with the Iriethylhepteiioiic: obtained by Wallach by I he decoinpositioii of cinole'ic anhydride ; it. is isomeric with that, found in oil of lelrion-grass (Ahstr., l&%k, i, 4l11). and, when heated with zinc chloride, is converted into dihydrometa- xylene, C,H,,, boiliug a t 134".h sniall part of the licai*eol is present in the oil in combination with acetic acid and higher acids of the same series. C. H. B. Oxidation of Inactive Campholenic acid. By AUG WTE B ~ I A I , (Ccmpt. wnd., 1895, 121, 213-216 j.-When oxidised with nitric w i d of sp. gr. 1.27, inactive cnmpholenic acid jields hydroxycam- I'horonic acid, melting at 167-16&@, isobutjric acid, and t w o dibasic acids, C7H,,04 and C6Hl?04. The acid CiH1204 is very solnble in water, benzene, or ether, crystallises from a mixture of benzene aud light petroleum, and melts a t 83.5'. l l s c2ilcium salt, C7H,,04Cn + 3H,O, crystallises in flattened, orthorhoiiibic prisms. The m h y d n 2 e melts at 38*5O, and boils at 270"; in prgsence of benzene, it reacts with aniline, auci yields the compourd Cc,til102*CO*N.HPh, which crystallises from d i l u t e alcohol, melts a t 146', and, when distilled with water, is con- CO verted int,o tlie irnido-compound, C5Hlo<Co>NPh, which nielts at 121.5O.The acid C,H,,O, seems to be a glutaric derivative; i t s ethylic salt boils at 235-238°. The acid C,H,,O, melts a t 144O, and is very soluble in water ; i t s ethylic salt boils a t about 230", aiid its unhi,LZride a t about 920' ; the plze?zlllaiiiido-derirative melts at l 8 5 O , and the pl~e;zylirnido-deriva- tive at &Go. C. H. B. Action of Nitric Peroxide on Campholenic acid. By AUGGSTE BEHAL and VICTOR Br,AtsE (C'ompt. 9-end., 1895, 121, 256- 259).-W hen nitric pcroxide is passed over inactive campholeiiic acid until the latter has absorbed n, molecular proportion of it, a, blue liquid is formed, and when this is treated with a cold saturated56 ABSTRAOTS OF UHEMlCAL PAPERS.solution of potassium hydrogen carbonate, a blue oil remains undis- solved and soon solidifies. When this product is dried and crystal- lised from alcohol of BOO, cer.1LZeonitrosocnmyhoZenoZide, CloHl5PYTO3, is obtained in thin lamelltle, which melt at 134.5', and have a blue colour similar to that of copper sulphate. It has a neutral reaction, and is insoluble in alkali hjdrogen carbonates. If an alcoholic solu- tion is exposed to diffused light €or some days, a white, amorphous iiiodification, Zeuconitrosocanzplolenolide, separates. Unlike the blue compound, it is insoluble in ordinary organic solvents, but when heated with them, or alone, it is reconverted into the blue modifica- tion, of which it seems to be a polymericle, although its molecular \\eight could not be determined.C eruleoni t rosocam ph ol enolide, when treated with aIco h 01 ic po tauh, jields R red azo- or azoxy-derivative, which is decolorised by sodium amalgam, and regenerated by oxidation with mercuric oxide. The product of yeduction by the amalgam reduces Fehling's solution in the colci. When boiled with tin arid acetic acid, the ceruleonitroso- c:impholenolide yields an unsaturated lactone, wliich melts at 31.5", aud an amine acetate, which melts at 9i'. Excess of nitric peroxide converts campholenic acid into the compoiind ClnH,,NO,, which melts at 175O, and has been described by several previous obsei-vers as nit~rocampholenic acid.It has, 1 owever, no acid function; it is neutral to litmus, and does not. decompose alkali hydrogen carbonates. When boiled with potas- sium hydrogen carbonate, i t yields didehydrocampholenolide, CI,,kil,02, :L crystalline compound, wbich melts at 31*5', and boils a t 193' under :I pressure of 17 mm. When boiled with alkali hydroxides, it is con- verted into dihydroketocampholenic acid, C1nH1603, which crystallises Irom benzene or dilute alcohol i n prismatic needles, and melts a t 1%' if heated rapidly, or at 112' if kept at this temperature for some time, It begins to change into a lactone abore 1W0, and a t 150', it yields the original lactone. The acetate of the amine, obtained bj- reduction of so-called nitrocampholenic acid, crystallises well from absolute alcohol, and melts at 97".It would seem that the so-called nitrocampholenic acid is really R nitrocampholenolide ; it has SL .lactonic function, and the NO, group seems to exist in two forms, which are probably tautomeric: the constitution of the lactone and amine being analogous, although the position of the ethylene linking is somewhat uncertain. The ketonic acid probably has the constitution COOH*CH,*CHR'*COK, and cerrleoaitrosocampholenolide the coiistitution 9 0 -0-C; R-N 0 CHZ-CHR' * C. H. B. Campholic acid. By GUEHSET ( A m . Chin2. Phys., 1895, [7], 4, 239-365).-The greater part of the work contained in this paper has previously been pi1 blished (compare Ahstr., 1894, i, 254 ; 1895, i, 61, 240, 295, and 383.Also Errara, Abstr., 1892, 1345; 1893,ORGANIC UHEMISTRY. 5 i i, 108). It is shown that carnpholic acid is practically not acted 011 by hydrochloric or hydrobromic acid at 20U'. Campholene hydriodide (Abstr., 1894, i, 234) melts a t about 5.2" when rapidly heated. The nitrosochloride (Bhhal, Abstr., 1895, i, 240) forms an indigo- blue crjstalline mass, and melts at 25' when rapidly heated. The author thinks most of his results support the hydroxyketone formula of campholic acid suggested by Friedel. By OTTO HELM ( A ~ c h . PhaTm., 1895, 233, 191-199 ; compare Tschirch and Aweng, Abstr., 1895, i, 384). -Gedanite does not contain free succinic acid, although Aweng states that i t does; the dealer had, doubtless, sent him as gedanite what was really a specimen of succinite (ordinary amber).Gedanite further differs from succinite i n that i t contains 2-3 per cent. more carbon and about as much less oxygen; i t contains some sulphur, but less than succinite does. A much larger proportion o€ gedanite dissolves in various solvents than is the case with succinite; it is evrn entirely soluble in linseed oil. There is a variety of succinite knowii as " soft " or "friable amber " (" m i i ~ b e ~ Succinit "), which is intermediate in its properties between gedanite and true succinite. C. F. B. J. J. S. Gedanite, Succinite, &c. Opoponax from Burseraceae. By A. Bhult (Arch. Pharnz., 233, 209--252).-The substance once known by this name had a rather un- pleasant odour, and was probably derived from a Persian member of the T/mbeZZifei-l;e.The substance now known as opoponax contains a pleasant smelling ethereal oil, which is used as a perfume ; the samples examined by the author contained plant lixngments which showed them to bc derived from some member of the genus B ~ l s ~ n t o d e n d r o n , order Buwei*acece-probably from U. KafaZ. It contains 19 parts per cent. of resin, 6.5 of ethereal oil, and 70 of gum, besides plant fragments. The resin contains ~~-pnnax-~e~se?z, C32H540J, soluble in light petroleum ; /3-pmaz-.l-ese.r~, C%LHjZ05, insoluble in light petroleum, but soluble in ether ; and ~nnaresisiotannol, CuH5008, iiisoluble iii light petroleum, and only slightly soluble in ether, but soluble in alcohol, and also, unlike the preceding two, in alkalis.These are yellowish-brown bubstances, which can be powdered when coId, but arc plastic when warm ; it was riot found possible to hydrolyse themt nor could well- characterised substances be obtained from them in any way. The echereal oil possibly contained a terpene ; the portion of higher boil- ing point yielded, when hgdrolysed, an alcohol, Cj6HgS0, boiling at 2.50-255' (uncorr.), and, apparently, a fatty acid (? butyric). This oil is obtained from the drug by treating it witli superheated steam ; the residue then coutains a new substance which is not present in the original drug. This is cI~i?*o~zoZ, C28H480, a white, crystallised sub- stauce, soluble in ether. and hot alcohol, and melting a t 176' (uncoi~.) ; it yields crystallised mwmcefyl and ~noizolei~zoyl deyivatires, melting respectively a t 196' and 186' (uncorr..), and is oxidised by per- manganate in hot acetic acid solution to chil-ouolic acid, C,,H,,O,, il white, amorphous substance, which me1 ts a t 1 U O -108', dissolves in alkalis, but not in water ; and, in alcoholic solution, reddens litmus58 ABSTRACTS OF OHEJlIOAL PAPERS.paper. Opoponax also contains an alkaloid, which could not, horn- ever, be obtained crystallised. Unlike the oils from Persian Umbel- tverce, it contaifis 110 umbelliferone and no S L I ~ P ~ U ~ * . 3Iecctt balsain also contains resins resembling those of opoponax in character ; resins, that is, that cnmot be hjdrolysed, and so cannot have the constitution of et,lierenl salts. To “ indifferent ” resins, which have the charactel.neither of ethereal salts, acids, nor alcohols, Tschirch has given the name of “ resens.” C. I?. B. Sagapen. By 31. HOHENADEL ( A ~ c h . Pharm., 1895, 233, 259- 286).--Tliis substance is obtained fisom the stems and fruits of a Persian species of Ferula, order Umbellkferm, as was shown by an examination of the plant fragments contained in the drug, The sample examined by the nnthor contained resin, 56.8 ; ethereal oil, 5.8; water, 3.5; gum, 23.3; and impurities 10.6 per cent. The purified resin is yellowish-brown, and is brittle when cold, plastic when warm, melting at 74-76’; it yields a sublimate of umbclli- ferone when heated, and, when hydrolysed by boiling with sulphuric acid, i t is decomposed into umbelliferone and sagaresinotannol, of which two substances it is the ethereal salt. Sagaresinotannol, C?4H2BOS7 is a brown substance soluble in alkalis, and yielding a pre- cipitate with ferric chloride : it yields monncetyl and iizonohenzoyl tlericatives, and is oxidised by nitric acid t o styphnic acid (trinitroi-esor- ciriol).The 56.8 parts of purified resin contains 40 of sagaresinostznnol, 15.7 of combined, and 0*11--0.15 of free urnbelliferone. The ethereal oil contaiDs 9.7 per cent. of sulpliur. and probably contains an ethereal salt of ralcric acid; the bluish fraction boiling at 210-270° W R S found to resemble, as regards its absorption spectrum, the similar bluish or greenish fractions, of much the same boiling poixit, obtained from the oils of galbanurn, asafetida, chamomile, valerian, Japanese valerian, millefoil, absinth, and Itlula Helenium.The substance con- tained in it, ‘L azulene,” is not, however, present in the original oil, but is formed during the process of fractionation. Digitalin. By HEIKRICH KILTANI (Arch. Pharnz., 1895, 299- :3!0).-“ ‘l’he glucosides ohtained from the seeds of Digitalis pwpiirea consist. to the extent of a t least one-half, of digitonin, which can easily be obtained crystallised ” by digesting Digitalinum pur. pub. geymmzic. with four times ita weight of 85 per cent. alcohol. ‘“l’hey contain Digifalinunz z’erum (digitalin) as the essential constituent, to which alone their action on the heart is due ; the existence of ’ d gitalein ’ is, to say the least, doubtful. In addition they contaiii a, weil-crystallised organic compound containing calcium and potassium.Digitonin and Digitalinum ver?m, are both, when pure, very sparingly soluble in water. The ready solubility of the mixture of glucosides (Digitalinum pur. p z h . ) is due solely to the presence of 1-esinous amorphous substances, in addition. Digitogenin was not detected in Nerck’R samples. It is certain that the crystals, which Schmiedeberg described as digitin, were nothing but digitonin.” The author has worked o u t the following method, by means of which Digitalinurn vemm is now prepared on the large scale :- C. F. B.ORCISSIC C BESIISTRT. 5!, L L One part by weight of Digilaliizri~z pi*. pri1r. is dissolved, bar means of a gentle heat, in four of 95 per cent. alcohol. The cold solution is stirred or shaken, and five parts of ether (sp.gr. 0.72) are, mean- \vhile, added, and the whole allowed to remain for 24 hours in a, vlosed vessel. The alcohol-elhereal solution is then clmwn off, weigtieci o r measured, and the weight of solid matter in i t (= A) (letermined by evaporating R portion. The ether. and most of the ;~lcohol are tlien distilled off under reduced pressure nntil the mciglit of t h e residual solution is 1.6 A ; 2.4 A parts of water are then added, and the mixture is allowed to stand for 24 hours iri a closed vessel. Tho crude digitalin which has separated is now broaght on to a filter, nllowed to drain without snction being applied, wnslied with 10 per ceilt. alcohol, and, finally, with water, and dried on poroiis plates or i i i a vacuum. The dry substance is then ‘recrystallised’ from 95 per cent.alcohol, with the addition of animal cbarcoal.” T t is thus obtained in white granules. C. F. B. p-Digitoxin. By HE~SRICH Kr r,IAxr (Arch. P~CLWL., 1895, 233, 311--320).-The leaves of Iligitalis pwpiirea contain neither digi- tonin nor digitalin, but a new glucoside, /j-digitoxiii,, Cz,K,sOlo + 5&0, can be obtained from them by successive extraction with water and 50 per cent. alcohol. This is contained more largely in the alcoholic extract; the total yield of the pure substance was about 1 gram per kilo. of the leaves. It forms white crystals, which, when anhydrous (From chloroform-alcohol solution), are still unmelted at 240°, but otherwise (fiBom 85 per cent. alcohol) soften a t 145-150°.When hjdrolysed with alcoholic: hydrochloric acid, it yields p-digitogenin, CzlH,,Or, and a substance, difgitoxose, which crystallises after the manner of glucose, but was found, unexpectedly, to liarc the com- position C,H,,04. Schmiedeberg’s “ digitoxin ” was probably an impure specimen of the substance described above ; the author proposes to call it, pro- visionally, a-digitoxin, distinguishing his own cornpoiitid by t,he prefix p. C. F. B. Quassole, a Substance accompanying Quassin. By E. MERCK (Chem. Ceirtr., 1895, i, 435 ; from Ber. u. tl. Jahr., 1894, 19- iW).-Q&z~assoZe, CdoHi,,O + H,O (?), is obtained from crude quassiu by extraction with ether ; i t crysttillises in colourless plates, and melts at 149-151”. I n R mixture of ether and chloroform [alu = - 4 2 * 6 O , and in chloroform alone = --Go.In alcoholic solution, it gives a pale vellow coloratioii with ferric chloride ; in chloroform solution, a deep Eed coloration with concentrated sulphuric acid, and differs from quassin by its absence of taste. Quassole dissolves i n fuming nitric acid, b u t the orditiary concentrated acid is apparently without actiotl. Arternisin, a Substance accompanying Santonin. i 3 ~ E. MERCK ((Jlrenz. Centy., 1893, i, 436 ; from Ber. ii. d. JLrhr., 1891, 3-6). --.-1~tentisin, C,,tf 1804, is obtained from the last mother liquors i n the technical treatment of the seed of Arfernisia nzaritima. It is freed from saritorkin by recrystallisation from chloroform, being deposited J. B. T.60 ABSTRACTS O K Ckl1EJllGXL PAPgEHS.in combination with 1 mol. of the solrent, which is evolved at 90". It me1t.s a t 200°, gradually turns yellow in the air, and is more readily soluble in water and dilute alcohol than santonin; [a]= = -84-3c. The ferric chloride reaction is not characteristic ; when heated with soda (10 parts) and water (40 parts), a fugitive carmine-red colorn- tion is produced, and, like santonin, it gives the same colour with alcoholic soda. Physcihydrone and Protophyscihydrone. By OSWALD HESS E (Anizalen, 1895, 286, 376 ; compare Abstr., 1895, i, 300).-Physci- liydrone bas t,he composition ClsHl404, and protophyscihydrone the formula C15Hiz04. M. 0. 3'. Artemisin is apparently a hydroxysantonin. J. B. rr. Phenylcoumalin and Pseudodicotoin. By O~WALD HESSE (Be,.., 7895, 28, 2507--2509).-1n reply to Ciamician and Silber (Abstr., 12395, i, 554), the author states that he was the first to show that." dicotojin " is a compound of cotoin and phenylcournalin. The melt-- ing point of phenylcoumalin is still given 3s 61°, whereas Ciamiciaii and S i l k give 65'. The investigation of Tod's pseudo-dicotoiii cannot be continued for lack of material. J. J. S. Derivatives of Cinchorneronic acid. By SIEGFRIED BLUNEK- FELD (Jlonatsh., 1895, 16, 693--729 ; compare Meyer, Abstr., 1894, i, 425, and Pollak, Abstr., 1895, i, 39L).--DiethyZic cinchomeronate, CjNHs(COOEt), is coiivenieiitlg prepared by the further ethylation of Strache's ethylic hydrogen cinchomeroiiate (compare Abstr., 1890, 1157). It is a colourless, odourless oil, having a burning taste and turning yellow on cxposure to light, ; it decomposes when distilled under ordiiiarg pressure, boils at 172.1' (cow.) under a pressure of 21 mm., and does not solidify at -660".:It mixes with alcohol, ether, benzene, xyleiie, and light petroleum i l l all proportions, gives a platinochluride, 2C,NH,( COOEt),,H,PtCl,, which crystallises in small, yellow iieedles, and melts and decomposes at 14%--144". I t forms alkyl additive products, which, on hydrolysis with silver oxide, yield the ethylbet aiue of cinchomeronic acid, CgHgNO,, a compound analogous to apophyllenic acid (compare Roser, Annuleu, 1886, 234, 119), and from which the silrei. salt, CgH,AgN04, crystallising in lonq? slender, colourless needles, a.nd t,he hyd?*ocliioride, C9HgN04,HC1, melting with decomposition at 214-216', may be formed.Ci.izc/iomeronamide, C,NH,(CONH&, obtained in quantitative yield by the action of ammonia on diethylic cinchomeronate, is insoluble in benzene aaid ether, dissolves in water and etliylic alcohol, melts with evolution of gas a t 163-165", again solidifies, and finally melts and decomposes ;it 225'. With potassium hSpobromite, cinchomeronamide yields both /3- and r,-amidopy;.idiiiecarboxylic acids i n addit,ion t o a11 intermediate product. The hydrochlorides of these carboxylic acids are resolved by the action of lieat int,o p- and yttmidopjridine respectively. G. T. B!. Collidinepiperidine. Bay PEYER KXKDSEN and RICHARD WOLYFEN- S'I'EIN (Ber., 1695, 28, 'L.Li5-2276).-Bromocollidine readily reactsORGAN10 CHEMISTRY.61 with piperidine to form coZ?idi?zeplpe7.idine, C1?HzoNr, hrdrogen bromide k i n g also formed. The new base boils at 279-2532", and forms a hychochloridc, C13HlllN2,2HC1. Coniine reacts i n a similar manner, the corresponding derivative bcinq formed. The pZat;no- chloride of collidineconiziie, C,,H26N,,BHzPtC16, crystnllises in small, red prisms, and melts and decomposes a t 244-245". The authors assume that the bromine remores the hydrogen atom combined with Quinoline Derivatives substituted in the Nitrogen Ring. By ALFRED KINI~ORN and PESOYER SHERVAS (AnnaZeu, 1895, 287, 26-49 ; compare Abstr., 1891, 8;J).-2'-Quinolylacrylic acid is the substance emplojed in the prepamtion of those compounds described i n the present paper ; its barium salt crystallises in white needles, with 2Hz0, the szlcer salt darkens when exposed to light, the ethplic salt melts at 73', and the aniide at, 175-176'.2'-Quinolylpropionic acid melts at 122-123', and not at 115" as previously stated (Zoc. cit.); the calcium salt is anbpdrous, the platinochboride melts and decomposes at 19'7O, and the aiilide melts at $-QuinolyZpropylic alcohol, C9NH6*CH,*CH2*CH2*OH. is obtained by reducing 5Y-quinolylacrylic acid with sodium amalgam in alkaline solution, or by means of tin and hydrochloric acid ; it crystnllises from petroleum in lustrous needles, and melts at 115'. Oxidation with potassium permanganate gives rise to 2'-quinolyl propionic acid. 2'-QuinolyZglyceric acid, C9NH6*CH(OH)-CH(OH)*COOH, is ob- t ained by oxidising 2'-quinolylacrylic acid with potassium perman- ganate; i t crystallises from dilute alcohol in white leaflets which contain 3H20, and in this condition melts between 100' and 130°, slowly losiag water, and becoming bIack.The au?*ochZoricZe crystal- lises in yellow prisms, and melts at 174O, the barium salt is anhy- drous, the ethylic salt mclts at 107--105O, and the methylic salt at 140-141O. 2'-Quinolylacetic acid has been already described (lop. cit.) ; the ylatiiiochloride is dimorphous, the ?wthyZic salt melts a t 72", and the ethylic salt, a t 6 i 0 . Much evidence is adduced to shorn that the product of condensn- tion between 2'-quinol~lacetnldehyde and orthamidobenzaldehyde is identical with Weidel's 2'-3'-diquinolyl. By LEOPOLD RGGHEIMER (,4nnalen, 1195, 287, 50-97 ; compare Abstr., 1889, 2*32, and 1894, i, 55)..-!i'he authoy prefaces the description of his experiments with a discussion of the constitution of liippurotlavin and its derivatives ; the structural jarmula already put forward (Zoc.cit.) continues to be adopted, and attention is drawn to the quinonic character of the substance. Hippuroflavin (dibenzo~lisop~~aziizeqz~inone), C18H10NZOl, has been already described in some detail (Zoc. cit.) ; the following clerivatives have been prepared for the first time. Dih?ldrol~i~~urOJEavindianilitie (DianilidodihycEroxydibe,lzoyl-nn-di- Ijydropymxine), CJoH24N,0A, is obtained by heating hippuroflavin on the nitrogen of the reduced pyridinc base. A. H. 149-1 50'. 11. 0. F. Hippuroflavin.62 ABSTRACTS OF CHEXICAL PAPERS. the water bath with excess of aniline and glacial acetic acid ; it melts and decomposes at 158-160', and does not dissolve in common solvents, purification being effected by converting i t into the potas- siqinz salt, which is tlien decomposed by the addition of water t o the alcoholic solution.When caustic soda is added in small quantities to dianilidohippuro. flavin suspended in warm water. the amidanhydride of dibenzylamido- diaiiilidosuccinic acid, , is formed; the solid product obtained on acidifying the filtered liquid i s dissolved in ammonia, and treated with calciiim chloride, in order to remove the acid as calciiim salt. The amidanhydride cqstallises from alcohol in small needles, and melts with effer- 1 escence a t 266--227O ; the calcium salt forms slender, colourless needlcs, containing 3H20, and precipitates are formed when a neuti*al solution of the ammonium salt is treated with solutions of uetsllic salts.(dinzethy lanilidodih ydroxydi- benzoyl-nn-dihyd?.op~~a~i~e), (&!H?,SN~O~ is obtained from hippuro- flavin and methylaniline ; it melts a t 2 3 8 O , previously becoming dark y el I ow. HippwoJEaz.iu bismetliglnnilide, C,,H2,N4O4, is obtained from the foregoing substance by the action of boiling nitrobenzeue ; i t melts at 233-234O. Dill yclrohippuro~a~ind;o1.t7~otolziidide (diorth otoluidobenzo?lldihy~?.~x~- ~ ~ n - d i h y d r o ~ y , . a z i r , e ) , C32H28N404, is colourless, and melts at 2:35--238O. y i el d ing ort ho to1 ui (3 in e and hipp?wojaz.inort h o toluiclid e, C26H,9N30,, which crystallises from benzene in stellate aggregates of needles, all4 inel t s a t 208- 209'.Hippui.olllr.ritryu1.afo77tidide, C2,H1,N,O4 and hjpr)ZC,.oJEaz:inxylidille melt at 246" and 223-225' respectively. D i h ydrohip~?L1.oflaz.i?2dia micle (dial i t i d od ibewzzo y 1 dih y d roxy -nn- dih y dyo- p!p.nzine), Cl8HI6NJO4, is ohtained by the action of ammonia on hip- proflavin; it melts at 240°, and begins t o darken at 220-225". Hilz~puroJla.r.iiidiamz'ne, C,,H,,N404 is obtained by treating the fore- going compouiid with alcoholic ammonia in sealed tubes at 105O, for four hours ; it melts a t 237-233'. Two new Bases in the Urine of the Insane. By MARTIN KRCGEE (Chem. Centr.., 1895, i, 292-293 ; from Du Bois-lieynzoud's Awh., 1894,553-555).-l'he one base, CIOH13NY02, is, from its reseni- Llance to guanine, termed epiguaniiie, and crjstallises from water i n slender needles, aiid from highly dilute ammonia in silky, lustrous prisms ; it dissolves in acids, in sodiiim carbonate solution, and in soda; from the last solvent, lustrous, broad needles are deposited, which probably consist, of a sodium derivative. The nitrate forrtis polyhedral crystals ; the chi*omate is deposited i n 1 ustrous prisms, the p l a t i w - c/i Zoi-ide in long, orange-i*ed prisms.The picrute and aui-ochloride c~ystallise in needles. 'I'he base gives precipitates with ammonia, silver nitrate, copper sulphate, and sodium hydrogen snlphite, but not with mercuric chloride, normal, basic, or ammoniacal lead NHBz*v(NHPh)*F (NHPh)*COOH co - NBz Dih ydrohippzirofZaz.inbismcth ylanil ide M.0. F.ORGANIC CHEMISTRY. 63 acctate. from t h e mother liquor of epiguanine. The secmd base was obtained onl:, in very sinall quant,ity J. B. T. Hydrogenation of Quinine. By I’;DUAI:D LIPP?,:ANN and F n ~ s z FLEISSXER (AIounts7~, 1895, 16, 630--6:37).-When dissolved in abso- lute alcohol arid treated with rnetallic sodium, quinine yields a reduc- tiou product which is appareritly a t.ctmhydroquinine. It is an amorphous, brittle mass, which is sparingly (lissdved by water, but is exceedingly soluble in alcoliol, benzene, and chloroform. The bascs has f,he odour of quinoline, yields fluorescent solutions when dissolved in sulphuric acid and nitric acid, and gives t h e quinine reactioti with ammonia and chlorine water. With a feebly acid solutioii, ferric.chloride gives an intense green coloration, which o n further additioii of t h e reagent turns reddish-brown. These colour reactions arc’ characteristic of t h e base, which also forms t h e following nnstablc salts : a normaZ kydi-ochloride, C20H2eN202,HCI + H20, a n czciii! hydro- chloride, a nomzal sulphate, a n ucid sulphate, and a plat inochlode, C,,H,,N,O,,H,PtCi,. On heating with excess of acetic anhydride, only one acetyl group entew t h e molecule, t h e compound C,,H,,AcO,N,, being formed a s a viscous mass. Tetrahydroquinine therefore contains only one lijdroxyl group, and from its behaviour with hj-drochloric acid, whereby hydrochlorohydroapoquinine is fornied, i t would appear that the double liitkage existing between t h e carbon atoms in quinine is not broken away during the addition of the four atoms of h j d rogen.IIydroquiuine has a powerful toxic effect, small doses causing sus- pension of respiration with ~ O S S o l voluntary and reflex movement, and ultimately convulsions aiia deiith. G. 1’. 11. Merochinine. By WILHLLM KOENIGS (Bey., 1895, 28, 1986- 1991).-Merochinine, which is obtained, a s already described by tlie author (Abstr., 1894, i, :392,477), by tho hjdrolytic decomposition of cinc’uine and chinine, and by the direct oxidation of cinchonine wit11 chromic acid, is converted into 3 : 2-metliSlethylpyridinL. by heating with hydrochloric acid and mercuric chloiide at 250”. As i t also contains t h e inlido-group, i t is in all probability the carboxylic itcicl of a liydropyridine base of t h e formula C8H,,N.All attempts to convert i t irito the ccwresponding pyridinecnrboxylic acid by removal of hydrogen or by elimination of hydrogeii bromide from bi.omome1.o- chiiiiiie have been unsuccessful, as the carboxyl group is i n all cases simul tR neously eliuiinated. When oxid ised with p t a s a i u n i pet-mit~i - ganate, i t is coiiverted into cinclioleuponic acid, and t h o carboxj 1 group must therefore occupy the same position as one of t h e carbox3-1 groups of the latter compound. From his researches, Skraup has concluded t h a t i n the so-called “ second reaidue ” of the cinchona alkaloids, a viiijl group is combined \\ i th one of t h e carbon atoms of the hydropgridiiie ring, and this con- olusioii has been supported by voii Miller and Rvhde (Abstr., 1895, i, A:%>) ; in that case, rrierocliinine, wltich is obtained from tbis second residue, would also coutuin t h e vinyl group, probably in combination witl: tlie 2-carboil atom of the pyridine group.The presence of this64 ABSTRACTS OF CHEMlOA L YAFKHs. group in cinchonine is borne out by the following results. The author and Comstock have shown (Abstr., 1887,281) that ciuchonine readily combines with 2 atoms of bromine, and on treatment \rith boiling alcoholic potash the product loses 2 mols. of hydrogen bromide, forming dehydrocinchonine, which must therefore either contain two ethylene linkages or an acetylene linkage. S o direct proof of the presence of the latter has been obtained, but it is found that, 011 oxidation, one carbon atom of dehydrocinchonine is eliminated as carbonic anhydride, with formation of cinchotenine.The lattel- has been also obtained by Skraup by the oxidation of cinchonine ; i t is ft saturated compound, aiid contains a carboxyl group, in addition to the hydroxyl group of the cinchonine, and therefore the dehydro- cinchonine, from which it is prepared, cannot contain two ethylene linkages, but must contain an acetylene linkage, which is formed from the vinyl group of cinchonine by removal of hydrogen. Bromomerochinine hydrohomide, CgNHlpBr02,HBr, is obtained by the action of bromine water on merochinine, and is identical with the compound obtained by Comstock and Koenigs by the action of bromine water on the bFe-products of the oxidation of quinine and cinchonine with chromic acid, and to which they at that time ascribed the formula C,NH,,Rr20 + $H20.It forms rhombic spheno'ids, melts and decomposes at 248-250°, and is reconverted into niero- chinine by treatment with zinc dust and sulphuric acid, all attempts, however, to convert it into n pyridine or lower hydropyridine deriva- tive were without success. When bromomerochinine hydrobromide is boiled wi t,h water, i t readily loses one atom of bromine, and on long-continued boiling the second bromine atom is eliminated, hydrozymerochinine, C,NH,,O,, being formed, On adding ether to a solution of this compound in methylic alcohol, it crystallises out with 1H20 ; this is evolved at 110', the anhydrous substance melting and deconiposing a t 254'. The hydyochloridc, C,NH,,O3,HC1, forms stellate groups of needles me1 ting at 208-210O ; the ~~Zatinoc7~Zoride small, lustrous, orange-yellow crys- tals melting and decomposing a t 240' ; and the aurochloride needles melting and decomposing a t 181'. The acetgl derivative is very soluble in water and alcohol, aiid yields an azwochloride which melts a t 2 1 4 O , with evolution of gas.It is only oxidised by alkaline potas- sium permangannte on warming, whilst merochinine and bromomero- chinine are oxidised in the cold, and whereas merochinine readily undergoes etherification when hydrogen chloride is passed into i t s solution in methylic alcohol, the bromo- and hydroxy-derivatives can only be etherified with difficu1t.y in this way. Higher brominaked derivatives of merochinine may be obtained by heating bromomerochinine hydrobromide with bromine a t looo, o r by the action of bromine on the hydrochloride of merochinine ethy lic ether in chloroform solution.One of these is a colci~rless, crystalline compound melting aiid decomposing a t 184", and is the hydro- bromide of either a tribromomerochinine, or of a monobromomei-o- chinine dibromide. H. G. C.ORQAKIC CHEMISTRY. 65 New Methods for the Preparation of Tropinic acid. B~RICHARD WILLST;~~L.TER (Eer., 1895, 28, %277--3380).-L)ih~droxytropidine, CH -C H (OH).CH( OH j --CH, contains two hydroxyl groups, which aiy united to adjacent carbon iltoms; and when treated with c*li1+omic acid, it is c o n v e r t d into tropinic acid, identical with that, obtained by ttie oxidabion of tropine.This proves t h a t two adjacent carbon atoms of dihjdroxytropidine, and therefore also of t,r.Ipine, serve t o form the two carboxyl groups of tropinic acid, C0OH.C E3 <(J NMe*C H, . c H, H'>CH*COOH. Tliis is in agreement with the above formula proposed for ths acid by Melaling (Abstr., 1832, 358), whilst it is inconsistent with Ladenburg's formula for the same sub- stance. A. H. Scopoleines (Ethereal Salts of Scopoline), By E. MERCK (Chenz. Centr., 1895, i, 434-435 ; from Bcr. 2. d. Julzr., 1894, 15- 18).-The only sccpolei'ne found in nnt,nre is scopolamine, the scopo- lc'ine of tiwpic acid, which occurs in ScnpZicc ,j(tpi~zicu and S. atro- p vides, a 1 i d i s id e n t i c'al w i t.h h y o sci 11 e . A c et Isoc~p o 1 e iue, C, B ,?N 02Ac, forms white crystals melting a t 250" : the m~?-ochlwide melts at 1%-197".Renzoy l s c o l ~ o l ~ i ' i ~ e , C,H ,2NOrBz, is c r j s t.al line, aud me1 ts at 68-70"; the 1Lytlrochloricle melts and decomposes a t 849-250' ; the hyd7dromitle crystallises in ctolonrless p r i b r n s melting at 245- 247' ; t h e i~ili-trte, pltrtiizocliloride (m. p. 200--201'), azwochloride ( i n . p. 188"), niercwochloride (m. p. 14fi--I42'), and p i c m t e (m. p. %UO-20lo) have also been prepared. CSH,,NO,*CO*CH:~BPI~, slowly becomes crystalline ; its nitrate melts at 172-173° ; the hydro- bromide has also been prepared. By E. MEKCK (Cheiiz. CeTLtr., 1893, i, 434 ; from Ber. ii. d . Juh7-., 1894. ?-ll).-l'he object of this investigation was the deteruiinatioii of the physiological action of the fatty acid deriva- tives of trope'ine.The majtrrity have 110 special influence; lactyl- tropei'ne exercises a well-marked effect on the heart, but it is not a mydriat.ic. AcefyZtwpri'?Le, C8H,NOAc, is a pale yellow syrup, boiling a t 235-237" ; the azwocldoi*ide melts a t 19:3O. Lactyltropei',ce, CBH,,NO-CO*CHMe*OH, cr-ystallises in colou~~lcss needles, and melts at 74-75O ; its lz!ld~ochloride, hydriodide, nitrate, sdphatr, arid uuro- chloride (m. p. 143-14fj0) have been prepared. Succi?zyltmpez?te, ~!,H,(CO.C,B,NO),, yields a JLydrotronz.ltle and a n azcrochloride; ttie forrrler is colourless ; the latter cryst,allises in yellow plates. The same derivatives of walyl-, tartryl-, and hipptlrgl-tropei?ie have also been prepared ; the a~~roc/,lor-~des melt a t 203-204", 2:3:j0, and 1:10--l!M' respectively.Tartryl tropejine is c*oloui*less and crystal- I I nc. Parameth y ihommr tropiue, C,H,,N 0.C O.CH( OH).CB H ,&, pre- p;hi-ed b y tlie action of dilute hgdrochloiic: acid on tropiiie para- ulcthylmandelate, is c Y j ~ b t a l l i i i C ; its Ul/.rUcILl~Jritlr: iiiclr,s at 192-1 gS0. ,N Me --- C H,, \c H,-- --CH,' Cis~~ianzo~lscopolezne, J. B. T. Tropeines, J . B. 1'. YOL. I . X X i. f66 ABSTRACTS OF CHIEMIOAL PAPERS. Angostura Alkaloids. By HEINRICJI BECKL-RTS ( A d . .PhRr?)t., 1895. 233, 410--423).--The alkalo'ids cuspwine, cuspai*ndine, gnlipine, and gnlipidine are obtained together from the ethereal cxtract of the bark of Cic.cparia trllfoZi/rtn, Eiigler (Galipen qtjicinali.9, Hancock) (Abstr., 1892, 642).Derivatives of cusparine only are described in the preserit communication. The purification of this compound from traces of galipine is exfremely dit€icult, and is hest accomplished by repeated recrystallisation from light petro- leum; criteria of its purity are i t s melting point (89") and t h e formation of coloiirless salts with acids. The alkaloid gives the following colour reactions. With concentrated sulphuric acid, a dull red, changing to cherry colour. Fuming nitric acid produces a yellow solution ; t h e residue, after evapomtion and treatment with potash, becomes orange. Frohde's reagelit Kives a brown solution, which changes Kuccessively to violet, bluish-green, and deep blue ; when warmed. t,he blue colour is obt,aimd more readil?, and it, is pro- duced immediately with the concentrated reagent,. Sulphuric acid c'o titaining titanic.aiihjdritle and fnrf tirnldehyd e respectively gives a reddish-brown and a bi-owlish-red solutiou. I3v t8he tiction of bromine water on cusparine hydrgbrornide, the riibromide, C.,,H ,?YO,.HBr,Br,, is formed as a pale yellow, amorphous powder nieltiiig a t 11 i o ; when t.reated with alcohol, hard yellow prismatic needles are obtained ; they melt at 23tjo, and probably consist of cwspwine dibromidc, C,,,H,,NO,,Br,. The platinochloride crystallises with C;H,O. Cmpa- Tine ?nethocl~ZoriLJe, C,,H19N0,MeCI, preparcd from the methiodide (Zoc. cit.), ci*yst,allises in lemon-colon~~ed needles 2nd melts a t 1 90". I t s platinochloride, (C20Hl,N0,R~e)2PtCI,, is deposited i n lustrous golden needles melting a t 210' ; the auru~l;lori~?e forms reddish- brown needles and melts at, 152-153'.MethyZcmpa?*ir,e, C,,,H,,N 0,Me + -!jH,O, is prepared by the action of potash o r silver oxide on cusparirie niethiodide ; it crystallises from dilute a,lcohol in colourless nredlea, from water in pearly lustrous plates, and me1 ts at 190'. The kydwdwomide crystallises with 10H20 in slender, lustrous, yellowish-green plates. The hydro- chloride crystallises n i t h 2*5H20 in hard, dxllate needles. The p7atii~ochZoritJe, ( C2,H1,NO,Me),,B2Pt,Cl~, forms golden, lustrous needles and plates nielting at 210'. l'he methiodide, C,,,H,,NO,Me,MeI, CTFS- tdlises in slender, jellow, lustrons needles ; i t melts at I%', darkens on exposill-e to light, and has a n intensely hitter taste. Caspari.iie stlr.iodide, C2,,H,9N9:I,EtI, is depcxited in yellow, lustrous needles, darkens when exposed to light, and melts at 201'. The chloride crystallises in lemon-colonred needles melting a t 156". l'he pZn/inr.chZo7*ide is deposited in golden, st el late, rhombi c prisms me1 ti it g- at 178'. I ~ t I ~ ~ Z c z r s ~ / r . ~ . i ~ i ~ , ~ ~ , , H , ~ N 0 ~ 1 1 : t, prepared by the action of sod:% 011 the cthiodide, c i ~ y ~ t ~ l l i ~ e ~ in coIou~~lc'ss, transparent prisms, a n d melts at 1 90--101.0. Tlic snine coniponnd, together with tlie ?iyd7~.tr, C,,H,,NO,I<t + HzO, i s fornicd by t h e interaction of tlie ethiodide and silver oxide ; i t crjstallises in lustrous plates, and melts a t 114--115". By H. PnhlMEI;F:lIKF: (A~71. Phaiw., 18'35, 233, 1.'7-174).--'l'lie pulverised ~ , o o t of h'ei*be, is ,I. B. rr. Alkaloids of Berberis Aquifolium.ORGANIC OHEMISTRY. 67 aycifoldum was repeatedly extracted with water containing a little ;icetic acid, the extract was concent,rated and filtcred from berberine acetate and other substances, and from t h e filtrate, by saturating it wit,h sodium sulphat.e, oxyacarithine WAS eventu:illy obtained, whilst berbamine was ohtained by snturtting tlie filtrate from the oxyacan- thine with sodium nitrate. These two alkalo'itls wei'e then purified by crjstallisation of their hydi*ochlorides from water. New experi- ments were made with them, and some hitherto tloubt,ful points finw.lly decided. Some properties cf berberine, as t o which contra- dictory statements exist, were also re-examined. Ozyncanthine.-This substance Ilas the composition C,,H2,N03 ; ih is a monacid base, and is identical in composition and properties with t h e product obtained by Hesse from B. zzdgnris. It, van be oh- tained A S a white, amorphous precipitate, which me1t.s at l~0-16U0 ; or, bg crIstallisafioii from 90 per c+ent,. alrohol, in coloui*less crjstals which melt at 208-21d0. I n alcoholic solution a t ZOO, i t has the specific rotation [a],, = + 1 7 4 O 5', amd i t forms a well ci-ystallised compoiirrd with l ~ v o - , but not with dextro-, rotatory t-nrtarrc acid. It contains an hpdroxyl group, for, altliough acetic: chloride and aretic anhy- dride seem to exercise a dehydrating actim on it, j e t bensoic chlo- ]aide converts it into a mo?tohcnzoyl dtriraiiw. of which the platim- chloride, wit.h 8 H20, and niirocliloride, with 2H,O, were prepared. I t probably contains 2 met,hoxyl groups ; t h e numbeis obtained by Zeisel's method point, curiouslg enough, t o I$. It reacts as a tertiary base with naethglic iodide, yielding a n additice compound, C ,,H,,NO,,MeI + 2H,O ; 1i:ilf of the water is lost at looo, t h e rest a t 110'; it melts when mliydrous at 248-250°, and can be converted by means of silver oxide int,o au alkiiline quaternary ammonium base, the plntinochloridc, with 5Hz0, and aurochloride, with H,O, of which were prepwed. Oxyacanthine gives the usual alkaloid reactions. The following snlta were prepared and analysed :-Hydrochloride, specific rotation [ a ] D = + 163' 49', ~?.yiIr-o2,i.(,,r,idc, hydriodirle me1 ting a& 256-25Y0, nif?wtt., all with 2H20 ; normal sujphnte, anrochloride, both with 4H,O ; platinochloride with 3H,O. I>'erbnnziize.--This has the composition ClRH,9K03, a s was shown by the analysis of i t s hydi*ocJiZoridc, with 2H,O, and platiuochloridc, with 5H20. It was obtained in small quantity only, and appears to contain 1-2 methoxyl groups. Berberiue.-This nlkalo'id yields a normal $ulphate, with 3Hz0, i n addit,ion to t h e hydrogen sulphate ; i t also forms a st,able hydrogen carbonate, CZOHliNOJ,H2COS + 2H20, and a, stable hjdrocyaniclcb. Metliylic, ethglic, and amylic iodides form additive corripounds wit,)) 1,a*hei~;ne, Ltit t1ie.e qnateimary animortiuin dei-ivntives Are not v t ~ y st:tblt: ; they do nota yield the corresponding chioi-ides when t,reated with silver chloride, bcrberine hydrochloride being formed instead. C. F. 13. Identity of Baptitoxine and Cytisine. By PIICTER C. PT,L.(;GE (:lwh. /'harm., 1895, 233, 89.I.-~9!)).-H;tt)tiL9xine, obtdincd by ~ ' 0 1 1 Sjclii.ocder froin the root uf fiaplisia fi?Lc/oi-;a,'is shown to be identical68 ABSTRACTS OF OtlJ3MlC;XL PAYERS. with cytisine. The seeds afford a better source of the alkalo'id ; those of B. uustralis contain 2.85 per cent. of cytisiue, and those of L'. tinctoria probably an equal amount. Estimation of Alkyl Groups attached to Nitrogen. By JOSEF HERZIG aiid HANS NEYER (Mouat.sh., 1895, 16, 5!49--608 ; compare Abstr., 1894, ii, 2l!j ; lE95, i, SlO).-The autliom have previously (loc. cit.) described a, method for the detection and estimation of alkyl groups attached to nitrogen, and have shown that, by a modi- fication of the process, the meLhox:l and ethoxyl groups present can also be determined. A large number of suhstances have now been examined, and the results obtained i n part agree with accepted con- stitutions, amd in other. cases contradict them. The alkalo'ids, harmirie and harmaline, each contains one methoxyl group, but 110 meth.y1 attaclled to nitrogen (cornpare Fischer, Abstr., 1889, 730, and Fischer and Tauber, Abstr., 1885, 829). Sparte'ine contains no methyl group attached to uitrogen (compare Ahrens, Abstr., 1888, 6111, and Ahrens' norspartehe is only an impure form of sparte'ine. Pilocarpine contains oril;y one methyl group attached to nitrogen and no ruethoxyl group, the authors theiefore coiiclude that either Hardy and Calmel's to1 mula, which gives three methyl groups directly attached to nitrogen must be incorrect, o r that their method bf estimation is unsuited to t h i s compound. The methyl derivative of the met.hylbet;i'iile of papaverinic acid, which melts ai 126', conttiins foni. niethoxjl groups (raompare C. F. B. Scliranzhofei., Abstr., 1894, i, 59 and 151). G. 'r. M. Pauqine. By E. MERCK (C'heni. Ceiztr., 1895, i, 4t-14, from Ber. u. J. Juhr., 1SY4, 11-15)6-l'au~ine, C,,H,,N,O, + ti*,SH,O, is the alkslo'id of the " pnuc;o nut,:' the fruit of Pentaclethra mac?*oy?iyZZa; i t crystallihes in golden plates, melts a t 12t;", is insoluble in ether and chlorofoi-m, and a por*t,ion is decnrnposed when i t is reci-ptallised from wnt er. The h!idwchZoritle, C2,H3,N5O3,2HCI + 6H,O. melts a t 245-247'. The plathiochloride, Cz7H3,Nb05 H2PtCI, + 6H,O. is brownish-red, c q stalline, and irlelts at 145'. The pic?*ccfe crgstallises in ga.r.net,-red prisms melting a t 22b". Bx the actioii on pauqine, of potash, or of concenti-ated hydrochloric acid, at I&', dimethylamilie is eliminated. J. B. T. Matrine, the Alkaloid of Sophora Angustifolia. By PIETER C. P L U G ~ ~ E (Arch. P~AYUI., 1895, 233,441-443).-Kag:ni has receritly published, in Japanese, n coniniunicat.ion on the alksloiid in the root of h'ophom ang?ts/,$oliu, whivh he terms rnatyijle, C,,H,,N,O ; it melts tLt. about SO', is, in aqueous solution, dexti.ogjrate, and gives precipi- h t w , wliich are fr*equeiltly crystalline, wit.11 t,he usual alka.lo'id re- tig~ii ts. l'h e y lut LuucliZor~ d e , c 16 H,,N,O :H2P t C Is, and tli e u i ~ r o c h l ~ ~ t ? e , (~,,H,,N,O,HAiiCl,, ha\ e been prepared by PITacEti? and tlie author has obtained R crystalline j i ~ , ompri7d/>. The lethal dose of matrine is l'tiger than that of cgtisihe, aiid the conipouiids differ in phpsio- logical uctiori. 3 . l3. T.

ISSN:0368-1769    

DOI:10.1039/CA8967000001

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

INORGhWICl CHEMISTRY. 1'; I n o r g a n i c C h e m i s t r y . Conversion of Chlorine into Hydrogen Chloride. By RICHARD LoRmz (Zeit. anorg. Cliern., 1895, 10, 74--77).-Chlorine is com- pletely converted into hydrogen chloride by passing it, mixed with steam, through a tube filled with coke, and heated to IL faint red heat. The action is expressed by t h e equation 2Cl + H,O + C = 2HCl + CO, and so comp1et.e is itc that the gases issuing from the hot tube do not contain suEcient chlorine t o give a reaction with potassium iodide and starch. After absorption of t h e hjdrogen chloride by means of water, t h e residual gas is almost pure carbonic oxide, containing only a very sniall qu&tit,y of carbon-ic anbydridc. E. C. R. Crystallisation of Bromine. By HER'RTK ARcrro\$-sKI (Zeit.anorg. Chern., 1895, 10, 25-226).-Bromine crystallises from a very concentrated solution i n carbon bisulpliide at -90" i n slender, car- mine red needles, having a somewhat similar appearance to chromic, anhydride. The cryskals are pure bromine. Bromine, when suffi- ciently cooled, solidifies to a dark brown mass, which has a crjstallinc fracture, but not so well defined a metallic lustre as iodine. E. C . R. VOL. LXX. ii. 318 ABSTRACTS OF CHEMIOAL PAPERS. Compound of Selenium with Arsenic. By A. CLETER and WILEELJI MUTHEIANN (Zeit. aitorg. Chenz., 1895, 10, 117-1 47).-The authors attempted to prepare conipounds of arsenic acid in which the oxygen is partially replaced by selenium. For this purpose, arsenious acid dissolved in concentrated potassium hydroxide was mixed with selenium, also dissolved in potassium hgdroxide. A complic.t,ted reaction takes place, a small quantity of selenium is deposited, but the only compound which the authors were able to isolate was a potassium polyselenide, described below, Potassium nxyselenoarsenate, K6As2Se50s + 10H20, is obtained by treating arsenic pentnselenidc with potassium hydroxide.The arsenic pentaselenide ( 5 grams), prepared by melting a finely ground mixture of arsenic and selenium in a porcelain crucible, is gradually added to a concentrated solution of potassium hydroxide (10 grams), the mixture being cooled with ice; it is then filtered into absolute alcohol (300 c.c), and the orange-red, crystalline mass thus obtained is washed with alcohol and dried on a porous plate.It is andogous to the salt Na,As2S305 + 24H20, described by Geuther. It rapidly decomposes and darkens on exposure to air and moisture, selenium being deposited; i t dissolves easily in water, forming a greenish- yellow solution, and then decomposes rapidly with deposition of red selenium. With salts of the heavy metals it gives dark, amorphous precipitates ; with barium salts, a reddish-white compound, which decomposes very rapidly. When treated with acids, it yields arsenic pent aselenide. Arsenic pentuselenide, As2Se5, prepared by melting its constituents toget her: has propcrt,ies similar to those of Ulsmann’s triselenide. When heated in the air, it decomposes: and red selenium and a greyish- black sublimate are formed. If prepared by decomposing the preceding compound with acid, it forms a reddisb-brown powder.It dissolves t o a greenish-red solution in alkalis and ammonia, and is reprecipi- tated unchanged by acids; it is insoluble in dilute acids and con- centrated hydrochloric acid, and is slowly decomposed by warm, dilute nitric. acid, very rapidly by cold, fuming nitric acid, whereby arsenic and selenious acid are formed. I t is insoluble in water, alcohol, ether, and carbon bisulphide, and has neither taste nor odour. Potassium metaselenoarsenate, KAsSe3 + 2H20, is obtained by adding arsenic pentaselenide to a solution of selenium in potassium hydr- oxide; the mixture, after being heated for some time, is filtered into alcohol, a small quantity of water is added, in order to dissolve other compounds which are formed a t the same time, and the product is then dried on B porous plate.It crystallises in reddish-yellow prisms, and is easily soluble in hot water, but the solution soon decomposes, with deposition of selenium ; alkaline solutions are somewhat more stable. Acids precipitate arsenic pentaselenide from the aqueous sorution with evolution of hydrogen selenide. With lead and silver salts, it gives a black precipitate ; with barium salts, a reddish-white precipitate, which rapidly decomposes. Potassium thioselenoarsennte, K,As,Se,S3 + 12H20, is prepared by adding arsenic pentasulphide to a solution of potassium sulphide,1NORGANIO CEEMISTRY. 19 heating the mixture to boiiing, and filtering the solution into alcohol ; the compound then crystallises out in orange-red needles. It is unstable on exposure to air and moisture, melts to a reddish-yellow liquid at the warmth of the hand, and is fairly stable in aqueous solu- tion ; the aqueous solution, when treated with acids, gives a brownish- red precipitate of the pentaselenide mixed with sulphur, hydrogen sulphide being evolved. Sodium oxyselenoamenate, 3NazSe,3Na20,As20, + 50H20, is ob- tained by warming arsenic pentuselenide with a concentrated soh- tion of sodium hydroxide ; a new hydrate of sodium monoselenide, described below, is at first precipitated, but on filtering, and mixing the filtrate with alcohol, the oxy-compound crystallises out in white, elongated prisms, which are fairly stable on exposure to air.It is easily soluble in water ; acid precipitates selenium from the solution and an arsenic selenide is not formed.With lead and silver salts, it gives a black precipitate ; and with barium chloride, a white, amor- phous precipitate which is easily soluble in warm water. Sodium selenoarsenite, Na,AsSes + 9H20, is formed together with other salts when arsenic pentaselenide is boiled with a solution of selenium in sodium hydroxide ; on concentrating the filtered solution in a vacuum, a mixture of white needles and orange-red tetrahedra is obtained. On separating these by levigation, a small quantity of the tetrahedra are obtained. It8 is unstable on exposure to air, becoming coated with grey selenium; i t is easily soluble in water, and the brown solution when treated with dilute acids gives a brownish-red precipitate with evolution of hydrogen selenide.Sodium thioselenoarsenate, Na6As2Se5S:3 + 18H20, prepared in a similar way to the corresponding potassium salt, crystallises in golden-yellow spangles, or in beautiful, long needles which are fairly stable, bat slowly darken and decompose on exposure to air. It is easily soluble in water; and acids precipitate a brown compound from the dark- brown solution with evoliition of hydrogep sulphide ; towards acids and Ralts of the heavy metals, it behaves like the potassium salt. Potassii~rz triselenide, K2Se3 + 2H20, is obtained, as previously stated, in brown needles, when potassium selenide is mixed with arsenious acid dissolved in alkali ; the crystals rapidly decompose and become coated with grey selenium on exposure to air.It dissolves in water, and the solution when treated with acids, jields selenium and hyclro- gen selenide. Sodium momselenide, Na2Se + 10H20, obtained as medioned above, crystallises in beautiful white needles which rapidly turn red, then brown, and become coated with grey selenium; it is easily soluble in water, but insoluble in alkali hydroxides. It evolves hydrogen selenide on exposure to the air, or when treated with dilute acids ; melts to a brown liquid when warmed, and has the properties assigned to the sodium selenide obtained by Fabre. Helium and Argon. By HEINRICH KAYSER (Cheaz. News, 1895,72, 89).-The author records the discovery of helium in the free state in nature. I n the springs of Wildbad, in the Black Forest, bubbles of gas rise up, which, according to an old analysis of E’ehling, contain E.C. R. 3-220 ABSTRACTS OF CHEMICAL YAPIFRS. 96 per ccnt. of nitrogen. An analysis of this gas showed that after sparking with excess of oxygen aud removal of the residual oxygen with pyrogdlol, a residue was obtained which gave the spectra of argon and helium, Ihe latter being evidedy present i n quantity. Runge and Pasclien found two substances in the gas from clhveite and broggerite, and both these elements appear to be represented in the Wildbad gas. A s a place lias here been found in which the two gases represented by the na.me helinm are liberated and stream into the atmosphere, i t f'ollows that these must be normally present in tlieatmosphere. The author has found this to be tile case, and that argon prepared from the air of Bonn contains helium, the presence of the D, line in the spectrum being most ma~ked.H. C. A Possible Compound of Argon. By WILLIAM Rakisbu (Chenz. News, 1895, 72, 5l).-By making nn arc between two thin carbon rods, in an atmosphere of argon for some four hours, the volume of the gas increased about one-fifth, and was not altered by exposure to water, to caustic soda., or to ammoniacal cuprous chloride. It gave, in addition to a faint argon spectrum, a luminous, finely channelled spectrum, with certain lices nut coincident with argon lines (see Crookes, this vol., ii, 2). D. A. L. Fluorides and Oxyfluorides of Potassium. By G. MARCHETTI (Zeit. unorg. Chem., 1895,10, 66--73).-Anhydrous potassium titano- fluoride, K2TiFb, is prepared by rtdding the theoretical quantity of potassium hydrogen fluoride to a solution of titanium dioxide in an excess of hydrogen fluoride. I t cr3stallises in small, very lustrous leaflets, which are denser than the crystals of the hydrated fluoride, K2TiF,,H,0.I t can be orystallised without change from hot hydro- fluoric acid, but when dissolved in water i t is completely converted into the hydrated salt. Conversely, when t'he hjdrated salt is dis- solved in concentrated hydrotluoric or hydrochloric acid, it is con- T-erted into the anhydrous salt. The normal potassium fluoride compounds of niobium, molybder~nm, and tungsteu, of the formuh Nb02F2,2KF,H20, Mo02F2,2KF,H20, and W02F2,2KF,H20, respectively, behave in the same way. The oxgfluoride of molybdenum, Mo02F2,2KF,H,0, obtained by adding the theoretical quantity of potassium hydroxide to a solutiou of molybdic anhydride in hydrofluoric acid, taking care that t,he mix- ture revmains acid, crystallises from hot hydrofluoric acid in short, lustrous prisms of the composition Mo02Fr,2KF.The salt described by Delafontaine (Arch. Sci. Phys., 1867, 30, 244)) 31002F2,Ki(',H20, is probably a mixture of the two preceding salts, and, according to the author's results may also contain the oxyfluoride MoOFq,KF. The double fluoride OF tungsten, W021?2,2KL7,HE,0, is obtained i n a similar may to the molybdenum salt. The anhydrous salt crystallises in groups of large tablets. E. C. R. Some Alkali Phosphides. By C. HUGOT (Coinpi. rend., 1895, -121, 206--208).-When liquefied ammonia is brought in contactIXORQANIC CHEMISTRY.21 with a mixture of known quantities of red phosphorus and sodium or potassium, the sodammonium or potassammonium which is first formed is decomposed by the phosphorus wit>h liberation of hydro- gen, and the product remains in solution in the excess of ammonia. Potassium yields n red compound, P5K,3NH3, which when heated at 180' loses all its ammonia,, and leaves a brownish-red mass of the phosphide, P5K. Sodium yields a red product, P3Na,3NH,, which a t 180' loses all its ammonia, and leaves the phosphide P3Na. The potassium compound is not obtained quite pure, since potassa.mide is slightly soluble in liquefied ammonia, but this dit-ficnlty is not experienced in the casc of the sodium cornpound.Both phosphides are decomposed by moist air, with liberation of hydrogen phosphidc. Their other properties will be described subsequently. C. H. B. Determination of the Atomic Weight of Zinc. By THEODORE W. RICHARDS and ELLIOT F. ROGERS (Zeit. nnoiy. Chein., 1895, 10, 1-24).--The authors have determined the stoniic weight of zinc from the ratio of silver to zinc bromide and silver bromide to zinc bromide. The specific gravity of zinc bromide was found t o be 4.219 at 20". The zinc bromide employed in the first series of determinations was prepared by dissolving pure zinc oxide in pure hydrogen bromide, the pure zinc oxide being prepared by dissolving commercially pure zinc in dilute sulphuric acid, and allowi~g the solution to remain some weeks in contact with an excess of the nietnl. The filtered solution is then slightly acidified with sulphuric acid and treated with pure hydrogen sulphide until a considerable quantity of pure white precipitate is formed, and the filtrate from this is treated with chlorine water and fractionally precipitated with pure soda.The first precipitate, which contains iron and manganese is discarded, but the second precipitate after being well washed with water, is dissolved in pure nitric acid, treated with an excess of zinc carbonate, arid filtered ; the filtrate is treated with a small quantity of ammonium carbonate, and, after filtration, the zinc is precipitated with anirrio- nium carbonate. ' b e basic zinc carhonatc! tlius obtained is washed, heated in a platinum crucible by nienns of n spirit flame, and again washed and dried.The hydrogen bl-omide was prepared according to well- known methods, and puii tier1 by f mctionql distillation. I n the determination of the atomic weight, great care must be taken that the zinc bromide is free fkom every trace of water ; the metbod employed is that already described by the author for the analpis of strontium bromide (Abstr., 1895, ii, 314). The pure recrystallised or sublimed zinc bromide is heated for some time in n platinum boat i n R current of nitrogen containing hydrogen bromide, by which means all the water is removed without the slightest forrna- tion of oxybromide; the dry salt is then quickly transferred to .z desiccator and weighed. It is dissolved in water, precipitated with a slight excess of silver dissolved in nitric acid, and the silver brom- ide thus obtained is collected in a Gooch's crucible, and weighed.I n a second series of determinations, the filtrate was concentrated,22 ABSTRACTS OF CHEMICAL PAPERS. and the excess of silrer determined by precipitation with hydro- bromic acid. The first series of five experiments gave Zn = 65.459. The second series of four experiments gave Zn = 65.430 from the ratio Ag? : ZnBr,, and Zn = 65.423 fyom the ratio 2AgBr : ZnRI*,. The silrer bromide obtained in the last four experiments gave 57.444 per cent. Ag, which shows that the hydrogen bromide employed was free from chlorine and iodine, and that the precipitate contained no included zinc bromide. I n the third series of experiments, the zinc bromide was prepared by dissolving pure electrolytic zinc in pure bromine.A solution of zinc sulphate is prepared as described above, but after the trexhment with chlorine, pure soda is added, until a sniall precipitate is formed, and the mixture is allowed t o remain for some days, shaking occa- sionally ; the precipitate is then filtered off, and the zinc sulphate crys- tnllised from hot water. The solution of this zinc sulphate after being allowed to remain two days i n contact with pure electrolytic zinc in a platinum dish, is filtered, treated with ammonia, and electrolysed with a current of 1 to 14 amperes ; the zinc crystals formed being washed with ammonia, then with hydrochloric acid, aiid finally with water. The zinc is then dissolved in bromine, the solution filtered through asbestos, and the excess of bromine eliminated by heating on the water bath ; fiually the zinc bromide is either sublimed or distilled i n a special apparatus which is figured in the original paper, and so arranged that the sarople to be analysed is collected i n plati- num vessels.The zinc bromide is first dried at a gentle heat i n an atmosphere of carbonic anhydride, tben at a temperature slightly above its melting point in carbonic anhydride mixed with hjdrogen bromide, and finally a t 150' in a current of air until the exit gases show no trace of carbonic anhydride OP hjdi*o~en bromide. It is then weighed, dissolved in water, arid precipitated i n the dark with silver dissolved in nitric acid ; two equiralent solutions of silver afid hydrogen bromide are employed to determine the point at which au opalescence of equal intensity is produced in the clear supernatant liquid. Finally a slight excess of silver nitrate is added, and the pre- cipitate collected i n a Gooch's crucible and weighed.The mean of three experiments gave Zn = 65.402 from the ratio ZnBr, : 2Ag, and the mean of three other experiments give Zn = 65.406 from the ratio ZnBr2 : 2AgBr. The author coucludes that when 0 = 16 the most probable value for the atomic weight of zinc is 65.40. E. C. R. Electrolytic Preparation of Zinc and Lead. By EICHARD LOBENZ (Zeit. anoyg. Cherrz., 1895, 10, 78-116) .-Electrolysis of Fused Zinc Chloride.-The chief difficulty to be overcome in the electrolysis of zinc chloride, is to obtain the salt entirely free from water.The zinc chloride, which still contains water, is placed i n a V-tube of combustion glass, and heated t o quiet fusion. A carbon electrode is placed in each arm of the tube. Directly the current is started, a brisk evolution of gas, due to the presence of water, takes place at both electrodes; the gas evolved at. the positive electrode is at the com- mencement hydrogen chloride, but after some time chlorine is evolved ;INORGANIC CHEMISTRY. 23 meanwhile the evolution of gas a t the negative electrode diminishes, and zinc begins to be cleposited. During the deposition of the first few drops of metal, a brisk evolution of hydrogen takes place at the negative electrode. As the zinc which is deposited at first is not pure, b u t contains lead and other metals which may be present, the molten electrolyte is poured off into a similar V-tube as soon as the less posi- tive metals have been deposited, and the electrolysis is continued ; pure zinc is then deposited.The electrolyte, which now consists of pure zinc chloride, is a clear, limpid, highly refractive liquid, under which the molten zinc appears like mercury. It solidifies, on cooling, to a white, porcelain-like mass, and is the most hygroscopic substance the author has worked with. Fused lead chloride is easily electrolysed i n a similar way. Fused cadmium chloride is not so easily electrolysed ; chlorine is at once evolved at the anode, and at the cathode brownish-black clouds which dissolve in the electrolyte, whilst a small quantity of cadmium is deposited.The electrolyte contairis a lower chloride of cadmium, which can be obtained as a crystalline metallic powder by lixiviating the electrolyte with water; t h i s compound is diEcuit to dissolve in hydrochloric acid, and the solution does n o t at first give a precipitate with hydrogen sulphide, but, after some time, a jellow precipitate is suddenly deposited. I n the electroljsis of fused silver chloride, the silver is deposited as a brown mass, and when a small quantity of melted zinc or lead is placed in contact with the cathode, the silver dissolves in the molten metal. Silver chloride diesolves in zinc and lead chlorides, and, on subjecting the mixture to electrolysis, the silver is deposited first. The silver is also deposited when a zinc rod is placed in molten zinc chloride containing silver chloride.Copper chloride, dissolved i n zinc chloride, in which, however, i t is only slightly soluble, can be electrolgsed by employing a cathode of molten zinc, when all the copper is obtained as a zinc copper - alloy. Mixtures of zinc, silver, lead, copper, and cadmium chlorides on fusion give colourless electrolytes, which are easily manipulated. The addition of lead chloride t3 zinc chloride greatly increases the ease with which tlie fused salt is dehydrated by heat alone, and mag- nesium and calcium chloride produce the same effect. When such mixtures of fused metallic chlorides are electrolysed, the mPtals are deposited one after the other, and can be obtained pure by fractional elec trol pis. Mitli a mixture of lead and zinc chlorides containing cadmium chloride, after 20 amphe-minutes, the metallic regulus conisined 97-34 per cent.lead, 1.35 per cent. cadmium, and 1-30 per cent. zinc ; after 175 ampere-minutes, i t contained 1-50 per cent. lead, 2-55 per cent. cadmium, and 96.15 per cent. zinc, and after 335 amphre- minutes, pure zinc was deposited. With a mixture of lead, silver, and zinc chlorides, a separation of the silver and lead cannot be obtained ; after 2.5 ampGre-minutes, tlie legidus contained 60.6 per cent. silver, 8 per cent'. lead, and 7.5 per cent. zinc ; after 7.5 amp6re- minutes, S J per cent , 5 per cent., and 14 per cent. respectively, and24 ABSTRAOTS OF OHEMICAL PAPERS. after 27.5 ampere-minutes, 0.49 per cent., 95.96 pcr cent., and 2.5 per cent.; after 272.5 amphre-minutes, pure zinc was obtained. With a mixture of zinc: and silver chlorides, and employing a cathode of molten lead, the silver was easily separated; with a cathode of molten zinc, however, aEter 330 a.mpBre-minutes, the electrolyte still contained traces of silver. With II, mixture of copper and zinc chlorides, and employing a cathode of molten zinc, copper is deposited at once, befcre the current is started, and after 90 amphe-minutes pure zinc is obtained. A large number of experiments, fully described in the original paper, show that 0.9 volt is sufficient t o deposit zinc by this method, and a slightly lower roltage to deposit lead. The deposition of zinc is theoretical, 435.89 ampitre-minutes deposited 9 grams, whereas, theoretically, 8.86 grams should have been deposited.The author bases a method of wiritiing zinc and lead from their ores on the results of the above experiments. Ores containing chiefly zinc, with lead and small quantities of silver and cadmium, are roasted and treated with hydrochloric acid. When excess of acid is employed, the iron and aluminium are precipitated from the solution by the addition of zinc oxide, and the purified liquor evaporated and the residue fused. Ores which contnin chiefly lead are treated with dilute acetic acid, and the lead and silver. precipitated from the solu- tion by the addition of sufficient hydrochloric acid. After separa- tion of the lead and silver chlorides, the liquor is again used to lixiviate fresh portions of 01.0 until if becomes satnrated with zinc acetate. The acetic acid is then removed by treating the liquor with hydrogen chloride and distilling, and again used with fresh portions of the ore.A description of an apparatus suitable for carrying oat the operation on a technical scale i s given. The chlorine evolved during the electrolysis is converted into hydrochloric acid by the method described by the author (this vol., ii, 17). Chromates and Dichromates of the Heavy Metals. Bey JUL. SCEULZE (Zeit. anorg. Chem , 1895, 10, 148--154).-1n contradiction of the results obtained by Ihiiss and Unger (Abstr., 1895, ii, 355), the author has obtained the following chromiltes and dichromates in .a crystalline form. Copper diclrromate, CuCr,@, 4- 2H20, is obtained by saturating a cold solution of chromic acid, previously freed from sulphuric acid, with copper carbonate, aiid evaporating the greenish-brown solution under the air pump.It separates i n very lustroas, black crystals, is slightly hjgroscopic, and dissolves easily, and without decomposition, in cold water; when heated with water, however, i t decomposes, and is partially converted into a brown compound. It is identical with the salt described by Droge (Annalen, 101, 39). Copper chromate is obtained by heating the dichromate with copper oxide in a sealed tube at 220’. It crystallises in minute, brownish, transparent prisms, insoluble i n water, but easily soluble in acids or in chromic acid ; when boiled with water, it gradually decomposes, and yields the dichrornate and the salt 3Cu0,CrOa + 2Hz0.Cadmium dicliromate, CdCr207 + HzO, obtained in the same way E. C. R.1N 0 RGANIO CHEMISTRT. 23 as the copper salt, separates in orange-bromTn, cubic crystals, and dissolve.; easily, and without decomposition, in water. CatIrniunz chromate, obtained by heating the dichromate wit11 cadmium hydroxide, in a sealed tube, a t 200°, separates as a bright, orange-yellow powder, which appears crystalline under the micro- scope. When boiled with water, it yields the dichromate and :L brownish-yellow powder. The filtrate obtained in the preparation of the chromate, when allowed to remain for some time, deposited crystals containing 2H,O, and t h i s is the only chromate of tlie heavy metals which contains water of cryst allisation. Zinc dicAroniate, ZnCr20, + 3H20, crystallises in dark, reddisli- brown, crystalline crusts, and has similar properties to the above salts.Z i m chromate is obtained as a fine powder, which appears crystalline under the microscope; it is insoluble in water, easily soluble in acids, and is decomposed by boiling with water, yielding t l L c dichromatc and a greyish-yellow, crystalline basic chromate. Manganese carbonate dissolves in a cold solution of chromic acid in the proportion of 1 to 2, but the product obtained on evaporatioli was not crjstalline. It formed a black powder containing chromic oxide. Cobalt and nickel oxidea also dissolve easily in a cold solution of chromic acid in the ratio of 1 to 2. The author has attempted to prepare a chromic acid alum by adding potassium chromate to a solution of alumina in chromic acid, but in all cases potassium dichromate was formed.Carbides of the Metals of the Rare Earths. By OTTO PETTERS- E. C. R. SON (Bey., 1895, 28, 2419--2422).-Wlien the oxides of yttrium a i d lanthanum are mixed wit!i powdered carbon and reduced in a carbon crucible in the electric arc, carbides of the formulaMC, are produced- The end of the reduction is rendered evident by tlie appearance of flames, ayising from the vapour of the metal, which show a very brilliant spectixm, in which the most conspicuous lines are reversect. The carbides are crystalline and brittle, and have n golden yellow colour when freshly broken, but the surface is almost as rapidly at- tacked by the mcisture of the air as a fresh surface of metallic sodium, a thin grey layer of oxide being formed.They are deconi- posed by water with evolution of hydrogen aild carbnretted Lydrogeii, the hjdroxide of thc metal and graphitic carbon being deposited. Yttrium carhide has the sp. gr. 4.185, whilst that of Inratlzaimm carbide is 4.718; both of thc:e carbides contain 2-3 per cent. of graphitic carbon, wliich has not been included iii tlie conipositioir on which the formula is based. Draiyings are given of the simple electric furuace employed. A. H. Crystallised Anhydrous Manganese Sulphide. By A. MOURLOT (Compt. rend., 1895, 121, 20%--203).-W hen well dried. amorphous mairganese sulphide, mixed with a small quantity of s u l p ~ ~ u r , is subjected to the action of an arc from a current of 4U. ampAres and 20 volts for about 20 minutes, the upper part of tho fused mass, after cooling, is distinctly crystalline.With inore powerful currents, the sulpliide does not crgstallise so well. The26 ABSTRAOTS OF OHEMIOAL PAPERS. action of carbon bisulpllide and hylrogen snlphide a t a high tempera- ture on manganese prepared in the electrical ftirnace yields the amorphous sulphide only. The crystallised sulpliide is in the form of small, transparent, deep green octahedra, which have no action on polarised l i a h t ; sp. gr. = 3-92, hardness = 3.5 to 4. The fused sulphide is sufficiently hard to scratch qnartz ; sp. gr. = 4%6. The crystallised sulphide, prepared in the manner indicated, is identical in composition and physiFa1 properties with ulabandine ; i t has practically the saine chemical properties as the amorphous sulphide, but is less readily attacked by reagents.Fluorine has no action on it in the cold, but attacks it below a red heat with incandescence and the production of white fumes. Hydrogen is without action on the aulphide a t 1200°, and carbon does not reduce it under the influence of an arc from a current of 1000 amperes and 50 volts. C. H. B. Compounds of Ferrous Chloride and Nitric Oxide. By V. THOMAS (Compt. rend., 1895, 121, 204- 206).-The three compounds of ferrous chloride and nitric oxide (Abstr., 1895, ii, 271) have no appreciable tension of dissociation at the ordinary tenipernture either in a vacuum or in a current of a carefully dried, inert gas. Water dissolves the cornpourid, Fe2ClJ,2NO, without any evolution of gas, and no gas is evolved if the other two compounds art; added to a large proportion of water; but if water is allowed to drop on the solid compounds, gas is liberated in large quantity.Potassium hydroxide or ammonia behaves similarly with all three compounds, and produces a grejish-white precipitate which rapidly becomes bluish-green and, finally, black. There is no liberation of gas, and the liquid contains neither a nitrate nor a nitrite, nor ammonia; the solutions obtained by Gay's methods (Abstr., 1885, 1109), on the other hand, erolre large cliimtities of a mixt,nre of nitrous oxide and nitrogen. When the black precipitate, produced by alkalis in solu- tions of the Eolid compounds, is placed in a vacuum, it gives off a considerable quantity of almost pure nitrogen. If R solution of the compound Fe2C14,2N0 is precipitated with silver nitrate, there seem to be indications of the formation of silver hyponitrite ; but this sup- position could not be confirmed, and the phenomena are not shown hp the other two compounds.Nitric oxide is only very slowly absorbed by solutions of the compounds Fe2C14,N0 and 5Fe,C14,N0, and seems to act as an oxiclising agent. C. H. B. Ammonia and the Chlorides of Iron. Ey ALFRED S. MILLER (Arne?. C'lienz. J., 1895, 17, 570-571).-Anhydrous ferric chloride will absorb 6 mols. of ammonia, forming the cornpound FeC1,,6NH3 at ordinary temperatures ; five mol. are retained i n a perfectly dry atmosphere at the ordinary temperature, but a t 100' the compound becomes FeC1,,4XHB. The ammonia compound ia not deliquescent, and is insoluble in water, b u t loses ariimonia and chlorim when mashed ; it dissolves i n mineral acids, yieldiug red solutions.The compound showed a gradual dissociii tion ( s i c ) with formation of ammonium chloride, from 100° to 280' ; just below 280°, it was entirelyINORGANIC CHEBlIST BY. 27 dissociated. The compound absorbs dry chlorine with a considerable deyelopment of heat. Ferrous chloride absorbs approximately G mols. of ammonia at the ordinary temperature, forming a white powder, k'eC12,6h'H3, which readilj oxidises in air. Wherr heated at 100" in hydrogen, the com- pound became FeCI2,2NH,. Chromium Sulphate. By ALBERT RECOURA (Ann. Chim. Phys., 1895, [7], 4, 494--327).-This paper is mainly a re'sume' of work pre- viously published elsewhere (compare Abstr., 1891, 1430 ; 1892, 411 and 783; 1893, ij, 4iO and 528 ; 1894, ii, 382).It is shown that when a solution of the violet chromium sulphate is heated for some time at loo", i t becomes green, and that the solu- tion then contains free sulphuric acid and a basic salt formed accord- ing to theequatioir ~ C I - ~ ( S O * ) ~ + H20 = Cr,O(SO,), + HzS04. The salt thus formed is the sulphate of a radicle [Cr,0(S04)4](OH)2, which the author terms suZphochromyZ hydroxide. The violet sulphate, Cr,(S04)3 + 18H20, when heated to 90' loses water, and gives the compound Cr2S,Ol2 + 8H20, which is neither a sulphate nor yet a chromium salt. The same compound may be obtained from a solu- tion of the violet salt ; it is characterised by the ease with which it unites with 1, 2, or 3 mols of sulphuric acid or of a metallic sulphate, thus giving rise to the chromosulphuric acids and the chromo- sulphatea.Under special conditions, this compound can also unite with 5 or 6 mols. of sulphuric acid, yielding compounds with quite distinct constitutions and properties. The latter cowpounds are much less stable than the chromosulpluric acids; they lose sul- phuric acid a t 140°, and jield sulphochromic hydroxide, A. G. B. This is an acid of chromium which is characterised by the insolu- bility of all its salts. J. J. 8. Molybdenum Dihydroxychloride. By AD. VAXDENBERGHE (Zeit. unorg. Chew., 1895, 10, 47--59).--The author has determined the molecular weight of molybdenum dihydroxychloride by means of the boiliiig.point and fieezing point methods with the object of de- termining its constitution. The compound is prepared by heating molgbdic anhydride a t 200" in a current of dry hydrogen chloride ; it sublimes in lustrous, white crystals, and, when dowly cooled, in beau- tiful, bright yellDw needles, and is very hygroscopic. The determination of the molecular weight by means of the boiling point method was pcxformed in a modification of Beckmann's appa- ratus, and the molecular weight calculated from the formula M=Kp/Zt. With ether and acetolie as solvents, the numbers obtained agree with the theoretical value, 217, assnming that the cornpound is an atomic compound of the constitution MoO(OH),Cl,, that is, the action of hjdrogen chloride oti molybdic anhydride is analogous to its action on sulpburic anhydride. With methylic and ethylic slcol~ols as solvents, a smaller molecular weight, was obtained corresponding with t.hat required i f the compound I S dissociated iiito iis ionq, C1 and MoO,H,Cl.28 ABSTRACTS OF UEiEMICAL PAPERS.The determination OE t,he molecular weight by the freezing point method, using anhydrous acetic acid, gave results a.greeing with the numbers obtained with methylic alcohol by the boiling point method ; with water as tho solvent, however, numbers were obtained closely approaching 54.2, which is the number required, assuming that the compound is dissociated into the ions C1, CI, H and O:Mo*OH*O. The author has attempted, wifhout success, to determine tJie vapour deDsity of the conipound; it is already dissociated a t 15So and 181'.E. C. It. Molybdenum Bronzes. By ALFRED STAVENHAGEN and E. ENGELS (Bey., 1895, 28, 2280-2281).-When acid sodium molybdftte, Na6Moi02$, is fused find submitted to electrolysis, a substance is formed which crystallises i n quadratic prisms of a deep blue colour. It is insoluble in hjdrochloric acid, but dissolres in aqua regia and in alkalis. The substance contains 6 per cent. of sodium acd 62.7 per cent. of molybdenum, and is looked on by the authors as a sodium molybdenum bronze. A. H. Preparation of Tin Tetrachloride in large Quantities. By RICHLRD LORENZ (Zeit. ano?g. Chem., 189.5, 44-46).-Tin teti.3- chloride is most easily prepared by the action of chlorine on tin at the ordinary temperature. The most suitable apparatus is a tube closed a t one end, 5 to 6 cm.wide, anti 75 to 100 cm. long, fitted with a condenser and a tube, by means of which dry chlorine can be passed to the botlom of the tube, where it bubbles throngh a little tin tetrachloride. The tube is filled nearly to the top with granulated tin. 14 to 2 kilos. of the tetrachloride are easily prepared in about one hour. The product is pure, and boils at 114". E. C. R. Chemistry of the Cyanide Process for the Extraction of Gold from its Ores. By GEORGE A. GOYDER (Chem. Neuts, 1895, 72, 80-&2, 95--97).--1'ho amount of simple cyariide iu a solution con- taining certain double cyanides, such as the ziuc potassium cyanide in the final solution of the cjanide process, cannot be accurately estimated by titration nith standard silver nitrate in the presence of a littole potassium iodidb, because the final reaction is indistinct, nod, moreover, an amount of silver nitrate is used up by these double cyanides, which increases continuously with the temperature, with the amoiint of fresh simple cyanide added, and with the dilution. The author has observed that hydrocyanic acid does not decolorise phenolpht halejin, that potassium cyanide is alkaline to it, and that the double cyanides are neutral, and on t h i s has based the fallowing method of testing the final liquors for simple cyanide, which, how- ever, is not applicable in the presence of caustic alkalis or alkali carbonates ; alkali hydrogen carbonates do not interfere.100 C.C. of the solution is titrnted with decinormd hydrochloric acid, using 1 C.C. of 0.05 per cent. solution of phenolphthalein as indicator, 1 C.C. of acid = OtJOci5 1)er cent. of potassium cyanide. The estimation of all the cyanides, except the iron, mercury, or copper potassium cyauidte, mi19 be eflected by the silver nicthod i f the solution beMISERALOOIOAL CHEMISTRY. 29 mixed with half its volume of 5 per cent. caustic soda, filtered, and about 15 C.C. of the filtrate taken for titration. The following are the numbers per cent. obtained from the analysis of the final solution from the treatment of the Mount Torrens ore by the cyanide process. C u 0*0030, Z n 0.0178, Fe 0.0061, Ca 0.0145, Mg 0.0042, K 04609, Na 0.0645, C1 0.0875, CN 0-04i7, SO, 0.0401, CO, 0.0333, and traces of Co, Hg, Ag, and Au. Numbers, too, are given showing how the progress of the extraction may be followed by observing the- strength of the outflowing solution. Data are also furnished showing that without further comminu- tion little or no gold can be extracted by potassium cyanide from the tailings. Furthermore, i t is shown that hydrocyanic acid in the presence of air, aid the double cyanides of zinc and potsssium and of copper and potassium exert a solvent actionon gold, but that the cor- responding mercury salt does not'. Allowing one lot of cyanide solution to drain away from the ore undergoing extraction before adding a fresh lot m-as found to be destructive to the cyanide vithout commen- surate benefit. The destructiveness of ferrous and othcr soluble metallic salts is commented on. D. A, L.

ISSN:0368-1769    

DOI:10.1039/CA8967005017

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

MISERALOOIOAL CHEMISTRY. Miner a l o g i c a l Chemistry. 29 The Crystalline Form of chemically simple Substances. By XIXEDRICH RIKNN (2eit.physikaZ. Chem., 1895,16,529-545).-Retger3 has pointed out that most elements and diatomic compounds, as well as many triatomic compounds, crystallise either in the regular or i n tho hexagonal system (Abstr., 1894, ii, 348) ; he has, however, failed to recognise any further relation between this chemical simplicity and the crystalline form. The author finds, however, that such substances Leloriging to the hexagonal system fall into three groups, each char- acterised by similarity of crystal angles and habit,. (1) The mag- nesium type with a : c about 1 : 1.6, arid of hexagonal symmetry; this group includes zinc oxide, ice, tridymite (SiO,), gFeenockite (CdS), niccolite (“As), lead igdide, &c.(2) The arsenic type with a : c about 1 : 1.3, aud of rhombohedra1 symmetry ; this includes bismuth, sulpliur, tellurium, zinc, graphite, millerite (NiS), &c. ( 3 ) The quartz type with a : c about 1 : 1.1, and also of rhombohedra1 sym- metry; cimmbar falling in tliis group. Of elements and simple compounds belonging to the tetragonal system, an a-tin type and a rutile hype are distiuguished on the same lines. Some less simple compounds and also some pseudo-hexagonal substances can be referred t o these types. Retgers’s criticism of the author’s views (Zeit. physikal. Chem., 14, 522) are discussed. Silver Minerals of the Australian Broken Hill Consols Mine. By GEORGE S h i i m (Jou.1-n. and Proc.Roy. SOC., N.S. W., 1893, 27, 36&--375).--This mine, which is very rich in silver minerals, is where the new mineral willyamite (this vol., ii, 31) was found. L. J. S.30 ABSTRACTS OF OHEMICAL PAPERS. Dyscrasite occui's in large masses, sometimes weighing 23 cwt. and containing 80-83 per ceut. of silver ; the more common proportions of silver and antimony in this ore are AgjSb, Ag,Sb, Ae6Sb, Ag,?Sb. drgetatite is rare; a typical impure specimen gave $8 per cent. of silver. Stephanite occurs only in small -quantity, a specimen of SIP. gr. Pyrargyrite, amorphous, gave 56.3 per cent. of silver. Sternbergite occurs with dyscrasite and pyrargyrite, i t is of a bronze colour, with a blue tamish ; sp. gr. 4.34; it gave 33.94 Ag, 30.76 Fe, and a little antimony.Stromeyede is the principal ore of this mine ; i t is never crystalline ; contains about 30 per cent. of silver, and often a little antimony. Argentiferous tetrahedrite is also an abundant'ore, it usually coiitains about 20 per cent. of silver ; the richer ore (in silver) is lighter in colour and brighter in Instre than the poorer. Brongniardite is very rare, i t occurs with stromeyerite ; the purest is crypto-crysta:line and resembles argentite ; it is encrusted with grey lead carbonate, irto which it has been altered ; it coutains 34i per cent. of silver. Antimonial silver chloride ; pure silver chloride and bromide are comparatively rare in this mine, the larger masses are always nnti- monial, of a grey colour and with about 35 per cent,. of silver. Some of the masses enclose veins of the ordinary chloride, and patches of djscrasite, from the latter of which the mineral has pro- bably been derived.Bourizonite is massive and impure, with 5 to 7 per cent. of silver, dne to admixture of argentiferous tetrahedrite. A sample of the ore gave 29.0 8 9 25.0 3.0 5.7 22.5 3.0 [ 9.91 Chlorargyrite gave 73.1 per cent. of silver. lodyrite is fairly plentiful, always occurring in limonite. Galena contains verging amounts o€ silver, and Bas 65 t o 83 per cent. of lead ; i t is often altered to anglesite, this being afterwards alt8ered to cerussite. Cerussite contains about 60 per cent. of lead; silver is also present, The vein stuff of the mine is calcite and siderite, which in the Copper ores only occur in small About 50 minerals are mentioned or shortly described, Lorandite, a new Thallium Mineral.BS J~ZSEF A. KRC 4 NNER (Math. 6s TermCszett. Ertesito, 1894,12,471, and Ber. aus,Ung., 1895 ; 12, 262).-This new and rare mineral occurs as tabular or short pris- matic, mono-symmetric crystals on renlgar at Allchar, Macedonia ; the colour is cochineal- to kermesite-red, and the crystals are trans- parent, and can be bent like selenite. Analysis gave s. As (calc. from loss). TI. 19.02 (21 *47) 59.51 6 2 3 gave 67.1 per cent,. of silver. Pb. Cu. Sb. Fe. dg. S. Insol. Moisture [by diff.]. Also Johnstouite ? uppar parts is replaced by limonite. quantity. amoagst them being vanadinite, volgerite, and native sulphnr. L. J. S . This agree8 with the formula TlAsS,. L. J. S.NINERALOQICAL CHEMISTRY.31 Composition of Hermesite. By HENRI BAUBIGXT (Compt. rend., 1894, 119, 737-74O).-Partial analysis gave Sh 75.13, S 20.04 per cent, This agrees with the formula Sb20S2, or 2Sb2S3,Sb203, which was deduced from the early analysis of H. Rose, the only one that has been previously made of the mineral. Tartaric acid solution had practically no action on the mineral. L. J. S. Willyamite, a New Mineral from Broken Hill, N.S.W.-By EDWARD E”. PITrMAN (zeit. Kryst. Min., 1895,25, 291 ; from Journ. and Proc. Roy. SOC., N.S. W., 1893, 27, 366-368).-This new mineral was found with dyscrasite in a calcite and siderite vein. The crystal system is regular, and there is a perfect cubic cleavage; fracture uneven. Colour between tin-white and steel-grey ; lustre metallic ; streak greyish-black.H = 5 i ; sp. gr. 6.87. Analysis by J. C. H. Mingaye, gave Sb. co . Ni. 5. Total. I. 56.85 13.92 13.38 15.64 99.79 11. 56.71 13-84 13.44 15-92 99.91 There are also traces of iron, copper, and lead. The formula is CoS,,NiS,,CoSb,,NiSb,, which corresponds with ullmannite in which half the nickel is replaced by cobalt. Calsverite from Cripple Creek, Colorado. By WILLIAM F. 11. J. S. HILLEBRAND (Amer. J. Sci., 1895, [3], 50, 128-131) .-Tellurium has been prerionsly known to occur in the ores of this district, partly in combination with gold as gold-tellurium (sylvanite). Annlyses of the present mineral were made on material from three mines, namely, Prince Albert mine, I ; Raven mine, 11; and C.O.D. mine, 111. Te. Au. Ag. Insol. Fe,O,. Fe. S.Total. I. 57-27 38-95 3-21 0.33 0.12 - - 99.88 11. 47.69 33.93 1.47 5.80 - 5.41 6.17 100.47 111. 53.89 39.31 0.85 0.91 - 1.67 1.58 - In 111 also Mn, 0.23 ; Ca, 0.51 ; Mg, 0.10 ; 0, F, and soluble silica by difference, 0.95. These analyses, after deducting gangue, reduce to the formula (Au,Ag)Tez ; the amount of silver, in analysis I, agrees with that in Genth’s analyses, but is less in IIand 111. The mineral is of a pale bronze-yellow colour, the powder being greenish-grey ; sp. gr. 9.00. The imperfect and deeply striated crystals of pris- matic habit seem, according to Penfield, to be asymmetric, but with angles and axial ratios near to sylvanite. Nantokite from New South Wales. By ARCHIBALD LIVERSTDGE (&fin. Hag., 1894, 10, 326---327).--This mineral was found as- sociated with cuprite, native copper, cerussite and quartz, at the Broken Hill South mine ; when freshly fractured, i t is colourless and transparent with a highly vitreous lustre.On exposure, the mineral soon effloresces and becomes green. Analysis, by J. 0. Armstrong and A. D. Carmichael, gave L. J. S.32 ABSTRAOTS OF CHEMICAL PAPERS. cu. c1. Total. Sp. gr. 64.28 35-82 100.10 4.1 The mineral is soluble in ammonia, hydrochloric acid, and in it solu- t,ion of sodium chloride ; when heated with water, cuprous oxide is deposited, and some copper goes into solution as cupric chloride. Artificial Percylite. By CHARLES FRIEDEL (Bull. SOC. fran. ilk., 1892, 15, 96-101).-By the prolonged action of copper chloride aolution on lead hydroxide, a blue, crystalline powder was formed ; this consists of strongly birefringent tetragonal octahedra, having the characters of the tetraqona.1 variety of boieite (Abstr., 1892, i, 123), and also, in much smaller quantity, of cubic crystals corresponding with the cubic variety of boleite.Analysis of the material agreed with the formula PbCI*OH,CuCl*OH, and the name percylite is here giren (apparently to both kinds of crystals), t o distinguish it from the silver-holding boleite. [The first kind of crystals have since been named cunzengeite by Mallard, Abstr., 1895, ii, 115, and 1893, ii, 4171. Artificial Boleite. By CHARLES FRIEDEL (Bzdl. SOC. fran. ilfin., 2894, 17, 6-8).-A mixture of lead and silver hydroxides, in the proportion they exist in boleite, with some clay, was acted on by copper chloride solution for several months; the action was much slower than when cumengeite was formed (preceding Abstr.).In the clay were found Blue cubic crystals which were built up exact-ly like certain crystals of boleite ; having an isotropic cubic nucleus, surrounded by six truncated tetragonnl pyramids. The crJstals were too small in quantity and too impure for analysis, b u t t'heg certainly differ from those formed without the intervention of silrer. Boleite from New South Wales. By ARCHIBALD LIVERSIDGE (Jozcrn. and Proc. Roy. SOP. N.S. W., 1894, 28, 94-96).-This mineral occnrs a t the Broken Hill Sout8h mine with hematite and quartz ; i t is of an indigo-blnc colour with a strong vitreous lustre, and is foiind as cubes with a nearly perfect cubic cleavage.Analysis by Car- rnichael and Arms trong gave 0 H20 L. J. S . Phosgenite mas also formed by the above reaction. L. J. S. L. J. S . Ag. Pb. Cu. C1. (calc.). (calc.). Total. Sp. gr. 8.25 47.20 19.20 13.50 [6*10] C5.441 99.69 5-08 This agrees closely with the analysis of Mallard and Cumenge Liversidge determines the water directly as Rubies of Burma. By C. BARRINGTON BROWN and JOHN W. JUDD (Proc. Roy. SOC., 1895, 57, 387--394).-The famous ruby dis- trict of Upper Burma is situated 90 miles N.N.E. of Msndalsy, the principal mining centre being Mogok. The gneissic rocks of the district are of intermediate chemical composition, including biotite- gneiss, biotite-granulite and rarely biotite-schist ; interfoliated with these are more acid rocks, such as pegmatites, qiirzrtzitcs &c., also (Abstr., 1892, i, 123).6.39 per cent. ; this may be a little too high. L. J. S.XIXERhLOGICXL CIIEJIISTRY. 33 more basic rocks, such a s pyroxene-gneiss &c., these passing into ultra-basic pyroxenites, mid thirdly bands of ci*ystalline limestone. I n the acid rocks, tourmQline occurs, as in the adjacent rubellite district or Nyonngouk ; thc ba-ic rocks are rich in garnet, and in the lime- stone corundum and spinel of various colours occur. The limestoiles are more closeiy associated with the basic and ultra-basic rocks, which contain crystals of calcite, and, :is the amount of calcite in- creases, they graduate into the limestones ; i t being supposed that the limestones have been derived by the alteration of the basic felspars (anorthite) of the basic rocks.The liydrated aluminium silicates, liberated by the same alteration, having in the first place given rise to hjdrated aluminium oxides, which are afterwards converted into anhydrous alumina. In the limestones are also found numerous other minerals, such as phlogopite, gmphite, pyrrhotite, felspars (moonstone), nmphi boles, spyroxeiies, 1 apis lazuli &c. The subsequent alteratlion oE the rubies is seen as an inner zone of cliaspore passing outwards i n to various hydrous aluminium silicates- margsrite, vermiculite, mica, knolinite &c. ; these changes taking place along the primary and secondary solution planes, o r planes of chemical weakness, or‘ corundum (Judd, Jli?~. ,Mag.: 1895, 11, 40). Cerussite coated with Galena ; Manganite and Chloritoid from Michigan; Apatite and Hessonite in Pegmatite.By WILI.IAII 13. HOBBS (Amcr. J . Sci., 1895, [3], 50, 121-128).- Cerzissite in twinned, prismatic crystals, from near Missouln, Montana, was partially coated witli an extremely thin, bright film having a metallic lustre. Analysis gave PbO. C02. Fe,O,, Al,O,. SO2. S. Total. 80.83 15.51 0-55 2.15 trace 99-04 L. J. S. ----A The trace of sulphur and excess of lead indicate that the film coiisists of galena. As this tilm is only found on the cerussite, and not on the accompanying minerals, i t may be considered to be due t o the alteration of the cerussite, probably by the action of hjdrogen sulphide. From the parts of the crystals, so coated, gooil rnessnrements of the angles were obtained.Xu:7gmzite, from Lucy 111 ine, Nepaunee, Michigan, gave on analysis >In. HzO. BaCO,,CaCO,. MgCO,. 0 (calc.). Total. 60.29 10.10 0.58 2-98 26.35 100.30 The crystals are simple in form, but the habit wries slightly according as they are associated with barj-tes or not. The Sarytes is described. Chlorituid, as large porpliyritic crystals, occurs in blocks of phjl- litic schist on the south shore oi Michignmme Lake, Michigan ; in the rock also occur colourless mica, biotite, tourmaline, magnetite, and some small klades of chloritoid. The chloritsid crystals, some- times 6 cm. or inore across, are liexagonal in outline and tabular paidlei t o the base, and a1.e frequently twinned. The analysis, which was made on a crjstal enclosing magnetite, tl:is being mi’- TOL.LSY. i i . 434 ABSTtcACTS OF OHEMICAL PXPIFRS. rounded by a zone of quartz, is near1.y the same as that of the maso- nite of Natic, Rhode Island. SiO:. 6 1 2 0 3 . Fe203. FeO. NgO. C,tO. H20. P,05. Total. 3Fi.58 29-53 5-85 22.3s 0.76 1.38 5-94 trace 101.36 From the optical characters, the ci-ystjals seem t o be mono-symme- tric or aspimetric, with a close approach to the formcr. Apatite and Hessonite occur in the pegmatite veins cutting the gneiss about Canaan, Conn., along with other crgstallised minerals, such as white felspar and muscovite in large crystals, biotite and tourmaline. The cinnamon-coloured garnet is sometimes intergrown with felspar, producing a structure resembling graphic granite. The apatite is green in colour. L. J. S. Analysis of Monazite.By ALRER'I' THORPE (Chem. News, 1895, 72, 32).-Analysis of monazite from North Carolina gave P,O,. L R , ~ , . Ce203. Tho,. SnO,. X n 0 . CaO. Totnl. 28-43 23.62 25.98 18.01 1.62 1.33 0.91 99.90 L. J. S. Evansite from Tasmania. By HENRY G. SMITH (,Jozwra. and PTOC. Roy. Soc., N.S.W., 1893, 27, 382--.383).-This mineral occurs at Mount Zeehan, as Emall, globular excrescences, which are colonrless and of a vitreous lustre, or milky white and slightly opalescent. Brittle ; H = 4 ; sp. gr. 1.842. When heated, it, decrepitates, and gives off water, which, i n being alkaline (probably duc to sodium), differs from the original evansite. H,O. A1203 P,O,. Total. 41.266 40.186 18.114 (mean of 17.996 and 18.23'2) 99.566 This agrees with the usual formula 3A1,03,P205,18H20.The per- Tectly glassy beads contain neither fluorine, silicon, nor iron, but the A Bed of Aluminium and Potassium Phosphates in Algeria. By ADOLPHE CARNOT (Compt. rend., 1895, 121, 15 I--155).--The floor of a stalactitic cavern near Oran, in Algeria, is covered with a deposit, from 1 to 3 metres thick, of a brownish-red phosphatic earth, with white and variegated veins and spongy masses. The cavern and the deposit contain no bones of vertebrata. The white matter consists chiefly of aluminium phosphate mixed with a variable proportion of silica, and sometimes of calcium phosphate ; when red, it contains ferric oxide, and, when black, manganese oxide or cobalt oxide. The light, rounded, unctuous, agglomerated masses show no traces of crjstalline structure, and are to a large extent soluble in dilute acids and in ammonium citrate solution.One specimen had the composi- tion P20, 35.17, A1203 18.18, K20 5.80, NET, 0.48, CaO 0.31. SiO, 11.60, loss a t 100' 15-40, loss at 100-180' 10.55, loss at 180" to a red heat 4.35 ; MgO, F, C1, SOs, traces. Total = 99.841. I f the aluminium phosphate is supposed to be the normal salt, the ratio of the remain- i n g phosphoric acid t o the other bases is intermediate between that Aoalysis gave white, opaque, cellular portions are very siliceous. L. J. s.\IISKlthLOGICAL CLIEWISTKY. 35 of mnno~uet;~lli'c '1 :id hiilietallic phosphates, a n d tlie aqueous solution of the phpsphates is iieiitral t o b(*th methyl-orange and phenol- phthaleYn. The phob:ph,zte does not belonq to the same class as Gautier's mi?zcrt.ite (Abstl.., 1893, ii, 536, 577), and the author does not assign to it any defiiiits formula.It is most probable, howeyer, that the deposit has bem formed by the infiltration of water contain- ing ammoniiim phosp1l;zte. &., clerivetl from the oxidation of organic m:tttcr and phosphatcs of animal or vegetable origin, and also nlu- ininn derived froin mineral.; (lor. c i t . ) . Retzian. By 8. A. HJALMAR SJOGREN (Bull. Qeo?. In.st., Upsala, 1894, 2, 54--59).-This new srserinte occurs as orthwhombic crystals in the cavities of the manqanifcrous limestone of the Moss mine, Nordmavk, Sweden. It is o€ :L chestnut- to chocolate-brown colour ; lustre v:treous, xppromhing to greasy ; su\)translucent. There ia no cleavage. P1ec:chmisrn strong.Sp. gr. 4.15. The analysis is incom- plete owing to lack of material ; a constituent (amo:mtir,g to 10.3 per cent.), separated from the mangnnew precipitate, not, having been i dent i fi ed . As205. PbO. FeO. MnO. CsO. MgO. QiO?. H,O. Insol. 24.4 0.2 1 7 30.2 19.2 2.7 0.5 8.4 4.3 The mineral is thus closely related t o ot!ier hydrous manganese arsenates (allactite, syndelphite, dindelphite, hzm,zfibrite) from the same mine, and to fliiikite from the Harstig mine, Sweden ; none of these, however, contain any calcium, and some of them contain Mn203. Artificial Ggpsnm. By ALEXANDRE GORGEU (BulE. SOC. fran. Mh., 1894, 17, 8-9).-A flask containing calcium sulphite and filled with an aqiieous solution of sulphurous acid was corked up; after several years n part of the sulpliite was oxidisecl, and beneath the deposit ; i t tho bottom of the flask were thin crystals 1-3 cm.long. These at, the attached ends were opaque owing to enclosed sulphitc, but the transparent portions of the crvstsIs contained no sulphnrous acid, and on ignition lost 20.8 per cent. of water ; they showed tht: usual cleavage, twinning &c. of gypsum. Leadhillite Pseudomorphs in Missouri. By WARREN M. Foom (Amer. J. Sci., 1895, [:3], 50, 99--lOO).-Leadhillite has recently been described from Granby, Mo., by Pirsson and Wells, (Abstr., 1894, ii, 458). The pseudomorphs with the form o f scaleno- bedra of calcite consist often of cerussite, but sometimes of lend- hillite, either as epimorpbs o r replacing the whole of the calcite. Pure white leadhillite also occurs in the form of cubes after galena ; but i n most cases thc galena is represented by crusts and hollon- forms of a grey amorphous material, t h i s consisting of leadhillite con- taining some galena.Scattered through some crystals of Ieadhillite are to be seen the bright cleavages of galena. C. 13. B. L. J. S. L. J. S. IA. J. s. Kauaiite, a new mineral from Hawaii. By EDWARD GOLDSMITH 4-2 (Proc. Acad. Nut. Sci., Philadelphia, 1894, 105-Mi) .-T his vdcaiiic product is white or faint cream co'oured, and is Cull and powdery36 ABSTRACTS OF CHEJIICAL PAPERS. closely resembling clialk in appearance. Under the microscope, it is seen to consist of granules all of aboiit the same size, and it is pale blue by transmittent light ; sp. gr. 2.566.When heated, it decrepitates slightly and becomes dark g i ~ y , giving off an oily substance and acid water ; it becomes intensely incandescent before the blowpipe. It is soluble in acids only aEter ignition, but is dissolved by caustic alkali. Eliminating about 5 94 per cent. of carbonaceous matter, the results of the analysis are A1,03. K20. Na,O. &O. 803. 3979 7-37 1-72 33.56 17.55 This gives the formula 2A1,O,,3(K,Na,H),O,SO3. This highly basic sulphate is distinguished from others in being insoluble i n acids. Melanterite containing Zinc. By MOPOLD NICHEL (Zeit. IZrysf. Nin., 1895, 25, 316 ; from Bull. SOC. f r a n . Min., 1893, 16, 204).-- Massive, pale green concretions of melanterite from Laurion, Greecc, gave on analysis so,. PeO. ZnO. H,O. Total. 28-85 17.74 8.92 44.21 99.72 Formula (Fe,Zn)SOd,7H20.Sp. gr. 1.95. L. J. S. Artificial Powellite. By L~~OPOLD MICHEL (16~11. SOC. fran. Miu., 1894,17, 612-614).-0n heating to a high temperature a mixture of six parts of sodium molybdate, one of sodium tungstate, three of calcium chloride and two of sodium chloride, transliicen t, milky-white c~ystals of poweliite were formed ; these have the form of tetmgoiml octahedra, and are about 2 mm. i n diameter ; they have an adamantine lustre and are optically positive. MOO,. WO,. Ca. Total. sp. g’’. 62.37 10.23 26.41 99.01 4.62 L. J. S . Analysis gave L. J. S . Pirnelite and Asbeferrite. By EDWARD GOT~DSJIITH (Zeit. ILr!yst. JIin., 1895, 2.5, 281 ; from Proc. Acad. Nut. h‘ci., Philadelphia, 1893, 174--175).--PimeZite occurs as a soft, greasy, rery finely rnicaceous mineral of apple-green colour at Radnor, Delaware Co., Penn.; sp. gr. 2.596 ; given as probably mono-symmetric. I t is decomposed by boiling hydrochloric acid, leaving 31.1 per cent. of insoluble sandy material. The soluble part, which i q supposed t o be pimeiite, gave analysis I, from which the formula (Mg,Ni,H,)O,SiO, is derived. SO2. MgO. NiO. B20. Fe,O3 CnO. Mn. I. 45.93 34.44 7.69 1l.W - - - 11. 48.43 6.23 - - 33.90 ll.SO trace .Asbefer~ite occurs as a secondary product, mixed with pyrites and on calcite, at the iron mine near the Falls of French Creek, Chester Co., Penn. ; it is of a greyish-green colour, and consists of fine fibres matted together. Analysis I1 differs considerably from Igelstrom’s analysis of asbcferritc.On heating, the mineral becomes a rusty col o ur. I;. J. X.?rIlNERhLC! 3TCAL CHEMISTRY. 37 Felspar of the Acmite-trachyte of the Crazy Mountains, Montana, By T. E. WorAw and RALPH S. TARR (Zeit. Kq-yst. lVin.7 1895, 25, 281 ; from Bull. Nus. Cony. Zool., Huwad Coll., 1893, 16, No. 12).-The acmite-trachyte of this locality occurs as dykes, and contains felspar, Egirine, and sodalite in a ground mass of felspnr, aegirine, and either nepheline or analcite. The optical extinction angles and the composition of the large felspar crystals point to soda-microcline or anorthoclase ; analysis gaye Loss &02. A1203. CsO. SrO. BaO. K@. Nn20. ( 0 , O ) . Total. 62.31 22.63 0.63 0.57 0.77 4.79 7-68 0.72 100.10 L. J. S. Analyses of Sodalite from New Localities.Ry L. McI. EUQITER and G. J. VOLCKENNG (Anzer. J. Xci., 1895, [3j, 49, 465- 4fi6).-Under I is given the analysis of massive, cobalt-blue sodalite from the Laurentian system at Hastings Co., Ontario, Canada; the mineral shows a very distinct cleavage, and in thin section there are a, few cloudy patches due to decomposition. A similar specimen from the Urnls gave analpsis 11 ; in thin section a very perfect cleavage is seen, with commencing decomposition along the cleavage cracks. Anotber similar specimen from Congo State, Africa (111), showed in section only an imperfect cleavage and some decomposition; it is associated with limonite and decomposed felspar, and is the only known African occurrence cf the mineral. SiO,. Al,G,. CaO. Na20. K20. C1. Total. 0 = C1.Sp.gr. I. 37-34 31.25 0.38 25.01 0.74 6 79 101.51 1.53 2.303 11. 37-28 31.60 0.46 24.74 0.93 6.65 101.66 1.50 2.328 111. 37.85 30.87 0.51 25-43 0.22 6.46 101-34 1-46 2.363 L. J. S. Constitution of the Lithia Micas. By FRANK W. CLARKE (J. Anzer. Cliem. Xoc., 1893, 15, 245-250).--The micas have been con- sidered by Clarke to be derivatives of the normal aluminium orthosili- cnte, Al,( SiO,), (Abstr., 1190,460) ; in the lithia micas, however, there is an oxygen ratio lower than that of the orthosilicate, and they are further charecterised by the presence of fluorine. The lower oxygen ratio is explained by the partial replacement of SiO, by Si308, and the fluorine, which was previously explained by the presence of the group AlF, among the components of R', is now explained by assum- 0 ing that the clintonite type, R"<O>A1*Si04R's, is replaced by the molecule AlF2*Si04Rf3.In polylithionite, SiO, is entirely replaced by Si&, and Lorenzen's analyses may be represented by 5(AlF2,Si30eLi3) + Al(Si30a)3(Na2K)3. All the variations in composition of the lepidolites proper may be explained by the supposition that thc-se micas are mixtures of two tFpical molecules, namely, AIFz*Si3OaR,, where R' is principally lithium, and a muscovite molecule, Al3(Si04),R',, in which Rr3 may be K2H o r KH, ; some peculiarities are explained by a small admixture of the molecule AlE'2.Si308Al. Cookeite, which appears to be the38 ABSTKACTS OB’ CEENICAL PAPEHb. vermiculite of the lepidolite series, lins the fluorine replaced by hydroxyl, and we have a mixture of the three molecules, Al( OH),*SiO,Li,, A1(OH),*Si04H,, and A1 (OH),*SiO,AI.In the iron-lithin micas, zinnwaldite and cryophyllite, the case is more complicated, as the iron may belong to the molecule AIF,*Si,O,Fe” R‘, or to the biotite molecule Alz(Si04)YFo”2Rf2. Sornc zinnwaldites may be represented by mixtures of AlI?,*Si,O,FeLi and hl,(SiO,),K,, whilst cryophyllite is moat easily represented by AldX3KHz + 2( Al,X3Fe2H2) -I- 3 ( h i F,.XK,) + 4 (A1 F2*XLi3 j , in which X represents SiO, and Si30s in the ratio 1 : 3. Garnet from California. By FRANK W. CLARKE (Amer. J . Sci., 1895, [3], 60, 76--77).-A water-worn pebble, found 40 miles south of Los Angeles, closely resembled jade in being highly polished, very compact, and of an apple-green colour ; analysis gave SiOz.Al2O3. Fe203. FeO. CaO. MgO. Alkalis. Ignition. Total. L. J. S . 37.S4 22.84 0.79 0.26 36-66 0.44 0.13 1-74 100.40 Also traces of TiO,, Pz05 and CO, ; sp. gr. 3.485. Hydrochloric acid extracts about 16 per cent. of A1203, and about 20 per cent. of CaO. As a grossular garnet simulating jade, it is of interest. Almandine Garnet from the Hawkesbury Sandstone, Sydney, N.S.W. BYHENRY G. SMITH (Joum. and PTOC. Boy. &c., N.S. W., 1894, 28, 47-50) .-“ Precious Garnet, ” OCCUTS as sniall, irregular, reddish particles in a conglomerate (probably derived from granile) in the Hxwkesbnry sandstone. The colour is light, but sometimes deep red or purple; the mineral is isotropic, and shows a distinct cubical cleavage ; sp. gr. 3,902. Analysis gave L.J. S . Si02. A1203. Fe203. FeO. MgO. Mii. Total. 38-iO4 21.795 2.168 27.750 9.725 trace 100 142 The sesquioxides are a little too high for the garnet formula. L. J. S. Analysis of Anorthite from Raymond, NIaine. By WILLIAM H. MELVILLE (Bull. U.S. Geol. Survey, 1893, No. 113, IlO).-White crystals associated wit,h idocraae, cinnamon garnet, pyroxene, and scapolite; gave, on analysis, 43.13 30.95 1.04 19.71 0.31 1-29 0-69 0.22 2.80 100.14 Also traces of FeO, Mi10 and Li,O. H,O Lorson Si02. A1203. Fe20s. CaO. MgO. K20. Na,O. (at 100’). ignition. Total. L. J. S . Analysis of Prehnite from Fassa, Tyrol. By EDWARD A. SCHEEIDER (Bull. V.S. Geol. Survey, 1893, No. 113,ll2).-Tliis analysis was made in connection with the experiments noticed in the Abstract, 1892, 772.Si02. A1203. Fe2O3. CaO. (at 105’). (at 250-300”). ignition. Total. $3.32 25.50 trace 26.49 0.17 0.14 4.70 100*32 L. J. S. H2O H20 Loss on3fIKERALOQlCAL CHEMISTRY. 3 9 Analyses of BiLtite and Hornblende from Japan. By Busu- J I R ~ T<o,ro (Zeit. Xryst. iUiti., 189.5, 25, 687 ; lrom Joum. ColI. Sci., Itrip. Uw'c., !L'&t/G, 1893, 5, 225).--These minerals, from the amphi- bole- and biotite-granites, are described in a paper on the Archean formation of the Abukuma Plateau. The biotite (1) is dark brown, arid almost opaque, and is nearly optically uniaxial ; Hicia's analysis shows i t to be lepidomelane. The hornblende (11) is bluish-gresn in colour, and with ouly feeblc pleochroism. SiO,. Al,O,. FeO. CaO. MgO. Mn,O,. N%O. K20. Total. J. 36.60 l i - 0 5 21-23 trace 10.36 0.70 5.39 8.49 99 88 11.45.61 4.47 8.94 26.40 11-44, - 2.26 0 79 99.89 Analyses of Ottrelite, Pyroxene, Garnet, Epidote, Scolecite, and Xenotime. By L. G. EAKINS (Bull. U.S. Geol. Survey, 1893, No. 113, 11 l-l12).-0ttrelite (I) from the Ottrelite-plryllite rock occurring a t Liberty, Frederick Co., Maryland. Pyroxene (II), Garnet (111), Epidotc (IV), Scolecite (V), all from Italian Peak, Gunnison Go., Colorado. L. J. S. I. 11. 111. I v. v. SiO, ....... 23-40 47.53 36-88 37-22 45.90 TiO, ....... 1.19 - Ai203.. ..... 39.31 9.8s 10.34 24.09 26.51 Fe,03.. . . . . . 5.14 1.i9 17.51 12.80 - PeO.. - 0.i9 - ...... 21.94 0.91 3InO ...... tracc trace - 0.1 1 CaO ....... trace 25.46 34.S5 23-36 14-17 MgO ....... 2.18 14.43 0.43 trace trace Ns,O ......0.20 trace trace 0.06 trace K,O.. ...... 0.20 F .......... PLUS ....... trace - - - - - - - - H-0,. ...... 6-81 0.30 0-21 1-61 13.79 - - - 0.06 - - - - - ___ ____--- 10ci.37 106-30 100.22 100.10 100.37 sp. gr. ..... - 3.312 3.721 3.452 9.247 Xenotime i i om the gold washings at Brindletown, North Carolina (Abstr., 1S94, ii, 54) ; gave, on analysis, (TEr),O, (1nol. wt. SiO,. ZrOp. UOz. Tho,. AlZO3. k'e,O,. (LaDi),O,. 260). (21-een.. .. 5-46 1-95 4.13 trace 0.i7 0.65 0.93 56.81 Brown.. . 3.56 2.19 1 . i 3 trace 1.57 2.79 0.77 55.43 CaO. P,O,. F. H20. Total. Sp. gr. 0.21 30.31 0.06 0.37 99-85 4-66 0.19 29.i8 0.56 1.49 100.06 4-46 L. J. S. AnalyL es of Nickel-iron sulphiae, Bauxite, Felspars, and Piedmontite. By WILLLUI F. H~LLEBRAXL, (Bull. U.S. Geol. Swcey,40 ABSTRACTS OF CHEMICAL PAPERS.1833, No. 113, 109-1ll).-A nickel-ii*ozt si~7phide from Worthington mine, 25 miles west of Sudbury, Ontario. Greyish with a cast of yellow. Not pyrrhotite ; possibly a mixture of pyrites and polydymite. coo Fe. Ni. Mn. S. SO,. (calc. froiu CaO). CaO. 338.36 4.57 0.10 45-11 0.95 1 *49 1.91 MgO. Insol. H20 (at looo). Total. 0.41 4.80 0.55 98.25 B a u x i t e from near Jacksonville, Calhonn Co.? Alabama ; I, red, Lime, magnesia and alkalis were not looked for. SiO,. TiO:. A1201. Fc20,. P,O,. (at loo9). (on ignition). Total. IT, white. H ?O H9O I. 10% 2.53 41.GO 25-25 tr,ice 0.65 20.43 100.11 11. 21.08 2.52 48-92 2.14 trace 0.45 23.41 98-52 Felspars from the pegmatite veins in the gneiss a t Julies' Falls, Baltimore, Rlaryland ; I, white albite, composition Ab4Anl ; IT, flesh coloured niicroclirie ; 111, greenisli microcline.These are described in Johns Hopkills Univ. Circulam, 1893, 12, 07. SiO,. Al,O,. Fe203. FcO. CaO. Da0. MgO. K20. X%O. I. 63.72 22.2% trace 3.58 - 0.06 0.76 8.98 11. 65.06 18.41 trace 0.26 0.13 0.04 14-30 1-60 HI. 68.48 16.11 0.20 0.17 0.23 0.05 0.03 12.99 1.27 L--,--J IT20 1I:O I n t 1tU@). (abore 100'). Total. I. 0.09 0.43 99.88 11. 0.04 0 2(i 100-10 111. 0.06 0.26 99.55 All these contain traces of strontium and litliium ; in I11 quartz Piednzontite from rhyolite at Piiie mountain, new Monterey was not wholly separated. station, Maryland ; contains a little admixed ynartz. XLO,. Si02. A1,0,. Cc,O,. (Mol. wt. 295). Fe,O,. Mn,O,. MnO. PbO. 47.37 18.55 0.75 1.28 4.02 6-85 1.92 0.14 H,O XI20 CuO.CaO. MgO. KzO. Na,O. LisO. (at 1OO'). (abore looo). P,Oj. Total. 0.11 15.82 0.25 O.G8 0.23 trace 0.14 1.94 t,r,zce 100.05 L. J. S. Basalt from Bondi, N.S.W. l3~- J. MIL?;): CCRRAN ( J o z w ~ . and Proc. H G ~ . Xoc., N.S. W., 18942, 28? 217-231).--This rock, which contains olirine, augite, plagioclase, magnetite, sodali te, apatite, mica aEd a glassy base, is easily gelatinised by hydrochloric acid, 56.4 per cent. being soluble, and the solution 011 evaporiition deposits numerous cubes of Eodium chloride. Calculated frcin t,he chlorine,MINERALOGICAL CHEMISTRY. 41 the amount of sodalite in the rock is 8 per cent., this requires 1.92 per cent. of soda; as the other minerals (felspars) containing sodium are only present in small quantity, some of the soda is supposed to exist in the glassy base.The fresh rock, of sp. gr. 2-94!, gave analysis I, and the decomposed rock 11. Si02. A1203. Fer,O,. FeO. CaO. MgO. Nn,O. K20. TiO?. I. 43.5 14.60 5.40 8.28 8-70 6-16 7-38 2.95 0.10 11. 42.0 40.2 trace - nil nil 4.4 1.6 - c1. HaO. Total. 11. - 12.00 100.2 chromic oxide. L. J. S. I. 0.37 2.50 99.90 I contains also traces of phosphoric acid, and I and I1 traces of Analyses of Leucite- basalt from Vesuvius. By Ar~~~1t-i’ THORPE (Chem. News, 1895, 72,53).-Analyses of leucite-basalt, from Vesuvius, gave SiOz. A1203. Fe2O3. FeO. MnO. CaO. MgO. K,O. I. 47.23 18.23 4.21 4.49 1-36 8.63 4.68 S.00 11. 47.32 18.00 4.23 4.31 1.42 8.51 543 7.92 NaaO. TiO,. P20,. Total. I. 2.63 0.25 0.31 100.00 11. 2.70 0.36 0.20 100.00 The sp. gr. of the rock varied from 2.653 to 2.721. L. J. S. A Tempered Steel Meteorite. By EDWARD GoLDsaiITlr (PTOC. h a d . Nut. Sci., Philadelphia, 1893, 373--3i6).--This meteorite, weighing 267 lbs., was brought From near Godhaven, Disko Island, Greenland, by the Peal-y Expedition of 1891; when received it appeared quite fresh, but i t s o m became cracked and fell t o pieces. These pieces were easily separated into hard metallic granules (73.8 per cent. of the whole) and a magnetic powder. Tbe grnnules were extremely hard and difficult to cut (no diamond w?s found), but on being heated and slowly cooled, they became soft,, hence the above title to the paper ; their composition is given as Fe. Ni. Troilite. Magnetite. Silicate. SF. gr. 66-79 2-32 0.52 25.96 4.41 6.14 Traces of carbon, phosphorus and chromium were found, but neither copper nor cobalt, which are found in tlie Disko terrestrial iron, together with more carbon than here. The composition of the powder is given as Fe. NiO. Fe203. Fe,0,,2S03. Silicate. II,O. Sp. gr. 25.58 0.31 56.30 4.28 10.10 3-43 4-73 The “ Fe304,2S03 ” is called “ magnetic sulphnte,” as the whole of the powder is stated to be magnetic. L. J. S.Occurrence of Fluorine in certain Mineral Waters. By Josg CASAIZES (Zed. anal. Chem., 189.5, 34, 546--548).-The sulphu- retted mineral waters of Lugo and Gnitiriz (Galicia, Spain) contain so much fluorine t h a t it can readily be detected in the residue of 500 C.C. of the water. Quantitative eslimations i n the Guitiriz water. gave, by Fresenius's method, 0.02344, 0.02806, arid 0.02277 gram of sodium fluoride per litre ; by Carnot's method (Abstr., 1892, 911), 0.0268 gram. A single estimation in the Lug0 water showed 0.0249 gram per litre. The author inclines to the belief that. the presence of fluorides in mineral waters is more general than is com- monlg supposed. M. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8967005029

出版商:RSC    

年代:1896

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J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS OF PAPERS ON PHYSICAL, INORGANIC, MINERALOGICAL, PHYSIOLOGICAL, AGRICULTURAL, ANALYTICAL CHEMISTRY. AND 8. E. ABISTRONGC, Ph.D., F.R.S. J. DEWAR, LL.D., F.R.S. WYNDHAM R. DUNSTAN, M.A., F.R.S. A, VERNON HABCOURT, M.A , F.R.S. F. 5. KIPPINU, D.Sc. R. MELDOLA, F.R.S. W. RAMSAY, Ph.D., F.R.S. W. J. RUSSELL, Ph.D., F.R.S- J. MILLAR THOMSON, F.R.S.E. T. E. THORPE, Ph.D., F.R.S. I W. A. TILDEN, D.Sc., F.R.S. dbitm : C. E. GROVES, F.R.S. Sub- Qbitm : A. J. ~BEENAWAP. C. F. BAKER, Ph.D., B.Sc. A. 8. BLOXAX. C. H. BOTHAMLEY. I T . 8. COLMAN, Ph.D. If. CROMPTON. W. D. HALLIBUBTON, M.D., B.Sc., A. HARDEN, M.Sc., Ph.D. L. M. JONES, B.Sc. L. DE KOXINOE. A. R. LINU. 0. FORSTEB, Ph.D. F.R.S. A. LAPWOBTII, 11.S~. D. A. LOUIS. N. H. J. MILLEEI, P11.D.w. J. POPE. E. C. ROSSITER. M. J. SALTER. J. J. SUDBOROUBH, Ph.D., BSc. J. F. THORPE, P1i.D. J. B. TIWOLE, Ph.D. J. WADE, B.Sc. 8. T. MOODY, L),8C. L. J. SPENCER, M.A. 1896. Vol. LXX. Part 11. LONDON: GURNEY & JACKSON, 1, PATERKOSTER ROW.. 1896.LONDON - I~ABREIOSON AND soifs, PRINTERS IN OBDINA~EY TO HER NIJESTY, ST. UARTTN’S LANE.C O N T E N T S . ABSTRACTS OF PAPERS PC'BLISHED IN OTKER JOURNALS :- Geizeral ctnd Plzysical Chemistry. CROOKSS (KILLTAN). Spectrum of Helinni . . . . . . RUNGE (CARL) and F. PASCREN. The Constituents of the Gas from Clkveite . . . . . . . . . . . DORN (E.) and HUGO ERDXANK". Argon and its Fluorescence Spectrum . KAYSEE (HEIKRICH). Blue Spectrumof Argon . . . . . CBOOEES ( WILLIAM). Spectrum of Remsay's Compound of Carbon and Argon.. . . . . . . . . . . EDER (JOSEF M.) and A. VALENTA, . YOUNG (JANES) and CAAELES R. DARLIN~. Transferring Gases to Vacuum Tubes for Spectroscopic Examination . . . . . RIGOLLOT (H.). Action of the Infra-red Rays on Silver Sulphide . . SKINNER (SIDNEY). The Clark Cell when producing a Current . . SKINNER (SLDNEY). The Tin Chromic Chloride Cell . . . . MORISOT. New form of Battery . . . . . . . LE BLANC (MAX). Thermodynamics of Galvanic Polarisation . . DEWAR (JAMES) and JOHN A. FLEXING. Thernioelectric Powers of Metals . . . . . DEWAR (,JAMES) and JOHN A. FLEMING. Electrical Resistance of Bis- KRAKAU (ALEXANDER). Electrical Condnctiriiy and Dissociakion Tension of Palladium Hydride . . * . . . . ). . 'TAXXANN (GUSTAT). Influence of Presmre on the Electrical Conduc- tivity of Solutions .. . . . . . . . . ;XAHLESBERG (LOUIS). Complex Tartrates and Alkaline Solutions of Copper and Lead . . . . . . . . . . HERROUX (EDWARD I?.). An Iodine Voltameter for the Measurement of Small Cur~ents . . . . . . , . . . . 'SCTHERLAND ( WILLIAX). Fundamental Atomic Laws of Thermo- chemistry . . . . . . . . . . . . VIOLLE (JIJLE~). A~ASSOL (GUSTATE) and GUILLOT. Specific Heats of Superfused FbrmiE acids: apparatus for the Determination of the Specific Heat of Superfused Liquids . . . . . . . . . . ~LSZEWSEI (KARL). Determination of the Critical and Boiling Tempera- tures of Hydrogen . . . . . . . . . , LINEBARGER (CHARLES E.). Some relations between Temperakres, Pressure, and Latent Heat of Vaporisat'ion . . . .. KUENEN. The Condensation and Critical Plien~mena of mixtures of Ethane and Nitrous Oxide . . . . . . . . . . 'LEYOULT (PAUL). Thermochemistry of Cyanuric Acid . . . . LEYOULT (PAUL). Thermoctieminstry of Alkali Cyanurabes . , . ~UINCHAFT (J.). Zfeats of Combustion of some @-Ketonic Ethereal Salts BOIJFFARD (A.). Heat developed by Alcoholic Fermentation . . . Different Spectra of Mercury. . . . . . . . muth at Low Temperatures . , . . . . . Specific Heat of and Boiling Point of Carbon 1-2 PAGl E ii, 1 ii, 1 ii, 2 ii, 2 ii, 2 ii, 2 ii, 3 ii, 3 ii, 3 ii, 3 ii, 4 ii, 4 ii, 4 ii, 5 ii, 5 ii, 6 ii, G ii, 7 ii, 7 ii, 8 ii, 8 ii, 9 ii, 9 ii, 10 ii, 11 ii, 11 ii, 12 ii, 12i v CONTENTS. TA3fMAAN (GUSTAT). Dependence of the Volume of Solutions on Pressure . . . . .. . . . . . . STORTENBEEER (WILLEM). Solubility of Mixed Crystals . . . TECLU (NICOLAE). Estimation of the Velocity of Chemical Attrnction . HOITSEMA (C.). Equilibrium in the System HgO-S03--H,0 . . THOMSEN (JULIUS). The Colour of the Ions, a Function of the Atomic Weight . . - . . . . . . . . . THOlCZSEN (JULIES). Sapposed Croup of Inactive Elements . . . HILL (EDWIN A). . RIJN (J. J. L. VAN). New Extraction Apparatus . . . . . GUYE (PHILIPPE A.) and B. ROSSI. Dissociation of Optically Active Salts in Solution. . . . . . . . . . . HAMBURGER (PRIEDRICH). Colour Change of Dilute Solntions of Potas- sium Chromoxalate . . . . . . . . . . WIEDEMANN (EILHARD) and G. C. SCHMIDT. Emission of Light by Organic Substaiices in the Gaseous, Liquid, and Solid Conditions . HOLBORN (L.) and W.WIEW. Measurement of High Temperatnres . LE CHATELIER (HENRI). Some Melting and Boiling Points . . . MAQUENNE &SON). Expbsion of Endothermic Gases . . , . MATIGNON (CAMILLE) and DELTGNY. Nitro-substitutions . . , VARET (RAOUL). Combination of Mercuric Cyanide with Bromides . KPAFPT (FBIRDRICH) and W. A. DYES. Distillation with an Axtomatic Mercury Pumr . . . . . . . . . . . KOHLRAUSCH (FRIEDRICH). Density Determinations of extremely Dilute Solutions . . . . , . . . . . KLIMENKO (EUTHYXE) . Influence of Hydrochloric acid and Chlorides on the Photochemical Decomposition of Chlorine Water . , . THIELE (JOHANNES). Heating Apparatus for Drying Ovens . . . RIJN (J. J. L. VAN). A Modified Condenser . . , . . . MICHAELIS (HUGO). Modification of Liebig's Condenser.. . . EIJKMAN (JAN F.). Refractometric Observations . . . . . ETARD (ALEXANDRE L.). Molecular Origin of the Absorption Bands of Salts of Cobalt and of Chromium . . . . . . . NASINI (RAFFAELE) and G. GENNARI. Anomalous Rotatory Dispersion of Malic acid . . . . . . . . . . GCYE (PRILIPPE 8.) and C. GOEDET. New Examples of the Superposing of the Optical Effects of Two Asymmetric Carbon Atoms . . WALDEX (PAUL). Optically Active Derivatives of Succinic acid . . WALDEN (PAUL). Optically Active Derivatives of Phenplacetic acid : Optical Superposition . . . . . . . . . . WALDEN (PAUL). Optically Active Halogen Compounds . . . TREY (HEINRICH). The Birotation of Glucose. . . . . . WINTHER (CHR.). Theory of the Decomposition of Raceruic Com- pounds . . . . .. . . e . . . BORN ((3.). Flames and Iiluminating Bases . . . . . . LEwss (VIFIAN B.). Cause of Luminosity in the Flames of Hydrocarbon Gases . . . . . . . . . * . . OSTWALD (WILHELM) and TROR MARK. Red and Yellow Mercuric Oxides . . . . . . . . . . . . TOWEX (OLIN FREEMAN). Pproxide Electrodes . . . . . MEYER (GEORG). Potent,ial Differences between Metals and Electrolytes GOUY (A.). Electro-capillary Properties of Dilute Sulphiiric acid . . LEHMANN (OTHO). Passage of Electricity through Gases . . . LAN@ (ROBERT). Relation between the Dielectrical Constants of Bases and their Chemical Valency . . . . , . . . MALTBY (MARGARET E.). Determination of High Resistancea. . . BAUIL (A. E.). Determination of some Conductivities . . . . HOFB (JACOBUS W. VAN'T). The Dilution Law of Salts .. . . BARTOLI (ADOLFO) and ENBICO STRACCIATI. Specific Heat of Mercury Argon, Prout)s Hypothesis and the Periodic Law . PABR ii, 13 ii, 13 ii, 14 ii, 15 ii, 16 ii, 16 ii, 16 ii, 17 ii, 85 ii, 86 ii, 86 ii, 87 ii, 8T ii, 87 ii, 88 ii, 88 ii, 89 ii, 89 ii, 90 ii, 91 ii, 91 ii, 91 ii, 133 ii, 133 ii, 133. ii, 134 ii, 135 ii, 137 ii, 139 ii, 139 ii, 140 ii, 140. ii, 141 ii, 142 ii, 142 ii, 143 ii, 143 ii, 143 ii, 14% ii, 144 ii, 144 ii, 145 between0"and 30" . . . . . - . . . . -. ii, 145.CONTENTS, F B-~?LRTOLI (ADOLFO) and EXRICO SI RACCIATI. Specific Heztts of Platinum, Silver, Tin, Lead, and Copper . . . . . . . . LUGININ (WLADIMIR F.). Latent Heats of Vaporisation of Ketones and other Compounds . . . . . . . . . , BAUR (A. E.). Deterinication of Trausition Points.. . . , WATERXAN (I?. A.). Improved Calorimeter for the Application of the Method of Mixtures . . . . . . . . . . GRIPPITHS (ERNEST H.). Thermal Unit. . . . . . . PICKERING (P. SPENCER U.). Heats of Combination of Substances in the Liquid and Solid Conditions . . . , . , . . VARET (RAOUL). Combination of Mercuric Cyanide with Iodides . . VARET (RAOUL). Lithium, Magnesium, and Copper Cyanides. . . LOWENHERZ (RICHARD). Depression of the Melting Point of Sodium Sulphate by addition of Foreign Substances . . . . . ESTREICEER (THADDEUS). Pressure of Saturation of Oxygen. . . BATELLI (ANGELO). Thermal Properties of Vapours : Alcohol Vapour and its Relationship to the Laws of Boyle and Gay-Lussztc . WADDELL (JOHN). Vapour Preesure of Concentrated Solutions of Several Salts, especially Lithium and Calcium Nitrates .. . BILZ (HEINRICH). Deterniinatioii of the Molecular Weights of some Inorganic Substances . . . . . . . . . . BLANSHARD (CHARLES T.). Specific Volume and the acne& of the Elements . . . . . . . . . . . . TRAUBE (ISIDOR). Molecular Volumes . . . . . . . TRAUBE (ISIDOR). Molecular Volumetric Determination of Molecular Weights . . . . . . . . . . . . TRAUBE (ISIDOR). Molecular Voluinetric Method of Determining the Molecular Weight and Constitution . . . . . . . LAZARUS-BARLOW (W. S.). Initial Rate of Osmosis of Certain Sub- stances in Water and in Liquids containing Albumin. . . . L ~ A R (J. J. VAN). Formulm for Osmotic Pressure; Alterations of Solubility, Freezing Point and Boiling Point; and Heats of Solution and Dilution in Dissolved Dissociated Substances .. . . GORDON (VICTOR). Absorption of Nitrous Acid in Water and in Salt Solutions . . . . . . . . . . . . BEMMELEN ( JACOBUS M. TAN). The Partition Coefficients of Solutions in Liquid and Solid Substances . . . . . . . . PICKERING (P. SPEXCER U.). Sclf-recorded Breaks in the Properties of Solutions. . . . . . . . . . . . JONES (HARRY C.). Cryoscopic Relations of Dilute Solutions of Canc Sug:tr and Ethylic Alcohol . . . . . . . . . AUWERS (KARL). Relations between the Cryoscopic Behaviour of the Phenols and their Constitution . . . . , . . . PAT ERN^ (EMANUELE). Crjoscopic Behaviour of Substances having Constitutions similar to that of the Solvent . . . . . COLSON (ALBERT). Freezing of Solutions at Constant Temperature.. OARELLI (FELICE). Influence of Chemical Constitation of Organic Compounds on their Capability of Forming Solid Solutions . . SOYES (A~THUR AMOS) [and WALTER 0. SCOTT]. Thc Velocity Law of Polymolecular Reactions . . . . . , . . . KUSTER (FRITZ W.). NOYES (ABTHIJR AMOS) and WILLIAM J. HALL. Velocity of Hjdro: lysis of Salicin by Acids . . . . . . . . . GROTH (PAUL). Molecular Symmetry and Asymmetry . . . . FOCK (ANDREAS). Size of Crystalline Molecules . . . . . LEHMANN (OTHO). Running together and Healing of Crystals . . KBEIDER (D. ALBERT). Convenient Forms of Laboratory Apparatus , PULFRICH (CARL). A New Refractometer . . . . . . AXDERLINI (FRANCESCO). Atomic Refraction of Oxygen . . . LANDOLT (HANS HEIXRICH). Modified Form of Polarimeter for bhemi- cal Purposes .. . . . . . . . . A Rerersible Reaction of the First Order PAQE ii, 145 ii, 146 ii, 146 ii, 146 ii, 147 ii, 148 ii, 148 ii, 149 ii, 149 ii, 150 ii, 150 ii, 151 ii, 152 ii, 122 ii, 152 ii, 15-14 ii, 1.54 ii, 154 ii, 155 ii, 155 ii, 155 ii, 156 ii, 156 ii, 157 ii, 157 ii, 158 ii, 158 ii, 159 ii, 159 ii, 160 ii, 160 ii. 161 ii, 161 ii, 22% ii, 2301-i OOKTENTS. LIPPMANN (EDMUND 0. TO;?;). Cause of Birotation . . . . JAIIN (HANS). Loss of Energy of a Battery during Electrolysis . . CATTANEO (CARLO). Electrical Conductivity of Salts dissolred in Gl ycerol . . . . . . . , . . . . KELLNER (CAEL). Absorption of Acid and Alkali from Solut,ions by7 Platinum Black . . . . . . . . . . . LIRDE (C.). Production of very low Temperatures and Liquefaction of Gases .. . . . . . . . . . . . DIETERICI (EONRAD). Dependence of the Specific Heat of Water on the Temperature . . . . , . . . . . . LANXOY (S. DE). The Thermal Expansion of Salt Solutions . . . KAHLBAUM (GEORO W. A,). Normal Boiling Tube . . . . BLANSHARD (CHARLES T.). Boiling Point and the Genesis of the EIc- nients . . . . . . . . . . . . ZAMBIASI (GIULIO) . Phenomena observed a t the Critical Point . . ZAMBIASI (GIULIO). Disappearance of the Meniscus at the Critical Point TOEPLER (MAX). Gas and Vapour Density Determinations by means of a Pressure Balance . . . . . . . . . , 'rnAuslP: (ISIDOR). Extension of the Laws of Gay-Lussac and Arogadro to Homogeneous Liquids and Solid Substances . . . . . WOOD (R. W.). Degree of Dissociation at Zero Temperature.. . BECPMANN (ERNST), GOTTHOLD FUCHS, and VICTOR GERNHARDT. Determination of Molecular Weights. I11 . . . . , WOELFER (J.). Boiling Points of Solutions of Salts in Methylic and Ethylic Alcohols. . . . . . . . . . . AXPOLA (G.) and C. MANUELLI. . HARCOURT (A. G. VERNON) and WILLIAM Esso~. Laws of Connection between the Conditions of a Chemical Change and its Amount. 111. Further Researches on the Reaction of Hydrogen Dioside and Hydro- gen Iodide . . . . . . . . . . . . &TIOLATI (ARTURO). Stability of Imides of Dibasic acids . . . MIOLATI (ARTURO) and E. LONGO. Stability of Substituted Succinimides LEY (HEINRICH). Reaction Belocity of Intramolecular Changes in Stereo- isomeric Oximes . . . . . . . . . . . TAXMAN (GUSTAV). Action of Unorgmised Ferments .. , . LADENBURG (ALBERT). Molecular Symmetry and Asymmetry . . KAHLBAUX (GEORG W. A.). The so-called Liebig's Condensel- . . GUQLIELMO (GIOVANNI). Modification of Mohr's Balance and a simple Apparatus for Neasuring the Volumes of Solids . . . . LEMOINE (GEORGES). Relation between the Intensity of Light and its Action on Mixtures of Ferric Chloride and Oxalic acid . . . ZECCHINI (F.). New Molecular Refraction Formula . . . . KRUSS (GERHARD). Relations between the Composition and the Abso1.p- tion Spectrum of Organic Compounds . . . . . . NASINI (RAFFAELE) and G. GENNARI. Anomalies in the Rotatory Dis- persion of Malic acid . . . . . . . . . . GESNARI (G.). Rotatory Dispersion of Nicotine and its Salts . . . GERNEZ (DBsIRB). Rotatory Power of Superfused Rhamnose .. . EDER (JOSEF MARIA). Flames and Illuminating Gases . . . . WIEDEMANN ( EILHARD) and GERHARD CARL SCHMIDT. Luminosity of Pure Inorganic Compounds and of Solid Solutions . . . . RATZ (FLORIAN) . Dependence of the Dielectric Constant on Temperature and Pressure . . . . . . . . . . . HTORCH (LUDWIG). The Dilution Law of Electrolytes . . . . TAXMANN (GUSTAT). Specific €feats of Solutions . . . . . DUDLEY (WILLIAM L.). Relationship of the Heats of Vaporieation of Gases to their Density and also to their Boiling Points . . . SPRING (WALTH~RE) . Physical Alferation of certain Sulphur Compounds a t Temperatures below their Melting Points . . . . . SCIINEIDER (BEBNHARD TON). Melting Points of Organic Compounds . Use of Bromoform in Cryoscopy . PAGE ii, 230 ii, 230 ii, 23L ii, 232 ii, 232 ii, 232 ii, 233 ii, 233 ii, 233 it, 234 ii, 234 ii, 235 ii, 235 ii, 236 ii, 236 ii, 237 ii, 238 ii, 238 ii, 24.2 ii, 242 ii, 243 ii, 243 ii, 244 ii, 244 ii, 244 ii, 285 ii, 285 ii, 285 ii, 285 ii, 286 ii, 287 ii, 287 ii, 287 ii, 288 ii, 288 ii, 289 ii, 289 ii, 290 ii, 290CONTENTS.rii PAGE WILDERMANN (ME JER). Apparent and true Freezing Points, and Freez- ing Point Methods . . . . . . . . . . ROLOFF (MAX). Method for the Determinatioii of tho Freezicg Points of Concentrated Solutions . . . . . . . . . NERKST (WALTHER) and RICHARD ABEOG. The Preezing Points of Dilute Solutioiis . . . . . . . . . . . GARELLI (FELICE). Exceptions to the Lam of Freezing Point Depi*essions GARELLI (FELICE). Cryoscopic Behaviour of Substances of Similai- Con- stitution to the Solvent .. . . . . . . . AUWERS (KARL) [and W. R. INNES]. The Cryoscopic Behaviour of MOISSAN (HENRI) and HENRI GAUTIER. New Mkhod for the Deter: RIrLLER-E&ZBACH ( WILHELM) . Vapour Tension of Hjdrated Salts and the Constitution of the Combined Water . . . . . . KOHLRAUSCH (PEIEDRICH). The Dilution Law of Salt Solutions . . JAKOWKIN (A. A.). . SCHLUNDT (HERMANN). Chemical Kinetics of Oxidation. i. Speed of Liberation of Iodine in Mixed Solutions OP Potassium Chlorate and WARDER (ROBERT B,). Chemical Einetics of Oxidation. i1. Mathe- matical Theory of Oxidation Processes . . . . . . MARKOWNIPOFF, WLADIMIR. Mixer for accelerating Chemical Reactions WALTER (JOHANN). Pressure Tube for Laboratory Experimencs . . LE BLANC (MAX) and P. ROHLAND. Influence of Electrolytic Dissocia- tion, kc., on the Molecular Refraction .. . . . . M PGRANINI (GAETANO). Absorption Spectra of Some Chroinocyanates . BAYRAG (PIERRE HEIRI) and CH. CAMICHEL. Absorption of Light by Solutions of Indophenols . . . . , . . . WIEDENANN (EILHARD) and GERHARD CARL SCHYIDT. Fluorescence of Sodium and Potassium Vapour and its Importance in Astrophysics . PESCETTA (Mos2). Specific Rotation of a-Nitrocamphor in Various Solvents . . . . . . . . . . . . TAKRET (CHARLES). Multirotatioii of Reducing Sugars and of Isodul- citol , . . . . . . . . . . . . VIOLLE (JULES). Acetylene as a Photometric Unit . . . . LE BON (GUSTAVE). Dark Radiations . . . . . . . PERRIER (JEAIV). Properties of Rontgen Rays . . . . WIEDEXANN (EILHARD) and GERHARD CARL SCHMIDT.Discharge Phenomena in Rarefied Metallic Vapours . . . . . , BEKETOFF (NIKOLAI N.). Molecular Conductivity of Dilute Solutions , BREDIG (GEORG). Thermal Conductivity and Ion Velocity , , . AarAaAT (EXILE EXLAIRE). Specific Heats of Gf-ases and Properties of Isot hermals . . . . . . . . . . . GRIFFITHS (ERNEST HOWARD) md DOROTHY MARSHALL. Latent Heat of Evaporation of Benzene. . . . . . . . . MARSHALL (DOROTHY) and WILLIAM RAMSAY. Method of Comparing directly the Heats of Evaporation of different Liquids at their Boiling Points . . . . . . . . . . . . TAPSILLY. Strontium and Calcium Iodides . . . . . . LE CHATELIER (HENRY LOUIS). Heats of Formation of Manganese Com- pounds . . . . . . . . . . RONOWALOFF (DMITRI P.). Soiubility of Gases . . . . . WILDERMANN (MEJEB).Experimental Proof of the Laws of wn’t Hoff, Arrhenius, Ostwald, and Dalton for Dilute Solutions . , , . ZAXNINOTICH-TESSARIN (HUGO). Electrolytic Dissociation in Formic acid Solutions . . . . , . . . . . . KERKST (WALTHER) and RICHARD ABEGG. Freezing Points of Dilute Solutions . . . . . . . . . . . . Substituted Phenols in Naphthalene , * . mination of the Density of Oases . . . . . . Partition of a Substance between two Solvents STORCH (LUDWIG). Course of Chemical Reactions in Gases . . Hydrochloric acid . . . . . . . . . ii, 290 ii, 291 ii, 292 ii, 292 ii, 292 ii, 293 ii, 294 ii, 295 ii, 295 ii, 295 ii, 296 ii, 297 ii, 295 ii, 297 ii, 297 ii, 345 ii, 3%5 ii, 346 ii, 345 ii, 346 ii, 347 ii, 343 ii, 347 ii, 347 ii, 348 ii, 348 ii, 348 ii, 349 ii, 349 ii, 349 ii, 350 ii, 350 ii, 351 ii, 351 ii, 352 ii, 352...YIll CONTENTS . LOOXIS (E . H.). Freezing Points of Dilute Aqueous Solutions . . Looms (E . H.), Determination of the Freezing Points of Dilute Solu- tions . . . . . . . . . . . . . AI~CTOWSKI (HENRTK) . Solubility at the Solidifying Point of the Solvent . . . . . . . . . . . . HERTLEIN (HANS) . The Polythionates . . . . . . . TRAUBE (ISIDOR) . Moieculax Solution Volumes and Molecular Volumes of Organic Compounds . . . . . . . . CHININELLO (V.). Velocity of Reaction between Ethylic Jodide and' Silver Nitrate in Ethylic and Methylic Alcohola FLAVITZKY (BLAVIAN M.). Function correflponding with the Periodicity . . . . . . . KURBATOFF (A.). Extraction Apparatus for Liquids . . . . OSSIPOFP (IWAN P.). Lecture Experiment : Combustion of Oxygen in Ammonia .. . . . . . . . . . . PAT. MER (A . DE FOREST) . Wave-length of the I), Helium Line . . EDER (JOSEF MARIA) and E . VALENTA . Three different Spectra of UONNAN (FREDERICK GEORGE) . Electrolytic Dissociation and Ligb t Absorption . . . . . . . . . . . . BECQUEREL (HENRI) . Phosphorescent Radiations . . . . NOVAK (V.) and OTTOKAR BULC . Absorption of Rontgen Rays by Chemical Compounds . . . . . . . . . . RICHARD (GEORGES ADOLPHE) . Colour Photography : Substitiition of Oi*ganic Colmring matters for the Reduced Silver of Photographic Proofs . . . . . . . . . . . . DELVALEZ (GI.. ). Parasite Electrodes . . . . . . . CHESNEAU (GABRIEL) . Temperature of the Sparks produced by Uranium . . . . . . . . . . . . ALTSCHUL (MICHAEL) .Optical Method of determining the Critical Temperature . . . . . . . . . . . QUINAN (W . R.). Physical Aspects of Argon : the Ideal Thermometrical Substance for High Tempemtures . . . . . . . LINEBARGER (CHARLES ELIJAH) . Vapour Tensions of Mixtures of RIVALS (PAUL) . Thermochemistry of Chlorobenzoic acid and some of its Derivatives . . . . . . . . . . . RIT-ALS (PAUL) . Thermochemistry of the Amides and Ammonium Salts of some Chloro-acids . . . . . . . . . . SPEYERS (CLARENCE LIVINGSTONE) . Heats of Solution of some Carbon Compounds . . . . . . . . . . . . TXAUBE (ISIDOR) . Molecular Volumetric Method of determining the Molecular Weight . 111 . . . . . . . . . . BILTZ (HEINRICH) . Determination of the Molecular Weights of some Inorganic Compounds . . .. . . . . . . L O V ~ N (JOHAN MARTIN) . Affinity Constants of some Organic Acids . LOVEN ( JOHAN MARTIN) . Chemical Equilibrium in Ammoniacal Solutions of Magnesium Salts . . . . . . . . . . MEYERHOFPER (WILHELM) . Reciprocal Salt Pairs . . . . . SALZER (THEODOR) . Water of Crystallisation . . . . . DIERBACH (R.). A New Bunsen Burner . . . . . . . BERLEXOXT (G.). A New FractionatingColumn . . . . . PRECHT (J.). Modification of von Babo's Water Mercury Pump for the Production oE High Vacua . . . . . . . . EBNER (VICTOR VON) . Reversal of the Double Refraction of Gelatin- producing Tissues by Various Reagents . . . . . . . . . . of the Properties of the Elements ORTLOFF (W.). Eutropic Series . . . . . . . . Argon . . . . . . . . . . . . . Volatile Liquids . . . .. . . . . . . POXSOT (A.). Cryoscopic Investigations . . . . . . . QENNARI (G.). Velocity of Hydrolysis in Organic Solvents . . . LON@ (JOHN HARPER). Inversion of Sugar by Salts . . . . PA0 E ii. 352 ii. 353 ii. 353 ii. 353 ii. 354 ii. 354 ii. 355 ii. 355 ii. 355 ii. 356 ii. 405 ii. 405 ii. 405 ii. 406 ii. 406 ii. 406 ii. 407 ii. 407 ii. 407 ii. 407 ii. 408 ii. 405 ii. 410 ii. 410 ii. 411 ii. 411 ii. 412 ii. 412 ii. 413 ii. 413 ii. 414 ii. 414 ii. 415 ii. 415 ii. 415 ii. 415 ii. 457CONTENTS, FRIEDLANDER (SIEQFRIED). Argon . . . . . . . WOOD (R. W.). Absorption Spectra of Iodine and Bromine Solutions above the Critical Temperature of the Solvent . . . . . GUYE (PRILIPPE A.) and CHARLES GOUDET. Optical Superposition of Six Asymmetric Carbon Atoms in the same Active Molecule .GUYE (PmLIPrE A.) and CHARLES JORDAN. Rotatory Dispersion of Non-polymerised Active Liquids. . . . . . . . NAMIAS (RODOLFO) . Photochemistr? and Thermophotocliemistrp . KENRICK (FRANK B.). The Potential Difference between Gases and Liquids . . , . . . . . . . . ~ H L E (RUDOLF). Catalytic Action of Nitrous acid and the Potential oi Nitric acid . . . . . . . . . . . , STREINTZ (FRANZ). Polarisation and Resistance of u Galvanic Cell. . SCHOOP (PAUL). Measurement of the Electrochemical Forces of Accumu- lators . . . . . . . . . . . . . LUTHER (ROBERT). Electromotive Force and Partition Equilibrium . WALKER (MILO S.). Use for Laborat0r.y Purposes of the Electric Arc from the Low Potential Alternating Current . . . . . JONES (HARRT CLARY) and CHARLES R.ALLEX. Condustivity of Yttrium Sulphate . . . . . . . . . JONES (HARRY CLARY) and CHARLES R. ALLEN. Conductivity of Solu- tions of Acelylene in Water . , . . . . . . SCHALL (JOHN FRIEDRICH CARL). Dewease of Conductivity when the Water of Solution is replaced by Alcohol . . . . . . KORTRIGHT (FREDERICK L.). Heats of Electrolytic Dissociation of some Acids. . . . . . . . . . . . . IHLE (RUDOLF). Formation of Ammonia by the Electrolysis of Nitric acid . . . . . . . . . . . . . ZSIGNONDY (RICHARD). Absorption of Radiant Heat by Liquids . . KRAFFT (FRIEDRICH) and H. WEILANDT. Boiling Points in the Cathode- light Vacuum . . . . . . , . . . , TASSILT,Y. Thermocheulistry of Oxybroniides and Oxychlorides of the Calcium Group . . . . . . . . . . . GUINCHANT (J.). Heats of Combustion of Cyanogen Derivatives .. TANATAR (SIXEON M.). Heats of Solution and Neutralisation of Nitro- carbamide . . . . , . . . . . . . STOHMANN (FRIEDRICH CARL ADOLF) and RAYMUND SCHMIDT. Thermo- chemistry of Hippuric acid, of its Homologues, and of Anisuric acid. JOXES (HARRY CLARY) aiid CHARLES R. ALLEN. Vse of Phenol- phtfialeln in illusti.ating the Dissociating Action of Water. . . KRAFFT (FRIEDRICR) and A. STRUTZ. Behaviour of Soap-like Sub- stances i n Presence of Water. V. . . . . . . . KRAFFT (FRIEDRICH). A Theory of Colloidal Solutions , . . . GARELLI (FELICE). Solid Solutions formed by Non-isoinorphous Sub- stances . . . . . . . . . . . . TAFEL (JULIUS). Indirect Etherificetion. . . . . . . NOYES (ARTHUR AMOS). Catalytic Action of Hydrogen Ions in Poly- molecular Reactions .. . . . . . . . . WAGNER (MAX). Decomposition Velocity of Acids containing Sulphur and Nitrogen . . . . . . . . . . . G OLDHAMMER (DMITRI A.). Analytical Represeutation of the Periodic Sjstem of the Elements . . . . . . . . . TRAUBE (HERMANN). Optical Rotatory Power of Substances in tho Crys- talliue and Liquid states . . . . . . . . . LINEBARGER (CHARLES ELIJAH). The Dielectric Condmt of Liquid Mixtures . . . . , . . , . . . . SOKOLOFF (ALEXEI P.). Electrolysis of Water . . . . . TOMASSI (DONATO). New Electrolytic Apparatus . , . , . CARRARA (GIACOXO). Electrolytic Dissociation in Solvents other than Water . . . . . . . . . . . . . PAGE ii, 457 ii, 458 ii, 433 ii, 439 ii, 450 ii, 460 ii, 460 ii, 460 ii, 461 ii, 4til ii, 462 ii, 462 ii, 463 ii, 463 ii, 46-1.ii, 46& ii, 464 ii, 465 ii, 4% ii, 4Cti ii, 466 ii, 4ti7 ii, 4C7 ii, 4fB ii, 460 ii, 4 i O ii, 470 ii, .ti0 ii, 471 ii, 509 ii, 509 ii, 310 ii, 511 ii, 511x CONTENTS. SALVADORI (ROBERTO). Variation of Electrolytic Dissociation with Temperature : Freezing and Boiling Point Determinations of Aqueous and Nethylic Alcoholic Solutions of Chlorides . . . . . HAGENBACH (AUGUST). Thermo-elements of Amalgams and Electrolytes VARET (RAOUL). Thermochemistry of Nickel Cyanide . . . . ROG~YSKI (K.) and GIJSTAV TAXMANN. Adiabatic Voiume Changes in Solutions . . . . . . . . . , . e T ~ ~ ~ ~ ~ ~ ~ (ALEXANUR A.). Dissociation of Halogen Salts . . . ZOPPPLLARI (I.). Freezing of Dilute Solutions . . . . . ZorrmLaRI (I.). Cryoscopic Behaviour and Composition of some Ace- tates of feeble Eases .. . . . . . . . . GOLDSCHMIDT (HEINRICH) and R. U. REINDERS. Reaction Velocitj in the Conversion of Diazosmido- into Amidoazo-derivatives . . . WOOD (R. W.). A New Form of Mercury Air-pump . . . . POSTOI~EPF (J. J.). Automatic Apparatus for Filtration at High Tem- peratures . . , . . . . . . . . . WALDEN (PAUL). Chnracterisation of Optically Active Substances . . FREUKDLER (PAUL). Chlorinated Ethereal Tartrates . . . . IHLE (RUDOLF). Action of Nitrous acid in a Grove’s Element . . WARREN (HENRY NEPEAN) . A Non-sulphating Phospho-accumulatoi* . OETTEL (FELIX). Electrolysis of .Hydrogen Chloride without a Mem- brane. . . . . . . . . . . . . X~CTNTOSH (DOUGLAS). Calculation of the Conductivity of Mixtures of Electrolytes having a common Ion .. . . . . . LAszczmsxI (ST. TON). Conductivity of Solutions of some Salts in Acetone . . . . . . . . . . . LASZCZYNSKI (ST. VON). Electrolysis of Solutions of Salts in Acetone . HEMPEL (WALTHER). Estimation of the Heat of Combustion of Fuels . GOLCSCHXIDT, (HEINRICH) and R. U. REINDERS. Reaction Velocity of the Conversion of Diazoamido- into Amidoazo-derivatives . . . LICHTY (D. M.). Etherification of substituted Acetic acids . . . FREER (PAUC C.). Apparatus for Distillation in a Vacuum . . . HIQLEY (GEORGFB 0.) and B. J. HOWARD. Apparatus for Electrolysis of Hydrochloric acid . . . . . . . , . , PICKEL (J. M.). Lecture Experiment : Electrolysis of Hydrochloric acid . . . . . . . . . . . . . FahER (PAUL 0.). Apparatus for demonstrating that Two Volumes of Hydrogen and One Volume of Oxygen form Two Volumes of Water CAPXEGFIE (DOUGLAS JOHX) and H.WALES, Voltmetric Composition of Ammonium Chloride . . . . . . . . . GRAXONT (ARNAUD DE). Spectrum of Phosphorus in Fused Salts and GRAMONT (ARNAUD DE). Dissociation Spectra of Fnsei Salts of Alkali Metals. . . . . . . . . . . . . RICHAPZ (FRANZ) and CARL LOXNES. Convection Currents . . . BUCHERER (ALFRED H.) . Electromotive Force and Partition Equilibrium TOWER (OLIN FREEMAN). Potential Differences a t the Surface of Con- tact of Dilute Solutions . . . . . . . . . LOEENZ (RICHARD). Electrolytic Deconiposition of Fused Zinc Chloride LOWEXHERZ (RICHARD). Influence of Etliylic Alcohol on the Electrolytic Dissociation of Water . . . a . . . . VILDERMASN (MEJER).New Method of Determining Freezing Points . ABEQG (RICHARD). Freezing Point Depressions in very Dilute Soluticjns Eli-ALS (PAUL). Etliylic Salts of the Chloracetic acids . . . . RIVALS [PAUL). Acetsl and Chloraeetal . . . . . .) . MARSHALL (DOROTHY). Heat of Vaporisation of Formic acid. . . STACKELBERQ (ED. vox). , ALOY (J.). Thermochemistry of Uranium Conipounds . . . . CAYALIEH, (J.). Measurement of the Heat of Formation of Triethylic Vapour . . . . . . . . . . . certain Metallurgicid Products . . . . . . . Heat of Di~eolution of Sodium Chloride . PAGE ii, 512 ii, 513 ii, 513 ii, 513 ii, 514 ii, 514 ii, 515 ii, 515 ii, 516 ii, 516 ii, 553 ii, 553 ii, 554 ii, 554 ii, 555 ii, 556 ii, 555 ii, 556 ii, 556 ii, 556 ii, 557 ii, 557 ii, 557 ii, 55’7 ii, 558 ii, 558 ii, 585 ii, 585 ii, 585 ii, 586 ii, 586 ii, 586 ii, 587 ii, 587 ii, 587 ii, 588 ii, 5’38 ii, 589 ii, 589 ii, 589COXTENTS.Xi Phospliate by the Action of Phosphorus 0x-j-chloride on Sodium Etlioxide . . . . . . . . . . . . ROBERTS-AUSTEN (WILLIAY CHASDLER). Diffusion of Metals . . JAKOWKIN (ALEXAKDR A.). Relation between Osmotic Pressure and tho Law of Active Moiecules . . . . . . . . . C'OHEN (EKNST). The Course of Chemical Reactions in Gases . . . ROTHXUND (VICTOR). Inff iience of Pressure on Reaction Velocities . LEA (MATTREW CAREY). Xcw Relations betvieen the Atomic Weights of the Elements . . . . . . . . . . WALDEN (PAUL). Optical Rotation of Stereoisomerides . . . . COLLIE (JOHN NORMA") and WILLIAX RAMSAY. Behaviour of Argon and Helium when submitted to the Electric Discharge .. . Lovfx ( JOHAX MARTIN). Temperature Coeficient of the Electromotive Force of Silver Cells . . . . . . . . . . KRAFFT (FRIEDRICH) and H. WEILANDT. Sublimation Temperatures in the Cathode-light Vacuum . . . . . . . . . ARCTOWSKI (HENRYK). Solubility of Solids in Gases . . . . ARCTOWSKI (HENRYK). Sublimation Velocity of Mercury Halo'id Salts . AI~CTOWSKI (HENRYK). Sublimation Tension of Iodine . . . . PONSOT (A). Determination of the Freezing Point of Dilute Aqueous Solutions . . . . . . . . . . . . TOLLOCZEO (ST.). Influence of Chemical Affinity on Solubility . , TOLLOCZKO (ST.). The Lowering of Solubility. . . . , . STACKELBERG (ED. TON). Influence of Pressure on Solubiliky. . . GOLDSCIIMIDT (HEINRICH). Etherification . , . , .. PBTERSEN (ExIL). Indirect Etherification . . . . . . LEA (MATTHEW CAREY). Relationships between the Colours of Atoms, Ions, and Molecules. 11. . . . . . . . . . DEBUS (HEIKRICH). The Origin of Dalton's Atomic Theory . . . LORENZ (RICHARD). Twin Elements . . . . . . . SALORION (FRITZ). Simple Method of Reducing Weight in Air to Weight in aVacuum . . . . . I . . . . Iwwgalnic OhernGstry. LOREFZ (RICHARD). Conversion of Chlorine into Hydrogen CLloride . ARCTOWSKI (HENRYE). Crystallisation of Bromine . . . . CLETER (A.) and WILHELM MUTHMANN. Compound of Selenium and Arsenic . . . . . . . . . . . . KAYSER (HEINRJCH). ETelium and Argon . . . . . . RAMSAY (WILLIAM). A Yossib!c Cornpound of Argon . . . . MARCHETTI ((3.). Fluorides and Oxyfluorides of Potassium . . . HUGOT (C.).Some Alkali Phospliides . . . . . . . RICHARDS (THEODORE W.) and ELLIOT F. ROGERS. Deterinination of the Atomic Weight of Zinc . . . . . . . . LORENZ (RICHARD). Electrolytic Preparation of Zinc and Lead . . SCHULZE (JuL.). Chromates and Dichromates of the Hea\-y Metals . PETTERSSON (OTTO). Carbides of the Metals of the Rare Earths . . MOURLOT (A.). Crystallised Anhydrous Manganese Sulphide . . . THOMAS (V.). Compoupds of Ferrous Chloride with Nitrous Oxide . MILL~R (ALFRED S.). Ammonia and the Chlorides of Iron . . . RECOURA (ALBERT). ChromiumSulphate . . . . . TANDENBERGHE (AD.). Molybdenum Dihydroxycldoride . . . STAVENHAGEN (ALFRED) and E. ENGELS. Molybdenum Bronzes . . LORENZ (RICHARD). Preparation of Tin Tetrachloride in large qunn- tities . . . .. . . . . . . . . , GOYDER (GEORGE A.). Chemistry of the Cyanide Process for the Extrac- tion of Gold from its Ores . . , . . . . . . SPRJNG (~TAI+TH&RE). Decomposition of Hydrogen Peroxide . . . PdGE ii, 590 ii, 590 ii, 593 ii, 593 ii, 593 ii, 594 ii, 633 ii, 633 ii, 635 ii, 636 ii, 635 ii, 635 ii, 636 ii, 636 ii, 636 ii, 636 ii, 637 ii, 6314 ii, 6:s ii, 639 ii, 639 ii, 638 ii, 640 ii, 17 ii, 17 ii, 18 ii, 19 ji, 2 0 ii, 20 ii, 21 ii, 21 ii, 22 ii, 24 ii, 25 ii, 25 ii, 2G ii, 26 ii, 27' ii, 2'7 ii, 28 ii, 28 ii, 28 ii, 92xii CONTENTS. VITALI (DIOSC )RIDE). Action of Hydrogen Peroxide on Ammoniacal Copper Compounds, preparation of Oxygen. . . . . . BRUXCE (OTTO). Formation of Ozone . . . . . . . HANTZSCH (ARTHUR R.) and WILLIAM SEMPLE. The so-called Oxy- sulphazotic acid or Nitrosodisulphonic acid.. . . . . HANTZSCH (ARTHUR R.). Dinitrososulphonic acid (Nitroxysulphurous a c i d ) . . . . . . . . . . . . . P~LABON (H,). Formation of Hydrogen Selenide . . . . . STAUDENYAIER (LUDWIG). Tellurium SPRING (WALTH~RE). A Hydrate of' Arsknic 'Trisiphide a i d it; SZARVASY (EMERICH). New Compound of Arscni:: and Selenium, and of Arsenic, Selenium, and Sulphur . . . . . . . . LARGLET (N. A,). Atomic Weight of Helium. . . , . . TROOST (LOUIS J.) and LLON V. R. OUVRARD. Combination of Mag- nesium with Argon and with Helium. . . . . . . R~YLEIOH (LORD) and WILLIAM RAXSAY. Argon, a new Constituent of the Atmosphere . . . . . . . . . . . SENDERENS (J. B.). Singular Case of Metallic Precipitation , . WETAS (HORACE L.) andE. B.HURLBUR'P. Double Halogen Salts oi Ammonium and Copper . . . . . . . . . FREY (He.). Formationof Nickel Carbonyl . . . , . . WELLS (HORACE L.) and B. B. BOLTWOOD. Double Salts of Caesium Chloride with Chromium Trichloride and Uranyl Chloride . . BROWN (ANOS P.). . PHILLIPS (FRANCIS C.) . Possibility of the Occurrence of Hydrogen and Methane in the Atmosphere . . . . . . . . MEYER (VICTOR) and WILEELX RAUX. Combination of Hydrogen with Oxvgen . . . . . . . . . . . BBUHL (JUL~US W.). Hydrogen Peroxide . . . . . . BRUHL (JULIUS W.). Constitution of Water, and the Cause of its Dis- sociating Power . . . . . . . . . . . WHITEHEAD (CABELL). Separation of Tellurium from Copper Residues. SXITH (EDGAR F.) and JOSEPH G. HIBBS. Action of Gaseous Hydro- gen Chloride on Salts of the Elements of t.he Fifth Group of the Pei+iodic System .. . . . . . . . . . SMITH (EDGAR F.) and FRED L. MEYER. Action of Gaseous Hydrogen Chloride 011 the Salts of the Hlements of the Fifth Group of the Periodic System. . . . . . . . . . . WANKLYN (J. ALFRED). Data for Ascertaining the True Atomic Weight ofcarbon. . . . . . . . . . . . MOISSAN (HZENRI). Varieties of Graphite . . . . . . WILDE (HENRY). Helium and its Place in the Natural Classification of Elementary Substances , . . . , . . . . ECHLCESING (TH., jun.). Estimation of Argon . . . . , COHEN (ERNST). golubility of Silver Halogen Salts in Various Solvents . BRUGELXANN (G.). Prepartttion of Lime and Strontia Crystals , . DUFAU (E.). Normal Calcium Chromite . . . . . LEBEAU (PAUL). Preparation of Pure Berylliuni Oxide from Emerald .HART (EDWARD). Purification of Beryllium Salts , . . . . LEBEAU (PAUL). Beryllium Carbide , . . , , . . HENRY (LOUIS). Beryllium Carbide . . . , . . . ~URNAKOFF (NICOLAI). Constitution of Metallic Bases . . . . CEAEPY (GEORGES). Mechanical Properties of Alloys of Copper and Zinc . . . . 1 . . . . . . . CAXPBELL (EDWARD D.). Oxidation of some Gases with Palladinised Copper Oxide . . . . . . . . . . . ENGEL (RODOLPHE). Action of Hydrochloric acid on Copper. . . AUDEN (H. A.) and GILBERT J. ~?OWLEH. Act,ion of Nitric Oxide on Certain Salts . . . . . . . . . Decomposition by Pressure. . . . . . . . Cliemical Behaviour of Pyrites and Marcasite . PAGE ii, 02 ii, 93 ii, 95 ii, 96 ii, 96 ii, 96 ii, 97 ii, 98 ii, 99 ii, 99 ii, 99 ii, 106 ii, 107 ii, 107 ii, 107 ii, 108 ii, 162 ii, 162 ii, 162 ii, 163 ii, 16% ii, 164 ii, 164 ii, 165 ii, 165 ii, 165 ii, 166 ii, 167 ii, 167 ii, 167 ii, 168 ii, 168 ii, 169 ii, 169 ii, 170 ii, 170 ii, 171 ii, 171 ii, 172CONTEXTS.*.. xi12 OSMOSD (FLORIS). Tempering of Very Hard Steel . . . . . BRAITEWAITE (ISAAC). Reduction of Iron Oxides by Carbonic Oxide . MOISSAN (HENRI). Action of Silicon on Iron, Chromium, and Silver . BENNEFILLX (JAMES S. DE). Some Alloys of Iron with Molpbdennrn. Tungsten, and Chromium . . . . . . . . . BENNEVILLE (JAMES S. DE). Two Definite Carbides of Iron with Chro- mium (Moljbdenumand Tungsten) . . . . . . . ROSELL (CLAUDE A. 0.). The Ferrates . . . . . . . VIGOUROUX. Nickel and Cobalt Silicides. . . . . . . GROSVEYOR (WILLIAM M., inn.).New Solvents for Perchromic Acid . SMITH (EDGAR 3.) and 3. B~ERRITT MATTHEWS. Uranium Oxynitride and Uranium Dioxide. . . . . . , . . . FOERSTER (FRITZ). Alloys of Copper and Tin . . . . . PICCINI (AGGUSTO). Action of Hydrogen Peroxide on Fluorides ant1 OxSfluorides . . . . . . . . , . . WELLS {HORACE L.) and H. W. FOOTE. Double Fluorides of Caesium and Zirconium . . . . . . . . . . . SMITH (EDGAR F.) and HAIZRP B. HARRIS. Action of Phosphorus Pen- tuchloride on Zirconium and Thorium Dioxides. . . . . PALMAER (WILEELM). Iridioammonium Compounds , . , . TKOXSEN (JULIUS). Ratio of the Atomic Weights of Oxygen and Hydrogen . . . . . . . . . . . . PHIPSON (THOMAS L.). Origin of Atmospheric Oxygen . . , . PERATONBR (ALBERTO) and GIUSEPPE ODDO. Decomposition of some Trinitrides .. . . . . . . . . . . NASINC (RAFFAELE). Argon . . . . . . , . . EDWARDS (ARTHUR M.). Solubility of Silica . . . , . . ODDO (GIUSEPPE) and E. MANZELLA. Italian and other Cements . . ODDO (GIUSEPPE) and E. MANZELLA. The Setting of Cements . WARREN (HENRY N.). Manufacture and Commercial Separation of Beryllium . . . . . . . . . . . FUXK (ROBERT). Sulphur and Carbon in Zinc . . . . . KASSNER (GEORG). Orthoplumbates of the Alkaline Earths . . . GRUTZNER (BRUXO) and M. HOHNEL. Metaplumbates of tile Alkaline Earths . . . . . . . . . . . . MAURO (FRANCESCO). Thallous Fluoroxyniolybdate and Fluorox~hypo- molybdate . . . . . . . . . . . , FRANFOIS (MAURICE). Action of Phenol on Mercurous Iodide . . BOISBAUDRAN (PAUL E. LECOQ DE). Probable new Element in Terbix .VIUOUROUX. Manganese Silicide . . . . . . . . WARREN (HENRY N,). Electro-dissolution and its Uses . . . . ANTONT (UBALDO) and Gt. GIGLIO. Hydrolytic Decomposition of Ferric Chloride . . . . . . . . . . . . &roEsER (LUDWIG). Salts of Ferric acid . . . . . . , COSSA (ALPONSO). Platosomonodiamine Compounds . . . . CLEVEB (A.) and WILHELM MUTHMANN. Nitrogen Sulphide . . TROOST (LOUIS JOSEPH) and L ~ O N VICTOR R&N& OUVRARD. Origin of the Argon and Helium in the Gas from Sulphuretted Waters . . BOUCHARD. Origin of the Argon and Helium in the Gas from Sulphu- retted Waters . . . . . . . . . . MOUREU (CHARLES). Argon and Helium in a Mineral Water. . . LIMB (CLAUDIUS), Separation of Atmospheric Argon and Nitrogen . MAQUENNE (LBoN). Combination of Nitrogen with Metals of the Alkaline Earths .. . . . . . . . . , ROSSEL (A.). Combination of Nitrogen with Metals . . . . DESLANDRES (HENRI). Absorption of Xtrogen br Lithium at the GTTKTZ (ANTOINP). Lithium Subchioride . . . . . . SPRING (WaLTakREj. Influence of Time 0 1 1 the Welding of Pressed Chalk . . . . . . . . . . , , . Ordinary Temperature . . . . . . . . PAQE ii, 172 ii, 173 ii, 173 ii, 174 ii. 175 ii, 175 ii, 176 ii, 177 ii, 177 ii, 177 ii, 178 ii, 1'79 ii, 1'70 ii, 179 ii, 2& ii, 245 ii, 245 ii, 245 ii, 246 ii, 246 ii, 248 ii, 247 ii, 24'7 ii, 247 ii, 248 ii, 248 ii, 243 ii, 249 ii, 249 ii, 249 ii, 250 ii, 250 ii, 251 ii, 298 ii, 298 ii, 298 ii, 298 ii, 299 ii, 299 ii, 299 ii, 299 ii, 299 ii, 300siv CONTENTS. PETERS (FRAXZ). Action of Lead and of Potassium Nitrite on Lead Nitrate .. . . . . . . . . . . FRANQOIS (MAURICE). Action o€ Alcohol on Mercurous Iodide , ~IOISSAN (HENRI). Presence of Sodium in Aluminium prepared by Electrolysis . . . . . . . . . , . STILLMAN (JOHN M.) and XINNIE B. YODEB. Combination of Anhydrous Ammonia with Aluminium Chloride . . . . . . KUSTER (FE~EDRICH WILLIAH). Action of Ferric Salts on Iodides in Aqueous Soh tioii . . . . . . . . , . HEYPEL (WALTHER) and HERMANX THIELE. Atomic Wkght of Cobalt KLIMENXO (EUTHYXE) and BORIS KLIXENKO. Action of Hypochlorous acid on the Chlorides of Cobalt and Manganese . . . . . FEBEE (JuT.Es). Chromium Amalgam and some Properties of Chromium -MOURLOT (A.). Crystallised Chromous Sulphide . . . . . L ~ V Y (LUCIEN). Titanium Silicide and Crystalfised Titanium, .. P r c c ~ ~ r (Auctos~o). Alums of Vanadium Trioxide. . . . . 3fCCAY (&E Ron w.). Existence of Sulphoxyantimonates . . . PENNINGTON (MARY EXQLE). Derivatives of Niobium and Tantalum . HERTY (CHARLES H.). Mixed HaloTd Compounds of Platinum and PoCassium . . . . . . . , . . . . KASTLE (Z. H.) and J. H. BULLOCK. Preparation of Hydrogen Bromide and Hydrogen Iodide . . . . . . . . . . NORRIS (R. S.) and F. G. COTTREL. Properties of Liquid Hydrogen Iodide . . . . . . . . . . . OBNDORPF (WILLIAX R~DGFELY) and cf, L. TERRASSE. Molecular Weight cf Sulphur . . . . . . . . . . . , BESSON (ADOLPHE). Thionyl Bromide and Chlorobromide . . , BESSON (ADOLPHE). Action of Carbonic Chloride on some Hydrogen PARMENTIER (E.). Solubiiity of Sodium Thiosulphate in Alcohol .. MCCAY (LEROY W.). Sodium Thioarsenate . . . . , , GUNTZ ( ANTOINE). Lithium Hydride . . . . . . SPIEGEL (LEOPOLD). Magnesium Silver Nitrite . . . . . VELEY (VICTOR HERBERT). Inertness of Alkaline Earths with respect to Hydrogen Chloride . . . . . . . . . . REBUFPAT (ORAZIO). Hydraulic Cements . . . . . . SORENSEN (S. P. L.). Preparation of Pure Strontium Compounds . . CHALMOT (GUILLAME J. L. DE). Siiicides . . . . . . V ~ ~ o n ~ o u x . Copper Silicide . . . . . . , . . FRANFOIS (MAURICE). Action of Heat on Mercurous Iodide . . . WIEDE (0. FitITZ) and KARL A. HOFXANX. New Series of Metallic Ammonium Compounds . . . . . . . . . MARIE (C. and R. MARQUIS). Iron Nitrososulpliides . . . . SMETHAX (ALFRED). Influence of Oxide of Iron and Alumina on the Reversion of Superpliosphate .. . . . . . MOISSAN ( HENRI). Uranium Carbide . . . . , . . THOMAS (V.). Action of Nitric Peroxide on Stannic Salts . - . GRANGER (A.). Tin Tliiopliosphide . . . . . . . . PTCCINI (AUGUSTO). Alums of Titanium Sesquioxide . . . , GAUTIER (EMILE JUSTIN ARMAND) and H. H~LIER. Conditions which regulate the Combination of Gases. Union of Oxygen and Hydrogen a t Low Temperatures. . . . . . . . . , BARENDRECHT (H. P.). Dimorphism of Ice . . . . . . FRYE (COLIN C.). Oxidising Substance produced by distilling Aqueous Potaesiuni Permanganate and Sulphuric acid in a Vacuum . . BESSON (ADOLPHE). Action of some Hydrogen Compounds on Snlphuric Chloride . . . . . . . . . . . . SCHENCK (RUDOLF). Sulphur Nitride . . . . . . . CHALMOT (GUILLAME DE).Silicides of Iron . . . . Compounds. . . . . . . . . . TASSILLY. Zinc Oxyiodides . . . . . . . . PAOR ii, 300 ii, 301 ii, 301 ii, 301 ii, 302 ii, 303 ii, 302 ii, 303 ii, 303 ii, 304 ii, 304 ii, 364 ii, 305 ii, 305 ii, 306 ii, 356 ii, 357 ii, 357 ii, 855 ii, 355 ii, 359 ii, 359 ii, 359 ii, 360 ii, 360 ii, 360 ii, 360 ii, 362 ii, 362 ii, 362 it, 363 ii, 363 ii, 364 ii, 364 ii, 364 ii, 365 ii, 365 ii, 365 ii, 416 ii, 417 ii, 41'7 ii, 417 ii, 417CONTEXTS. S v PAGE dsLANoGLOU (P. L.). Combination of Atmospheric and Chemical Nitro- gen with Metals . . . . . . . . . . . TANATAR (SIMEON N.). Hyponitrous acid . . . . . . FERRAND (LIJCIEX). Thiophosphites . . . , . . . HILL (EDWIN A.). Argon and Helium . . , . . . , DEELEY (R. M.). Helium and Argon, and their places amo:ig the Elements .. . . . . . . . . . . PREYER (W.). Place of Argon and Heliuni in the System of the Elements . . . . . . . . . . . . TAVATAR (SINEON M.). Formation of Sodium Carbonate in Natuw . MOISSAN (HENRI). Lithium Carbide . . . . . . . VITALI (DIOSCORIDE). Action of Magnesiuni on Metallic and other Solutions . . . . . . . . . . . . CHARPY (GEOBGFES). Structure and Coiisf itution of Alloys of Copper and Zinc . . . . . . . . . . . . GUNTZ (ANTOINE). Properties of Metals separated from their Amal- gams. . . . . . . . . . . . . PHIPSON (THOXAS LAMB). Wew and abundant Source of the Oxides of Thorium, Cerium, Yttrium, Lanthanum, Didymium, and Zirconium . MOISSAX (HENRI). Cerium Carbide . . . . . . . MOISSAN (HENBI) and ~ T A R D . Carbides of Yttrium and Thorium.. WARREN (HENRY NEPEAN). Deposition of Aluminium from Aqueous Solutions . . , . . . . . . . . . APPRRT ( L ~ o N ) . Aluminia in @lass . . . . . . . MoIssaN (HENBI). Manganese Carbide . . . . . . . MOISSAN (HENRI). Nickel and Cobalt Carbides . . . . JORGENSEN (SOPUS MADS). Constitution of Cobatt, Chroiniuni and Rhodium Bases . . . . . . . . . . . B A U G ~ (GtEoaGFEs). Chroinous Ammonium Carbonate . . , . VANDENBERGHE (AD.). Preparation of Pure Molybdenum . . . VANDENBERGHE (AD.). Action of certain Gases on Heated Molyb- denum . . . . . . . . . . . . SCEXEIDER (ERNST ROBERT). Atomic mTeight of Tnngsten . . . MoIssm ( HENRI) and LENGFELD. A new Zirconium Carbide . . THOMAS (V.). Action of Nitric Peroxide and Air 011 Bismuth Chloride . MEYEB, (VICTOR). Fusibility of Platinum in a Wind Furnace fed with Carbon .. . . . . . . . . . . THOMSEN (JULIUS). Density of Hydrogen and of Oxygen . . . RIEGTER (E.). Decomposition of Silver Oxide by means of Hydrogen Peroxide . . . . . . . . . . . . CtRoss (THEODOR). New Electrolytic Nethod. . . . . . BESSON (ADOLPHE). Artion of Hydrogen Bromide and Hydrogen Iodide on Phosphorus Oxychloride . . . . . . . . FERBAND (LUCIEN). Thiophosphates . . . . . . . WEINLAND (R. F.) and 0. RUXPF. Sulphoxprsenates (Thioarsenates) . CCRALMOT (GUILLAME DE). Calcium Silicide . . . . , . DIDIER (GASTON). Basic Magnesium Nitrate. . . . . . HERTY (CHAELES H.). Recent Work on Double HaloTds . . . BAsKsRvILLE (CHARLES). Relations between Copper and Concen- trated Sulphuric acid . . . . . . . . . . SCHUTZENBERGER (PAUL) and 0.BOUDOIJA~D. Rare Earths in Mon- a2it.e Sands. . . . . . . . . . . . EEMARFAY (EU&NE ANATOLE). New Element in Rare Earths of the Samarinm Group . . . . . . . . . . MORSE (HARMON NORTHRUP), A. J. HOPKINS, and MILO 8. V i r ~ ~ l i ~ ~ . Reduction of Permanganic acid by Manganese Dioxide . . . GRANGER (A.). Crystallised Iron Sesquiphosphide . . . . . Fh~8-6: (JULES). Molybdenum Amalgam and some Properties of 1Molj-b- denum . . . . . . . . . . . . EOFMANN (KARL A.). A New Perthiomolybdic acid . . . . ii, 417 ij, 417 ii, 4J8 ii, 418 ii, 418 ii, 4.18 ii, 410 ii, 419 ii, 410 ii, 421 ii, 421 ii, 422 ii, 423 ii, 422 ii, 483 ii, 423 ii, 423 ii, &24 ii, 424 ii, 426 ii, 427 ii, 428 ii, 426 ii, 428 ii, 429 ii, 429 ii, 471 ii, 471 ii, 472 ii, 473 ii, 473 ii, 473 ii.473 ii, 474 ii, 474 ii, 474 ii, 475 ii, 475 ii, 47s ii, 476 ii, 476 ii, 476x r i CONTENTS. SOBOLEFF (M ). Physical Properties of Pl~o~phodoclecatnngstic acid . VENABLE (FRANK P.). Chlorides of Zirconium . . , . . BRIZARD (L.). Action of Reducing Agents ou the Nitroso-conipounds of Ruthenium . . . . . . . . . . . . OETTEL (FELIX). Electrolytic Formation of Hypochlorites and of Chlorat PS . . . . . . . . , . . . BAPER (K. J.). Manufacture of Potassium Chlorate . . . . MORLEY (EDWARD W.). Density of Oxygen , . . . . . Stany (GASTON). Tubular Ozone Generator . . . . . . ELBS (KARL) and 0. SCHONHERR. Formation of Persulpliuric acid . ELBS (KARL). Persdphuric acid . . . . . . . . RETUERS (JAN WILLEM). Posihion of Tellurium in the Periodic System HANTZSCH (ARTHUR RUDOLF). Hyponitrous acid .. . . , BESSON (ADOLPRE). Action of Hydrogen Bromide on Thiophosphoryl Chloride . . . . . . . . . . . . BORCHERS (WILHELX). Isolation of Lithium and of Beryllium . . ~ F L C (OTTOKAR). Electrolytic Silver Peroxide . . . . , GROSS (THEODOH). Experiments with Silrer Sulphide . , . . CARXOT (ADOLPHE). Crystals produced in the Dephosphorisation of Iron KIPPENBERGER (CARL). Reduction in Neutral Solutions . . . LEN HER (VICTOR). Lead Sulphiodide . . . . . , . ENXERLING (OsKaa). Enamel . . . . . . . . STICKNEY (DELIA). Reduction of Copper Sulphides , . . . SCHUYTEN (M. C.). Action of Nascent Iodine on Mercuric Chloride . DUFAU (E.). Barium Tetrachromite . . . . . . . GOTTIG (CHRISTIAN), Behaviour of Aluminium with Ammonium Com- pounds ; Method of producing Chemical Change on the Surface of Commercial Aluminium .. . . . . . . . WHITNEP (WILLIS RODNEY). Chromium Salta . . . . . MOISSAN ( HENRI). Uranium . . . . . . . . . HITCRCOCK (FANNY R. M.), Tungstates and Moljbdates of the Rare Earths . . . . . . . . . . . . TENABLE (FRANK P.) and CHARLES BASKERVILLE. Zirconium Sulphite THOMAS (V.). Action of Air and Nitric Peroxide on some Halogen Bis- muth Compounds . . . . . . . . . . ANTONP (UBALDO) and ADOLFO &nccHEsI. Precipitation of the Sulph- ides of Platinum : Collo%lal Platinic Sulphide . . . . . ENGLER (CARL) and W. WILD. Ozone . . . . . . . DUBKEE (FRANK W.). Oxidation of Sodium Sulphide and Hydrosulphide to Sulphate by Electrolysis . . . . . . . . ARCTOWSKI (HENRPK). Volatility of Red Phosphorus , .. . UESSON (ADOLPEE). Action of Hydrogen Iodide and of Phosplioniunr Iodide on Thiophosphoryl Chloride . . . , , . . CHALWOT (GUTLIAME J. L. DE). Crystallino Silicon . . HIGLEY ( GEORGE 0.) and W. E. DAYIS. Action of Metals on Nitric acid MITLDEB (EDUARD) and J. HERINGA. Silver Peroxy-nitrate . . . PERROT (J. LouIs). Decomposition of Zinc Chloride by Water . . KNOBLOCH (J.). Preparation of pure Zinc Sulphate from crude Zinc Vitriol . . . . . . . . . . . . COPPOCK (JOHN B.). Cupric Sulphide . . . . . . . DELAPONTAINE (MARC). Colloyd Coxpounds of rare &Ie!ills . . . DONATH (EDUARD). Action of Water, &c., on Aluminium . . . DONATE (EDUARD). Chemistry of Iron . . . . . . . GUICHARB (M.) . Molybdenite and the preparation of Molybdenum .Laassors (AKSEL). Niobium . . . . . . , . . PRUNIER (LEON). Preparation of Sodium Thioantimonate (Schlippe’s Salt) . . . . . . . . . . . . . UOYDER (GEORGE A.). Chemistry of the Cyanide Ppocess for dissolving G o l d . . . . . . . . . . . . . BBIZARD (L.). Double Salts of Ruthenium and SilT-er . . . . PAGE ii, 477 ii, 478 ii, 47I1 ii, 617 ii, 517 ii, 518 ii, 518 ii, 519 ii, 519 ii, 520 ii, 520 ii, 520 ii, 520 ii, 521 ii, 521 ii, 522 ii, 522 ii, 523 ii, 523 ii, 523 ii, 524 ii, 524 ii, 524 ii, 525 ii, 525 ii, 526 ii, 527 ii, 527 ii, 528 ii, 558 ii, 559 ii, 558 ii, 560 ii, 560 ii, 560 ii, 562 ii, 562 ii, 562 ii, 562 ii, 562 ii, 563 ii, 563 ii, 563 ii, 564 ii, 565 ii, 565 ii, 566CONTESTS. xvii MORLET (EDWARD W.). The Density of Hydrogen . . . , RAMSAY ( WILLTAX).Helium, a Gaseous Constituent of Certain Minerals. Part IT. Density . . . . . . . . LOCXTER (JOSEPE KORMAN). Xew Gas obtained from Uraninite . , LOCGFER (JOSEPH NORMAN). Gases obtained from the Mineral Eliasite LOCKYER (JOSEPH NORMAN). New Gases obtained from Uraninite . . KUEKEN (J. P.) and WYATT W. RANDALL. Expansion of Argon and of Helium as compared with that of Air and Hydrogen . . . . RAYLEIOH (LORD). Some Physical Properties of Argon and Helium . WAGXER (MAX). Acids containing Sulphur and Nitrogen , . . SABATIER (PAUL). Nitrosodisulphonic acid . . . , . . VIGO~BOCX (EXILE). Action of Silicon on Metals . . . . . BOSSEL (A.). Diamonds from Stcel . . . . . . , . COLSOS (R.). Action of Zinc 3n the Photogi.tlphic Plate . . . . PELLAT (HENFKI). Vaporisation of Metals at the Ordinsry Tempem- ture .. . . . . . . . . , . . MO:SSAN (HENRI). Preparation of AlIoj-s . . . . . . GA~TIER (HEWRI). Fusibility of Metallic Alloys . . . . . URAXOER (A.). Action of Phosphorus on Metallic Chlorides . . . MOURLOT (A). Action of High Temperatures on certain Sulphides. . TOXMASI (DONATO). nesiloerisation of Lead by Electrolysis . . . COXBES (CHARLES). Aluminium Alloys . . . . . . . AKTOKY (UBALDO) and G. G J ~ L I . Hydrolytic Decomposition of Ferric Kitrate and Sulphate . . . . . . . . . . HEIDE (K. VOK DEB) and KARL A. HOFMANN. Compounds of the Lower Oxides and Sulphides of Molybdenum with Ammonia and with Potassium Cyanide . . . . . . . . . . MOISSAN (HENR~). Tirng&en , . . . . . . . . HALLOPEAU (L. A.). Zirconotungstic Compounds .. . . . THOXA~ (V.). Action of Iodine on Stannous Chloride . . . . MOISSAN (HENRI). Vanadium and Vanadium Carbide . . . . TIIONAS (V.). . MOISSAN (HENHI). Solubility of Carbon in Rhodium, Iridium, and Palladium . . . . , , . . . . . , MORLEY (EDWARD W.). Atomic Weights of Oxygen and Hydrogen . SLYAPE (HESRY Lloyd). Replacement of Chlorine in the Chlorides of Non-mcta!s by Bromine and Iodine . . . . . . . SABAZIER (PA~L). Nitrosodisulphonic acid . . . . . . METZNER (R.). Preparation of Selenic. acid . . . . . . STAXOE (MARTIN). Metallic Compounds of Triphosphoric acid , . MOISSAN (HENRI). Artificial Production of Diamonds . . . . MOISSAN (HENRI). Black Di:tmonds . . . . . . . Rai%ssy (WILLIAM) and JOHN NORMAN COLLIE. Homogeneity of Argon and Helium . . .. . . . . . . . WARHEN {HENRY NEPEAN). Quick Nitrogen Absorbent for the Libcra- tion of Argon, and the Manufacture of Metallic Lithium . . . GAUTIER (HENRI). Alloys . . . . . . . . . DOFAU (E.). Magnesium Cobaltite . . . . . . . . LOREXZ (RICHARD). Electro-chemical Method of preparing Metallic ‘Ef r drmides . . . . . . . . . . . LOXE&Z (RICHARD). Electro-chemical Method of Preparing Metallie Sulphides . . . . . . . . . . . BRAUNER (BOHUSLAV). Action of Hydrogen Sulphide on Solutions of Cupric Salts . . . . . . . . . . . VARET (RAOUL). Mercuric Oxysalts . . . . . . . ARCTOWSKI (HENRYK). Artificial Dendrites . . . . . . RAP (P. C.). Mercurous Nitrite . . . . . , . . MOISSAX (HEWRI). Lanthanum Carbide . . . . , . . RICHAR~S (PERCY ANDREW ELLIS). Action of Mercury Salts on Alu- minium .. . . . . . . . . . . Action of Nitric Peroxide on Antimony Trichloride . VOL. LXX. ii. 2 PA@ R ii, 595 ii, 595 ii, 596 ii, 597 ii, 597 ii, 597 ii, 598 ii, 599 ii, 599 ii, 600 ii, 601 ii, 601 ii, 601 ii, 601 ii, 602 ii, 602 ii, 603 ii, 603 ii, 6(3 ii, 604 ii, 605 ii, 606 ii, 607 ii, 608 ii, 608 ii, 609 ii, 609 ii, 640 ii. G41 ii, 641 ii, 642 ii, 643 ii, G44 ii, 615 ii, 616 ii, 646 ii, GE6 ii, 647 ii, 647 ii, 6B ii, 648 ii, 6%8 ii, 619 ii, 643 ii, 650 ii, GEOCOSTENTS. ... XVlll LORENZ (RICHARD). Preparation of Potassium Permanganate by Electro- cliemical Means . . . . . . . . . . . GRANGER (A.). Action of Halogen Compounds of Phosphorus on Iron. Nickel, and Cosalt . . . . . . . . . . LORENZ (RICHARD). Preparation of Potassium Dichromate by Electro- chemical Means .. . . . . . . . . . CHBBTIEN (PAUL). Combination of Iodic acid with other Acids . . HALLOPEAU (L. A.1. Action of Ammonia on Alkali Paratungstates . . LABORDE (J. B. VINCENT). Specific Gravity and Speciric Heat of Alloys of Iron and Antimony . . . . . . . . , TENABLE (FRANK P.) and THOMAS CLARKE. Zirconates . . . . DELAFONTAINE (MARC) and CHARLES ELIJA~I LINEBARGEE. Reaction between Carbon Tetrachloride and the Oxides of Niobium and Tant- a l u m . . . . . . . . . . . . . Action of Reducing Agents on Osmium Nitroso-com- pounds . . . . . . . . . . . , BRIZARD (L.). Kine ra loqicaE Chemistry. RIRRE ( FRIEDRICII). Crystalline Form of chemically pure Simple Sub- stances . . , . . . . . . . . . SMITH (GEOEGE). Silver 3Iinerals of the Australian Broken Hill Consols Mine a .. . . . . . . . . . KRENNER (J~ZSEF A ). Lorandite, a New Thallium Mineral . . . BAUBIGNP (HENRI). Composition of Kermesite . . . . . PITTMAN (EDWARD F.). Wilfyamite, a New Mineral from Broken Hill, N.S.W. . . . . . . . . * . HILLEBRAND (WILLIAM F.). Calaverite from Cripple Creek, Colorado . LIVERSIDGE (ARCHIBALD). Nantokite, from New South Wales . . FRIEDEL (CIIARLES). Artificial Percylite . . . . . . . LIVERSIDGE (ARCHIBALD). Boleite from New Souti Wales . . . BROWR (C. BARRINQTOR) and JOHN W. JODD. Rubies of Burmali . HOBBS (WILLIAM H.). Ceruasite coated with Galena ; Manganite and Chloritoyd from Michigan ; Apatite and Hessonite in Pegmatite . THORPE (ALBERT). Analysis of Monazite . . . . . . SMITH (HENRY G.). Evansite from Tasmania.. . . . CARNOT (ADOLPHE) . Bed of Aluminium and Potassium Phosphates in Algeria . . . . . . . . , . . SJOGREN (S. A. HJALMAR). Retzian . . . . . . . GORGEE (ALEXANDRE). Artificial Gypsum . . . . . . FOOTE (WARREN M.) . Leadhillite Yseudomorphs in Missouri .*, . . GOLDSMITH (EDWARD). Eauriite, a New Mineral from Hawaii . . MICHEL (IJ~OPOLD) Melanterite containing Zinc . . . . . MIC~EL (L~OPOLD). Artificial Powellite. . . . . . . GOLDSXITH (EDWARD). Pimelite and Asbeferrite . . . . . WOLFF (T. E.) and RALPH S. TARE. Pelspar of the Acmite-trachyte of the Crazy Mountains, Montana . . . . . , . . LEQUER (L. McI.) and G. J. VOMKENING. Analyses of Sodalite from New Localities . . . . . . . . . . . CLAREE (FRANE W.). Constitution of the Lithia Micas . . . . CLAREE (FRANE W).Garnet from California. . . . . . WMITH (HENRY G.). Almandine Garnet from the Hawkesbury Sandstone, Sydney, N.S.W. . . . . . . . . . . . XELVILT~E (WILLIAM H.). Analysis of Anorthite from Raymond, Maine . . . . . . . . . . . . SCHNEIDER (EDWARD A.). Analysis of Prehnite from Fassrc, Tyrol . K O T ~ (BENDJIR~). Analysis of Biotite and Hornblende from Japan . FRIEDEL (CHARLES). Artificial Boleite . . . . . . PA QB ii, 650 ii, E5Ch ii, 651 ii, 651 ii, G5Z ii. 652 ii, 653 ii, 653 ii, 653 ii, 29 ii, 29 ii, 30 ii, 31 ii 31 ii, 31 ii, 31 ii, 32 ji, 32 ii, 32 ii, 38 ii, 33 ii, 34 ii, 34 ii, 34 ii, 35 ii, 35 ii, 35 ii, 35 ii, 36 ii, 36 ii, 36 ii, 37 ii, 37 ii, 37 ii, 38 ii, 35 ii, 38 ii, 38 ii, 39COSTENTS, XIX PAGE EAKINS ((3. L.). Analysis of Ottrclite, Pyroxene, Garnet, Eyidote, Scole- cite, and Xenotime .. . . . . . . . . HILLEBBAND ( WILLKAM F.). Analysis of Nickel Iron Sulphide, Bauxite, CURRAN (J. MILNE). Basalt from Bondi,'N.S.k. . . . . . THORPE (ALBERT). Analyses of Leucite-basalt from Vesuvius . . . GOLDSXITH (EDWARD). A Tempered Steel Meteorite . . . . CASARES (Josii). Occurrence of Fluorine in Certain Mineral Waters . 3Ioss (RICHARD J.). A Graphitic Schist from Co. Donegal . . . BECKE (FRIEDRICE). Wurtzite from Mies, Bohemia . . . . IPPEN (J. A,). Artificial Cinnabar . . . . . . . . GOODWIN (WM. L.), Nickeliferous Pyrites . . . . . . BAUNHAUER (HEINRICH). Skleroklase (Sai*torite) from Binn. . . SJOGREN (S. A. HJALMAR). Safflorite from Nordmark, Sweden . . DAXOUR (AUQUSTIN A.). Piorite . . . . .. . . BRIEDEL (CHARLES). Artificial Martite . . . . . . . SJOGREN (S. A. HJALMAR). Pyroaurite from the Mossgrufva, Nordmark, Sweden , . . . . . . . . . . . BOURGEOIS (LEON). Artificial Crystallised Carbonates . . . . SJOGEEN (5. A. HJALXAR). Fluid Emlosures in Uypsum) . . . BRAUNS (REINHARD). Artificial Anhydrite . . . . . . FRENZEL (AUQ.UST). Serpieritc, Lautite, and Pseudobrookite . . MICHEL (L~~oPoLD). Hautefeuillite, from Bade, Norway . . . SJOQREN (53. A. HJALMAR). Caryinitc . . . . . . . EJOGREN (S. A. KJALMAR). Soda-berzelite from Lhgban, Sweden. . SJOGREN (5. A. HJALMAR). Lhngbanite from the Sjogrufva, Sweden . GENTIL (LOUIS). Apophylite from Algeria . . . . . . SJOGBEN (5. A. HJALMAR). Prolectite, a New Mineral of the Humite Group . . . . . . . . . . .. ~ ~ O G R E N (S. A. HJALMAR) . Composition of Chondrodite, Kumite, and Clinohumite from Nordmark . . . . . . . . SJOGREN (3. A. HJALMAR). Soda-ricbterite from LLngban, Sweden . DAMOUR (AUGUSTIN A.). New Analyses of Chloromelanitc . . , GENTIL (Lours). Andradite-garnet from Algeria . . . . . BACKSTROM (HELGE). Artificial Aegirine . . . . . . HAERINGTON (BERNARD J.) . Composition of Canadian Limestones and Dolomites . . . . . . . . . . . . KLEMENT (CONSTANTIN). Procees of Formation of Dolomite-rock . . HATCH (FREDERICK H.). Lower Carboniferous Volcanic Rocks of East Lothian . . . . . . . . . . . . TEALS (J. J. HARRIS) and JOHN HORNE. Borolanite, a New Igneons Rock HIBSCH (J. E.). Analyses of Augite and Nepheline-Leucite-Teplirite from Bohemia . . . . . . . . . , .BOUCHARD (CH.). Argon and Helium in Mineral Waters . . . CHABEI~ (CAMILLE). Composition of Water of the Pacific , . . SCHEBZER (W. H.). Native Sulphur in Michigan , . . . . MOISSAN (HENI~I). Black Carbonado from Brazil . . . . . &foIssAN (HENRI). Graphite from a Pegmatite . . . . . KIRPLAND (J. BOOTH). Gallium and Indium in a Blende from Peel- wood, N.S.W. . . . . . . . . . . . LOVISATO (DOMENICO) . The Senarmontite of Nieddoris, and the minerals accompanying it, Arite, Breithauptite, Gersdorffite and Smaltite , LINCE (GOTTLOB ED.). Hercynite from Vdtellina . . . . , FOOTE (WARREN M.). Northupite, a New Mineral . . . . , SXEY (WILLIAM). Nature of Stinkstone (Anthraconib) . . . . PENFIELD (SAMUEL L.) and JULIUS H. PRATT. Optical properties of Lithiophilite and Triphylite .. . , . . . , GAUTIER (E. J. ARMAND). Genesis of Natural Phosphates and Nitrates MALBOT (H.) and A. MALBOT. Phosphates from Algeria.. Phosphatic Rock at Bougie having the Composition of a Superphosphate . Felspars, and Piedmontite . . . . . . . . 2-2 ii, 39 ii, 39 ii, 40 ii, 41 ii, 41 i i , 42 ii, 108 ii, 108 ii, 208 ii, 109 ii, 109 ii, 109 ii, 109 ii, 110 ii, 110 ii, 110 ii, 110 ii, 111 ii, 111 ii, 112 ii, 112 ii, 313 ii, 113 ii, 114 ii, 114 ii, 114 ii, 114 ii, 115 ii, 115 ii, 115 ii, 116 i;, 116 ii, 116 ii, 117 ii, 117 ii, 117 ii, 117 ii, 152 ii, 182 ii, 182 ii, 183 ii, 183 ii, 183 ji, 184 ii, 184 ii, 184 ii, 185 ii, 185xx CONTENTS. PLISK (GUSTAT'). Kentrolite from Ltingbaii . , . . , . SCliMELCX (LUDWIG). Thorium and Yttrium Mineral3 of Norway, .BENNEVILLE (JAMES 8. DE). Analjses of Beryl . , . . . LEBEAU (PAUL). Analrses of the Emerald . , . . . . LACROIX (ALPRED). Optical Properties of some Compact and Earthy Silicates . . . . . . . . . . . . KATZER (FRIEDRICK). Opal, Anddusife, Tourmaline, Sillimanite, Cordi- erite, Pinguite, and Hoeferite from Boliemia . . . . . ZSCHAU (E.). Zeolites of the Syenite, near Dresden . . . . WALLERANT (Fa.). Isomorphism of the Felspars (nlbite-anorthite) . BAXKELSBERG (CARL F.). The Leucite-nepheline Group . , . HOFFMAHN ((3. CHRIsrIaw). Ilvaite, EIarmotome, Opal, Thinaite, Sclieelite, Chroniiferoas Muscovite, Gersdorffite, and Nickeliferous Pyrrliotite, from Canada . . , . . . . . HILLEBRAED (WILLIAM F.). Wide-spread Occurrence of Barium and Strontiumin SilicateRocks .. . . . . GEIICIE (Sir ARCHIBALD) and J. J. IIARRIS TE~LL. Banked Gabbros 0; ' S l i y e . . , . . . . . . . . . . WEED (WALTER H.) and LOUIS V. Prnsso~. Igneous Rocks of Yogo Peak, Montans . . . . . . . . . . . SPErGHT (R.). Olivine-andesite of Banks Peniiisuln, N.Z. . . . MARSHALL (PATRICK). Tridyinite-trachyte of Lyttleton, N.Z. . . MIWGAYE (JOHN C. H.). . HOWELL (EDWIN E.). The Cherokee and El Capitan Meteorites . . M O~SSAN (HEXRI). Meteorites . . . . . . . . CRAIG (ANDREW W.) and N. T. &I. WILSMORE. Water from Lake Corangnmite, Victoria. . . . . . . . . . STEIGER (GEORGE). Water from Nashville, Illinois, and from the Soap Lake, Washington . . . . . . . . . . HILLEBRAND (WILLIAM F.). Analysis of Watcr from Ojo Gdiente, New Mexico . . . . . . . . .. . . YABMENTJER (F.). Bituminous Mineral Waters containing Ammonia . CARD (GEORGE W.). Ylatinurn, Pickeringite, and Magnesia zinc alum from New South Wales . . . . . . . . . LOSAXITCH (SIMA M.). Analyses of Gold, Xeerschaum, Amber, and Magnetite from Serria . . . . . . . . . JOHN (CONRAD )I. TON) and C. F. EICJILEITER. Analyses of Austrian Minerals . . . . . . . . . . . . TORRICO P MBCA. Vtma,diferous Cod from Peru . . . . , HELM (OTTO). Burmite, a new .Amber-like Resin from Upper Burmah . SCHNEIDER (R.). Composition and Constitution of Cubanite (Cupro- pyrite) . . . . . . . . . . . . CESABO (GIUSEPPE). Artificial Precious Opal . . . . . TSCHELXAK (GUSTAV). Emery from Naxos . . . . . , HOLLAXD (THOMAS H.). Magnetite from the Madras Presidency con- taining Manganese and Aluminium .. . . . . . MULLER (WILHELM). Artificial Hematite, and Magnetite . . . STABOJEV:~ (A.). Analyses of Magnesite, Dolomite, Mica, and MagneIite from Servia, . . . . . . . . . . . TBAUBE (HERXANN). Iglesiasite, Tarnowitzite, and Hemirnorphitc from Silesia . . . . . . . . . . . . NORDEWSKI~LD (GUSTAF). Spodiosite from Nordmark . . . , CARD (GEORGE W.). Celestite from Bourke, N.S.W. . , , , HAXMOND (P. T.). A Supposed Sulphocarbonate of Lead . . . BRUNLECHNER (AuG~sT). Zinciferous Melanterite, Seelsndite, and (' Zinkmmganerz . . . . . . . . . NOBDENEKIOLD (GUSTAF). Kentrolite from Jakobsberg . . . . SPEZIA (GIORGEO). Action of Water on Apophyllite , . . . HOPFMANN ((3. CHRISTIAN). Lepidomelane, Actinolite, Andradite, (Xrossular, Hornblende, Clinochlore, Talc, Diallage, Damouri to, Meteorite from Moonbi, Tamworth, N.S W, PAGB ii, 186 ii, 186 ii, 186 ii, 187 ii, 187 ii, 18'7 ii, 189 ii, 189 ii, 183- ii, 190 ii, 191 ii, 191 ii, 192 ii, 192 ii, 193 ii, 193 ii, 193 ii, 199 ii, 194 ii, 194 ii, 194 ii, 193 ii, 251 ii, 252 ii, 232 ii, 252 ii, 259 ii, 253 ii, 253 ii, 253 ii, 254 ii, 254 ii, 254 ii, 255 ii, 255 ii, 256 ii, 256 ii, 256 ii, 257 ii, 257CONTENTS. XXi Sei*icite, Cookeito, Cobaltiferous Lollingite, Bismuthit e, Strontianite, and Native Iron from Canada .. . . YL ~TANIA (GAETANO). Xiphonite, a New imphibole [Hornblendej from Etna . . . . . . . . . . . . JANNASCH (PAUL) and P. WEINGARTEN. Chemical Composition and Constitution of Vesuvian [Idocrase] and Wiluite . . . . MEBRILL (GRoRaE P.). . HOLLAND (THOMAS H.).Hislopite . . . . . . . . HOLLAND (PHILIP) and EDMUND DICKSON. Alteration of Diabase and Granite : Formation of Clay . . . . . . . . ZALESKI (STANISLAUS vox). Amount of Silica aiid Quartz in Granites . CARD (GEORGE W.). Fuller’s Earth from Wingen, N.S.W. . . . KUNZ (GEORGE FREDERICK). Phosphorescent Diamonds . . . BUCCA (L.). Artificial Formation of Magnetic Pyrites (Pyrrhotite) . IGELSTROM (LARS JOHAN). Plumboferrite from the Sjo Mine, Sweden . ARCTOWSKI (HENRYK). New method of Producing Artificial Oligiste (HEematite) . . . . . . . . . . . KLOCENANN (FRIEDRICH). Nickel Ore [Ger~dorfEke] fEom the Upper H a m . . . . . . . . . . . . . IGELSTR~M (LARS JOHAN). Rhodophosphite and Tetragophosphite, two New Minerals from Horrsjoberg, Wermland . . , . . PENNINGTON (MARY ENOLE).[Uolumbite from Wakefield. New Hamp- shire] . . . . . . . . . . . . . HAMBEBG (AXEL). Inesite from Jakobsberg, Sweden . . . . ARZRUNI (ANDREAS). Forsterite from Monte Somnia . . . . REBUFFAT (ORAZIO). Guarinite . . . . . . . . CHESTER (ALBERT H.). Caswellite, an altered Biotite from Franklin Furnace, N. J. . . . . . . . . . . . WEINSCHENK (ERNST). Andalusite and Spessartite from Bodenmais, Bavaria . . . . . . . . . . . . SOLLAS (WILLIAM JOHNSON). BAUER (MAX). Jadeite from “ Tibet ” . . . . . . . FARRINGTON (OLIVER CuMMmas). Jadeite from Mogoung, Burma . BAVER (MAX). Jadeite, Albite, and Glaucophane, from Tammaw, Upper Burma . , . . . . . . . * . LUDECKE (OTTO). Epidotkfrom theHarz . . , . . . BARVI~ (HEIBRICH). Alteration of Garnet . . . . .. WEINSCHENK (ERNST). The Garnet Group . . . . . HOLST (NILS OLOF). Beaumontite from Sweden . . . , . REBUFFAT (ORAZIO). Analysis of Emerald (1) . . . . . FRANCO (P.). Amphibole [Hornblende] and Sodalite from the Trachyte of Montesanto, Naples . . . . . . . . . HOLMQUIST (P. J.). Knopite, a New Mineral near Perofskite, from Alno, Sweden . . . . . . . . . . . , BLUMRICII (Jos.) [Hainite in the] PBonolites of North Bohemia . . WEIDMAXN (SAMUEL). Quartz-Kerrttophjre of the Baraboo Bluffs, Wisconsin . . . . . . . . . . . . FBESENIUS (CARL REMIGIUS). Analysis of the Victoria Spring, at Ober- lalinstein . . . . . . . . . . . , KASINI (RAFFAELE) and FRANCESCO ANDERLINI. Examination of Terres- trial Emanations for Argon : Gas from the Thermm of Abano . . LUZI (WILLI). Graphitoid .. . . . . . . . WALEER (T. L.). Sperrylite . . . . . . . , . HAMBERG (AXEL). Etching of Calcite . . . . . . . PENFIELD (SAMUEL LOUIS) and JULIUS HOWARD PRATT. Thaumasite from West Paterson, New Jersey. . . . . , . . HERZ (WALTER). Salvadoritc, a new Copper Iron Sulphate . . , KOSMANN (HANS BERXITARD). Borates in the Stassfurt Abraum SaIts . RINNE (FRIEDRICH). Action of Sulphuric and Hydrochloric acids on HeuIandite: an Artificial form of Silica . . . . Origin and Composition of Onyx Marbles . ARZRUPI (ANDREAS). Artificial Cassiterite . . . Crystalline form of Riebeckite . ii, 251 ii, 259 ii, 259 ii, 260 ii, 261 ii, 261 ii, 262 ii, 262 ii, 306. ii, 306 ii, 30? ii, 302- ii, 307 ’ ii, 30F ii, 30% ii, 308. ii, 308 ii, 309 ii, 309 ii, 310 ii, 310. ii, 310- ii, 311; ii, 31% ii, 312: ii, 312 ii, 312 ii, 312 ii, 313 ii, 309 ii, 313 ii, 313 ii, 314 ii, 314 ii, 315 ii, 366 ii, 366 ii, 366 ii, 366 ii, 36’7 ii, 368 ii, 368 ii, 368xxii CONTENTS.ZEMJATSCHENSKY (PIETR A.) . Desmine [Stilbitc] and Laumontite from the Caucasus . . . . . . . . . . , NORDENSKIOLD (NILS ADOLF ERIK). Fluorine in ApGphyllite . * LINDER (A.). Clarke and Schneider’s Constitutional Forniulu for Ser- pentine . . . . . . . . . . . . RAKSOME (I?. LESLIE) and CHARLES PALACHE. Lawsonite, a new Rock- forming Mineral from California . . . . . . . . FEOXME (JOHANNES) , Minerals (Zeolites, &c.) of a Thnringian Amphibole- graiiitite . . . . . . . . . . . . HEBERDEY (PH.). Qehlenite and Wollastonite in Slags from Yrzibranz . FORBES (E. H.). Epidote from Huntington, Mass., and the Optical Pro- perties of Epidote .. . . . . . . . . USSING (N. V.). Mineials of the Nepheline-syenite of Greonland . . THADDI~EFF (EOKSTANTIN). Thc Olivine Group . . . . . PENFIELD (SAMUEL Lours) and E. E. FORBES. Fayalite from Kockport, 1Slass., and the optical Charncters of the Olivine Group . . . ADAMS (FRASK I).) and BERXARD J. HARRIWTON. A New Alkali Horn- blende, Hnsting-ite, and s Titaniferoru Andradite from Dungannon, Ontario . . . . . . . . . . . . SOLTMANN (RUDOLF). Chemical Beha.\-ionr of fiome naturally occurring Titanium Compounds . . . . . . . . . . SCHWEIXITZ (EYILE ALEXANDER DE). Meteorite from Fors-J% Co., Xorth Carolina , . . . . . . . . . ~ T O L B A (PRANZ). Nstire Gold from Eule, Bolreniia . . . . LEMBERG (JOHAISN).Microclien~ical Renctiocs of Minerals of the Lamprite Group. . . . . . . . . . . NATARRO (LUCAS FEBNANDEZ). Quiroguite . . . . . . LAUR (FRAXCIS). Composition of Bauxites . . . . . . ROHRER (R.). Ht-ematite from Elba . . . . . . . EOSMANN (HANS BERNARD). Magnetic Iron Hydroxide, . . . SCHWAGEE (ACOLPH) and C. WILHELX TON GUMBEL. Analyses of Bavarian Minerals . . . . . . . . . . WULFIKGF (ERKST A.). Pyroxene from Renfrem . . . . . VIOLA (C.). Albite from Crete. . . . . . . . . LOVREKOTI~ (ST.). Zoisite from Stjris . . . . . . . SALOMOIS ( WILHELM) . Wernerite (Dippre) from Breno, Lombardy . HANANANN {JOSEPH). Moldavite from Bohemia . . . , . HOSKINS (A. PERCY). Glauconite from Co. Antriin . . . . CROCQ (J.). Cobalt in the Sands of Woluwe-Saint-Lambert . . . NASON (FRANK L.).Limestones of Sussex Co., New Jersey . . . REIBEXSCAUH (ANTON FRITZ). Mineral Waters from Styria . . . DIXTRICH (H.). Water from Klebelsberg Spring, Ischl . , . . REIBENSCHUH (ANTON FRITZ). Mineral Water from Radein, Styria . FRESENIUS (CARL REMEGIUS) . Variations in Cornposition of Mineral Waters at Different Periods . . . . . . . . COHEN (ExIL). A Salt Lakein the Trsnsvaal , . , . . CESAPO (GIUSEPPE). Alteration Products of Blende , . . . GIN (GUSTAT). Ochres . . . . . . . . . . SCHTCKENDANTZ (FEDERICO). Analyses of Argentine Minerals . . COOKSEY (THOMAS). Basic Sulpliate of Iron from Mount Morgan, Queensland . . . . . . . . . . . . EONINCE (LTJCIEN Lours DE). Artificial Hydrated Magnesium Silicate . CESARO (GIUSEPPE). A Silicate probably belonging to a New Mineral Species .. . . . . . . . . . . FRIEDEL (Gtsoaam). Zeolitea, and the Substitution of various Sub- FRIEDEL (GEOIWES). A New Artificial Silicate . . . . . FRIEDEL (OEORGES). Antclcite. . . . . . . . . EICHLEITER (C. FRIEDRICH), Natrolite from Momvia . . . . FOTJLLON (HEINRICE TOX)). Asbostos from Bosnia . , , . . ~ T O L B A (FRAXZ). Limestolie from Eon&prns, Bohemia . . . stances for the Water they contain . . . . . . ii, 369 ii, 369 ii, 369 ii, 350 ii, 3’70 ii, 371 ii, 371 ii, 3 2 ii, 3i2 ii, 373 ii, 374 ii, 374 ii, 375 ii, 429 ii. 430 ii, 430 ii, 430 ii, 431 ii, 431 ii, 431 ii, 432 ii, 433 ii, 433 ii, 433 ii, 434 ii, 434 ii, 434 ii, 435 ii, 435 ii, 435 ii, 435 ii, 435 ii, 435 ii, 436 ii, 479 ii, 479 ii, 480 i;, 480 ii, 480 ii, 481 ii, 481 ii, 482 ii, 482 ii, 432 ii, 4e3COKTENTS.xxiii CANAVAL (RICHARD). Altered Biotite and Tremolite from Stgria , . IPPEN (J. A). Dolomite from Graz . . , . , . . MERRILL (GEORGE PERKINS). Disintegration of Granite in the District of Columbia . , . . . . . . . , . HUNTINGTON (GLIVER WHIPPLE). The Smithville Meteoric Iron , . ZSCHIMXER (E.). Hyacinth (Quartz) in Gypsum, nem Jena . . . MARTENS (PABLO). A New Cobalt Mineral . . . , . . GAUTIER (FERDINAND). Formation of Tin Veins . . . . . MARLOTH (R.). Origin of Nitrates in Griqualand West . . . . CARXOT (ADOLPHE). Aluminium and Potassium Phospbtes , . PISANI (FBLIx). Thaumasite . . . . . . . . , CARD (GEORGE WILLIAM). Pickeringite from New South Wales . . PACKARD (R. L.). A Blue Mineral, Supposed to be Ultramarine, from New Mexico .. . . . . . . . . . REJCR (ALFICED). Synthesis of Topaz . . . . . . . XRUSCH (P.). [Phillipsite from Wingendorf, Prussian SiIesia] . . FOUQUB (FERDINAND). Felspars of Igneous Rocks . . . . . HENDERSON (J. 35. C . ) . Mica-Syenite from Rothschanberg, Saxony . HIBSCH (J. E.). [Analpsof Sericite, Augite, and Waters from Bolieniia] JAQUET (JOHN BLOCKLEY). Serpentine after Amphibolite . . . CURRAN (J. MILWE). A Mineral Spring a t Bungonia , , . . DAMBERGIS (ANASTASIUS E.). The New Hot Springs of Bdipsos and Gialtra . . . . . . . . . . . . SCHCLZE (ERWIN). Classification of Minerals according to the Periodic System . . . . . . . . . . . DOHERTP (W. M.). Arsenic in Coal . . . . . . . CIEESTER (ALBEIET HUNTIEGTON). Acanthite from Colorado , . . JEREX~EFF (PAVEL V.TON). Pseudornorphs of Copper Oxides and Sulphicles . . . . . . . . . . . . ALEX~EFF (WLADIXIR). Pitkeringite from the River Bfann District . CHRUSTSCHOFF (K. TON). Analyses of Samarskite, Pyrochlore. Tantaiite, and Niobite [Columbite] . . . . . . . . . GLINKA (SElmEr g.). Cheiuical Coniposition and c&ical Properties of Russian Albite . . . . . . . . . . . ZEXJATSCHEFSKP (PETR A.). Glauconite . . . . . , JANNASCK (PaTsLj. [Andalusite or Dumortierite in Argentine Granite] , WEINSCHEXK (ERNST). Epidoteand Zoisite . . . . . . COLOMBA (LUIGI). Glaucophane from Beauine . . , . . ERDMANN (HUGO). Occurrence of Ammoniaral Nitrogen in ancient Igileous Rocks . . . . . . . . . . . SCHULTEN (AUGUST BEEJAXIN, BARON DE). Reproduction of Sodium BZagnesium Chlorocarbonate, Sodium Magnesiiini Carbonate, Darap- skite, and Hydrargillite (Gibbsite) .. . . . . . HOPMANN (A.). Witherite from Przibwm . . . . . , PETH~ (GYULA). Chrysocolla in Andesite-tuff. . , . . , CARNOT (ADOLPHE). Variations in the Composition of Apatites . . ASTON (EXILY ALICIA) and THOMAS GEORGE BONNEY. An Alpino Nickel-bearing Serpentine . . . . . . . . . OHELIUS (C.). PEARCE (RICHARD). Mode of Occurrence of @old in the Ore [Rhyolitej of the Cripple Creek district . . , . . . . . PEARCE (RICHARD). Cripple Creek Ores. . , . . . . XNIGHT (F. C.). A Suspected New Mineral from Cripple Creek . . HYNDMAN (HUGH H. F.) and THOXAS GEORGE BONNEY. Analyses of Spherulites and Matrix of Rocks . . . . . . . HILLS (RICHAILD C.). The Costilla Meteorite . . . . . . RENARD (ALPEONSE FRANQOIS).Meteorite of Lesves . . . . FELICIANI (G.). Acid Spring near Rome (Ponte Molle) . . . . NEUMANN (SIGISMUND). Water from the Chalybeate Spring of 6vBri . Water of the Kaw River and its Tributaries . . . , . [Analyses of Orthoclase from an Odenwald Granite] BAILEY (EDGAR HENRY SUMMERFIBLD) and EDWARD c. $RANKLIN. PAGE ii, 483 ii, 483 ii, 483 ii, 484 ii, 528 ii, 5.29 ii, 529 ii, 529 ii, 529 ii, 530 ii, 530 ii, 530 ii, 531 ii, 532 ii, 532 ii, 533 ii, 534 ii, 534 ii, 534 ii, 535 ii, 566 ii, 566 ii, 565 ii, 566 ii, 566 ii, 567 ii, 567 it, 568 ii, 568 ii, 568 ii, 569 ii, 570 ii, 610 ii, 610 ii, 611 ii, 611 ii, 611 ii, 612 ii, 612 ii, 613 ii, 613 ii, 614 ii, 614 ii, 614 ii, 615 ii, 615 ii, 615XXiV CONTENTS. WEINSCHENK (ERNST). The “ Dilute Coloration ” of Minerals .. SCHL(ESING (TH., jun.). Nitrogen and Argon in Fire-damp . . . KELLAS (ALEXAXDER) and WILLIAM RAMSAY. Examination of Gases from certain Mineral Watess . . . . . . , . TILDEN (WILLIAM AUGUSTUS). An attempt to determine the condition in which Helium and the Associated Gases exist in Minerals . BROWNE (FRANK). Japanese Coal . . . . . . . . ABT (AKTAL). Magnetic behaviour of Pyrrhotite . . . . . P~LPP (M~R). Pyrrohotite from Bor& . . , . . . . LIVERSIDGE (ARCHIBALD). Some New South Wales and other Minerals PENFIBLD (SAMUELEWIS). Pearceite and the Crystallisation of Poly- basite . . . . . . . . . . . . . BAUMHAUER (HEINRICH). Rathite, R new Binnenthal Mineral . . LASPEYRES (ERNST ADOLPH HUQO) and E. KAISER. Calcistrontite, “Feather O1*e,” &c.. . . . . . . . . , FOOTE (H. W.). Pollueite, Manganocolumbite, and Microlite from Rumford, Maine. . . . . . . . . . . MOSES (ALFRED J.). Mineralogical Notes [Seapolite, kc.3 . . . , Physiological Chemistiy. REID (E. WAYYOUTH) and FREDERICK J. HAYBLY. Cutaneous Respira- GOTTLIEB. Action of Mustard and Pepper on Digestion . . . . HAEDY (W. B.) and F. F. WESBROOK, Wandering Cells of the Alimen- ROHMANN (FRANZ) and J. LAPPE. The Lactase of the Small Intestine . TANGL (F.). Influence of the Vaso-motor Nervous System on Meta- bolism . . . . . . . . . . . . MUXK (IMNANUEL). Metabolism . . . . . . . . STOCKMAN (RALPH). Iron in Food . . . . . . . . STOKVIS (B. T.). Sugar as a Food . , . . . . . . Mosso (UGOLINO). Sugar as a Food . . . . . . . HARLEY (VAUGHAN).Sugar as a Food . . . . . . . TSUJI (C.). Mannan as Human Food . . . . . . . WOODS (CHARLES D.) and C. S. PHELPS. Feeding Experimcnts on Sheep . . . . . . . . . . . . . RAMM (E.). Feeding Experiments with Brushwood . . . . KBLLNER (OSCAR), A. ~(OHLER, and F. BARNSTEIN. Examination of Foods from Farms where Cattle suffered from Brittleness of the Bones . . . . . . . . . . . . . PICKERING (JOHN W.). , EUNKEL (Jos. A.). E’ormation of Blood from Inorganic Iron . . . TANGL (F.) and VAUGFHAN HARLEY. Physiology of Blood Sugar . . STEWART (GEORGE N.). Circulation Time . . . . . . SCHENCK (Fa.). Muscular Work and Glycogen . . . . . FURTH (OTTO vos). Prote’ids of Muscle Plasma . . . . . RIXGFER (SIDNEY). Antagonism between Salts of Cslcium and those of Sodium, Potassium , and Ammonium .. . . . . . GOURFETN (D,). Toxic Substance from the Supra-renal Capsules . . PREGL (FRITZ). X u c ~ ~ ~ E r ~ t e . r i t w o f Sheep . . . , . LEATHES (J. B.). Artificial HydrEemic Plethora . . . . . HAMBURGER (HARTOG J.), Physical Factors in Absorption . . MUXK (~MMANUEL). Potassium Thiocyanate in Saliva . . . . OECHSNER DE CONIBCK (WILLIAM). Elimination of Calcium Compounds in Rachitis . . . . . . . . . JOLLSS (ADOLF). Uiobilk . . . . . . . . WALLER (AUWJSTUB D.) Action of Anesthetics on Nerve . . HALDANE (JOHN S.). Action of Carbonic (?side on hian . . tion in the Frog . . . . . . . . . . taryCana1 . . . . . . . . . . . Action of Drugs on the Embryonic Heart. PAQB ii, 654 11, 655 ii, 655 ii, 655 ii, 656 ii, 656 ii, 657 ii, 657 ii, 658 ii, 658 ii, 660 ii, 6€Q ij, 661 ii, 42 ii, 42 ii, 42 ii, 43 ii, 43 ii, 43 ii, 43 ii, 44 ii, 44 ii, 44 ii, 44 ii, 44 ii, 45 ii, 46 ii, 46 ii, 49 ii, 47 ii, 48 ii, 48 ii, 48 ii, 49 ii, 49 ii, 49 ii, 50 ii, 60 ii, 50 ii, 60 ii, 51 ii, !52 ii, 52QJNTENTS.XXV FILEHNE (WILHELM) and H. KIONKA. Respiratory Metabolism . . DASTRE (A.). Action of Salts on the Gastric Digestion of Fibrin and of Acids on the SalineDigestion of Fibrin . . . . . . ABELOUS (J. E.) and 0. BIARBBS. . BOURQUELOT (BMILE) and EUGBNE GLEP. Action of Blood Serum on Glycogen and Maltose . . . . . . . . . XAUFMANN (MAURICE). Formation of Glycogen in the Animal Organism DASTRE (A.), Formation of Glpcogen in the Animal Organism , . DASTBE (A.). Glycogen in the Lymph . . . . . . . FRANXEL (SIGMUND). Thjreo-antitoxin .. . . , . . RICEET (CH.). Uropoyetic Diastase . . . . . . . PIZZI (AUGUSTO). Composition of the Milk of Various Animals . . CAZENEUVE (PAUL). Sterilisation of Milk acd the Lactic Fermentation . MORNER (KARL A. H.). Protei'ds of Normal Urine . . . , . ACKERMANN (EDWIN). Excretion of Creatinine during Xuscular Work on a Mixed Diet. . . . . . . . . . , Ronss~. Resistance of Invertin to Heat . . . . , . . TERNCN (HORACE M.). Respiration in Marine Invertebrates . . . WISSEL (ERNST). Gas Formation in the Human Stomach . . . LEATHES (a. B.). Exchange of Liquid between Blood and Tissues . . LAZARUS-BARLOW (W. S.). Initial Rates of Osmosis of certain Substances in Water and in Liquids containing Albumin , . . . . STARLING (ERNEST H.). Intravascular Injection of Peptonc .. WOLTERING (H. W. F. C.). SEBELIEN (JOHN). Effect of Feeding Corns with Whale and Herring &leal, especially as regards Milk Production . . . . . . WICKX fA.) and HUGO WEISKE. Digestibility and Nutritive Value of Pumpkin Seed Cake and Buckwheat Grain . . , . . HOPKINS (F. GOWLAND). Pigments of the Pierids . . . . WINTER (J.). Constancy of the Freezing Point of Milk and other Organic RUPPEL (W. G.j. T7ernix caseosa . . . . . , . . JOHNSON (Sir GEORGE). The absence of Sugar from Normal Urine proyed by a New Method . . . . . . . . . GRBHAKT (NESTOR). Poisonous Effects of Acetylene . . . . BERTHELOT (MARCELLIN). Poisonous Effects of Acetylene . . . MOISSAN (HENILI). Poisonous Effects of Acetylene . . . . ERUGER (MARTIN) and GEORG SALOMON. Constitution of Xeterosan- thine and its Physiological Action .. . . . . . BALK (EDMUND). Derivatives of Hydrastine and Narcotiric . . . LEHMANN (PRANZ). Metabolism experiment on Sheep with a Pettenfiofer Respiration Apparatus . . . . . . . . . BAUMANN (EUGEN). Normal Occurrence of Iodine in the Body . . MARTIN (CHARLES JAMES). A Rapid Method of Desiccating and Steri. lising Serum . . . . . . . , . . , DUNLOP (JAMES CRAUFORD). Excretion of Oxalic acid . . . . STOCKMAN (RALPaj. Experimental Ansmia in Dogs . . . . ABRAM ( JORN HILL). Ace tonuria . . . . . . (. . GABBOD- (ARCHIBALD E.) and F. G; OWLAND HOP KIN^. Hsmatoporphyri- nuria . . . . . . . . . . . . . XAYO (N. S.). Cattle Poisoning by Potassiiim Nitrate . , . . BBOCINER (L.). Poisonous Effects of Acetylene . . . . . BOTRQUELOT (EMILE ELI$) and EUG~NE GLEY.Digestion of Trehalose MENDEL (LAFAYETTE B.). Passage of Sodium Iodide from the Blood to the Lymph. . . . . . . . . . . . TOMES (CHARLES S.). Chemical Composition of Enamcl . . . NOEL-PATON (DIARXID). Relation of the Liver to Fats . . . . COUVBEUR (E.). Transformation of Fat into Glycogen in the Silkrorm duriDg MetamorpLosis . . . . . . . . . Oxidising Power of the Blood . Absorption of Iron Salts Liquids . . . . . . . . . . . LIEBLEIN (VICTOR). A Dermoid Cyst . . . . . . PAQB ij, 118 ii, 118 ii, 119 ii, 119 ii, 119 ii, 119 ii, 119 ii, 119 ii, 119 ii, 120 ii, 120 ii, 120 ii, 12L ii, 195 ii, 196 ii, 196 ii, 122 ii, 196 ii, 197 ii, 19f ii, 197 ii, 198 ii, 198 ii, 199 ii, 199 ii, 199 ii, 200 ii, 200 ii, 200 ii, 203 ii, 201 ii, 262 ii, 263 ii, 263 ii, 263 ii, 263 ii, 264 ii, 264 ii, 264 ii, 264 ii, 26-4 ii, 315 ii, 315 ii, 315 ii, 316 ii, 312svvi CONTENTS.MAGALLUX (A. B.). Assimilated Iron Compounds in Animal and Vegc- table Cells . . , . . . . . . . , . REID (E. WAYNOUTH). Intestinal Absorption of Peptone . , . SCH~NDORFF (BERNHARD). Urea in Animal Organs . . . . LOEB (JACQUES). Physiological Action of Want of Oxygen . . . ATHANASIU and PAUL LANGLOIS. Comparison of the Physiological Action of Cadmium and Zinc Salk . . . . . . . NEPVEU. Indican and Indole in the Tissues of Tumours . . . ALBANESE (MANFREDI). Behaviour of Caffe‘he and Theobromine in the Organism . . . . . . . . . . . . BONDZY~SKI (STANISLAS). The Cholesterol of Human Faces , . . WEISKE (HUGO). Digestibility of the Pentosans ctf Vegetable Foods .SGHONDORFF (BERNHARD). Partition of Urea between Blood Corpuscles and Serum . . . . . . . . . . . . KOEPPE (HANS). Osmotic Pressure of Blood Plasma, and the Formatioii of Hydrochloric acid in the Stomach. . , . . . . LEVIX (ISAAC). Fat Absorption . . . . . . . . KRUMXACHEB (OTTO). Influence of Muscular Work on Proteld Meta- bolism. . . . . . . . . . . - . KATZ (JULIUS). Mineral Constituents of Flesh . . . . . BLUXENTHAL (ARTHUR). Action of related Chemical Substancea on Striped Muscle . . . . . . . . . , . DRECHSEL (EDMUND). Chemistry of some Marine Animals . . SBLDNER (FRIEDRICH) and WILLIAX CAMMERER. Analysis of Human Milk . . . . . . . . . . . . . SOLBERG (E.). Composition of the Milk Fat of the Cow, the Goat, and the Reindeer .. . . . . . . . . . RUMPF (THEODOR). Excretion of Ammonia in Disease . . . . HALLERVORDEN (E,). Excretion of Ammonia in Disease. . . . CABXERER (WILLIAM). Uric acid, Xanthine Bases, and Phosphoric acid iii Human Urine. . . . . . . . . . . EBSTEIX (WILHELM) and ARTHUR NICOLAIER. Excretion of Uric acid . SCHLOESING (TH., Jun.) and JULES RICHARD. Detection of Argon in the Air-bladder of Fishes and Physalidse . . . . . . WHITE (ARTHUR Ha). Nutrition of the Frog’s Heart . . . OLIVER (GEORGE). A New Hsemoglobinometer . . . . . OLIVER (GEORGE). Estimation of the Number of Blood Corimscles . HOENE (R. M.). Coagulation of Blood . . . . . . . STARLING (ERNEST HENRY). Absorption of Fluids from Connective Tissue Spaces . . . . . . . . . . . SCHAFER (EDWARD ALBERT) and B. MOORE.Extirpation of Salivary Glands . . . . . . . . . . . . STOCKMAN (RALPH). Iron in the Liver and Spleen. . . . . SJOQUIST (JoEN). Gastric Digestion . . . . . . . DUNLOP (JAMES CRAUFORD). Action of Dilute acids on Metabolism . GEORGENBURQER (JEANNOT). Hamoglobin and its Derivatives . . H~FNER (CARL GUSTAT). Solubility of Carbonic Oxide in Solutions of Hamoglobin : Dissociation of Carbonic Oxide Hamoglobin . . HURTHLE (KARL). Compounds of Fatty acids and Cholesterol in Blood-serum . . . . . . . . . . . LAZARUS-BARLOW (W. S.). Formation of Lymph . . . . . LEHMANN (KARL B.). Hygienic Studies on Copper. . . . . TIRMANN (JOHANNES). Absorption of Iron by the Organism . . . SEEGEN (JOSEF). Muscular Work and Glycogen . . . . . EE~JGER (TH. RICHAED). Elimination of Carbonic AnhTitride from Phosphocarnic acid by Hydrolysis .. . . . . . BAUMANN (EUGEN) and EENST Roos. Iodine Conipound in the BAUMANX (EUGEN). Iodine in the Thyroid . . . . . . Boos (EBNST). Action of Thyroidin . . . . . . . Thyroid . . . . . . . . . . . PAQE ii, 317 ii, 318 ii, 318 ii, 316 ii, 319 ii, 319 ii, 319 ii, 319 ii, 375 ii, 376 ii, 376 ii, 376 ii, 3i7 ii, 377 ii, 378 ii, 3’78 ii, 378 ii, 319 ii, 379 ii, 379 ii, 379 ii, 43G ii, 437 ii, 437 ii, 437 ii, 437 ii, 435 ii, 438 ii, 439 ii, 484 ii, 484 ii, 495 ii, 485 ii, 485 ii, 485 ii, 486 ii, 487 ii, 487 ii, 48’7 ii, 487 ii, 4-87 ii, 488 ii, 377OONTENTS. xxvii WEINTILAUD (WILHELM). Nucleih and the Formation of Uric acid . WEINTRAUD (WILHELM). Formation of Uric acid in Man . . . PEKELHABING (COBNELIUS ADRIABUS).Fibrin Ferment and Nucleo- proteid . . . - . . . . . . . . EtEsrNE (L.). Chemicitry of Mitosis . . . . . . . EDMUNDS (ARTHUR). Rennin and Milk Curdling . . . . . ALLEN (F. J.). Effect of Borax on Milk Curdling . . . . . REY (J. G.). Excretion and Absorption of Lime . . . . . SALKOWSICI (EXNSTLEOPOLD). Pentosuria . . . . , LEMAIRE (F. A.). Milk Sugar in the Urine after Child Birth. . . WEINTRAUD (WILHELX). Relationship of Levulinic acid to Aceton- uria . . . . . . . . . . . . . M'EINTRAUD (WILHELM). Excretion of Uric acid and Xanthine Bascs by theFzeces . . . . - . . . . . . BMALE (FRED. J.). Solubility of Uric acid in Urine. . . . . MORDHOBST (C.). Precipitation of Urates within and n itliout the Body. . . . . . . . . . . . . BAGINSKY (ADOLF) and PAUL SOXMERFELD.Alloxuric Substances in the Urine of Children in Disease. . . . . . . . DAIBER (A.). Indicaii, Indoxylsulphuric acid, and Conjugated Glycu- ronio acids in Urine . . . . . . . . . . BEANDENBURG (KURT). Poisoning with Potassium Chlorate . . . PADEBI (CESARE). Physiological Action of Cadmium . . . . CURCI (ANTONIO). Physiological Action of Thallium . , . . ROSEMANN (RUDOLF). Toxicity of Acetylene . . . . . . LUSINI (VALEBIO). Physiological Action of Ureides. I. Alloxan, Alloxantin, and Parabanic acid . . . . . . . . LIKHATSCHEFP (ALEXIS). Physiological Action of Gentisic acid . . ALBANESE (MAXBREDI) . Physiological Action of Caffe'ine and Theo- bromine . . . . . . . . . . . . BUKGE (RUNO TON). Alkaloids of Hydrastis canademis. , . . WICEE (A,) and HUGO WEISEE. Influence of Fat and Starch on Meta- bolism .. . . . . . . . . . . ELLINGER (ALEXANDER). Nutritive Valuc of Gland Peptone . . , FRIEDL~NDER (GEORG). Absorption of Prote'ids in the Small Intestine . HEINE (L.1. Molybdic acid as a Microscopic Reagent . , . . KWSEL (ALBRECET CARL LUDWIG MARTIN LEONHARD). Thymin from the Spermatozoa of the Sturgeon . . . . . . . MITCEELL (CEARLES AINSWORTH). Composition of Human Fat . . G~RASD (ERNEST). Decomposition of Amygdaliu in the Animal System HOLDEFLEISS (P.). Importance of Digested Crude Fibre as Food . . BIONDI (CESABE). Fermentative Processes in the Organs . . . COHNSTEIN (WILRELX). Theory of Lymph Formation . . . . moss^ (MAX). Formation of Sugar in the Liver . . . . . MENDEL ( LAFAYETTE B.). Paralytic Intestinal Juice .. . . MORACZEWSEA (SOPHIE TON). Alterations in the Blood in Anaemia . RUMPF (THEODOB). Excretion of Ammonia in Disease . . . . TAMMANN (GUSTAT). Action of the Kidney in the Light of the Theorp of Osmotic Presenre . . . . . . . . . . EIJKMAN (C.). . KELLAS (ALEXANDER). Percentage of Argon in Atmospheric and RespiredAir . . . . . . , . . . . HALLIBURTON ( WILLXAX DOBISON) and T. GEEGOB BRODIE. Action of Pancreatic Juice on Milk . . . . . . . . . M~NZEB (EGMUND) and P. PALMA. Metabolism in Poisoning by Carbonic Oxido and Nitrobenzene . . . . . . . . . MALPEAUX. Use of Sugar in Cattle Feeding . . . . , . MARCGSE (GOTTHELF). Nutritive Value of Case'in . . . . . REID (EDWARD WAXMOUTH). Intestinal Absorption , . . STOXVIS (BAREND JOSEPH). Hzematoporphyrinuria . . . Gaseous Exchanges in the Inhabitants of the Tropics PAGE ii, 4S8 ii, 488 ii, 488 ii, 489 ii, 489 ii, 489 ii, 489 ii, 490 ii, 420 ii, 490 ii, 490 ii, 490 ii, 491 ii, 491 ii, 491 ii, 491 ii, 491 ii, 491 ii, 492 ii, 492 ii, 402 ii, 492 ii, 492 ji, 535 ii, 536 ii, 536 ii, 536 ii, 537 ii, 537 ii, 570 ii, 570 ii, 616 ii, 616 ii, 616 ii, 617 ii, 617 ii, 618 ii, 618 ii, 618 ii, 661 ii, 661 ii, 662 ii, 662 ii, 662 ii, 663 ii, 663xxviii CONTENTS.EVE (0.0.). The Bssophil Constituent of Sympathetic Nerre Cells . PICKERIN@ (JOHN WILLIAM). Physiology of the Embryonic Heart . GR~HANT (NESTOR). Estimation of Ethylic Alcohol in the Blood after Introduction of the Liquid into the Veins, or of the Vapour into the Lungs . . . . . . . . . . . . PICKERING (JOHN WILLIAX). Blood Coagulation in Albinos ., , LAZARUS-BARLOW (W. S.). . PAVY (FREDERICK WILLIAX). Sugar Formation in the Alcohol Coagu- lated Liver. . . . . . . . . . . . FISCHEB (EYIL) and W. NIEBEL. Behaviour of Polysaccliarides with certain Animal Secretions and Organs . . . . . . MARTIN (CHARLES JAEES). Separation of Collo'ids and Cr-ptallok?s . UMBER (F.). Influence of Food containing Nucle'in on the Formation of Uric acid . . . . . . . . . . . . WALTI (LVDWIG). Influence of Atropine on the Secretion of Urine . COLLS (PERCY COOPER). Creatinine . , . . . . . KRAVM (WILLIAM). A new Solrent for Urinary Pigments . . , ZUNTZ (NATHAN). Phloridzin Diabetes . . . . . . . ZULZEB ((3.). Alloxuric Substacces in the Urine in Nephritis. . . EREHL (TZDOLF) and MAX MATTIIES. Febrile Albuminosuria .. CALVERT (JAMES). Effect of Drugs on the Tracheal Secretion . . BOKOBNY (THOMAS). Toxicological Notes on Ortho- and Para-com- pounds . . . . . . . . . . . Initial Rate of Osmosis of Blood Sernm Chemistry of Vegetable Physiology aid Agricu7t w e . RIETSCH (M.) and M. HEISELIN. Fermeiitation by Apiczllated Yeast: Influenee of Aeration on Fermentation by Elliptical Yeast a t a High Tempera.ture . . . . . . . . . . . MULLEB (EL). Effect of Abundant Application of Nitrogen on Assimila- tion and Respiration in Plants . . . . . . . . KINOSHITA (Y.). Consumption of Asparagine in the Nutritiou of Plants EINOSHITA (Y.). Assimilation of Nitrogen from Nitrstes and Ammonium Salts by Phaenogams. . . . . . . . . . DAIKUHARA ((3.). Reserve Prote'in in Plants . . . . . .LOEW (OSCAR). Formation of Yrote'ids in Plant Cells . . . . LOEW (OSCAR). Active Albumin as Reserw Material in Plants . . GRUSS (J.). The Function of Diastase in Plants . . . , . CHO I J.). Hydrogen Peroxide in Plants . . . . , . . EINOSEITA (Y.). Occurrence of two kinds of Mannan in the Roots of Conophallws konjakzc . . . . . . , , . . YOSHIMURA (K.). Compositioii of some Mucilages . . . . BERTBAND (GABBIEL). Laccage in Vegetables. . . . . . EINOSHITA (Y.). Asparagine in the Roots of Neluinbium nzlc?yemna . PLUWE (PIETER C.). Occurrence of Cytisine in various Pnpiliouacea . KEEMLA (H.). Composition of Pure Fruit Juices . . . . . HEME (OSWALD). Bark and Leares of Drimys granatensis L. . . HERPELDT (E.) and ALBERT STUTZBR. Amount of Fat, Sugar, and Tannic acidin Coffee .. . . . . . . . WIBTERSTEIN (ERNST). Composition of Pachyma cocos and JZ3litia Eapidescens . . . . . , . . . . . . LE BON (G.). Kola nut . . . , . . . . . TEOMP DE HAAS (R. W.) and BERNHARD TOLLENS. Coeo-nut Shells . BALZIIPND. Composition of some French and other Oats harvested in 1893 . . . . . . . . . . , . . BARBEY (GASTON). Cuscuta epitFgymum . . . . . . . INOUPE (M.). Preparation and Composition of Tofu . . . , SCHREIBER (C.). Action of Lime and Magnesia on the Soluble Phosphoric acid of the Soil . . . . , , . . , . . PAQ II: ii, 663 ii, 663 ii, 664 ii, 664 ii, 664 ii, 665 ii, 665 ii, 665 ii, G66 ij, 666 ii, 666 ii, 666 ii, 667 ii, 667 ii, 661 ii, 667 ii, 668 ii, 53 ii, 53 ii, 54 ii, 54 ii, 55 ii, 55 ii, 5 8 ii, 59 ii, GO ii, 60 ii, 60 ii, 61 ii, 61 ii, 61 ii, 6 2 ii, 62 ii, 63 ii, 63 ii, 64 ii, 64 ii, 6 4 ii, 65 ii, 65 ii, 66COXTEXTS.PAGNOXT,. Assimilable Nitrogen and its Transformations in Arable Soil , YOSHIMURA (K.). Beliariour of Hippnric acid in Hoils . . . . SOEW (OSCAR). Behaviour of Eippuric acid in soils . . , . OBEBLIN (C.). Effect of Carbon Bisulphide on Exhausted or ‘( Sick” Soils . . . . . . . . . . . . . RATTERER (KOSRAD). Saline Soil and Water from Persia . . . WETS and C. SCHREIBER. The Potash and Phosphoric acid required by Cultirat ed Plant J . . . . . . . . . . ULBRICHT. Value of Bone Phosphates . , . . . . . WAaEr‘ER (PATJL). Citrrlte Solubility of Basic slag as expressing its MlIunurial Value . . . . , . . . . . . PASSERIBI (N.). Chlorine in Rain Water . . . . . . YCHLCE~IIG (J.J, THEOPHILE). Losses of Nitrogen in Waters of Infil- tration . . . . . . . . . . . . RASILE (G.). Mannitol Fermentation in Sweet Wines . . . . CHASSEFAXT (ALLYRE). Action of Metallic Salts on the Lactic Ferinen- tation . . . . . . . . . . . . . CROSS (CHAELES F.) , EDWARD J. BEVAN, and CLAUD SMITH. Chemistry of the Barley Plant . . . . . . . . . . SOSTEGXI (L.). Tannin Colouring Matters of Red Grapes . . . MULLEX (HERXABB). Plipiology of Yeast and the Importancc of Selected and Pure Cultures for Wine Fermentation . . . SALKOWSKI (ERNST L.). The Sugar that forms in the Auto-Digestion of Yeast . . . . . . . . . . . . . ~YASTUKOFF. Measui*einent of tlie Reducing Power of pure Yeasts . , OMELIANSKI (V.). Fermentationof Cellulose . . . , . . RIVI~RE ((3.) and BAILHACHE.Ethylic Alcohol from the Fermentation of Aqhodefus ++amosus and Scilla inaritima . . . . . STOKLASA (JULIUS). Assimilation of Elementary Nitrogen by Plants . MOLISCH (HANS). The Mineral Food of Lower Fungi . . . . BEHRESS (J.). Physiological Studieson Hops . . . . . LOOKEREN (C, J. TAN) and P. J. VAN DEB TEEN. Formation of Indigo in Plants of the Order Indigofera . . . . . . . SCRROTTER-KRISTELLI. Occurrenceof Carotene . . . . . SCHELZE (ERNST). The Nitrogenous Constituents of Young Green Plants of the Vetch, Tli’cia sativa . . . . . . . . . BACZEWSXI (MAX). The Seeds of Nephelium Zappaceurn and the Fats contained therein . . . . . . . . , . 3 3 1 ~ ~ 6 ( B ~ L A VOJ). Chemical Composition of Capsicum . . . , WINTERSTEIN (ERBST). Constituents of the Tissues of Fungi.. , WINTERSTEIN (ERXST). Constituents of the Cell Membrane of Various Crjptogams . . . . . . . . . . . OSBOEXE (THOMAS B.) and CLARK 0. POORHEES. Protei’ds of Cotton SEED. . . . . . . . . . . . . KONIG (F. JOSEF) and EMIL HASELHOFF. Tnjury to Plants by Nitrcgen Acids. . . . . . . . . . . . . OTTO (R.). Effects of Strychnine on Plant Development , . . SCHULZE (BERNRARD). Black Siberian Lupins . . . . . PATTERSON (HARRY JACOB). Effect of Different Manures on the Composi- tion and Combustibility of Tobacco . . . , . . . BALLAXD. Composition of Rice Imported into France . . . . PITSCH (OTTO) and J. VAN HAARST. Are Nitrates Indispensable for the Growtli of Plants ? . . . . . . . . . . KONIG (F. JOSEF) and EMIL HASELHOFF. Assimilation of the Nutritive Matkers of Soil by Plants .. . . . . . . . ~ N Y D E R (HAXRY). Composition of Eathe and Cultivated Soils : Effect of Coutinuous Cultivation on their E’ertility . . . . . ZIomYrmsrsa (WILEELM). citrate Solubility of the Phosphoric acid of BasicSlasz . . . . . . . , . . . . XXiX PAGE ii, 66 ii, 67 ii, 67 ii, 67 ii, 68 ii, 68 ii, 68 ii, 6s ii, 69 ii, 69 ii, 121 ii, 122 ii, 122 ii, 122 ii, 201 ii, 202 ii, 202 ii, 202 ii, 203 ii, 203 ii, 207 ii, 207 ji, 207 ii, 208 ii, 208 ii, 209 ii, 209 ii, 210 ii, 210 ii, 210 ii, 210 ii, 211 ii, 211 ii, 211 ii, 212 ii, 212 ii, 213 ii, 219 ii, 214 LIEBENBERG +ON. Phosphate Manuring . . . . . . . ii, 214xxx CONTESTS. SCXULZE (BERNHARD). Pigeon Manure . . . . . . . WESBROOE (F. F.), Growth of Cholera Bacilli in Sunlight . . . PHIPSON (THOMAS L.).Origin of Atmospheric Nitrogen . . . ZIEGENBEIX (E.). Metabolism and Respiration in Sprouting Potato Tubers . . . . . . . . . . . , STOELASA (JULIUS). Assimilation of Lecithin in P1ant.s . . WYPLEL (N.) [ ? WYPFEL]. Effect of Chlorides, Bromides, and Iokdes; BERLESE and LIVIO SOSTEGNI. Effect of 'Copper Salts on the k r o i t h o i the Vine and on Soil . . . . . . . . . , HASELHOFF (EMIL). Injurious Action of Cobalt and of Barium on Plants BERTRAND (C~ABRIEL) and ALFRED MALL~VRE. Pectase , . . . BOURQTJELOT (EMILE E.) and GABRIEL BE~TRAND. Lacrase in Fungi . GAIN (E.). Amount of Substances soluble in Water in Plants . . QRANDEAU (L.). Sulla, (Haydoarum coranarium) , . , . . FEILITZEN (C. VON). ImporLance of Potash as Plant Food . . . PAGEOT (G.). Application of Phosphates and Superphosphates to Acid Soils .. . . . . .) . . . . . . GRANDRAU (L.). Application of Phosphates and Superphosphates to Acid Soils . . . . . . . . . . . . MAERCEER (MAX). Investigations [on Manures] at Hallo . . . HIEPE (WILLIAM L,). Fractional Fermentation of Cane Sugar with Pure Yeasts . . . . . . . . . . . BEOWX (HORACE T.) and GEORGE HARRIS MORRIS. Bacterial Infection by Air-sown Organisms . . . . . . , . , BEOWX (ADRIAN JOHN). Bacillus subtilis . , . , . . BOUPQUELOT (EMILE ELI$) and H. H~RISSEY. Alcoholic Fermentation produced by substances secreted by Aspsvgillus siger , . . LABORDE (J. €3. VINCENT). Fermentation of Maltose, by the Mould Eurcitiopsis Gayod . . . . . . . . BOURQUELOT (EMILE ELIB). Fermentation of Maltose, by the M o d Eurotiopsis Gayolti .. . . . . . . . . GILIMBEBT (UON). Action of Friedlander's P.neumococcus on sugars . ADENEY (WALTER ERNEST). Nature of Fermentative Changes in Natural and Polluted Waters and in Artificial Solutions as indicated b7 the Composition of the Gases in Solution , . . . . MOSSO (UGOLINO). . REY-PAILHADE (JOSEPH DE). Philothion and Laccase in Germinating Seeds. . . . . . . . . . . , . JAY (HENRY). Distribution of Boric acid in Plants . . . . TREUB (M.). Hydrocyanic acid in Paltgim edub . . , . . SCHXEEGAXS (AUGUST). Methylic Salicylate and Salicylic acid in the MAQUENNE (L~oN). Accumulation of Sugar in the Roocof t i e Beet . TSCHIRCH (WILLIAM OSWALD ALEXANDER). Toxicity of Copper Salts . PAGNOUL (A.). Transformations which Nitrogen undergoes in the Soil .DEHBRAIN (PIERRE PAUL). Effect of Carbon Bisulphide and of Horse Dung on Denitrification . . . . . . . . . PASSERIXI (NAPOLEONE). Action of Sodium Chloride and Nitrate, and . LECHARTIER ((3.). Analysis of Soil by Plants , . . . . . DEHBRAIX (PIIBRE PAUL). Field Experiments [with Wheat and Barley] at Gt-rignon in 1895 . . . . . . . . . . SALFELD (AUGUST). Employmenti of Quicklime in the Cultivation of Leguminoseae . . . . . . . . . , . PPIANISCHNIKOFF (DM.). The Processes of Germination . . . AEBY (J. H.). Nitrogen Assimilation by Plants . . . . , GONNERMANN (M.). A Diastatic Ferment in the Sugar Beet . . . SCHULZE (ERNST). Occurrence of Arginine in the Tubers and Roots of czrtnin Plants . . . . . . . . . . onAlgfe . . . . . . . . Effect of AlkaloYds on the Germination of Seeds Root of Polygala of Virginia , .. . . . , of Phosphates on the Solubility of the Potassium of the Soil . PAGE ii, 215 ii, 265 ii, 265 ii, 266 ii, 266 ii, 266 ii, 267 ii, 267 ii, 267 ii, 268 ii, 268 ii, 268 ii, 269 ii, 269 ii, 269 ii, 269 ii, 320 ii, 321 ii, 231 ii, 321 ii, 321 ii, 321 ii, 322 ii, 322 ii, 326 ii, 326 ii, 327 ii, 327 ii, 328 ii, 328 ii, 328 5,329 ii, 321) ii, 330 ii, 330 ii, 331 ii, 332 ii, 380 ii, 381 ii, 381 ii, 383COhTENTS. xsxi PAGE BOURQUELOT (EMILE ELI&) and GABRIEL BEBTRAND. Coloration of the Tiasues and Juice of certain Fungi when exposed to Air . . . BERSCH (WILHELX). Composition of Medlars. . . , . . BERSCH (WILHELM). Composition of Melons . . . . . . SMETS and C. SCHREIBER. The Potash and Phosphoric acid required by Cultivated Plants .. . . . . . . . . TACKE (BRUNO) and others. Behaviour of the Leguminous Nodule 'Bacteria towwds Caustic Lime. . . . . . . . . . BIL'LWILLER ( JOHANN) . Nitrogen Assimilation of some Pnpilionacea! , SIGMUND (WILHELM). Effect of Chemical Agents on Germination. . CLAUDEL and J. CEOCHETELLE. Effect on Germination of some Sub- stances used as Manures . . . . . . . . . GOETZE (K.) and THEODO~~ PFEIFFER. Formation and Behaviour of the Pentoses in Plants and Animals . . . . . . . . CSERHATI (ALEXANDER). Combustibility of Tobacco . . . . B R ~ A L (EMILE). Reduction of Nitrates in Arable Soil . . . . BURRI (R.), E. HERFELDT, and ALBERT STUTZER. Causes of Loss of Nitrogen in Decaying Organic Matter, especially Farmyard and Liquid Manure .. . . . . .) . . . . LARBAL~TIHER (A.) and L. MALPRAUX. Mauurial Effects of Magnesium LOEW (OSCAR) and SEIROKU HONDA. Effects of Different Amounts of Lime and Magnesia on the Development of Pine Trees . . . FERNI (CLAUDIO) and GIUSEPPE MONTESAXO. Inversion of Cane Sugar by means of Micro-organisms , . . . . . . . BERTRAND (GABRIEL). Bio-chemical Preparation of Sorbose . . , SCHULZE (ERNST). Nitrates in Seedlings. . . . . . . HBBERT (ALEXANDRE). Saps . . . . . . . . . GIUSTINIANI (ERCOLE). Constituents of Nettles . . . . , NACKEN (W. . Chemical Characteristics of Bilberry Juice . . . SCHLCESING ~ E A N JACQUES THBOPEILE). Nitric acid in the Waters of the Seine and its Chief Tributaries . . . . . . . BEESON (J. L.). Apparatus for estimating the Water-holding Power of S o i l s .. . . . . . . . . . . SAPOSCHNIKOFP (W.). Prote'ids and Carbohydrates of Green Leaves as Products of Assimilation . . . . . . . . . STOELASA (JULIUS). . NATJMANN (OTTO). The Tannin of Fungi . . . . . . STBOHYEE (FRIEDRICH), H. BRIEM, and A. STIFT. Nutrition and Formation of Substance in Sugar Beet in the Second Year of Growth . . . . . . . . . . . . SCHNEIDEWIND (W.) and H. C. MULLER. The Nutritire Substances of Beet-root . . . . . . . . . , . . OTTO (R.). Amount of Acid in Rhubarb Stems and in Rhubarb Wine . LINDET (GO.). Identification and Isolation of Acids contained in Plants . . . . . . . . . . BOUBQUELOT (EMILE ELIS). Presence df a Gflucoside of Methylic Sali- cylate in Monotropa liypopithys, and a Ferment which hydrolysee it . EHBICH (E.).Nitrogen Compounds of Malt and Beer Worts . , STIFT (A.). Composition of the Flower Dust of Sugar Beet . . , SCHLCESINGC (JEAK JACQUES TH~OPHILR). Sitrates in Potable Waters . BEBTRAND (GABRIEL). A new Oxydase or Soluble Oxidising Ferment of Vegetable Origin . . . . . . . . . . PUPIEWITSCH (KONSTANTIN A.). Assimilation of Nitrogen by Moulds . BENECKE (W.). Mineral Nutrition of Plants . . . . . . SCHULZE (ERNST). Occurrence OF Glutamine in Plants . . . . BURRI (R.), E. HERFELT, and ALBERT STUTZER. Causes of Loss of Nitrogen in decaying Organic Matter . . . . . . . SCHULZE (EBNST). Cell-wall of Cotyledons of Lupilaus Zuteecs and Lzcpinus anyustifolia . . . , . . . . . . Compounds and of Iron Sulphate . . . . . . The Position of Arsenic in Plant Production , ii, 383 ii, 353 ii, 384 ii, 384 ii, 439 ii, 440 ii, 441 ii, 442 ii, 443 ii, 444 ii, 444 ii, 445 ii, 445 ii, 446 ii, 493 ii, 494 ii, 494 ii, 494 ii, 495 ii, 495 ii, 495 ii, 496 ii, 537 ii, 538 ii, 538 ii, 538 ii, 538 ii, 539 ii, 539 ii, 540 ii, 540 ii, 541 ii, 541 ii, 571 ii: 571 ii, 572 ii, 572 ii, 572 ii, 618xxsii CONTENTS.JENTYS (STEF.). Decomposition and Assimilation of the Nitrogen Com- pounds of Stable Manure . . . . . . JOHNSON (SAXEEL WILLIAN) and EDWARD H. JENKTNS. kethLds o'f Determining the Arailability of Organic Nitrogen in Fertilisers. . LOGES (GUSTAV). Action of Vegetable Acids on Insoluble Phosphates in Presence of Nitmtes . . . . . . . , . . BAPP (R.). Influence of Oxygen on Yeast Fermentation . . . G~RARD (ERNEST). Fermentation of Uric acid by Micro-organisms .GODLEWSKI (EMIL). Nitrification . . . . . . . . XARCILLE. Nitrification . . . . . . . . . . BOKORNY (TEOMAS). Comparative Study of the Poisonous Action of various Chemical Substances on Bigs and Infusorirt . . . . GBUSS (J,). Digestion of Cellulose by Enzymes . . . . , BX~AL (EmLE). Decomposition of Vegetable Matters . . . . REMY. Man- urial iequirements of Rye . . . . . . . . . Assimilation of the Nutritive Matter of the Soil by Rye. Analytical Chemistry. BLEIER (O.}. New Forms of Gas Burettes . . . . . . BERTXELOT (MARCELLIN). Inertness of Oxidising and Reducing Agents in Analyses in the Wet Way . . . . . . . . BUGHES (JOHN). Estimation of Water in Commercial Ammonium Sul- phate. . . . . . . . . . . . , RAIKOW (P. N.). Detection of Chlorine, Bromine, and Iodine in Organic Compounds .. . . . . . . . . . YORTMANN (GEORG). Electrolytic Estimation of the Halogens . . SCHTJYTEN (M. C.). Estimation of Iodine in Organic Liquids . . . ASB~TH (ALEXANDER TON). Estimation of Sulphur in Pyrites . . SMITH (R. GREIG). Detection of Sulphates, Sulphites, and Thiosulplicltes in presence of each other . . . . . . . . . BLOXAM (W. POPPLEWELL). Qualitative Analysis of a Mixture of Hy- drogen Sulphide, Sulphite, Polysulphide, Thiosulphate, and Sulphate. CAUSSE (HEXRI E ). Estimation of Organic Kitrogen by the Kjeldahl Process . * . . . . . . . . . . NEUBAUER (HUGO). Estimation of Phosphoric acid by the Molybdic Method . . . . . . . . . . . . GRUEBER (VON). Analysis of Artificial Manures . . . . . FBIEDHEIW (CARL) and PAUL MICHAELIS. Gravimetric Estimation of Arsenic .. . . . . . . . . . . VILLTERS (A.) and M. FAYOLLE. Boric acid . . . . . . JAY (HENBI) and DUPASQUIER. Estimation of Boric acid . . . HALDAXE (JOHN $3.). Estimation of Carbonic Oxide in Air . . . SMITH (ERNEST A.) . Gold and Silver in Copper and Copper Matte . JOLLES (ADOLF). Detection and Estimation of Mercury in Urine . . XONINCK (LUCIEN L. DE). Volumetric Estimation of j?latinochlorides ; Estimation of Potassium, Ammonium, Nitrogen, and Platinunt . . RENRIQUES (ROBERT). Quantitative Separation of Benzene from Light Petroleum . . . . . . . . . . . . GOYDER (GEORGE A.). Analysis of the Cyanide Solutions used in the Extraction of Gold , . . . . . . . . LABORDE (J.), Estimation of Glycerol in Fermented Liquora . . PARTHEIL (ALFRED). Estimation of Ulycerol in Wine and Beer ., STIFT (A,). Estimation of Pentoaes and Pentosans in Diffusion Cuttings, Sugar Beet, and some Food Stuffs . . . . . . . X~ITIG (F. JOSEF). Relative Proportion of Glucose and Levulose in Sweetwines , , . . . . . . , . . KISTIAKOFFSKY (WIUDIYIB A.). Estimation of Glycogen in Liver and Muscle , . . . . . . . . . PAGE ii, 619 ii, 620 ii, 620 ii, 668 ii, 665 ii, 668 ii, 669 ii, 669 ii, 669 ii, 670 ii, 670 ii, 70 ii, 70 ii, 70 ii, 70 ii, 21 ii, 71 ii, 71 ii, 71 ii, $2 ii, 72 ii, 73 ii, 74 ii, 74 ji, 75 ii, 76 ii, 76 ii, 76 ii, 77 ii, 77 ii, 77 ii, 77 ii, 77 ii, 78 ii, 79 ii, 79 ii, 80CONTENTS. xsxiii PAGE fIlJrZlXGA (D.1. Estimation of Glycogen : Detection of Albumoses in Presence of Glycogen . . . . . .. . . . FREYER (FRANZ). Estimation of Formic acid. . . . . . DEXIGFBS (GEORGFES). The Resorcinol Test for Tartaric acid . . . BECKVRTB (HE~NRTCH) and H. HEILER. Esaminat’ion of Fats by incans of t l t e Rpf rac tome ter . . . . . . . . . . RECKURTS (HEIRRICH) a n d F . OELZE. DeerFat , . . , . GOSKE (A.). Lard Analysis . . . . . . . . . BUSSE ( WALTZR) . Examination of Pepper . . . . . . J ~ V S S E (WALTER). Nutmeg . . . . . . . . . K ~ H N (M.). Margarine Cheese and its Analyeis . . . , . KijN~a (F. JOSEP) and A. BONER. Ccimposition of Ment Extract . . BOUER tA4.). Precipitation o€ Albumoses by Zinc Sulphate . . . khrTZER (ALBERT). Estimation of Gelatin in Meat Extracts and Com- mercial Peptones . . . . . . . . . . JEKETT (FRANK F.). Arrangement for Washing Precipitates with boiling water .. . . . . . . . , . . . IinErDEa (D, ALBERT). Estimation of Perchlorate , . . . GIACOMELLI (LEOPOLDO). Qualitative h a l y s i s of mixtures of Sulphites, Carbonates, and Sulphates . . . . . . . . . GOOCH (FRANK A.) and W. C. REYNOLDS. Reduction of Selenious and Selenic Acids by Hydriodic acid . . . . . . . Coocn (FRANK A.) and P. S. EVANS. Reduction of Selenic acid by H>*drochloric acid . . . . . . . . . . GOOCH (PRANK A.) and W. S. SCOVILLE. Reduction of Selenic Acid by Potassium Bromide in Acid Solution . . . . . . . SHFRIIAX (H. C.). Estimation of Nitrogen in Fertilisers containing 1v itrates . . . . . . . . . . . . RUSYAN (E. G.) and IIAsvEY w. WTLEY. Estimation of Small Quantities of Phosphoric acid by the Citmte Method .. . WINTON (A. L.). Conditions affecting the Accuracy of the Estimation of Potassium as Platinochloride . . . . . . . . BASILE (G.) and E. DE CELLIS. Estimation of Lime in Soils . . . STONE (GEORGE C.). Volumetric Estimation of Zinc, and a new Indicator for Ferrocyanidee . . . . . . . . . . SPICA (MATTEO). Volumetric Estimation of Copper . . . . HAEE (C. L.). Qualitative Sepa~ation of the metals of the Iron Group . GJACOXELLI (LEOPOLDO). Qualitative Separation of Chromiiim and Tron . . . . . . . . . . . . KOSES ( WILLIAX A.’ and W. N. BLINKS. Estimation of Benzene in Illuminating Gas . . . . . . . . . . LOHRSTEIN (THEODOR). Densimetric Estimation of d-Gliieose in Urine . BESAKA (CARLO). The Polarising Microscope and Zeiss’ . Refractometer applied to Rutter Analysis .. . . . . . . . BEAL (W, If.). . CAZENEUTE (PAEL) and E. HADUON. Trustworthiness of Creamometers for the Estimation of Fat in Pasteurised Milk . . . . . KAXTFMANN (MAURICE). Estimation of Urea in Blood and Tissues . ~CfloNDORFF (BERNHARD). Estimation of Urea in Animal Organs and Liquids . . . . . . . . . . . . OECHSNXR DE COXINCK (WIcL1ar.x). Detection of Creatinine in Urine . RRUYLAPTS (GUSTATE). MorphineReactions . . . . . SLPKE (b. L. VAN). Estimation of Albumin in Milk . , . . KRUSS (QERIZABD) and H. KR~SS. New Method of Quantitative Spec- trum Analysis . . . . . . . . . . . PENFIELD (SAXUEL L.). Separation of Minerals of High Specific Gravity KASFLE (J. If.). New Reagent for Bromine and Iodine. . . . BVGARSZKY (STEFAN). Quantitative Separation of Bromine and Chlorine DEzrlvsTEDr (MAXIMILIANO) and CBSaR AIIRESS.Estimation of sul- W L LXX. ii. 3 VEDHODI (VIKTOR). Analysis of Fish Oils , f . . . &timation of Volatile and Insoluble acids in Butter ii, 80 ii, 80 ii, 80 ii, 81 ii, 81 ii, 81 ii, 82 ii, 8.2 ii, 82 ii, h.2 ii, 82 ii, 83 ii, 84 ii, 123 ii, 123 ii, 124 ii, 124 ii, 125 ii, 125 ii, 125 ii, 126 ii, 12G ii, 126 ii, 126 ii, 127 ii, 127 ii, 128 ii, 128 ii, 128 ii, 129 ii, 129 ii, 130 ii, 130 ii, 131 ii, 132 ii, 132 ii, 132 ii, 215 ii, 216 ii, 216 ii, 216xsxir CONTENTS. phurous Anhydride and Sulphuric acid in the Products of Combus- tion of Coal Gas . . . . . . . . . . . HEIBER. Estimation of X’itrogen in Pertivian Guano . . . . DAN (W. VAN). Kjelda’tl’s Method and Ylutinochloridea . . , SPICA (PIETRO).Toxicological Estimation of Phosphorus . . . DAWYD~W (L.). Testing for Arsenic in the Presence of Selenium . . JANNASCH (PAUL): Decomposition of Silicates by Boric acid . . . HCIIL~ESING ( h . , jun ). Kst imation of Argon . . . . . MAUZELTCS (ROBERT) and ALBERT VESTERBERG. Estimation of Calcium and Magneeium Carbonates in Soil . . . . . . , CVSHMANN (ALLERTON S.) and J. HAYES-CAMPBELL Volumetric Esti- mation of Lead . . . . . . . . . . . SMITII (EDUAR F.) and DANIEL L. WALXACE. ElectrdFtic Separations. JANNASCH (PAUL) and E. TON CLOEDT. Separation of Manganese from Zinc in Ammoniacal Solution by means of Hydrogen Peroxide under prcssure . . . . . . . . . . . ATKINSON (ELIZABETH A.) and EDGAR F. SMITH. Separation of Iron from Beryllium . . . . . . . . . . . JANNASCH (PAUL) and If.KAMNERER. Separation of Arsenic from Iron and Manganese . . . . . , . . . . STEAD (JOHN EDWARD). Chromium Estimations . , . . . JANNASCH (PAUL) and E. VON CLOEDT. Sleparation of Chroniium from Manganese, Iron, and Aluminium . . . . . . , RILLEBRAND (WILLIAM Z.). Warning against the Use of Flnoriferous Hydrogen Peroxide in Estimating Titanium . . , . . SMITH (EDGAR F.) and HAHBP B. EARRIS. Electrolytic Estimation of Ruthenium. . . . . . . . . , * . ~ I R S C H S O H N (EDUARD). Testiiig Ethereal Oils . . . . . CLENNEL (J. E.). Estimation of Simple Cyanides in Presence of Complex Cyanides and certain other Substmces . . . . . . BETTEL ( WILLIAK). Chemical Analj sis of Cyanide Working Solutions . XLIMONT (J.). Estiniation of Rosin Oil in Mineral Oil .. . . RIEGLER (K). Estimation of Total Solids and Alcohol in Wine by an Optical Method . . . . . . . . . . . GERRAHD (ALFRED W.). The Cjano-Cupric Estimation of Glucose . BUCHNFR ( G ~ o n a ) . Analysis of Urine : Esf innatiou of Small Quantities of Sugar by means of Nylauder’s Bismuth Solution . . . . ~IATREEOFER (Jos.) Estimation of Sugar in Preserred Fruits. . . J~LOWPTZ (ED ). Estimation of Cane Sugar in Malt . . . . I\ LAX (M.). Estiniation of I~ormaldehyde . . . . . . ME\ ER (RICHARD) and HEINBICH MEYEIt. E9timation of Benzoyl- aad I<ONINOK (LEONARD DE). Separation of Solid and Liquid Fatty Acids . Rrr;;aLER (E.). Estimation of Uric Acid by Feliling’s Solution . . tjcI[oEPp (a. J. L.). Detection of Salicylic acid in Beer . . . . BOI~NTHAOER (Asiiloa). Exantination of Oil of Bergamot .. . L l ~ E r z t n (14 .). Bstimutinn of Fat in Milk . . . . . . LONGI (ANTONIO). Rapid Estimation of Fat in Milk: a. New Lacto- hutvrometer . . . . . . . . . . . I%’ESSO$ (DAVID). Examinat,ion of Lard for Impurities . . . . I~LIIIER (OTTO). Apparatus for Gas Analjsis . . . . . . ~ ~ ~ O Q E R (MAX). Apparatus for Quantitative E1ectrcl;rsis . . . JANNASCH (PAUL) and P. WEINGARTEN. Estimation of Water in Si 1 icates . . . . . . . . . . . . BFEGAMI (F.). Cit-rate Method of Determining Phosphoric acid . . 2 DwARDs (VINCENT). Xspid Estimation of Insoluble Phosphate . . XONINGH (LEONARD UE). Teding for Arsenic in Alloys of Tin and L e a d . . . . . . . . . . . . READ (E. J.). Apparatus for the Estimation of Sulphur in Iron . . FUNK (ROBERT).Estimation of Sulphur and Carbon in Zinc . . . Acetgl-Groups . . . . . . . . * . . PAGE ii, 217 ii, 217 ii, 218 ii, 228 ii, 219 ii, 219 ii, 219 ii, 219 ii, 219 ii, 220 ii, 220 ii, 220 ii, 221 ii, 221 ii, 222 ii, 222 ii, 223 ii, 233 ii, 223 ii, 224 ii, 224 ii, 224 ii, 225 ii, 225 ii, 225 ii, 225 ii, 226 ii, 226 ii, 226 ii, 227 ii, 227 ii, 225 ii, 228 ii, 228 ii, 228 ii, 271 ii, 272 ii, 272 ii, 273 ii, 273 ii, 273 ii, 274 ii, 2i4CONTENTS. PAGE KOXINGH (LEONARD DE). Ettiimtion of Sulphurous Anhydride in Car- bolic Powders . . . . . . . . . . . LPNGE: (GEORG). . K~NINGII (LEOSAIPDE). Detection slid Estimation of Barium Sulphate UICFBE (ALFRED C.\. Volumetric Method of Lead Analysis . . . ENGELS (CARL). . R:DEAL (SAXTEL) and SIGXUND ROBENBLTJX. Analysis of Clirome-iron Ore, Ferrochromium, and Chrome-steel .. . . . . BETTEL (WILLIAM). Technical Analpis of Cyanide-working Solutiona . GLASENAPP (M.). Estimation of Pusel Oil in Rectified Spirit by Rose’s Process . . . . . . . . . . . . OPPESMANN (G ). Ed imation of Sugar . . . . . . . BORXTRAGER (BRTHUI~). Influence of the two Lead Acetates on the Estimation of invert Pugnr by the Fehling-Soshlet Method . . LANGE (GERHaRD). Eatirnation of Ceflulose . . . . . . DRAUEYDORFF (GEORG). Forensic Cheniibtry . . . . . . RONYN [G.). Detection of Formaldehyde . . . . . . KICHMOND (HENRY DROOP). Volatility of Fatty acids and Laws de- duced therefrom . . . . . . . . . . . KRWGER (MARTIN). Estimation of Uric acid in Urine . . . . WILLIAMS (Ro WLAND). Iodine and BrQmine Absorptions of Linseed Oil .. . . . . . . . . . . . HENRIQUES (ROBERT). Saponification in the Cold : Saponification Numbers and Reichert-Meissl Xumbers . . . . . , MANCEAU (E.). Estimation of Tannin in Wines . . . . . KIPPENBERGER (GAEL), Titration of Alkalo’ids with Iodine Solution . KOI ISCR (RUDOLF). Estimation of Creatininc in Uriiie . . . . UOTT (DAVID B.). Auay of Opiiini. . . . . . . , UYNEY (JOHN C.). Estimation of Aconitine , . . . , . CRIPPS (RICHARD A.). Assay of Ipecacuanha . . , . . . €IEWI.ETT (RICHARD T.). Ehrlich’s Diazo-reaction . . . . . LANDSTBTNER (I~ARL). Colour Reactions of Prot e‘ids with Nitrous acid and Piienols . . . . . . . . . . . SCHATEENIKOFF (M.) and IWAN M. SETSCRENOFF. Gas Analysis , . DENIGFS (GEORGES). Characteristic Colour reaction for Chlorates ., BLOUNT (BERTRAM). Estimation of Oxygen in Commercial Copper . MULDER (EDUARD). Tnfluence of Sulphurous Anhydride in Coal Gas flame^ on Qnnntitatire Estimations . . . , . . . GOOCH (FRANK AUSTIN) and A. W. PIERCE. Estimation of Selenious and Selenic acids * . . . . . . . . . WILLIAMS (C. B.). Estimation of Phosphoric acid in Soils by Precipita- tion with Molybdic Solution and Titration of the Ammonium Pliospi~omolybdate . . . . . . . . , KILGORE (B. W.). Estimation of Phosphoric acid by the Molybdate- Magnesia Method and by a Volumetric Method . . . . KILGORE (U W.). Estitnution of Pbosphoric acid by titration of the Ammooiiim Phosphomolybdtlte with Standard Alkali . . . GLADDIKG (THOMAS S.) . Gravimetric Method of Estimating Phosphoric mid as Ammonium Phoqhomolybdate .. . . . . DENIG~S (GEOKQES). Three &err Reagents for Nitrites . . . . BARTHE (LEONCE). Estimation of Boric acid . . . . . HEIDENHAIN (HEINRICH). Estimation of Carbonic Anhydride by Absorp- tion . . . . . . . . . . . . . MAWROW ( W.) and WILHELM MUTHMAKN. Estimation and Separation of Copper . . . . . . . . . . . . R,isrna (W. B.) and VICTOR LERHEP. Electrolytic Method for estimat- ing Mercury in Cinnabar . . . . . . . . . MOISSAN (HKNRI). Analysis of Aluminium and its Alloys , . . ATCIIP (GEORGE). Volumetric Estimation of Mitnganese . . . TARUGI (N.). Detection of Cliromlttes and Arseiiites . . . . Separation of Quartz from other Taricties of Silica Estimation of Manganese and Tin by Electroljsis . ii, 275 ii, 275 ii, 275 i i , 275 ii, 276 ii, 276 ii, 27G ii, 277 ii, 258 ii, 278 ii, 278 ii, 275 ii, 280 ii, 280 ii, 281 ii, 281 ii, 281 ii, 282 ii, 282 ii, 283 ii, 283 ii, 283 ii, 281! ii, 254 ii, 284 ii, 338 ii, 332 ii, 333 ii, 333 ii, 334 ii, 334 ii, 335 ii, 335 ii, 336 ii, 336 ii, 337 ii, 337 2,338 ii, 338 ii, 335 ii, 339 ii, 340xxuvi CONTENTS.I’ENNINGTON (MARY ENQLE). Niobium and Tantalum . . . . GILL (AUGUETUS H.) and HFRBERT APPLETON RICHARDSON. Estimation of Nitrites in Potable Ti-aters . . . . . . . . XrcHaaDs (ELLEN H.) and a. W. ELLMS. Colouring Matter of Natural Water. Its Source, Composition, and Estimation . . . . DIBDIN (WILLIAM JOSEPE). Microscopical Exuiriination of Water. . GILL (AUOVSTUS H.). and SAMUEL P. HUNT. Estimation of Methane and. Hydrogen by Explosion . . . .. . . . SESTINI (Pausio). Effect of adding A l ~ n i to Wine . . . . PY. Analysis of Bruit Sugars, Syrups, and Preserves . . . . WILEY (HARVEY WASHINGTON). Estimation of Levulose in Honeys and other Substances . * . . . . . . . . HERON (JOHN). . RITTER (GOTTPRIED TON). Estimation of Uric acid in Urine . . PEARMAIN (THOMAS HAMES) and CRESACBE GBOBUE MOOR. Coniposi- tiop and Analysis of Coiidensed Milk . . . . . . ITALLIE (LEOPOLD VAN). Iodine Number of Lard . . . . GORTER (K.). . MANKIBWICZ. Detection of Strychnine in a Medico-Legal Case . . JOLLES (ADOLF). A Delicate Test for Albumin in Urine. . . . LI I~OPF (ALEXANDER P.) . Gas Pipette of Simple Construction . . DENIGES (GEORQES). A new Cyanometric Method and its Applications . MABERY (CHARLES FREDERIC). [Estimation of Sulphur by Combustion in Air-] .. (I . . . . . . . . . . MABERY (CHARLES FREDERIC). Estimation of Sulphur in Illuminating Cias . . . . . . . . . . . , . MORSE ~HARHON NORTHRUP) and A. D. CHAHBERS. Standardisation of Po~assium Permanganate and Sulphuric acid . . , . , LINDEUNN and MOTTEU. Volunictric Estimation of Phosphorus . . MEILIARE (G.). The Moljbdic Reagent . . . . . . PATTINSON (JORN) and HUGH EALTIN PATTINSON. Estimation of Phos- phorus in Iron and Iron Ores . , . . . . . . MACH (F.) and MAX PASSON. Application of the Citrate Process to Wagner’s Method for the Estimation of Citrate Soluble Phosphoric acid in Basic Slags . . . . . . . . . , A NTOYY (UBALDO) . Detection of Chromates and Arsenat es . . . HATTENSAUR (GEORG). Estimation of Arsenic in Crude Sulphuric acid .STEAD (JOHN EDWARD). Estimation of Arsenic in Iron Ores, Steel, and Pig lron . . . . . . . . . . . . XMIILL~RE (G.). Estimation of free and combined Carbonic Anhydride in Carbonated WaterR . . . . . . . . . . TARUGI (N.). Exclusion of Ammonium Sulphide from Qualitative Analysis . . . . . . . . . . . . CAMERON (ALEXANDER). Estimation of Alkali Salts in Fireclays, Manures, &c. . . . . . . , . . . . BTANGER (W. HARRY) and BERTRAM BLOUNT. Testing of Hydraulic Cements . . . . . . . . , . . . LUNGE (GEOBG). Colorimetric Estimation of Iron . . . . . HEAL (CARLTON B.) and HENRY RICHARDSON YROCTEB. Analysis of used Liquors in Chrome Tannage . . . . . . . . MANN (IT.), M. KRUGER, and BERNHARD TOLLENS. Estimation of Pen- toses and Pentosans by the Purf uraldehgde Distillation Process.. O’SULL~VAN (JAMES). Hydrolysis and Estimation of Sugar . . . . RAUMER (ED. TON) and ED. SPAE’PH. Specific Gtravity of Milk Serum : Estimation of Lactose in Milk . . . . . . . . HXRON (JOHN). Polarisation arid Analysis of Black Beers, Worts, and Caramel . . . . . . . . . . . . MoRRrs (GEORGE EARRIS). Analysis of Beer, with some remarks on the Unfermentable Reducing Residue . . . . . . . ELION (H.). Est-ipiation of the Dry Substance in Malt Wort and Beer . Estimation of the Extract of Malt in the Laboratory Van de Moer’s Reaction and the Detection of Cjtiecine TAGE ii, 340 ii, 340 ii, 340 ii, 341 ii, 341 ii, 342 ii, 342 ii, 342 ii, 348 ii, 343 ii, 333 ii, 316 ii, 334 ii, 31.4 ii, 385 ii, 383 ii, 387 ii, 387 ii, 344 ii, 388 ii, 388 ii, 389 ii, 389 ii, 389 ii, 390 ii, 390 ii, 390 ii, 301 ii, 391 ii, 392 ii, 302 ii, 392 ii, 393 ii, 393 ii, 394 ii, 394 ii, 394 ii, 39 E ii, 895CONTENTS. X STERN (ARTHUR LANDAUER).Estimation of the Extract of Malt . . REBI~RE ((3.). Estimation of Alkali Benzoates . . . . . BRENZINGER (KARL). Estimation of Parasulphanilic acid . . . LT~PINOIS (E.). Acidity of Urine . . . . . . . . JAY (HENRY). Volatile Acids of Wines . . . . . . . SIDERSKY (D.). Simultaneous Estimation of Organic and Inorganic Acidity in Beetroot Juice . . . . . . . . . LEWKOWITSCH (JULIUS). Analysis of Fats : Colour Reactions . . SCHWEITZER (HUGO) and EMIL E. LUNQW~TZ. The correct Iodine $Sum- ber . . . . . * . * . . . . BISHOP (W.). Estimation of the Oxidisability of Oils . . . . HALPHEN (GEoRaas].Detection of Vegetable or Animal Oil in Mineral O i l . . . . . . . . . . . . . SCHWEITZEP (HUGO) and Ex15 E. LUNGWITZ. Commercial Analysis of Lard . . . . . . . . . . . SCHWEITZER (HUGO) and EMIS E. LUNGWITZ. Analysis of Lard Oil : SCHWKITZEB (HUGO) and EMIL E. LUNGWITZ. Analysis of Whale Oil . PARRY (ERNEST JOHN). Rantal Wood Oil . . . . . . SPAETH (ED.). Analysis of Soap : . . . . . . . SCHWEITZER (Huao) and EMIL E. LurmwIrz. Detection of Soap in Lubricants. . . . . . . . . . . . KREMEL (ALOIS). Detection of Aloes in Mixtures . . . . . F O R ~ N E K (EMAXUEL) . Identification of Alkalolds and Glucosides . KISSLINQ (RICHARD). Estimation of Nicotine and Ammonia in To- bacco. . . . . . . . . . . . . . DOBRINER (PAUL) and WILHELM SCHRANZ. Estimation of small amounts of Aniline in Toluidine, and of Tolriidine in Aniline .. . . DOBUINER (PAUL) and WILHELM SCHRANZ. Estimation of Water in Aniline and in Ortho- and Paratoluidine . . . . . . KEBLER (LYMAN F.). Estimation of Morphine in Opium . . . PBOCTER (HENRY RICHARDSON). Estimation of Tanning Matter . . ZANQEMEISTEP ( WILHELM). A Colorimeter : Colorimetic Estimation of Hamoglobin . . . . . . . . . . . CARNOT (ABOLPHE) . Volumetric Analysis of a Mixture of Chlorides, Hypochlorites, and Chlorates . . . . . . . . CARNOT (ADOLPHE) . Analysis of a Mixture of Chlorides, Chlorates, and Perchlorates . . . . . . . . . . . BRAND (J,), Detection of Fluorine in Beer . . . . . . ASB~TH (ALEXANDER TON). New Process for estimating Sulphur in Organic Compounds . . . . . .. . . , WAGNER (PAUL). Estimation of Citrate 8oluble Phosphoric acid . . ENGBL (RODOLPHE) and J. BERNHARD. Estimation of Arsenic . . GAUTIER (EMILE JULES ARMAND). Estimation of Arsenic . . . JORGFENSEX (GUNNER). Volumetric estimation of Boric b i d . . . PEIPFRS. Estimation of Carbon in Iron . . . . . . . WUST (F.). A New Apparatus for estimating Carbon . . . . DUPASQUIER (J.). Separation of Calcium from Strontivlm and Barium . LEGLER (LUDWIG). Estimation of Zinc in Dried Apples. . . . NISSENSON (H.) and B. NEUMANN. Estimation of Copper by Precipita- tion with Sodium Thiosulphate . . . . . . . . Low. The Iodide Assay for Copper. . . . . . , . GEOLUES. Estimation of Alum in Wines . . . . . . ILINSKI (MICHAEL YON). Detection of Cobalt by Nitroso-&naphthol . BAILEY (HENRY).Analysis of Tin Slag . . . . . . . KISSLIKG (RICHARD). Testing Petroleum by Fractional Distillation . CARPENTIER (E.). Detection of Paraffin in Olive Oil . . . , FOERSTER (OTTO). Estimation of Oil of Mustard . . , . . LEWKOWITSCH (JULIUS). Assay of Glycerol for the manufacture of Dynamite . . . . . . . . . . . GUNNING (JAN WILLAM). Estimation of Water in Raw Sugars . . 3-2 .xxvii PAGE ii, 396 ii, 396 ii, 396 ii, 397 ii, 397 ii, 397 ii, 398 ii, 398 ii, 398 ii, 399 ii, 399 ii, 399 ii, 399 ii, 400 ii, 400 ii, 400 ii, 4&1 ii, 441 ii, 401 ii, 4@2 ii, 403 ii, 403 ii, 443 ii, 4M ii, 447 ii, -447 ii, 447 ii, 4 8 ii, 448 ii, 448 ii, 449 ii, 4!49 ii, 449 ii, a 9 ii, 450 ii, 450 ii, 450 ii, 450 ii, 451 ii, 451 ii, 451 ii, 452 ii, 452 ii, 452 ii, 452 ii, 453s xx viii COXTEKTS.STIFT (A.). Estimation of Peatoses and Pentosans by means of the Furfuraldeliyde Reaction . . . . , . . . . KJELDAHL (JOHAN GUSTATE CHRISTOPHE THAKSAGER). Behaviour of Sugars towards Alkaline Copper Solution . . . . . . OST (I~BRMAKN). Estimation of Sugars by Means of Alkaline Copper Potassium Carbonate . , . , . . . . . . STOBODA ( HANNO). Behaviour of Basic Lead Acetate towards Sugar Solutions . . . . . . . . . . . . SCHEURER-KESTNEP (AUGUSTE) . Estimation of the Acidity of some Pyroligneous Products . . . . . . . . . VITALI (DIOSCORIDE). Oxalic acid and Putrefttction . . . . WALLER. Improvement in Riibl’s Chloro-iodine Process . . . LXVIN (P.). Testing Vegetable Oils and Butter . . . . . SPAETH (ED.). Estimation of the Acetyl Numbers of Lard, Cotton Seed Oil, and Tallow .. . . . . . . . . . VOQEL (H.). Testing of Lard . . . , . . . . . JEAN (FERDINAND). Analysis of Lard and Similar Pats . . . . DTJPONT (J.). Detection of Cotton Seed Oil in American Lards . . BUCHKER (GEORG). Rapid Estimation of Wax-substitute in Beeswax . SCHWEITZER (HUQO) and EMIL E. LUNGWITZ. Testing Acetone . , SCHUYTEN (M. C.). Volumetric Estimation of Antipyrine . . . CAMPBELL (EDWARD D.) and E. 13. HART. Estimation of Hjdrogen by means of Palladious Chloride . . . , . . . . S JOQTJIST (JOHN), Estimation of Free Hydrochloric acid in Gastric Juice . . . . . . . . . . . . . HEFELMANN (RUDOLF) and PAUL MANN. Detection of Fluorine in Seer. NIVIBRE ((3.) and A. HUBERT. Detection of Fluorine in Wine . , HEATH (a. L.). Estimation of Sulphur in Refined Copper , .. KELLER (HARRY FREDERICK) and MAAS. Estimation of Sulphur in Roasted Copper Ores and Cupriferous Pyrites . . . . . PHILLIPS (PRABCIS C.). The Evolution Metrhod of the Estimation of Sulphur in White Cast Iron . . . . . . . . LUNGE (GEo~~G). Estimation of Sulphur in Pyrites. . , . . BALLAND and MALJEAN. Detection of Free SulFhuric acid in Leather . BARTON ((3. E.). Arsenic in Glycerol . . . . . . . SHIMER (PORTER W.). Estimation of Graphite in Pig-iron . . . SZYFER (L.), Estiniation of Lime by an Alcoholic Solution of Potash S o a p . . . . . . . . . . . . . FaEsENIUs (CARL REMIBIUS) and E. HINTZ. Solubility of Barium Sulphate . . . . . . . . . . . Ruoss. Volumetric Estimation of Metals precipitable by Alkalis, and Applications of the Rfethod.. . . . . . . . LESC~EUR (HENRI) and CL. LEMAIRE. ‘Golumetric Estimation of Zinc . ECKENROTH (HUGO). Analysis of Galena. . . . . . . APINDBEWS (LAUNCELOT). Analysis of Alloys of Lead, Tin, Antimony, and Arsenic . . . . . . . , . . . BORNTRAQER (HUGO). Solution of Ignited Ferric Oside and other Xetallic Oxides . . . . WELLS (HORACE LEXUEL) and W. L. MITCHELL. Volumetric &tima-- tion of Titanic acid and Iron in Ores . . . . . . . BLAIR (ANDREW A.) and J. EDWARD WHITFIELD). Ammonium Phospho- molybdate, and the Reducing Action of Zinc in the Reductor . . DUCLAUX (EXILE). Estimation of Alcohols and Volatile acids . STUTZER (ALBERT) and R. MAUL. Estimation of Fnsel Oil in Refined Alcohol . ‘ . . . . . . . . . . . TOLLENS (BERNHARD). Detection of Pentoses by Precipitation with Phloroglacinol .‘ . . . . . ”. . - . . . HEFELMANN (RUDOLF). Estimation of Sugar by the Copper Method . STROHMER (FRIEDRICH) and A. STIFT. Estimation of Crystallisable Sugar in Raw Sugars . . . . . . . . . . PAGE ii, 453 ii, 453 ii, 453 ii, 454 ii, 454 ii, 454 ii, 454 ii, 454 ii, 454 ii, 455 ii, 455 ii, 455 ii, 456 ii, 456 ii, 456 ii, 496 ii, 496 ii, 497 ii, 497 ii, 497 ii, 498 ii, 498 ii, 498 ii, 499 ii, 499 ii, 499 ii, 499 ii, 499 ii, 500 ii, 501 ii, 501 ii, 501 ii, 502 ii, 508 ii, 503 ii, 504 ii, 504 ii, 504 ii, 503 ii, 505CONTENTS. xxxix WOLESKY (I?.). Detection of Wood Pulp in Paper . . . . MEDICUS (LUDWIG). Estimation of Aldehyde in Spirits of Wine . . CRISMER (LBox). Critical Temperatures of Solutions : a New Constant for the Identification of Oils .. . . . . . . MJOEN (J. ALFRED). Fatty Oils of Xecnle co?*nutum and of the Seeds of Stmphaiatus hispidus and Ryoscynmus niger . . . . . STBOIIL (A). . V AUBEL (WLLHELH). Estimition of Benzidine and Tolidine . . . \‘A UBEL (WILHELV). Behaviour of Naphthols and Naphthylamines with Nascent Bromine . . . . . . . . . OTTO (ROBERT). Behaviour of Warcotine and Papayerine in the Stas- Otto Method of detecting Alkaloids . . . . . . . HLRSCHSOHX (EDUAED). Detection of Patty Oils in Copaiba Balsam : a New Test for Gurjun Bidsani. Detection of Colopltony in Guaia- cum Resin and Balsams of Tolu and Copaiba . . . . . SPAETH (EDUARD). Estimation of Jalap Resin in Medicines. Detection of Strychnine in Corpses . . . . . . . . . KorvrNaH (LEONARDE). Estimation of Water in Superphospltates .LUi>WIG (EUaEN). Use of Aldehydes containing Ozone for the rletection of small quantities of Iodine in presence of Chlorine and Bromine . JANNASCH (PAUL) and H. LEIINERT. Estimation of Sulphur in Inorganic Sutphides . . . . . . . . . . . . AVCHY (GEORGE). Drown’s Method of Estimating Sulphur in Pig Iron. CONE (EDWIN I?&). Estimation of Pyri-liotite in Pyrites . . . . HOPKINS (CYRIL G.). New Safety Diztillation Tube for Nitrogen Estinia- tions . . . . . . . . . . . . . YEITCH (F. P.). Modifications of Pemberton’s Tiohmetric Method of estimating Phosphoric acid in Fertilisers . . . . . , RKICH (ALFRED). [Analysis of Silicates containing Fluorine] , , BLAIR (ANDREW A.). Estimation of Carbon in Steel . . . . NANTIER (A.).Rapid and exact Estimation of Lime in Soils . , , HEIDENREICR (MAX). Quant tative Analysis by Ele~trolysis . . . JANNASCH (PAUL). Delicate Form of the Mercury Iodide Keaction. . JANNASCH (PAUL) and H. LEHNEBT. Separation of Mercury from other Metals by heating the Sulphides in a currelit of Oxygen . . . JANNASCH (PAUL). Separation of Manganese from Copper and Zinc and of Copper from Zinc and Nickel. . . . . . . . MIXER (C. T.) and If. W. DUBOH. Sarnstrom’s method of estimating Manganese in Iron Ores . . . . . . . . . STOKE (GEORGE (2.). Volumetric Estimation of Manpnese . . . JANNASCR (PAUL) and H. LEH~ERT. Sepiration of Metale in Alkaline Solution by means of Hydrogen Peroxide. XV. . . . . TARUGI (N.). Detcctiori of Cttrttniates and Arsenites . . . . HAZEN (ALLEN). Estimation of the Coloura of Natural Waters .. EGELING (CORNELIS GELDENSTEEDEN). Detection of Lvad and Copper in Potable Waters . . . . . . . . . . ANTONY (UBALDO) and T. BENELLI. Estimation of small quantities of Lead in Water . . . . . . . . . . . HOPMAN (J. J.). Estimation of Sodium Salicyltlte in presence of ‘‘ Ichthjol ” . . . . . . . . . . . WILEP (HARTEY WASHINGTON). Determination of the Heat of Bromin- ation in Oils . . . . . . * . . . . ~ ~ A I N W R I O H T (J. HOWARD). Estimation of the Solid Fat in Artificial KAXBUROER (HARTOG JAKOB). Estiinaticm of added Water i n Milk by taking i t 3 Freezing Point . . . . , . . . . KIJBLr (MELCHIOR). New method of Testing Quinine . . , , l l E s s E (ORWALD). Testing Qcinine Sulphate . . . , , KbSLEn (LYMAN F.).Acidimetric Estimation of Vegeta5le Alkaloxds : a Study of Indicators . . . . , . . . . Iodine Number and Refractive Index of Cacao Butter Mixtures of Vegetable and Animal Fats and Oils . . . PAG 1: ii, 505 ii, 505 ii, 506 ii, 506 ii, 506 ii, 507 ii, 337 ii, 508 ii, 508 ii, 508 ii, 541 ii, 51.2 ii, 542 ii, 513 ii, 543 ii, 543 ii, 543 ii, 5-14! ii, 544 ii, 545 ii, 5-45 ii, 545 ii, 546 ii, 546 ii, 547 ii, 547 ii, 547 ii, 548 ii, 543 ii, 549 ii, 549 ii, 549 ii, 549 ii, 550 ii, 550 ii, 550 ii, 550 ii, 551Xl COXTEXTS. LEWIN (Louxs). A forensic Examination for Strychnine . . . . KILIANI (REINRICH). Detection of the Glucosides of Digitalis and the Products of their Hydrolysis by means of Sulphnric wid eontainitig a Ferric Salt , . . . . . . . . . . . PEINRMANN (ICAm).Cubebs and its Sdulterants , . . . . HOPPE-SEYLBR (GEORG). P. Hoppe-Seyler's Double Colorimetric Pipette KONINGH (LEONARD DE). Estimation of Solid Matter it1 Eeef-Tea . . BLEIER (OTTO). Apparatus for Gas Ana1,ysis . . . . , . RIEGLER (E.). Standardisation of l'hiosulpliate bp Todic acid. . . RIEGLER (X.). Volumetric Estimation of Soluble Ioclides . . . ENQlER (CARL) and w. WILD. Stymation of Ozone from Hydrogen Peroxide and recognition of Ozone in thc Attnosphere . . . HINDS (J. I. D.). Photometric ~letliod fcr the Estiination of Lime and Sulphuric acid . . . . . . . . . . . JANNASCH (PAUL). New Method of converting Sulphates into Chlorides AUFSCHLAGER (HEINLICH). Action of Fused Polpul~hides on Nitro- genous Organic Substances . . . . . . . . REITXAIlz (OTTO).t.'itrate-Solublc PhGFphOriC acid. . . . . PASSOX (Max). Cowlparatire Methods for Estimating Citrate-soluble Phosphoric acid in Bmic Slag . . . . . . . . GORGES. Source of E k o r as to tito Presence and Estimation of Boric acid ALLEN (ALFI ED HENRY). Preparation of pure Hydroflnoric acid . . JaNxasc~ (PAUL) bnd 0. WEIL'ENREICH. Deconiposition of Silicates by Soric acid . . . . . . . . . . . . JANrrascH (PAuI). Bchaviour of Minerals of the Andalusite Group towards Decompoeing Agents . . . . . . . . TOGEL (J. H.) and H. HAFFCTE. Estimation of Potabsium . . . TRAUBE (HERIIIANN). Microchemical Reactions [of Bsrium m c l Silver]. RITTER.(GOTTFRIED TCN). Estimation of Zinc in Organic Falts . . SCERODER TON DER KOLK (J. L. C.). Louble Compounds of Aniline and Metallict salts .. . . . . . . . . . BROOKS (CECIL J.). Estimation of Tin . . . . . . . LECCO (MARCO T.). Occurrence uf Ioc!ine in Waters . . . . ROXIJN (GtYsBmtT). Estimation of ditsolred Oxygen . , . . BASSETT (HEKEY). Analyeisof Anthracene . . . . . . FXESEKTTJS (HEINRTCH) and C. J. S. MAKIN. Estimaiion of Phenol in Soaps and Disinfectants . . . . . . . . . TOLLENS (BERNARD). Estimation of Pentoses and Pentosans by the Furfuraldehyde Method . . . . . . . . KJELDAIIL ( JOHAN GUSTAV CHRISTOPEE THORSAGER). Estimation of Siigars by Fefiling's Solution . . . . . . . . CAUSSE (HENRI EUG~NE). Estimation of Glucose. . . . . BECKMANN (ERNST). Examinationof Honey. . . . . . RICHMOND (HENEY DROOP) and L. XIDGELL EOEELXY. Detection of Formulin . . . . . . . . . . . . HEHNER (OTTO).Detection of Formalin . . . . . . . SMITH (HAXRY M.). Estimation of Formaldehyde. . . . . H ~ A S (B.). Estimation of Tartar and Tartaric acid in Wines . . ALLEN (ALPRED HENRY). Composition and Analyeis of Commercial Cream of Tnrtar . . . . . . . . . . ALLEN (ALFRED HEXRP). Estimation of Quinino . . . . . CARREZ (C.). New Reaction for Antipgrinr and for Quinice . . . THAN (CARL VON). A Compensation Uethod in Basometry . . . STAHL (KARL F.). Volumetric Estimation of Hjdrofluoric acid . . GLADDING (THOMAS S.). Estimation of Sulphur in Pyites . . . SABATIER (PAUL). . WINTON (A. L.). A Modified Ammonium Molydate Soltit ion. . . LOXD (NATRANIEG WUIGHT). dimple Method for Deterinining tlie Neutrality of the Ammonit m Citrnte Solution used in tlie Analjsis of Ferrtilisers . (i . , . . . . . . . . Detection of Nitrites by rncans of Cuprous Salts ii, 551 ii, 552 ii, 554 ii, 558 ii, 573 ii, 573 ii, 573 ii, 574 ii, 574 ii, 574 ii, 574 ii, 575 ii, 5 i 5 ji, 575 ii, 5'75 ii, 576 ii, 576 ii, 57'; ii, 578 ii, 5% ii, 558 ii, 579 ii, 559 ii, 579 ii, 380 ii, 580 ii, 580 ii, 580 ii, 582 ii, 5S2 ii, 583 ii, 583 ii, 51.3 ii, 588 ii, 584 ii, 534 ii, 584 ii, 021 ji, 621 ii, 622 ii, 622 ii, 622 ii, 623CONTENTS. xli I’AGE ERTAST (A. P.). HEYRTET. S~paraiioii of the Insoluble Phosphoric acid derired from Bone Phosphate from that derir ed froin Mineral Phosphate Rapid Estimation of Carbonic Aiilrjdridc in the Atinosphcre, k c . . . . . . . . . . * . . . HOITJEMA (C.). The End-point in Gay-Lussac’s Method of Silver Titra- tion . . . . . . . . . . . . . KUSTRR (FRIEDRTCH WILHELM). Soliiiility of Barium Sulpltnte . . Lorar (ANTONIO) and L. BONATTA. Voluinetric Estimation of Lead . XicHnL~oN (HUDSON H ) and S. AVERY. Electrolytic Estimation of Iron, Nickel, and Zinc. . . . . . . . . . . AUCHY (GEORGE). Sources of Error in Volhard’s and Similar Methods of estimating Manganese in Steel . . . . . . . WILEY (HARVEY WASHINGTON) and ERWIN 33. EWELT,. Estimniion of Lactose in Milk by Double I)ilution and Polarisation. . . . TITALI ( DIOSCORIDES). Toxicological Exainination for Mercuric CJ anide VLZER (FERDINAND) and HEINRICH SETLEL. MOULIN (L.). A New Test for Aspsragiiie . . . . . . JAWOROWSEI. Test for Cinchona Alkalo’ids . . . . . . PETIT (AFGUSTE) rind P. TERRAT. Fstimation of Caffeine in Tea . , QEDRODI (VIKTOR). Estimation of R’irotine and Ammonia in T C J ~ ~ C C O . CAZENEFVE (PAUL). Distinction between Magent a a i ~ ! “ Acid Magenh.” BELAR (ALBIN). Examination of Xed Wines for Poreign Colouring Matters . . . . . . . . . . . . SCHJERNING (NIELS CHRISTIAN HENBIK). Quantitative Separation of Yrotei’ds in Beer Wort . . . . . . . . . RALKE and IDE. Estimation of Phosphorcarnie acid . . . . BRE IRLEY (H.). Auto-pneumatic stirrer. . . . . . . BTLTZ (HRINRICH). A Modified Form of Measuring Flask . . . NORACZEWSKI ( WACLAW VON). Estimation of H-jdrocliloric acid in the Gastric Juice . . . . . . . . . . , BOUCHER (G. G.). Estimation of Sulphur in Cast Iron or Steel . . JANNASCH (PAUL EHXHARDT) and 0. HEIDENREICH. Zstimation of S~ilphur in Inorganic Sulphides. VT. . . . . . . LUNGE (GE~RG). Precipitation of Barium Sulpliate by means of? Barium Chloride. . . . . . . . . . . DOBRINER (PAUL) and WILHRRLM SCIIRSE’Z. Estimation of Sulphui-io Anhydride in Fuming Sulphurir acid : Estimation of Sodium Sul- phide . . . . . . . . . . . . PEIRCE (A. W.). Gravimetric Estimation of Sclenium . , . . 3)UBBERS (H.). Experiments 011 tlie Citrats-solubility of Basic sligs . PHEJPS (J. K.). lodometric Estimation of C:arbonic nerd . . . GEELMFYDEN (H. CHR.). Kew Bar\ ta Tube . . . . . . RICHARDS (JOSEPH W.). Separation of Silver from Gold bg Volatilisntion NEFBAUER (HUGO). Estimitticn of Magnesia as Rlagtiesiii~n l’yrophos. pliate . . . . . . . . . . . . . XONINCK (LUCIEN LOUIS) and EUGENE PROST. Volumetric Estimation of Zinc by means of Potassium Ferrocyanide . . . . . JANNASCH (PAUL ERRHALLUT). Separation of Mercury from Arsenic, Antimony, and Copper by Ignition in a Current of Ox~gen . BREARLEY (EI.). Estimation of Nickel in Steel . . . . . RIEGLER (E.). Standardisation of Permanganate . . . . . FI~ESENIUS (CARL RExraIus) and E;. HINTZ. Examination of Cons- mewial Thorium Nitrate and Separation of Thorium and Cerium . J ~NXASCH (PAUL EHRRARDT) and 8. GROSSE. Separation of Bisniutti from the Metals of the Copper and Iron Groups by heating their sdts in aCurrent of Dry Hydrogen Chloride . . . . . . FRTTSCHE (P.). Estimation of Ethylene i n Gaseous Mixtnres . . . PAS~ON (MAX). Estimation of Esbential Oil of Mustard in Feettifig Cakes. . . . . . . . . . . , . FABRE (CHARLE~). Egtimation of Potassium . . . . . Analjsis of Wool-grcase . ii, 623 ii, 624 ii, 624 i;, 624 ii, 625 ii, G25 ii, 627 ii, 627 ii, 628 i i , C28 in, 628 i , 619 i , 629 ii, 629 ii, 630 ii, 630 ii. 630 ii, 631 ii, 632 ii, 671 ii, 671 ii, 6’71 ii, ti71 ii, 671 ii, 673 ii, 6’72 ii, 673 ii, 673 ii, 673 ii, 674 11, 674 ii, 674 ii, 675 ii, 675 ii, 676 ii, 6’76 ii, 677 ii, 6’77 ii, 6’78 ii, 678sl ii CONTESTS. REID (EDWAR~ WAYMOUTH). Esiimation of Oxygen in Blood . . GEELMUPDEN (E. CHR.). Messinger's Met hod of Estimating AcetoiTe . BORXTRAGER (ARTHUR). Examination of Oil of Bergamot . . . HEFELMANN (RUDOLF) and PAUL MA". Siinple Process for teatiug Linseed Oil, Boiled Oil, and Paints . . . . . . . KAm (ALEXANDER). Iodine Numbers of Pure and Boiled Linseed Oil . FfLSINQER (F.). Iodine Number of CacaoButter . , . . . HENZOLD (OTTO). Extracting Fat, from Cheese for Testing Purposes . I<II>~JENBERGE~C (KARL). New Method for Quantitative Isolation of Alkal oi'ds , . . . . . . . . . . . KIP PEN BERG EL^ (KARL). Titration of AlkaloYdq with Todine SolutioB . LRDDEX HUZSEBOSCH (MARIUS L. &. VAN). 'Iecting Cinchona &xtract . I<ELLER (c. c.). Reactions of Ihgitalin . . . . . . . SinzEI: (ALBERT). Cheaicul Examination of Cheese . . . . P A 0 6 ii, 678 ii, 679 ii, 679 ii, 8x0 ii, 680 ii, GSO ii, 680 ii, 681 ii, 682 ii, 682 ii, 683 ii, Gb3

ISSN:0368-1769    

DOI:10.1039/CA89670FP036

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

42 P h y s i o 1 o g i c a 1 C h e mi s tlr y. Cutaneous Respiration in the Frog. By E. WAYMOU~H REID and FREDERICK J. HAMBLY ( J . Yhysiol., 1&5, 18, 411--424).--The vital o r secptory activity of the epithelium lining the a i r passages lias been recently called on to account for some of the l~henomena of rekpirstion. The present research deals with this qucJstion in con- nection with the skin of the frog, which in that auimal forms an important coadjutor to the lungs. The appsratus and method used me described a t length : the principle of the method is, that t,he skin just removed from the animal is used as a diaphragm, across which the amount of gases passed is estimated. Tile amount of carbonic anhydride whicli passes through the skin, from the inner to the outer surface, is practically the same as that which passes in the reverse direction. There is thus 110 el ideiice of secretory activity.W. D. H. By GOTTLIEB (Bxp. Stat. Rcct,/rd, 1895, 7, 148-149 ; from Verhuncll. L\rotu~-. X e d . T7er.? Heidetberya, 5).-Observxtions of th:: constant and regnlar secre- tion of the paricreatic: juice, by means of a canula, in the paiicreatic duct of a rabbit, slirJwed t h a t the introductiou of mu-tad or pepper into the swcIiacii causcd the secretion to be ttiree or iour umes as laige ; the juice was somewhat abnormally watery, h u t possessed t h e s a s e digestive properties. X. H. J. M. Wandering Cells of the Alimentary Canal. By W. B. HARIJY and F. F. WESBROCIK ( J . Yhysiol., 1895, 18, 49&-524).-The main bulk of the paper is liistological, beiug a continuation of' former work.The cells fall into the three main classes of oxyphile, babophile, and hyaline celis. A notewoithy fact made out is the existence of a layer of basophile cells a t the base of the epithelial cells covering the villi. A large nuniber of animals were investigated ; in rats fed on ;I flesh diet, the cells altered to the csxnivorou, type, the basopbile cells becoming more numerous, and scattered and mjgr ated in l a y num- bers between the epitheliuu cells ; the granules of the oxyphile cells Action of Mustard and Pepper on Digestion.were scarcely preserved by absolute alcohol, a i d did not stain readily. The absorption of iron appears to be carried out br the hpaline cells. TTT. D. H. The Lactase of the Small Intestine. 1:s FRANZ R~~HMANN and J.LAPPE (Bey., 1895, 28, 2506-2507; compare Pautz and Vogel, Abstr., 1895, ii, 403).-The authors have investigated the action of the small intest.ines of‘ calves, oxen, and yourig and old dogs, on solutions of uiilk sugar. Fhe intestines were also extracted with chlorofcxm, with tiiymol solution, and with sodium fluoride solution, and the action of these extrilcta on the milk sugar studied. I n all cases, with the exception of OX intestine, after digestion for several hours, dextrose could be identified i n the solution by means of its osazone. Alcohol prceipitates from tbe above extracts of the intestine a sub- starice which will also liydrolyse milk sugar. Qnai!titative experiments as to thc amount of dextrose formed wele also made.J. J. S. Influence of the Vaso-motor Nervous System on Meta- bolism. By F. TANGL (P$ziger’s A ~ c h i v , 1895, 61, 563-582).- Dogs were curarised, their s p i r d cord divided i n the neck, artificial respiration being kept up. The peripheral end of the spinal cord was stitnulsted, and observations made on the rectal temperature, and g:iseous interchanges before and during stimulation. The geiiersl conclusion drawn is that electrical stimulation of the whole vaso- motor system of nerves produces a fill1 of the temperatnre of the internal parts of the body, arid that tliis is due not only to increased loss of’ heat, but also to diminished developmerit of heat. W. D. H. Metabolism. By IMMAXUEL M u m (PJliiger’s B r c h i ~ , 1695, 61, 607--619).-l’his is a suppiernentary paper to one previously pub- lished (Abstr., 1895, ii, 78), and is chiefly conccmed with answering various criticisms, and explaining some parts more fully.The prs- vious general cunclusions of the author are maintained. W. L). H. Iron in Food. By I~ALPH STOCKMAN ( J . Y h p X . , 1895, 18, 484--489).-Almost t h e o d y data, with regard to the amount of iwil i u food, are those of Boussinganlt (Cow@. ?*end., 74, 1352), wd liis results are too high. Tlte great difficulty iu wclrk of this kind is corn- pl:,te incineration ; whicli, in the present research, was acconiplishcd by heating the ash with a mixture of hydrochloric and sulphuric acids ; the residue was then taken up with dilute sulphuric acid, re- duced with zinc, and titrated with potassium permanganate.The ordinary daily diet was found to coutain about 9 or 10 mil!i- grltnis of iron ; but i n chlorotic pciple, who talcc but little food, the amouiit u a s about 3 milligrams. The following articles c;f diet were also analj-sed in the same way. Milk from 2 to 4.3 milligrams per litre. Oatmeal 3.5 milligrams per 100 grams (dried). Bread from 0.61 to 0.85 milligrams per 100 grams (dried).44 'at. Ibs. 0 *33 0 '38 0 -19 0.26 ABSTRACTS OF CHEMICAL PAPERS. Carbo- Heat liyd rstee. ralue. --~--- Ibs. cal. 5 -89 14000 6 -13 14500 4 -60 11500 4 -65 12100 Yellow ox marrow 2.5 to 4 milligrams per 100 grams (dried). Red calf marrow '7.6 to 8.7 ., 7 , Beefsteak 3.9 mi1ligrn1.m per 100 grsnis (dried). 1 ) W. D. H. Sugar as a Food. By B. T. STOKVTS (Brit.Med. J., 1895, ii, 12tO-1282). By UGOLIKO Moss0 (ihid., 1282). By VAUGRAN HARLEY (ibid., 1282 -1284).-These three papers constituted the opening of' :I, discussion at the an+nual meeting of the Brit. bled. Assoc. (1895). Harley and Moss0 support the doctrine that sugar is the great source of muscular energy ; this, however, is strongly contested by Stokvis, who severely criticises the elgographic method. Mannan as Human Food. By C. TSCJI (Bul. COX A g k Imp. Uiziv., !f'ok!g?lo, 1894, 2,10.3-105).-l+om the tuberous roots of Conc- phaZlus konyaku, a food, consisting of colourless, gelatinous tablets, is p r e p a i d , and is largely consumed in Japm. It is made by mixing the grouiid root with slaked lime (1 part) and water (2 parts), after which it, is boiled with lime water until i t forms a gelatinous mass.When boiled with 3 per cent. snlphuric mid, the root yielded 55.86 per cent. of mannose, assumiiig the whole of the sugar present t o be mannose, as is very probable. The ~nannan present in the root must be digested by the enzymes in the intestines, and transformed into mannose or a dimannose, corresponding with the maltose made from htarch. Attempts to convert t!ie mannan of k o n y n h into a sugar by means of diastase from malt were unsuccessful. W. D. H. N. H. J. M. Feeding Experiments on Sheep. By CHARLES D. WOODS and C. S. PHELPS (Ann. .Rep. Storrs Ayric. J f ~ p . Stot., CO?~~Z., 1893, No. 6, 28-42, and 1894, No. i , 92--106).-h the first series of experi- ments, five sheep were fed for 12 weeks on a wide ration (maize meal, hay, and turnips), another lot of fye being fed with a narrow ration (linseed, pea and maize meal, bran? and hay), after which they were alangh tered, weighed, the various portions separated, and analjsed.Similar sheep mere slaughtcreii niitl analysed at the commencement of the experiments. The second set of experiments was similar, but the sheep were kept in a yard in groups instead of in pens. The following tables sunmarise (1) the daily amount of digestible food aclually eaten to produce a gain of 1 lb. live weight; (2) the perceutage composition of the fresh edible meat produced under the different conditions in both years. --- Wide ration, 1893.. . . Narrow miion, 1893.. ), 1894..,. >) 1894.. --I-- Ibs. Ibs. 6 -99 I 0.83 7-31 1 0'81 ti '02 1 '23 6 - 2 0 1 1.30PHYSIOLOQI CAL CEEMISTRT. 45 At commencement 1893 Wide ration, 1893 .. . . ,, 1804 .. .. Narrow ration, 1893 . . 3 Y9 1894 9 , 1894 .. In fresh meat. I In dry meat. Prote'in. 41 -4 36'6 34 -9 32.6 36**5 35-8 Ash. 2 . 5 2'0 1.9 1'8 2'0 2 ' 0 Fat. Water. -- 58 -4 55.2 57.3 52.0 58'8 54.1 5G *1 61 *4 63 -2 65 *G 61 -5 62.2 Digest,ible Amide Crude protei'n. nitrogen. fat. 0 -70 0-017 3-29 1 *ol! - 2.66 0 *6S 0,069 1.20 1-30 0 039 0.94 -- -- __I Crude fibre. 21-24 27-15 39.77 46.02 --- Protei'n. -- 17.3 16 -3 14 -9 15 *G 15 -0 16 -1 Ash. The resnlts show that the character and composition of meat depends largely on the food. The 1893 results illusbrnte strikiiigly the fact that water and fat can replace each other to a greiit extent ; whilst the protein is about the same in both series (wide and narrow rations), the meat of the narrow ration animals contains 1.5 pcr cent.more water and 1.6 per cent. less fat than the flesh of the wide ratioii sheep. Otherwise tlie results are not very decisive. N. H. J. M. Feeding Experiments with Brushwood. Bg E. RAmf (h'ied. Centr., 3895,24,445-448 ; from Landw. Juhrb, 1894, 23, 789-834). --In consequence of the scarcity of food in 1893, cxperirnents were made at Poppelsdorf in which cows, hoi-ses, sliecp, and goats were partially fed with brushwood. Corns proved to be most, suitable for the cxperinients, as tliey consumed the material i n suficisnt quantity, and did not, with one exception, suffer from indigestion. They received a constant ration of sugar beet, dried brewers' grains, earth- nut cake and salt,, together with wheat chaff (5 kilos.), which was successively replaced by birch (9-12), copper beech (6-11), and hornheam brushwood (4-5 kilos.) per day.The brushwood was freshly ground each day, and was given in different degrees of fineness. The effect of brushwood was to decrease the yield of milk, raise the percentage of fat, and, in some cases, to shorten the period of lactation. It was of great importance to have the wood very finely ground. Only the buds and bark seem to hare a value as food, a large portion of the \rood being found undigested in the faxes. Of the different woods, birch gave the best, hornbesm the worst, results. Thc following numbers shorn the percentage composition of fine beech brusliwood meal ( l j , medium and coarse beech (2), copper beech (3), hornbeam (4). - 1 2 3 4 - Dry matter .5s '47 62 -81 $2 *23 S l . 6 7 -- Crude prote'in. 3 -65 3 -35 3 .07 3 -43 IS-free extract. 24 *84 28 '54 2G '77 30 -06 I Pure ash. 0 -99 0 -96 1 *O$ 1 *14 ---4 ci ABSTRACTS OF CHEMICAL PAPERS. The percenttcge amount of lime was (2) 0.389, (3) 0.438, (4) 0,377 ; of magnesia. (2) 0.107, ( 3 ) 0 103, (4) 0 15s; of phosplioric acid, (2) 0 143, (3) 0.146, nrd (4) 0.125. The results show that' in years of scarcity of the ordinary foods, brushwood dmerves attention. Some animals, however, cannot be fed with it at all, and i t is unsafe to employ i t For lon? periods as an csclusire substitute for forage. Examination of Foods from Farms where Cattle suffered from Brittleness of the Bones.By OSCAR KFLIJER, A. KOHLER, and F. BARKSTEIN (Bi~d. Cmtr., 1895, 24, 441-443 ; from ~ S a c / ~ s . landw. Zeit., 1894, No. 15).-AnElyses werc m:de of five samples of hay and three of straw, produced in the dry sewon of 1803. The aniount of phosphoric acid was, in every case, very low. There is no direct evidence to show that bone brittleness can ay'se from want of phosphates, but Fiirstc-r, Stillnig, and von &ring proved that it may be caused by insuficient supply of lime. Inasmuch as lime and phosphoric acid always occiir in the same relative amounts in the bones OF young animals, a deficiency of phosphates in the food may cause Rn insufficientJ deposit of lime in the bones, and with older animals, deficiency may cause a withdrawal of both phosphoric acid and lime from the bones, which would thus become brittle.The disease can generally be cured by good feeding and a dailyallowance of bone meal (30 to 60 grams) ; 011 farms where bone softening prevails, the crops should be well manured, especially with soluble phosphates. Fittbogen showed that plants, when insufficiently watered, am unable to take up phosphoric acid in suEcient amounts. Action of Drugs on the Embryonic Heart. By JOHN W. PICKERING ( J . Physiol., 1895, 18, 470483).--This is a series of further experiments in answer t o ccrtain criticisms by His (Cent?-. Phpid., 1894, 8, 11). The chief points made out are the following : -'l'he combined accelerator and augmentor action of small doses of alcohol on the heart of the embrjo cliick, reaches its maxirnuni at about 38" ; a t low temperatures, even smd1 doses of alcohol rapidly depress the cardiac rhrthm.A temperature of 40" and upwards has a marked influence on the action of alcohol on the embryonic hf.art ; the frequency becomes too rapid to record, and the force of the beats is much diminished. A dose of alcohol, which, a t 20°, is a depressant, has an accelerator action at higher temperatures. The maximum accelerator action of alcohol is attained more rapidly at a lower than at a higher temperature ; the depressant, action is affected siinilarly. The cardiac stoppage produced by moderate closes of alcohol at a l o w temperature can be usually removed by heating, or by the application OF electrical stimuli ; similarly, the cardiac stoppage produced by small doses of alcohol at a high temperatare, can sometimes be removed by cooling ; electricd stimulation, Iiowever, induces a condi- tion not unlike tetanus.A dose of 0.1 milligram of veratrine (dis- solvecl in 0.65 per cent. sodium chloride solution) acts as a dcprcssatit to the embryonic heart a t 20°, but, at a temperature above 30", pro- duces a marked acceleration of cardiac frequency ; n dose of 0.3 rnilli- N. H. J. M. X. H. J. M.PHPSIO L,OQICAL CHEMISI’RT. 47 1. O.OitC(i 5. 0,0363 2. 0 -0388 6. 0 *0384 3. 0.0236 7. 0.0368 4. 0.0334 - Percentnge of Fe,O:, in blood in successive weeks gram of vcratrinc is fatal a t 20°, whilst a t 42’, the avcragc! reduction of cardiac frequency is t ~ o beats per miniite. Ammonia, acting nt; 38O, lias R mnrked accelemkiyg ackion. Former experiments haT-e shown that in eady embryos, br.fo1.e tlio beart n e n w are developed, mascarine has no action ; it, however, depresses the cardiac rhythm of chick embryos older tha!i 200 honrs, its action culminating in diastolic stoppage, which can be removed by the subsequent, application of atropine sulphnte.:IS in frogs. The restomtion is onlj- putially complctc., i f msscatrine stoppage has been induced. The action of mascarine nitrate is more marked a t snl)- normal temperatures, :uid caii often be removed by the application of heat. W. D. H. 7- 1. 0.0445 a. 0 0234 3. 0,0503 G . 0 *0227 3. 0.0259 7. 0.0195 4. 0.0303 - Formation of Blooii from Inorganic Iron. By 30s. A. Kun.Kcr, (P’iigw’s 11 i*chip, 189.5, 61, 595--606).-As a contribution to the disputed qnestiorr whether inorpnic iron is absorbed and contribn tes to blood (hmrnoglobin) formation, experiments were made on two puppics ; one rect>i\-ed milk, in which the amount of iron was as~~eiq- tailled, the other the same food p l u s iron.The milk coiitained ahout I niilligrr~~n of metallic iron (1.4 milligram Fe,O3> per litre. The cxtra iron given daily was 30 drops of liquor ferri albuminat of f h e German Pharmacopceia (= 4.4 milligrams of iron). During life, tho blood was examined at, weekly intervals. After drath, other organs were submitted to an:dysis. The main facts we given in the follow- ing table. I t shows a greater amount of iron in tlie dog to which iron had been administeyed. Weight. -~~~ ~ ~ I Dog A, with iron.I Dog B, without iron. Total Fe.,O,. grams 151 -3 7 *3 30 *2 9 -9 - After death. gram 0.0252 0 0043 0 0013 0 *0014! 0 -0301 1. Total blood.. ....... 2. Liver ............. 3. Splven ............. 4, Kidneys.. .......... 5 . Ribr ............... Weight. p i n s 133 *8 7 - 2 27 -0 11 -1 -- I Total Fe,O,. gram 0 *o 404 0 ‘0317 0 ‘0043 0.0025 0’0011 Physiology of Blood Sugar. By F. TAFGL and VAUGHAS HARLEY (Zyiiger’s ~l.rc/ziv, 1895,61,551--559).-Most phrsiologists look on thc liver as the source of the sugar in tho blood ; support is lent to this doctrine by the f w t that i f the liver is excised or excluded from the circnlatii>n, sugar disappears from the blood. Interference with tlie cirenlation of the liver by ligature of the intestinal arteries lessens its activity (compare Slosse, DIL Rois Reymords Arch., 1890, 482, on4s ABSTRACTS OF CHEMICAL PAPERS.the diminution in nrea so produced), and the present experiments in dogs sliow that this is true for its sugar forming functioii; the quantity of sugar in the blood markedly diminishing (from 42 to 92 per cent. in different experiments) after the ligature of the arteries in question. W. D. €I. Circulation Time. By GEORGE N. S m w A n T (Brit. Med. J., 1895, ii, 1287).-Thc method employed consists i n the injection o€ msthy- lene blue into a vein and watching for its appearanco in the carotid artery. This simple method gives identical results with the elec*trical method of the author. The mem pulmonary time in a clog is 9-55 seconds; and i n different animals this varies as the diameter of a sphere of the same mass as the animal, and having the same specific gravity.The circulat,iori time in a man is probably about 15 seconds, which is considerably shorter than that stated by the oldel. experimenters. W. D. H. Muscular Work and Glycogen. Ry FR. SCHENCK (Pjliiger’s Aychiv, 1895, 61, 535-543) .-Seegen ( U I L Hois Il‘eymowd’s Archie., 1595,242), from experiments on dogs in which he stimulated the nerve of the qnadriceps muscle, concludes that, the glycogen m~liicli dis- appears will account for only five per cent. of He looks on the sugar of tile blood as the normal source of rniisculatl* energy, and glycogen as a reserve called into use only when work is excessive. The present article tr,i.verses these statements, and speaks in favour of PBiiger’s theory.Tlie chief objections raised are that tho work done in Seegen’s experiments was not maximal, and that no proof is given that the glycogen which disappears is burnt up ; i t mipht, a,s indeed Seegen appears to admit, be converted into sugar, how then is the mgar of the blood to be distinguished from that originating from glycogen ? W. n. H. Proteids of Muscle Plasma. By OTTO VON F~~RTII ( A I - c ~ . exp. Path. Yha~rn., 1895,36,231--274).-Muscle plasma was obtained from muscles free from blood by extracting them with physiological salt solu- tion. This coagulated spontnneously, and the clotted proteid formed is called myopen-fibrin, 01’ myosin-fibrin. The protejids in the muscle piasma are three in number, namely paramyosinogen 17 to 22 per cent,.of the total proteiid, myosinogen or myogen 77 to 83 percent. of the total prote’id, and traces of serum albumin probably derived from the re- mains of blood and lginph left in the muscles. The whole paper is written rery largely in reference to previous work by Kiihnc and Halliburton (Abstr., 1557, 954). The work of IIalliburton is confirmed in its main point, namely that there are two pi-ote’ids in tho muscle plasma, paramyosinogen and myosinogen which enier into the formation of the muscle clot ; t h e action of a specific ferment to bring about this change was not specially investigated. The principal new fact made oiit is that para- niyosinogen passes into this condition of myosin-fibrin directly ; whilst it) the pssage of myosinozen into the state of inyopi-fibrin, It is not necessary to open the artery. the work done.PHTSIOLOOICAL CHEMISTRY.49 there is an intermediate soluble stage coagulated by heat a t the Imemarkably low ternperatnre of 40°. Parit?nyosi?zogen is a typical globulin, and is regarded as identical wit11 Kuhne’s myosin. Myosii~ogen is described as differing from a globulin in man,)- particulars ; it is spoken OF as a prote’id s u i gene&. The prote’id in the muscle serum, described as myoglobulin by Halliburton, is not regarded as a, definite substance, but only as a part of the myosinogen which has escaped coagulation. The pheno- menon described by Halliburton as recoagulation of myosin, is regarded only as a reprecipitation of globulin. Peptones, albumoses, nucleo-prote‘ids were not found (compare Whitfield.Abstr., 1894, ii, 358). The muscle plasma from fishes’ muscle contains amther prote’id called rnyoproteid. It gives the usual prote’id reactions, and is readily digested by gastric juice ; it is neither coagulated by heat, nor precipit- able by removing the salts by dialysis. It is precipitated by neutral salts like globulins. It is precipitable by acetic acid, but is neither a mucin nor a nucleo-proteid. The same substarice was found in crab’s muscle, Antagonism between Salts of Calcium and those of Sodium, Potassium, and Ammonium. By SYDNEY RINGER (J. f h y s i o l . , 1895,18, 425--429).--Milk to which rennet and calcium chloride have been added clots readily, whilst the presence of sodium chloride hinders, or in larger amounts prevents, this action; the chlorides of potassium and ammonium act similarly, but less power- fully than that of sodium.This antagonism is limited to the preci- pitation of the casein as a clot, and does not affect the chemical change from casejinogen to casejin produced by the rennet ferment. The same antagonism exists in relation to blood clotting, and to muscular contrachior! as evidenced by experiments on the frog’s heart, only in the last case potassium chloride is a more powerful antagonist thau sodium chloride. W. 1). H. Toxic Substance from the Supra-renal Capsules. By D. GOURFEIN (Compt- reqzd., 189& 121, 311--314).-The glycerol extract of the supra-renal capsules contains protejids which are precipitated by alcohol, and have little or no toxic effect, together with substances which arc not precipitated by alcohol and are highly toxic.As the latter are not decomposed by heat, the capsules can be extracted with hot water, the solution precipitated by alcohol, and the clear liquid evaporated on a water bath. The product when injected sub- cutaneously causes death in 8 short time, and seems to act on thc central nervous system. The proportion of the poison in the supra- renal capsules is variable, but no similar effects are produced by extracts of the spleen or the muscle of the same animals treated in the same way. By FRITZ PREGL (P’iiger’s Archi,,, 1895, 61, 359-406) .-The intestinal juice has been investigated chiefly in carnivora. The only previous experiments on herbivora were made on a goat by Lehrnann, who found the juice had no digestive action.The present experiments were made on a lamb. W. I_). H. C. H. B. SUC~US Entericus of Sheep. VOL. LXX. ii. 550 ABSTRACTS OF CHEMICAL PAPERS. The juice was collezted by a modificat'ion of the Thiry-Vella method, from 3 to 5 grams of juice being obtained from the loop per hour. I t is a mucous, strongly alkdine fluid, which is rich in prote'id, and tends, like pancreatic juice, to set into a jelly spontaneously ; its specific gravity is about 1.014. It contains about 0.2 per cent. of urea. The following analysis is given in parts per 1000. Sodium carbonate ............. 3.69 Albumin and globulin.. ........ 18-09 Albumoses and mucin .......... 1.27 Urea ......................... 2.29 Other organic substances .......3.31 Ash... ....................... 1.27 Water.. ...................... 970.05 On proteids, cellulose, pentoscs, and fats, i t has no digestive action, but it converts starch and glycogen into dextrose with intermediate dextrins ; it inverts cane sugar and maltose, but not lactose. Artificial Hydrzemic Plethora. By J. B. LEATHES (&it. Med. J., 1195, ii, 1287).-The experiments briefly recorded go against the secretion theory of lymph formation. By HAKTOG J. HAhrBuRGER (Brit. Med. J., 1895, ii, 1287).-The disappearance of fluids from the serous cavities can take place either by the lymphatic or blood vessels; ihe process is not one of osmosis, for both isotonic and hypertonic solutions disappear, and Heidenhaim concluded that a vital activity of the epithelium must occur to account for the pheno- mena.The force a t work is believed to be imbibition of the molecular kind, such as occurs with gelatin and other homogeneous substances, and this imbibition may be exhibited by the cells or by the cement substance between them; this is of course limited in tt dead animal, but in n living one the circulating fluid removes the absorbed liquid. A working model to lrluslrate this has been constructed as follows: a cylinder of gelatin is taken to represent a capillary, and enclosed within a wider glass cylinder to represent the tissue spaces ; both cylinders are now filled with a fluid like serum, and if a stream is kept up through the gelatin cylinder, the fluid is absorbed from the space between the two cylinders, and is replaced by fresh fluid allowed to flow in through a side tube.The hydrostatic pressure of the fluid is also to be taken into amount. W. D. H. W. D. H. Physical Factors in Absorption. Absorption occurs, however, in a dead animal. W. D. H. Potassium Thiocyanate in Saliva. By IMMANUEL MUNK (P'iiger's Archiv, 1895, 61, 620-622) .-In reference to Nencki's work on thiocyanic acid in the stomach, itl is pointed out that in the dog, it is absent in the saliva ; horse's saliva is also free from it. W. D. H. Elimination -of Calcium Compounds in Rachitis. By WIL- LIAM OECHSNER DE CONINCK (Conjpt. rend., 1895, 121, 262-263).-PHYSIOLOGICAL CHEMISTRY. 51 I n cases of rachitis, the quantity of calcium in the nrine gradually diminishes in the same manner as the quantity of niagnesiuni.When e1imir;ation of magnesium is small, however, that of calcium is rela- t,ively high, and this result has led the author t o conclude that in yachitis the calcium of the osseous system is partially replaced by magnesium. Chabri6 has arrived at A similar conclLzsiou with L- respect to osteomalagia (compare Abstr., 1895, ii, 455). C. H. B. Urobilin. By ADOLF JOLLE~ (PJEiiger’s Archia, 1895, 61, 623- 637).-Urobilin was first described by Jaff6 in febrile urine, later, Maly obtained from bilirubin, by reduction, a substance he called hydrobilirubin, which he considered to be identical with urobilin, and Vierordt pointed out that normal urine contains other pigments as well. MacMunn distinguishes between normal urobilin and febrile or pathological urobilin, which differ in their optical characters ; fresh urine containing little or no urobilin often becomes darker on ex- posure to the air, and this he considers to be due to the oxidation of a chromogen, urobilinogen.Both MacMunn and Hoppe-Seyler have obtained ui-obilin by artificial means from haematin. MacMunn and Le Nobel both doubt the absolute identity of urobilin and hydrobili- rubin. Pathological urines, dark from the presence of supposed bile-pigment, have shown in many cases, on examinatim, that the increase of urobilin is the cause of the deep colour of tbe urine (urobilin-icterus) ; whilst recently A. Katz (Wiener Hed. ?Voclz., 1891, Nos. 26-32) has shown that this increased excretion OE urobilin is due to metabolic changes having their seat in the liver, which if they me prolonged produce hamiful changes in the liver cells.The present paper points out that urines containing a small amount of bile-pigment will, after standing exposed to the air for several days, no longer show any bilirubin whatever, nrobilin having taken its place. The source of the urobilin in the faces is also doubtless the bile-pig- ment, unaltered biie-pigment never occurring in normal faxes. Urinary nrobilin shows two well-marked characters : (1) a green fluorescence, -which appears when tlle urine is rendered alkaline with ammonia and a few drops of zinc chloride solution are added ; (2) a well-defined ab- sorption band between the lines 7, and F ; i t was necessary to determine if auy other urinary pigments give the same characters.Gmelin’s test for bile-pigment consists in adding fuming nitric acid; the colonr changes t o blue, violet, red, brown, and finally jellow, the yellow end product, of oxidation being called choletelin ; these coloured products, with the exception of the last, when reduced by zinc and hydrochloric acid, all show absorption bands, and give with ammonia and zinc chloride a green fluorescence. The absorption bands given by the red and brown pigments are in the neighbourhood of the E’ line, but not so sharply defined as in the urobilin spectrum, which, however, theg closely resemble. I n some urines, pigments can be separated which give all the characters of the red and brown oxida- tion products of bilirubin, whilst others again yield a substance identical with choletelin, which is the highest oxidation product of bilirubin, and is, in fact, regarded as the yellow pigment of normal urine; for the details of the method of separating the pigment 5-252 ABSTRAOTS OF CHEMICAL PAPERS. from urine by lead acetate, &c., the original paper must be consulted. In conclusion, two classes of urobilins are distinguished from one another, pathological urobilins, which are reduction products of bili- rubin, and physiological u~obilins, which are oxidation products of bili- rubin.These terms are used in R different sense from that in which MacMunii uses the terms normal and pathological urobilin ; but the idea that normal or physiological urobilin is an oxidation product of blood or bile-pigment should be credited to MaoMunn. Among the physiological urobilins is reckoned the substance which darkens on exposure to the oxygen of the air.The source of physiological urobilin is considered t.o be the bile- pigment; pathological urobilin lias usually the same origin, but it can come from blood pigment directly after extravasations of blood. W. D. H. Action of Anaesthetics on Nerve. By Au~us~ns D. WALLER (Proc. Physiol. Soc., 1895, 45--47).-A frog's sciatic nerve is laid on two pairs of electrodes, one pair being exciting, the other pair non- polarisable, and leading to a galvanometer ; ou excitation, the elec- trical change in the piece of nerve connected with the electrodes is noticed. The whole is contained in a chamber, through which gases or vapours in known amount can be passed.In large amount, carbonic anhydride produces primarily abolition, secondarily augmen- tation of the effect observed, whilst in small amount (for instance, with expired air) there is primarily augmentation. Ether produces prolonged abolition, followed in time by recovery, whilst chloroform produces abolition, but no recovery occurs ; other anaesthetics were also investigated. The most important point made out is regarded as evidence OE the production of carbonic anhydride in the nerve itself, conse- quent on activity, for after prolonged excitation the effects of inter- mittent stimulation is to produce an increase of the galvanometric change, just as though a small percentage of the gas had been added to the surrounding air. W. D. H. Action of Carbonic Oxide on Man.By JOHN S. HALDANE (J. Physiol., 1895, 18, 430-462) .-The expei*iments made by the aGthor on himself show that the symptoms caused by carbonic oxide depend on the extent to which the haemoglobin has been saturated ; the percentage saturation of the haemoglobin of the red corpuscles may be estimated during life by a simple colorimetric method. Carbonic oxide is a " cumulative " poison. The symptoms do not become sensible during rest until the corpuscles are about one-third saturnt'ed ; with half saturation, t,he symptoms (respiratory distress, headache, &c.) become urgent. Similar symptoms are experienced by mountaineers a t high altitudes. When air contaiiiing this gas i5 breathed, about half of that actually inhaled is absorbed, except when absorption is coming to a standstill. The time required for the production of sensible symptoms in an adult depends on the t'ime required for the inhalation of about 660 c.c., or fhe absorption of about 330 C.C. of the pure gas; this time ill different animals varies with the respiratory exchsnge perVEGETABLE PHYSIOLOGY AND AGRICULTURE. 53 unit of body weight, and is about 20 times as long in a, man as in a, mouse ; hence a mouse can be used as an indicator in a coal mine before men penetrate into it. The maximum amount of carbonic oxide capable of being absorbed by the blood from air containing a given small percentsge depends on the relative sanities of oxygen and carbonic oxide for hEmo- globin, and the relative tension of the two gases in arterial blood. The affinity of carbonic oxide for haemoglobin is about 140 times that of oxygen, and the oxygen tension of human arterial blood is, approximately, 16 per cent. of an atmosphere. Distinct symptoms, appreciable during rest, are not produced until about 0.05 per cent,. of the gas is present ; with about 0.2 per cent. urgent symptoms are produced. With a given percentage of carbonic oxide in air, a certain percentage saturation of the blood is reached within about 150 minutes, and is not afterwards exceeded, however long the breathing of the vitiated air is continued. The disappearance of the gas from the blood when fresh air is again breathed is always much slower than the absorption of the gas, and is chiefly due to dissociation of' carbonglhaemoglobin by the mass influence of the oxygen in the pulmonary capillaries, and consequent diffusion of the gas outwards through the alveolar epithelium. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8967005042

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 53 Chemistry of Vegetable Physiology and Agriculture. Fermentation by Apiculated Yeast : Influence of Aeration on Fermentation by Elliptical Yeast at a High Temperature. By M. RIETSCH and M. HEISELIN (Compt. rend., 1891, 121, 378-380). -When musts prepared from di*y grapes, with or without the addi- tion of saccharose, are fermented under similar conditions, the ratio of alcohol produced to sugar destroyed is higher with elliptical yeast than with apiculated yeast. Moderately dilute musts, fermenting with eIliptical yeast at about 36", are not appreciably affected by passing a current of air through them, but with stronger musts, the a6ration produces a distinct increase i n the amount of alcohol, and the beneficial effect is greater the stronger the must.In all cases, however, the advant'age gained by cooling the liquid to about 30° is much greater than that resulting from aeration, although the latter is still beneficial. A combination of the two processes gives the best results, and is especially to be recommended in hot countries, in which the musts are usually some- what concentrated. Precautions must of course be taken against ace tic fermentation. C. H. B. Effect of abundant Application of Nitrogen on the Assimila- tion and Respiration of Plants. By H. M ~ ~ L L E R (Bied. Centr., 1895, 24, 454-456 ; from Jakyesber. deut.-schweiz. Versuchs-stat., Wiidenszceil, 3, 52).-The results of the experiments which were made with potatoes and sugar beet were as follows. The application54 ABSTRACTS OF OHEMIOAL PAPERS.of large amounts of nitrogen to the plants caused increased leaf- development with greater percentage of chlorophyll ; starch formation in the leaves was impeded, the starch was more quickly dissolved, and there was less storage of reserve substances ; the amount of glucose was increased, and there was increased decomposition of nitrogen compounds, resulting in increased respiration of all parts, and in increased growth. With both plants, excessive or exclusive nitrogenous manure should be avoided. Roots which have been too heavily manured with nitro- gen should be used first, as they are the most subject to loss through respiration. pu'. H. J. M. Consumption of Asparagine in the Nutrition of Plants. By Y. KINOSH~TA (Bull. Coll. Agn'c., Imp.Univ., Tokyo, 1895, 2, 196- 199).-According to C. 0. Muller (Abstr., 1887, 70), regeneration of proteids froin asparagine can only take place in green leaves, light and the nascent state of carbohydrates being essential. I n order t o ascertain whether the process would go on in the dark, shoots of soja bean, which are rich i n asparagine, were fed with organic solutions, 2nd examined from time to time for asparagine. The solutions selected were : (1) 1 per cent. methylic alcohol with one-tenth of its bulk of saturated gypsum solution; (2) 1 per cent. glycerol solntion with gypsum, and ( 3 ) glucose solution. When placed in these solutions, t.he plants were 20-27 cm. long, and the roots and stems were rich in asparagine ; the cotyledons had been removed.Tests for reserve albumin, made during the experiment, showed it to be absent in the control experiment, and present in considerable amount in the shoots grown in sugar and glycerol. After about four weeks, the shoots of the control experiments showed a higher percentage of asparagine in the dry matter (28.7) than at the commencement (21.5 per cent.), whilst the shoots in methylic alcohol and glycerol solutions showed a respective reduction to 18.9 and 13.7 per cent. The production of dissolved proteids was thus coincident with decrease of asparagine. The increase in amount of asparagine in the control experiments was probably due to production from other Itmides. A less increase was observed in another control experiment (24.0) in which the cotyle- dons had not been removed, probably due to the protecting effect of the galactans and btlier carbohydrates gradually becoming soluble.Glycerol and methylic alcohol supplied t o the roots can, therefore, riot only hinder the production of aspamgine in the shoots, but also diminish the amount already present. Glycerol is the more effective ; it also fornis sugar. Since the shoots grew better in these solutions than in water, and showed the presence of dissolved prote'ids, it may be assumed that both methylic alcohol and glycerol can regenerate protejids from asparagine. Moreover, light cannot hare any direct action in supporting the process, although i t is indirectly of great importance in yielding the necessary Carbohydrates. Assimilation of Nitrogen from Nitrates and Ammonium Salts by Phaenogams.Br Y. KINOSH~TA ( B d . COZZ. Agyic., Imp. Univ., Toki~o, 1595, 200--208).-Barley was sown in sand con- N. H. J. M.VEQETABLE PEYSIOLOQY AND AGRICULTURE. 55 Barley in AmCl . . Maize in AmN03.. ,, N d O 3 . . } ,, NSNO3 .. } tained in three pots, and kept dark. After 16 days, the plants of one pot were taken out and analysed, whilst those of the second and tbird pots were watered with a 1 per cent. solution of ammonium chloride and a solution containing an equivalent amount of sodium nitrate respectively ; 500 C.C. of each solution was used during the week the experiment lasted. In a second experiment, maize plants, nearly 40 cm. long, were placed in solutions of ammonium and sodium nitrates (containing 1 per cent. of nitrogen), control plants being p!aced in distilled water. The following total amounts (in grams) of nitrogen, and of nitrogen as asparagine, were found.~~ At commencement. At conclusion. Total. As Asparagine. Total. As Asparagine. --- 2 * 027 0 '73 0.38 { t 2 0 -24 0 -656 { t:;;," 0 -977 3'51256 ABSTRACTS OF OELEMICAL PAPERS. plasma remain in one species the same, and that the formation of prote'ids commences with relatively simple atomic groups. As regards carbon compounds, the nutritive qualitj of acids is incressed by the entrance of alcoholic hydroxyl, that of alcohols increases with the number of HO-groups ; aldehyde and ketone groups increase the nutritiveness, the lower members of the fatty acids being more assimilable than the higher. Unsaturated ring systems are gene- rally unfavourable, whilst some compounds (such as yiiinic acid) con- taining a saturated benzene ring are very nutritive. Pyridine, pinacone, ethylenediamine, amidoacetal, glyoxal, meconic and oxalic acids do not support bacterial growth ; acetoxime, diacetonamine, citraconic and malejic acids do, but only with difficulty ; a t the same time, none of these compounds is so poisonous as to kill the bacteria, i f well nourished. It is of interest that whilst with male'ic acid it takes weeks to develop bacteria, fumaric acid supports bacteria well ; in citraconic acid there was no development for six weeks.Comparing the different monhydric alcohols, it was found that whilst 1 percent. methylic alcohol readily develops bacterial growth, amylic alcohol has t o be used diluted to 0.1 per cent.The fatty acids decrease in nutritive properties as their molecular weight increases ; formic acid, however, seems to be available only in the case of one kind of Lac- terium (Centr. f. Bacteriol., 12, No. 14) ; formaldehyde is poisonous, but its combinations with hydrogen sodium sulphite, and with am- monia can be utilised by a bacillus and by a kind of Dematium. As regards the manner in which acetic acid, for instance, is utilised, it is supposed that it is oxidised with formdon of form- aldehyde, carbonic anhydride, and water ; this would explain the favourable effect of the CH*OH-groups 01' the isomeric formaldehyde. In the case of the utilisation of formic acid (sodium salt), there would probably be first a transformation into glyoxylic acid, and then decornposit ion of this into formaldehyde and carbonic anhydride.Oxalic and parabaric acids and urea, &c., cannot be used as sourceR of carbon, because they cannot furnish formaldehyde. There is at present no explanation for the difference in the value of the stereo- iaomeric, male'ic, and fumaric acids. As a rule, compounds contain- ing the groups CH3, CH2, CHaOH, and CH2*OH can be used as sources of carbon, if not, poisonous, and if not too resistant to the attacks of bacteria. In the following lists (next page) the various corn- pounds are grouped thus : I, very good sources of carbon ; I T , moderately good ; 111, very poor ; and IV, useless, so far as observed :- The very remarkable observation of Huppe (Biol. Centr., 7, 702), that the nitrifying bacteria will develop in inorganic solutions may be explained by assuming part of the hydrogen of the ammonia to act on carbonic anhydride to form formaldehyde and water, and the subsequent condensation of the formaldehyde to sugar.Substances which support the life of azrobic bacteria are generally, but not always, suitable for mould-fungi. Compounds differ con- siderably in their power of developing fungi, for whilst isobutylic alcohol yields 9-10 per cent. of fungoid matter, asparagine yields nearly 22 per cent. Maleic, citraconic, mesacouic, dibenzylmalonic, and diethylsuccinic acids cannot be utilised by moulds, whilstVEGETABLE PHYSIOLOGY AND AQRICULTURE. 57 m nlonic, succinic, and methjl- and ethyl-succinic acids are well utilieed. TTTith regard to nitrogen, potassium ferrocyanide is not a, very suitable compound, wliilst hydroxylamine and diamide are poisons ; azoiniide can only be used highly diluted.The nitrogen compounds have always to be transforwed into ammonia before protein formation can begin ; anaarobic microbes effect this br reduction, asrobic by oxidation. In the assimilation of elementary nitrogen by microbes, ammonium nitrite is probably first formed, and the nitrous acid rapidly reduced to ammonia. T. Glycerol. Mannitol. Sugars. Lactic acid. Succinic acid. Tartaric acid. Citric acid. Beta'ine. Alanine. Leucine. Asparagine. Gtlutamine. Creatine. 11. Metbylic alcohol. Kthylenic glycol. Acetone. Acetic acid. Fumaric acid. Pyruvic acid. Levulinic acid. Glycocine. Methy lamine.C h oline. Allantoh. Caff e'ine. Methylic cyanide. 111. Phen 01. Acetoxime. Uiacetoneamine. Valeric acid. Maieic acid. Citraconic acid. Benzoic acid. Lecithin. Trime thy lamine, Strychnine. Hexamethyleneamiiic Aniidobenzoic acid. Glyoxylic acid. ~~ Pinacone. Sulphonal. Amiduacetal. Oxalic acid. Meconic acid. Picric acid. Antipyrine. Dimethploxy-m- diazine. E thy lenediamine. Yyridine. Urea. Parabanic acid. Guttnidine. Sulphur seems to he present in the proteids of fungi, as in other proteids, as *SH. Sulphates have, therefore, to be reduced. Sul- phonal, CMe,:SO,E&, is a suitable source of sulphur i n presence of easily assimilable carbon, but not otherwise. Chlo~ophyll Plants.-In the higher, as in the lower plants, it must be assumed, whatever compounds are utilised for their growth, that the carhon compounds are so broken up as to produce formaldehyde, and that the nitrogen must lie liberated as ammonia.AS regards the different forms of nitrogen produced by the decomposition of protejids, asparapine, leucine, and tyrosine, phenylamidopropionic and amidovaleric acids, arginine and allantoin have been found ; urea bas not been detected, but guanidine occurs in the shoots of Yicia sativa. Schulze's observation that whilst amido-acids formed during the first period of germination decrease in quantity, asparagine increases, is of very great importance; when sugar takes part in the formation of prote'ids from asparagiiie, it furnishes the deficiency of carbon. Prote'ids might be formed in the following manner:- By reduction in presence of glucose, asparagine might yield aspartic aldehyde, and the ammonia liberated would immediately, in presence of glucose, form another molecule of aspartic aldehyde; 3 mols.of this aldebyde (CaH,N02) may be supposed to condense with elimi- nation of water (2 mols.), and yield an intermediate compound, (C12H17N304), 6 mols. of which, with hydrogen (6 mols.) and hydrogen sulyhide (1 mol.), would yield albumin of the forrniila C72H112N1AS032, and water (2 mols.). Glucose would again be required for the rednu-58 ABSTRAOTS OF OHEMICAL PAPERS. tion. On the assumption that the aldehyde and amido-groups are prevented from acting on each other, and that in the reduction the 12 aldehyde groups are converted into secondary alcoholic groups, CH-OH, the final product (active albumin) would be of extra- ordinary lability, containing 12 aldehyde and 18 amido-groups in 1 mol.With the loss of its aldehyde character it would be changed to passive albumin. It is obvious that passive albumin i q not pro- duced by direct synthesis, but is the product of the transformation of the directly formed actire, unstable albumin. Active Albumin as Reserve Material in Plants. By OSCAR LOEW (Bull. C'oll. Agri., Imp. Univ., Tokyo,1894,2,23--33).-The author and Bokorny have shown the presence in plants of a protein sub- stance, apparently in solution, which gives certain reactions, of which living protoplasm, owing to its great lability, is incapable, and which neither dead protoplasm nor the known soluble prote'ids show. The substance has the r6le of a reserve material, being used up during the growth and multiplication of cells.Many dgre and parts of higher plants show, under the influence of caffexne (0.1--0.5 per cent.) or oE antipyrine (0.5 per cent.), anumber of minute, transparent, colourless globules, which gradually unite to iorm larger globules or droplets, at the same time losing their original motions ; all the !!j'pi~*ogyi*ce are specially adapted for these observations. When the objects are placed in water, the globules disappear, as the caffe'ine leaves the cells by osmosis, and the cells continue t o live as before the treatment ; if, however, the cella die during the treatment, o r are killed by poisons, the droplets also change their properties, thus showing close chemical resemblance of t.he matter in the protoplasm and in the droplets, the latter becom- ing turbid, and losing their solubility.When spirogyra-th reads, con- taining freshly formed droplets, are exposed to ether vapour, the cells are killed in a fern seconds, and, i n about 20 minutes, the globules lose their brightness and their solubility. In the dissolved state, the substance is quickly changed by the death of the cells in which caffeine never produces globules. Spiro- yyra Weberi, treated for one minute with very dilute aqueous iodine, yields globules with caffeine, but not after 10 minutes' treatment with iodine. The substance is, therefore, a proteid differing from ordinary soluble proteids by being separated in globules by caffe'ine, &c., and by its very great lability.I n the coagulated state, the globules show all the properties of ordinary coagulated prote'ids. When the proteo- somes, as these globules are termed, are treated with ammonia they are solidified, the amiiionia entering into intimate combination. This fixation of ammonia, which recalls the formation of pyrrolines from 1 : 4 ketones, is explained by the presence of aldehyde groups in the proteosomes, which are able to reduce silver nitrate, even after treat- ment with animonia; the reaction with silver nitrate mas also obtained with the proteosomes of Symphorocarpus racemoszis, which is free from tannin, and from which every trace of sugar was re moved. N. H. J. 31.VEGETABLE PAYSIOLOGY AND AGRICULTURE. 59 The fact that proteosomes represent the active albumin was proved by cultivating Spirogyra in nutritive solutions without and with nitrogen (potassium nitrate). In the first case, the stored-up albumin was used up so thoroughly that, after two or three weeks, caffe‘ine failed to produce proteosomes ; whilst in the second case, there was an intense formation of proteosorues with caffe’ine after three weeks, more active albumin having been produced.than was required. Changes of temperature have great influence on the amount of active albumin present, and phosphates iuterfere with its accumula- tion (Loew, “ Physiol. Functions of Phosphoric acid,” BioE. Centr., 2, 280). Active albumin was found in a great variety of plants and in various parts of plants, but not in animals. The separation of globules by caffe’ine or smtipyrine is probably duc to a very loose combination in which the original chemical nature of the albumin is not otherwise altered, but i t is also possible that the bases effect a loose kind of polymerisation ; at any rate t,he original state may be restored by washing out the bases with water.Strongel. ba’ses (guanidine, methylamine, &c.) produce grauules which do not form droplets, and which soon became insoluble in water ; inorgamic bases produce minute granules and rapid death of the cells (compare Loew and Bokorny, D. c h m . Kyaf tquelle im lehenden Protoplasma, Miinchen, 1889; Bot. Centr., 1889 and 1893; FZora, 1892, 127 ; Bokorny, Prings. Jalwb., 19 and 20 ; P$iiger’s Archiz9, 45 and 50). pu’. H. J. M. Function of Diastase in Plants.By J. GRCSS (J. Pha~m., 1895, [ 6 ] , 2, 275-276 ; from Apoth. Zeit., 1895, 307).-Diastase may be readily detected in the cells of plants by digesting the tissue, for a sufficient length of time, with a solution of guaiacum in absolute alcohol, and then immersing sections of it in a dilute solution of hydrogen peroxide; a fine blue colour is developed in those cells which contain the enzyme. The author finds that diastase is always present in those parts of the plant from which it is necessary that starch should be removed for purposes of nutrition. As the amylolytic power of diastase is inhibited by the presence of more than a certain limiting amount of glucose7 it would seem that in assimilation, the formation of glucose precedes that of starch, and continues as long as the sugar is removed by ciuxlation.When, however, the sugar commences to accumulate beyond the requirements of the organism, it undergoes polynierisation to maltose and eventually to starch, which, in the presence of glucose, is not hydrolysed by the diastase 7 as soon, however, as the glucose is reduced by circulation below the inhibitory proportion, the starch is hydro- lysed by the diastase, and the supply of soluble nutritive material thus maintained. The amylolytic power of diastase is increased in presence of salts of the alkalis and alkaline earths, aiid by asparagine, &c. Jx. W.60 ABSTRACTS OF CHEMICAL PAPERS. Hydrogen Peroxide in Plants. By J. CHO (Bull. COU. of A g k , Imp. Unit.., Tokyo, 1895, 2, 225-227).--4 iaeply to Bach (Abstr., 1895, ii, 239).Twenty-one species of plants were treated as described by Bach. In nine cases, a coloration was observed, but not the colour produced in the control experiment; moreover, the extracts gave the same reaction after treatment with platinum black, which mould have destroyed any hydro en peroxide, it’ it had been present. The colora- tion observed is pro$ably only obtained when the leaves have been partly killed by the oxalic acid solution, so that certain readily oxidis- able compounds are enabled to leave the cells by osmosis, and yield coloured products by oxidation in presence of aniline oxalate. Occurrence of two kinds of Mannan in the Roots of Cono- phallus Konyaku. By Y. K~NOSHITA (Bull. Coll. Agric., Imp. Univ., Tokyo, 1895, 2,.205-206).-1t was shown by Tsuji (this ~ o l ., ii, 44) that the root of Conophallus contains a large amount of an anhydride of mannose ; it is now shown that two kinds of mannan are preflent. The finely ground root was repeatedly extracted with boiling water untsil the extract was no longer slimy. The residue yielded mannose when boiled with dilute acid, and the slimy extract, on the addition of alcohol, yielded a copious, nearly white, flocculent precipit’ate ; the latter, when dried at looo, was no longer soluble in water, but yielded mannose when boiled f o r some hours with 4 per cent. sulphuric acid. This mannan differs from that obtained from yeast by Sadkowski (Abstr., 1894, i, 222) in losing its solubility on drying, but agrees i n its behaviour with basic lead acetate (no precipitate), ferric chloride, and ammonia (gelatinous precipitate), copper snlphate and sodium hydroxide (thick, blue precipitate), and also with Febling’s soln- tion.The slimy mannan was not altered by the diastase of malt, by inver- tase, or emulsin, and Osaaa’s experiments on dogs showed that it is digested with much more difficulty than starch. An enzyme capable of saccharifying the mannan must, however, exist in the konyaku root, and the author hopes to isolate it. N. H. J. M. N. H. J. M. Composition of some Mucilages. By K. YOSHIMURA (BUZZ. COZZ. Ag~ic., Imp. Uniz.., Tokyo, 1895, 2, 207--208).-The slimy extracts of the various plants were concentrated, precipitated with alcohol, the washed precipitates boiled with sulphuric acid (6-4 per cent.), nen- tralised with barium chloride, filtered, and concentrated to syrups.Portions of these were evaporated with nitric acid and examined for rnucic acid, other portions were mixed with pheny lhydrazine acetate, whilst others again were examined with phloroglucinol and hydro- chloric acid for pentoses. The mucilage of Xterculia plantanifolia (joung shoots) consists OE araban with some galactan ; t h a t of Colocasia antiquowm (tuberom roots) probably consists only of a polyanhydride of diglacose. The mucilages of Vitis pentaphylla (stems and leaves), and Opuntia (fleshy stems), chiefly consist of galactan, those of (Enothcra Jaquinii (stems and leaves), and Kudzura japonica (young leaves and stems), contain galactan and araban. Finally, the osazones were prepared.N. H. ,J. M.VEGETABLE PHYSIOLOGY AND AQRIDULTURE. Gt Laccase in Vegetables. By GABRIEL BERTBAND (Con@. rend., 1895,121,166-168) .-An alcoholic solution of gum guaiacum becomes blue in presence of air and a very small quantity of lnccase ; if the proportion oE the latter is considerable, the blue coloration may change to green and eventually to yellow. This reaction is very convenient as a test for laccase, and by means of i k , combined in most cases with the actual isolation of the lnccase, the author has recognised the presence of this substance in the roots of the beet, carrot, and turnip, the tubers of the dahlia, pbtato, and Jerusalem artichoke, the rhizome of balkier, apples, pears, chestnuts, quinces, lucern, clover, rye-grass, asparagus, and the flowers of the gardenia.As a rule, only those organs of the plant which are in a state of active develop- ment contain any notable proportion of laccase. I n dealing with roots, rhizomes, tubers, and parenchymatous fruits, the juice may be precipitated with alcohol immediately after its extraction, but, in the case of green organs, the juice should be satu- rated with chlorofoi~m and allowed to remain for 24 hours, when it will coagulate spontaneously, and only the filtered liquid is treated with alcohol. C. H. B. Asparagine in the Roots of Nelumbo Nucifera. By Y. KTNO- SHITA (Bztll. Coll. Agric., Imp. Univ., Tokyo, 1895, 2, 203--204).-The root of Nrlumbo nucifera is rich in starch, and is used in Japan, in the boiled condition, as food. The following analytical results were obtained by Kellner :-water, 85.84 ; the dry suhstaiice gave : crude protein, 7-75 ; fat, 1.44 ; fibre, 7.19 ; non-nitrogenous extract, starch, &c., ’78.59 ; ash (free from carbon and carbonic anhydride), 3-03 per cent.Asparagine has been detected in comparatively few roots; the roots of Althwa contain 2, of Glycirrhizu (Plisson), 0.8, of Scorzoneya (Gorup), 0.6, and potatoes (Schulze), 3 per cent. The dry substance of Nelumbo yielded nearly 2 per cent. of asparagine. N. H. J. M. Occurrence of Cytisine in various Papilionaceae. By PIEYER C. PLUGGE (Arch. Pharm., 1895, 233, 430--441).--Cytisine is con- tained i n the followinq Papilionaceae :-(I) Cytisus Laburnunz, L., (Laburnum culgaris, Grisebach) ; (2) C. alpinus, Mill ; (3) C. supinus, Jacq.; (4) C. elongatus, W. u. K. ; ( 5 ) C. Weldinii, Vis ; (6) C. sessi- folizcs, L. ; ( 7 ) C. himzitus, L. ; ( 8 ) C. bi$orus, L’her ; (9) G. Abchin- geri, Vis ; (10) C. nigricans, L. ; (11) C. pyoliferus, L., 31s ; (12) Cytisus Adami, Poit ; (13) C. ratisbonensis p-minor, Schaf ; (14) C. ratisbonensis, Schaf; (15) C. polytrichus, &I. B. ; (16) Genista race- mosus, Marnoch ; (17) G. ranzosissimu~, Ten ; (18) G. Spicatus; (19) Ulex euwpcezis, L. (Gerrard’s Ulexine) ; (20) Sophoya speciosa ; (21 j 8. tomentosn ; (22) S. secund@ora, Lagizsca ; (23) Baptisia tinctoria (v. Schroeder’s baptitosime) ; (24) B. Australis ; (25) Euchresta Hor$eldi, Benn. The following members are free from cytisine :- (1) Cytisus nigricans; (2) C. sessilifalius, L. ; (3) C. argenteus, L.; (4) 0. capitatus, Jacq. ; (5) Genista tinctoria, L. ; (6) G. pilosa, L. ; ( 7 ) G. ariylica, L. ; ( 8 ) G. gemanica; (9) Siophora japonica, Dc. ; (LO) S. japoiAicc pendida; (11) Sophora afinis. The author has in-62 ABSTRACTS OF CBEMIOAL PAPERS. -- 1 2 3 4 5 6 vestigated Nos. 20-25 in the first class, and Nos. 9-1 1 in the second. ~'%yhora, speciosa contains cytisine to the extent of 3-23 per cent., and as the infusion of the seeds is identical with cytisine in physiological action, the presence of a second alkaloid is improbable. These results confirm the author's previous statement that Wood's " sophorine " and cytisine are identical. 8. secundidoru, Lagasca ( Virgilin secundijoya, Cad.), also contains in its seeds 3.4'7 per cent. of cytisine. The alkstlo'id in the seed of Euchresta HorsJieldii, Benn, was identified hy means of its colour reactions and tho analysis of it3 auro- and platino- chlorides, as cytisine.Cytisine gives, in addition to the reactions already known, a violet -red coloration with concentrated sulphnric acid and potassium permanganate, the intensity of the violet tint gradually increasing. J. B. T. Composition of Pure Fruit Juices. B.y H. KRENLA (Bied. Celztr., 2895, 24, 498 ; from Zeit. .f. Nahrun~smittelhygic~~e PA. TVarenkunds, 7 , 365--370).-The juices of the following fruits were annlysed : (1) cherry ; (2) currant ; (3j gooseberry ; (4) cranberry ; ( 5 ) cider Fpple; and (6) melon. The results are given in grams per litre of luice. The acid is calculated as malic acid, and the sugar (reducing) as invert sugar.Balling's extract . -- 166 *0-266 08 103 *0-167 '1 91 -1 110~0 169-5 99 -5 i EZO. CaO. MgO. PZO5. ----- ----- Acid. 1 Sugar. Nitrogen. 1 Ash. --- --- 2 *128 -2.549 3 '13- 7 '23 21.2 -23% 13 -1 22 -7 11 *07 1 '73 0 -206-1 '230 0 -106 0 -229-0 *501 0 -270 0 -126 0 *099 100 '6-172 '6 48 *5-86 *S 59 *7 74 -5 104 *1 41 -4 The sp. gr. were as follows: (1) 1*0639-1*1023; (2) 1*0400- 1.0644 ; (3) 1.0355 ; (4) 1.0462; ( 5 ) 1.0653 ; (6) 1.0387. Black cheri-ies gave much more sugar and extract than red ones. Benzoic acid was found in cranberry juice. N. H. J. M. Bark and Leaves of Drimys Granatensis, L. By OSWALU HEME (Annalen, 1895, 286,369-376).- The statement that the bark of Drimys Granatensis contains coto'in has led the author to submit it, to examination, the leaves having been iuclucied in the investigation, t.he result, of which shows that cotoh is not present in either bark 01.leaves. Three new substances have been isolated, drimin, diimjssic acid, arid drimol.YEQETABLE PHYSIOLOQY AND AGRICULTURE. 63 Dyinzin, Cl3HI4O4, is obtained from fhe pulverised bark, which is extracted with ether, the etherea! solution evaporated, and the yesidne extracted with boiling petroleum ; the insoluble portion is then dissolved in ether, and light petroleum added, when an oil is thrown down. On evaporating the solution and dissolving the reeidue in alcohol, ether precipitates drimin, which separates from alcohol as a micro-crystalline powder of pale brown colour ; it melts at 256'. Drimyssia acid has not been characterised; it was obtained from the liquid filtered from drimin, and has the properties of an acid.Dvinzol, CzeHts02, is obtained from the leaves by extracting with ether, evaporating the solvent, and dissolving the residue in alcohol ; i t crystallises from alcohol i n small, white needles, and melts at 73-74'. The ucelyZ derivative, C2sH57Ac0,, crysiallises in small, white leaflets, arid melts at 4 2 4 3 ' . The action of hydriodic acid (sp. gr. = 1.7) gives rise to the iodide, C29H5iI0, which crystallises from hot glacial acetic acid in small needles ; by the action of alco- holic potash, drimol is regenerated. Amount of Fat, Sugar and Tannin in Coffee. By E. HERFELUT and ALBERT STUTZER (Zeit. angut. Chem., 1895,469-471) .-The fat, or rather the ethereal extract, of coffee seems to be much increased by the roasting process ; a sample of Santos coffee gave on analysis 10.86 per cent.of water and 8.15 per cent. of fat, whilst after roasting it yielded 2.43 per cent. of water and 16.58 per cent. of fat, New Granada coffee showed 10.45 of water and 13.10 per cent. of fat ; after roasting, 2.18 per cent. of water and 15-44! per cent. of fat. Java coffee, however, showed a large decrease in fat, its moisture and Kqt being respectively 10.05 and 14-00 per cent. before, but 2.96 and 11.30 pel. cent. after roasting. The iodine and saponification figures of the fat before or after roasting do not admit of any definite conclusions. Tbe authors have not been able to detect actually existing sugars, but a little may be formed by hydrolysis of the tannin under favour- able conditions.As regards the caffetannic acid, the authors have not been able to get anything like trustworthy results by estimatinc the sugar formed on hydrolysis with tartaric acid ; treatment wit11 aqueous soda also failed. Experiments to isolate the tannin as a M. 0. F. bromo-derivative also proved unsatisfactory. L. DE K. Composition of Pachyma COCOS and Mylitia Lapidescens. By ERNST WINTERSTEIN (An&. Pharm., 1895, 233, 398-409).- Two specimens OF Pachyma Coaos gave the following analytical re- sults :-Prote'in substances = 0.56-1*00 ; substances allied t o chitiii = 0.60-1.00 ; ethereal extract = 0*35-0.42 ; ash = 0.06-0.25 ; water = 16*86-12*09 ; d-glucose = 1.40-1*13 ; fongus-cellulose = 2.85-3.24 ; pachymose = 76.21-79.84 per cent.The ethereal ex- tract probabIy consisted of cholesterol. Gnmmy matters are also present in small quantity. Pachymose is an anhydride of d-glucose similar to paradextran and paraisodextrm ; when hydrolysed it yields 97 per cent. of d-glucose. The low content of ash is note- worthy. My Zitta Zupidescens is composed as follows :-Protein sub-64 ABSTRACTS OF CHEMICAL PAPERS. stances = 2.36 ; substances allied to chitin = 0.91 ; ethereal extract = 0.10 ; ash = 0.20 ; water =14*56 ; fungus-cellulose = 2.80 ; saccharo- collo'ides = 88-98 per cent. No carbohydrate soluble in cold dilute alkali is present; after prolonged heating with alkali, a slimy sub- staxce was isolated, which is similar to Tollens's saccharo-colloydes. F u l l details of the analytical methods are given.J. B. T. Kola Nut. By G. LE BON (Expe?.. Stat. Record, 1895, 7, 148 ; from U.8. Consular Rep., 1895, Apr., 537-.540).-The fresh kola nut possesses remarkable stimulating powers, whilst the dried tiu ts do not. l t contains caffe'ine (2.35 per cent.), theobromine (0.023 per cent.), and a red glucoside (1.3 per cent.), which after mastication is largely transformed into caffe'ine. Experiments with caffeine and theobromine showed that when mixed in the proportions i n which they occur in the nuts, their sustaining power is equal to that of the nuts ; neither compound aloue has so great a stimulating effect as tho nuts. It is thought that the nuts are of extreme importance as a muscular stimulant. N. H. J. M. Coco-nut Shells.By R. W. TROMP DE HAAS and BERNHARD TOLLEKP (AnnaZen, 1895,286,303-306).-The hard, inner shells of coco-nuts mere finely powdered and extracted successively with cold, dilute hydro- chloric acid, cold dilute ammonia, boiling alcohol, and boiling ether. The dry powder was then heated for an hour on the water-bath with 10 parts of 4 per cent. sulphnric acid, and subsequently in a porcelain basin over the flame; the hot, filtered liquid was neutralised with calcium carbonate, and evaporated, yielding a syrup which was re- dissolved i n alcohol. This solution deposited 8 grams of xylose, 110 grams of the powdered shells having been employed. The specific rotatory power of the sugar thus obtained was [aIn = + 64.8' seven minutes after solution, diminishing to [a], = + l8.3O on the following day.The xylose obtained from coco-nut shells crystal- lises from alcohol in white needles, and is not associated with other sugars. The portion of shell-powder which remained undissolved by the hydrolytic agent, was treated with a mixture of 10 parts of con- caentrated sulphuric acid and two pa& of water. After 2& days, the liquid was diluted with 5 litres of water, and boiled for five hours in a reflux apparatus, filtered, and neutralised with calcium carbonate. The alcoholic solution of the syrup obtained on evaporation did not give the redction for pentoses, but yielded pure &glucose, which had a specific rotatory power [a]D = + 5 0 * 8 O , after remaining in solu- tion for a day. Twenty grams of the powder undissolved in the first operation yielded 0.5 gram of d-glucose. Composition of some French and other Oats harvested in 1893.By BALLAND (Compt. rend., 1895, 120, 502--5~)4).-Various samples of oats from known sources were examined in order to be able to identify the principal types offered in the French markets. The War Department excludes nearly all foreign oats from their stores. M. 0. F.VEGETABLE PHYSIOLOGY AND AOKlCULTUHE. 65 As regards chemical composition, the grey or black oats of Beauce contained over 10 per cent. of prote'ids, about 5 per cent. OE fat, and 7.5 to 9 per cent. of cellulose; the composition of samples from Champagne, Picardie, Vosges (except cellulose over 9 per cent.), Sweden, and of white Norwegian oats was similar. Russian oats (grey or black) contained: proteids 10, fat less than 4, and cellu- lose 11 per cent.United States oats: prote'ids 10, fat 5 per cent. Algerian oats: proteids less than 9.5, fat 5 per cent. White oats from St. Petersburg contained 14 per cent. of prote'ids ; other white Russian oats : prote'ids over 10, fat 3-4 per cent., and an excess of cellulose. The weight of the grains per thousand, which varies very considerably, is given in most cases, and also the percentages of kernel. N. H. J. M. Cuscuta Epithymum. By GASTOS BARHEY ( J . Pharna., 1895. [6], 2, li)7--118).-The common dodder is a parasitic plant of the order C'o?zz-oZz;uZacea?, and is said to possess diuretic and laxative propertiw, and to be a specific for gout. The author has examined the extract from 2 kilos.of the plant. The aqueous extract is acid, and jields 8 precipitate with potassium hydrogen carbonate, from which a yellow, amorphous powder, cuscutin, is extracted by ether. It is also pre- cipitated by dilute sulphuric acid, and the residual solution then re- duces alkaline copper tartrate. The alcoholic extract of the residue from the aqueous extract, yields a further quantity of cuscatin. Hesinous and fatty products were also isolated, together wifh a tannin iLnd a small amount of a crystalliue substance, having a faint odour of coumarin. Cusciitzn is insoluble in cold water, and only sparingly solnble in lloiling water yielding a yellow solution, from which it is precipi- tated in the amorphous form on cooling ; with conceiitrated hulphu- ric acid, i t gives a reddish-brown solution, having a green fluorescence ; i t is also soluble in acetic acid without change of colour.With ferric chloride, the aqueous solution gives a characteristic and very delicake violet-grey turbidity, red by transmitted light. C uscutin is very soluble in alkalis, givitig yellow solutions, which dye silk and paper, and stain the skin. Cuscutin is hydrolysec! by mineral acids yielding glucose, and a resinous subslance, cuscuretiu, and it is, therefore, a glucoside. No analytical data are furnished. Js. W. Preparation and Composition of Tofu. By M. INOUYF: (Bull. Coll. Agric., Imp. Univ., Tokyo, 2, 209--215).-1n order t o make up the deficiency of prote'ids in rice, the inland inhabitants of' Japan utilise various leguminous seeds, especially the soja bean.Two products prepared from this bean, miso and natto, have already beeu described (Kellner, Tokyo Bull., 1, No. 6 ; and Yabe, Abstr., 1895, ii, 130). A third preparation of soja beans, tofu, is obtained by pulping the beans after soaking them for 12 hours in water, boiling with water (3 parts) for an hour and filtering through cloth ; the liquid which resembles milk in appearance, and fresh malt i n taste, has a neutral or slightly acid reaction, but after several days becomes strongly acid (lactic acid), when the separat'ion of case'in takes place. I n VOL. LXX, ii. ti66 ABSTRACTS OF CHEMICAL PAPERS. manufacturing tofu, the fresh filtrate is treated with about 2 per cent. of concentrahed sea-water, the flocculent precipitate slowly pressed, and cut into tablets ; the product has the taste of milk casei'n.In the beaus themselves, the casein is in a soluble form in con- bination with potasaiiim or sodium, and is not coagulated by boiling, but is precipitated by the calcium and magnesium salts in the brine ; when tofu is boiled with 1 per cent. aqueous disodium phosphate, the case'in redissolves, yielding an opalescent solution, calcium phos- phate being formed. Tofu is sometimes subjected to the action of frost, when it con- tracts and loses a large amount of water; the product is called koridofu. The following numbers show the percentage composition of (1) the fresh milky liquid, (2) tofu (Kellner), (3) koridofu, and (4) yuba (prepared by evaporating the soja bean extract) :- N-free Fat and Water.Prote'ids. extract. licithin. Cellulose. Ash. 1 .. .. 92-53 3.02 1-88 2.13 0.03 0.41 - 0.43 2 . . .. 89.29 4-87 4.35 - 3 . . . . 15.32 41-43 15.05 23-65 1.48 3.08 4 . . . . 21.85 42.60 7.65 24.6 - 2.82 Tho milky extract left f o r two weeks contained 0.092 gram of lactic According to Osawa, tofu is as readily digested as beef. Action of Lime and Magnesia on the soluble Phosphoric Acid of the Soil. By C. SCI~REIBER (Exper. Xtat. Record, 1895, 7, 104, from Rev. Agr. Louvain, 1895, 4, 66-69).-Two mixed manures one containing dicnlcium phosphate, calcium sulphate and magnesium carbonate, the other sodium phosphate, and calcium and magnesium carbonates were applied to oats (to be followed by turnips) OE sandy, liurnus arid loamy soils. In each case, the first named mixture gave much higher results, the difference being most marked in the case of turnips ; this seems to be due to the calcium and mag- nesiiim carbonates oE the second mixture Yendering the phosphoric acid of the sodium salt insoluble; the action would be more com- plete during the second crop.The results of experiments on humus soil contirmed the author's previous conclusions, that the phosphoric acid combined with the humus of peaty soils, which is readily soluble i n alkaline ammonium citritte, is almost useless for Vegetation. I n some cases, humus acts on assimilable phosphoric acid in a manner analogous to calcium carbonate. Assimilable Nitrogen and its Transformations in Arable Soil. By PAGNOUL (Cmpt. rend., 1895, 120, 812--815).-A number of experiments wem made in which large cases were filled with soil, (60 kilos.), variously m:tnured, some of which were exposed, others sheltered from rain; all the cases were kept free from vegetation. An examination of the soil showed that the organic nitrogen is first transformed into ammonia, next into nitrous acid and finally into nitric acid.acid per 100 C.C. The dry tofu yielded 11.2 per cent. of lecithin. N. H. J. M. N. H. J. M.VEGETABLE PEYSIOLOGT AND AGRICULTURE, 67 The loss of nitrogen from bare soil may be considerable during heavy rains, but is entirely stopped by vegetation, such as grass. Tho application in August of carbon bisulphide (10 c.c.) to soil (2 kilo- grams) manured with cake, entirely checked nitrification until the end of September, but by the 16th October, 0.017 per cent.of nitric nitrogen was found ; in a sirnilax experiment without carbon bisul- phide there was considerable nitrification during September. The effect of carbon bisulphide was therefore not to destroy the nitrify- ing organism, but to paralyse it temporarily ; ammonia was produced during this time in considerable quantity amouuting to 0.027 per cent. by the 15th October. N. J. H. 31. Behaviour of Hippuric Acid in Soils. By K. YOSHIMURA (BUZZ. Colt. Agric., Imp. UYL~V., 2, 221-223; Note by OSCAR LOEW, 223 -224).-Of the total nitrogen of cow’s urine, about 10 per cent. is in the form of hippuric acid, of horse’s urine, about 2 per cent. Experiments were made to ascertain the absorptive power of soils for hippuric acid. The soils, one consisting of volcanic ashes and loam, the other a clayey soil, were found to have no power of retaining either the free acid or its sodium salt.Dilute solutions of sodium hippurnte containing potassium phos- phate and magnesium sulphate, are able to develop mould fungi and microbes. Solutions of sodium hippurste infected with surface and sub-soils were decomposed, ammonia being liberated ; the decomposition is more rapid under the influence of surface soil than of subsoil organisms ; only in one experiment was there an indication of nitrous acid with Griess’ reaction. Loew points out that the absence of nitrification in solutions of sodium hippurate is i n accordance with other similar observations. Sterilised solutions of ammonium formate and oxalate respectively (0.05 per cent.), with potassium phosphate and magnesium sulpbats, were infected from a culture from garden soil ; the formate yielded no nitrate, and the oxalate only a small amount, about one-tenth the quantity yielded by ammonium carbonate.Nitrificaton is nearly twice as quick in the dark a3 in daylight. There exists a bacillus (B. methy7icus) able to astjimilate formates (Centr. f. Bact., 12, No. 14). N. H. J. M. Effect of Carbon Bisulphide on exhausted or %ick,”(fatigu6s) Soils. Uy C. OBERLIN (Exper. Stat. Xecord, 1895, 7, 88-89; from Journ. Agr. Pract., 1895, 59, 459-464, 499-503, 535--540).-In applying carbon bisulphide for grape phylloxera, holes, 50-60 cm. deep, are made in the soil by means of iron rods, carbon bisulphide (50-100 c.c.) poured i n and the holes carefully plugged.The vines are generally removed, and other crops grown for six years. As compared with crops growing on soils not treated with cnrhon bisul- phide, those grown on soil so treated, were in niany cases decidedly superior, for example, oats, lucerne, hairy vetch and beans ; lucerne was especially bemfited ; on soil not treated with bisulphide, the crop 6-263 ABSTHXCTS OF CHEMICAL PAPERS. still failed after six years, parallel plots t o which there had been an application yielding vigorous growth. N. H. J. RI. Saline Soil and Water from Persia. By KONRAD NATTRRER (Monatsh., 1895, 16, 659--673).-The author giws an account of the composition and properties of the samples of soil and water brought from the steppes of south-west Persia by Ott,o Stapf.I n most cases, the samples contained those salts which are present in sea-water and in somewliat the same proportion, and the author therefore con- cludes tlmt the salt wastes have been formed by the evaporation o€ salt water which has been separated from the main body of the ocean by the raising of the level of the land in earlier geological times. G. T.M. The Potash and Phosphoric Acid required by Cultivated Plants. By SMETS and C. XCHREIBEE (Bxper. Stat. Record, 1895, 7, 107-108 ; from Rev. Agr. Loucain, 1895, 4, 78-79).--The rela- tive requirements of various plants for potash and phosphoric acid are as follows :-For potash : 0at.s (native) 18, oats (Flanders) 23, i)otatoes 37, spring wheat 43, flax 56, mastard 70, turnips 80. For phosphoric acid : lupins 27, potatoes 30, mustard 53, spring wheat 60, oa,ts (native) 64, flax 66, oats (Flanders), 75, turnips 85.The results were furnished by 267 pot experiments. N. H. J. M. Value of Bone Phosphates. By ULBRXCIIT (Bied. Ceiztr., 1895, 24, 478-479 ; from D. agrik.-chem. Vers.-Stut., Dalme, 3-8) .-The effective value of a bone phosphate depends on the amount of avail- able phosphoric acid in the soil. The results of experiments in which f o u r kinds of soil were manured, partly with bone phosphates and partly with superphosphate, showed the following increase in dry produce, due to superphosphate, as compared with the yield after t h e application cf bone phosphates. Increase on light soil 10, on soil poor in phosphates 25, on artificial sc;il made of quartz, sand, and kaolin, and free from phosphates, 294, and on soil exhausted by vegetation, 24 per cent.Bone meal may, under favourable conditions, have a considerable effect even when employed in the spring; but its action is much hindered by dry weather, especially if it is not sufficiently finely ground. Citrate Solubility of Basic Slag as Expressing its Manurial Value. By PAUL WAGNER (Bied. Centr., 1895, 24, 480; from Deut. Zni~dw. Presse, 1894,983-984).-There is no regularity in the relation of the percentage of free lime in basic slag and its citrate solubility, as is stated by Hogermann (Bied. Centr., 24, 130). As regards Hoyer- mann’s explanation of the increased citrate solubility of slags rich in lime after fusioii with sand, the author is of opinion that the calcium silicate foxmed during the fusion forms a readily decomposable calcium silicate-phosphate with the calcium phosphate of the slag.N. €3. J. hf. N. H. J. &I.VEGET-4BLE PHYSIOLOQY AND AQRICULTURE. tj!, Chlorine in Rain Water. By N. PASSERIN (AWL. L 4 q g ~ ~ i l . , 1S95, 21, 3Y9-400 ; from Bol. Sciiolu. agron. Scandici, lf393,12--22).--The following average amounts of chlorine in parts per million were found. 1890 ........ F j . 1 7.0 6.5 8.3 1891 ........ 3.4 4.5 3% 3.2 Spring. Summer. Autumn. Winter. The station is situated near Florence, all the wind coming from the sea except the north-west; the gauge is 75 kilom. from the west coast, and 107 Horn. from the Adriatic. At Antignano, near Leghorn, the average amount of chlorine in the rain is 116 parts per million. N. H. J. 31. Losses of Nitrogen in Waters of Infiltration. By J. J. Tri!:o- PHILE SCHLOSSING (Corrapt. Tend., 1895, 120, 526--530),-A number of samples of water were taken from French rivers at different points, and the nitric nitrogen determined. The samples were taken during the last prolonged frost, after t h e temperature had been considerably below zero for many weeks, during which the rivers could not have been fed by surface, but only by subterraneous, water; aquatic vegetation, which would otherwise take u p nitrates from the river;;, was, it is thought, practically suspended for the time. The results are given in parts per million. Seine in Paris, Feb. 9th, 2.09 ; 13th, 2.31 ; 19th, 2-25 ; 23rd, 2.93. ,, ,, in Monterean, 16th Feb., 1.99 ; 27th Feb., 2.08. in Charenton, 15th Peb., 2*55 ; 28th Feb., 2.75. Mame, Charenton, 14th E’eb., 2.i-34; 2Sth E’eb., 2.03. Yonne, Monteneau, 16th Feb., 2.21 ; 27th Feb., 2.52. Oise, Pontoise, 19th Feb., 2.78 ; 1st March, 2.43. Vanne, 4th March, 2.61. D huis, 8th March, 2.86. Avre, 7th March, 3.08. Eousingault determined nitrates in Seine water (Paris) in 185647, but obtained mnch lower results (Agronomie, 2, 65). The chief point of interest shown bg the above results is the uniformity in the amount of iiitrates at the different dates, notwitli- standing that the amount of water was reduced, at the later dates, to a t least half. From the average amount of nitric nitrogen (2.42 per million) tlie total annual loss per hectare is calculated for the basin of the Seiiie from the supposed amount of drainage. If the draiuage is one-sixth of the total rainfall (700 mm.), the loss per hectare of nitric nitrogen would be 2.8 kilos.; if one-fourth, 4.29 kilos. ; and if one-third, 5.65 kilos. The loss mould, however, be mainly from arable land, and not from woods, and meadows, &c. When calculated on arable land and vineyards alone, the loss (in the basin of: the Seine) is found to be 4.2, 6.44, or 8.48 kilos. per hectare, according t o tlie amount of drainage. The calculations, which are only provisionitl, indicate much less loss than was geiierally supposed to take place. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8967005053

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

Organic C h e m i s t r y . Explosive Double Salt of Potassium Cyanide and Potassium Nitrit4. By KARL A. HOFJIANN (Zeit. aizorg. Chew, 1895, 10, 259- 26l).-A good yield of sodium nitroferrocyanide is obtained by the action of a concentrated solution of ferrous sulphate on an aqueous solnt,ion containing equal weights of.' sodium iiitri te and potassj urn cyanide. TVitli the object of obtaining nn intermediate COmpouiid, which, by the action of ferrous sulphate, is converted into the nitro- ferrocyanide, tlle author has examined the action of potassium cyanide on potassium iiiti-ite. When a solution of the two salts is boiled, the cycznide is converted into ammonia, and potassium carbonate, formate, and nitrate. The do.rible saZt, KCN,KN02 + +H,O, is obtained by dissolving potassium nitrite (50 grams) aiid potassium cyanide (20 grams) in the smallest possible quantity of water and allowing the solution to eva- porate over sulphuric acid.Potassium cyanide separates first, and then the new double salt in short, characteristic prisms. It explodes with a loud report when heated at 4U0-500°, but does not explode 09 percussion ; on recrystallisation in a vacuum over sulphuric acid, it is partially decomposed into its component salts. With silver nitrate, the neutral solution gives silver cyanide and silver nitrite. E. C. R. Sodium Nitroferrocyanide. By KARL A. HOFJIAW (Zeif. army. Chem.., 1895, 10, 262-276) .--Sodi.rcm rLmidofer.1.ocyanide, FeC5N6 H,Na&H20, is obtained by reducing sodium nitroferrocyanide with 4 per cent. sodium amalgam9 cooling the mixture with ice and salt ; the product is precipitated with alcohol, re-dissolved in ice-cold water, and again precipitated.It crystallises in bright yellow needles, and its solii- tion decomposes at the ordinary temperature yielding ammonia, ferric hydroxide, and sodium ferrocyanide. With bleaching powder and dilute sulphuric acid, it gives a beautif a1 reddish-violet solution ; with ferrous sulphate, a bright greenish-blue precipitate ; with ferric chloride, a deep blue-green precipitate ; and with dilute hydrochloric acid, a green solution. When heated with sodium hydroxide, it yields ammonia, ferric hydroxide, and sodium ferrocyanide; when heated with hydroxylaniine and cli lute sodium hydroxide, it gives a reddish-yellow, and then .?I beautiful, bluish-red solution.The same compound is also obtained when a solution of s0diu.m nitroferrocyanide, cooled with ice and salt, is treated with gaseous ammonia; the product obtained crystallised, however, with GH2O. The silver salt, FeC,N6H2Ag3,3H20, is obtained in white aggregatas by addiug silver nitrate to the aqueous solution in the presence of neutral ammonium nitrate ; when treated with methylic iodide, decomposition takes place, and it residue, containing iron and cyaiiogen together with methyl- carbg lamine, is formed. T h2 forrna tion of amidoferrocyanide from 9. VOL. LXX. i,70 ABSTRACTS OF CHEXICAL PAPERS. nitrofei*rocyanide is a reduction process and not a substitution pro- ccss ; for amidoferrocyanide is formed, by the action of mono- and di- eth-j-lamine, a s well as by that of ammonia.When preparing the compound by the action of these ;\mines, hydrates, with 5H,O and 7H,O, were obtained. When nitroferrocyanide is treated with pure trirnethylamine, a brisk evolution of nitrogen takes place, and sodium ferrocpnide and ferric hydroxide are formed ; when a 10 per cent. alcoholic solution of triinethjlamine is eniployed, amidoferrocyanide is formed. Sodium amidoferrocyanide is either not altered or entirell- decomposed by acetic anhydride, benzenesulphonic chloride, alcohol and carbon bisulphide or chloroform. When treated with iodine dissolved in potassium iodide or in alcohol, i t gives a beautiful violet- red compound which easily decomposes into sodium ferrocyanide, ferI+ hydroxide, nitrogen,and ammonia.If contiiiuously oxidised with potas- sium permailgarlate in a1 kaline solution at the tempei-ature of melting ice, it yields sodium nitroferrocyanide. When treated with nitric oxide in ice-cold aqueous solution, i t jields the sodium ni troferrocyauide, FeCbN,Ntt10zH,7H,0, which crystallises in yellow needles, a i d loses 4+ mols. of water when allowed to remain over sixlphuric acid a t 50'. When the amidoferrocyanide (6 grams) is treated with sodium nitrite (1.2 grams) in ice-cold aqueous solution, and then acidified with acetic acid, a brisk cvvlut'ion of gas, containing nitric oxide: takes place, and the solution turns violet-red ; when this solution is made slightly alkaline and precipitated with alcohol, the conpmud, (Na,FeC,N,),NOKa, + 16Hz0, is obtained.It crjstallises in beautiful orange-j-ellow needles, gives an intense violet coloration with monium sulphide, and does not yield ammonia when heated with sodiuiii hydroxide. When treated with sodinni nitrite and acetic acid in ice-cold solution, it is converted into sodium nitroferi-ocpnide. If only 0.95 gram sodium nitrite is used for 6 grams of sodium amicio- ferroGyanide, the compound, (Na,FeC,N,)JYH, 16H20, is obtained ; this cyystallises in sulphur-yellow plates, gives a beautiful bluisli-red solution with hydroxylamine and sodium hydroxide, a greenish-blue precipitate with ferrous chloride, an intensely blue precipitate with ferric: chloride, and a violet solution with sodium nitrite and acetic acid. When heated with sodium hydroxide, it yields ammonia, and with small quantities of sodium nitrite it yields sodium nitroferro- cyanide.Frorii the abore reactions, the author points outl that the amido- group in amidoferrocyanides behave in a very different manner from anlido-groups in organic compounds, and he coiicludes that it is com- bined with iron as expressed in the formula NHz*Fe(CN),Na,, E. C. R. Action of Carbonic Anhydride, Water, and Alkalis, on Solu- tions of Cyanuric acid and Alkali Cyanurates. By PAUL LEMOULT (Cmnppt. rend., 1895, 121, 404-406) .-Thermochemical considera- tions indicate that carbonic anhydride should displace sodium from trisodium cyanurat,e and convert the latter into the monosodium salt, and experiment confirms this conclusioii, the monosodium salt, being precipitated when the gas is passed into a concentrated solution ofORQANIC CBEMISTRY.71 the trisodiurn sait. Further, carbonic anhydride precipitates the acid from a concentrated solution of t h e monosodium salt. Direct experiment shows that, in aqueous solution, cyanuric acid is slowly converted into ammonia and carbonic anhydride. It is also found that the residue of thermal effect observed when the acid is neutralised with an alkali is much reduced if neutralisation is effected as rapidly as possible, but is greatly increased if the addition of successive equivalents of a1 kal i is extended over several hours. These rcsults confirm the author’s view that the apparent residual heat of neutralisation i s a consequence of tohe partial decomposition of the acid (this vol., ii, l l ) , this decomposition being accelerated by the presence of an alkali.Bivalent Carbon : Chemistry of Cyanogen and Isocyanogen. By JOHK U. NEF (Aimden, 1895,287, 265-359; compare Abstr., 1895, i, 3 and Y).-The author’s previous investigations on the subject of bivalent carbon have dealt with aromatic and aliphatic members of the isocyanide group, which are represented by the general formula R.N:C, and with fulniinic acid, wliich is expressed constitutionally by the formula CNOH. Attention is now directed towards cyanogen and iso- cyanogen: and regarding as possible the existence of three isomeric substances having the empirical formula C2N2, namely, cyanogen, N.C.CiN, cyanisocyanogen, N.C*N:C, and diisocyanogen, C:N*N:C (Thiele, Abstr., 1894, i, Cl), the author claims to have established by his experiments the conclusion that the cyanides are derivatives of isocysnogen, and that hydrogen cyanide itself mnst henceforth be looked on as hydrogen isocyanide, HN:C.Tlie foundation for this view is strengthened by the striking resemblance between the salts of hydroxyisocyanogen (fulminic acid) and derivatives of hydrogen isocyanide, the similarity being in some cases so close as to have given rise occasionally to confusion between the substances them- selves. If potassium cyanide is, in yeality, potassium isocysnide, KN:C, the chemical activity of an unsaturated compound will be displayed by this substance, it having been shown (Abstr., 1892, 1438) that the more positive the character of an unsaturated molecule, the more readily will additive compounds be obtained from it.It is shown by the author’s investigation that potassiuni cyanide does actually exhibit such behaviour, forming ethylic cjanimidocarbonate when treated in dilute, aqueous solution with ethylic hypochlorite i this reaction is analogous to the conversion of isonitriles into derivatives of mesoxamide by means of carbonyl chloride (Abstr., 1892, 14:33). Ethylic cyanimidocarhonate, C:N*C(NH ).OEt, is obtained by add- ing ethylic hypochlorite (9 grams) to a solution of potassium cyanide (18 grams) in five times the quantity of water, the liquid being con- stantly agitated, and maintained at a temperature of -10’. After adding about half the quantity of ethylic hypochlorite, the colour- less solution becomes tnrbid owing to the separation of an oil, which is extracted with ether and dried with calcium chloride ; on remov- ing the solvent, a n oil is obtained having sweet, but penetrating odour, and on distiiling this substance the greater part boils a t C.H. B. 9 272 ABSTRACTS OF CHEMICAL PAPERS 3-51' under a pressure of 30 mm., the higher fraction passing over at 80' under a pressure of 26 mm., and solidifging in the con- denser. The liquid is ethylic cganimidocarbonate, the solid being ethylic diimidoxalate, which is produced from the former compound by the action of alkali. Ethylic cyanimidocarbonate is a colourless oil having a sweet, but penetrating odour; it is sparingly soluble in cold water, and has the sp. gr. = 1.00 a t 15". It boils at 42', SO', and 60°, under pressures of 20 mm., 30 mm., and 42 mm., respectively, and when distilled under atmospheric pressure, hoils, and slightly decomposes at 133'.After st few days it darkens and ultimately becomes almost black, but the greater part can be recovered on distillation. Pro- longed digestion on the water bath with alcoholic potash or sodium ethoxide converts the substance into potassium cyanide, alcohol, and potassium cyanate ; aqueous alkalis give rise to ethylic diimidoxalate, alkali cyanide and cyanate. Ethylic cyanimidocarbonate is decom- posed by hydrochloric acid into ammonium chloride and ethylic cyanocarbonate; when heated with aniline on the water bath, it yields ammoiiia, hydrogen cyanide, alcohol, and ammonium cyanide, whiIst from the portion of the residue insoluble in cold alcohol, ethylic acetate extracts cyananiline.A'thylic dii?nidoxu?ate, OEt.C(NH )*C(NH)*OEt, is obtained by the action of dilute alkalis on ethylic cyanimidocarbonate ; it forms heavy colourless crystals which gradually become brown ; melts at 38" and has a slightly sweet, peculiar taste. The subsfdnce was obtained in an impure state by Pinner and Klein (Ber., 1878, 11, 1437), who passed cyanogen into alcoholic hydrochloric acid ; their preparation was brown and melted at 25'. The pure substance boils at 69", 80°, and 100Ounder pressures of 18 mm., 32 mm., and 82 mm., respectively ; under atmospheric pressure it boils and slightly deconi- poses at 172". It dissolves readily in water at 2 5 O , and on cooling the liquid at 5' it solidifies to a magma of white needles consisting of a hydrate which contains 11H20 ; it dissolves with difficulty in cold ether and water at 12', calcium chloride cotnpletely removing aatei- from the ethereal solution.Mercuric chloride produces a white, in- soluble precipitate when added to aqueous et hylic diimidoxalate. Ethylic diimidoxalate is not converted into a derivative of oxalic acid on treatment with aqueous alkalis, but on adding dilute hydro- chloric acid to the salt, heat is developed, ammonium chloride and ethylic oxalate being produced ; aniline at the temperature of the water bath gives rise to cyananiline. Ethylic imidocarbonate, HN:C(OEt),, is obtained by adding ethylic diimidoxalate (25 grams) to an alcoholic solution of sodium ethoxide containing 4 grams of sodium, filtering from sodium vyanide which separates at 60°, and extracting with ether the dilated liquid after treatment with caustic potash; it boils at 62' and 77' under pressures of 36 mm., and 80 mm.respectively, and when distilled under atmospheric pressure, boils and slightly decomposes at 138-140". The sp. gr. = 0.948 a t 23'. Ethylic imidocarbonate has been obtained in an impure state by Snndmeyer, from potassium cyanide, canstic soda, alcohol and chlorine; it is also prepared byORGANIC CHEMISTRY. 53 gently heating ethylic cyanimidocarbonate with alcoliolic sodium ethoxide. When ethylic inlidocarbonate is heated with alcoholic potash, potassinm cyanate is formed ; aqueous alkalis are without action on the substance. Btlq Zic iwtidoza Za t e, 0 E t o C NH) C 0 0 E t , is obtained by ag i t a tiag a solution of ethylic diimidoxalate (48 grams) in water (240 grams) with decinormal hydrochloric acid (333 gi-anis), and extracting the clear, neutral solution with ether; i t boils at 73' nnder a pressure of 18 mm., and under atmospheric pressure a t 175", when i t decom- poses.Mercuric chloride yields a white precipitale with an aqueous solution of the substance. Very dilute hydrochloric acid converts ethylic monimidoxalate into etliylic oxalate ; the hydrochloride of ethylic oxalate is formed when hydrogen chloride is passed into the solution in dry ether, and it is also obtained on submitting ethylic cyanocarbonwte to the same treatment. Sodium cjanide and ethylic carbonate are produced when ethylic monimidoxalate is treated with alcoholic sodiurn ethoxide a t - 10".Alcoholic sodium ethoxide at - 10" decomposes benzoic cyanide into ethylic benzoate and sodium cyanide, the same agent converting ethFlic cyanocarbonate into hydrogen cyanide and ethj-lic carbonate ; alcoholic hydilogen chloride, however, coriverts these substances into ethylic benzoylformate and ethylic iniidoxa late respectively. Ethylic cyanimidocarbonate is fci-med when cyanogen chloride or bromide acts on a dilute, nlcoholic: solution of potassiuni cyanide. When chlorine is led into a solution of potassium cyanide in dilute alcollol, cyanogen chloride, et hylic diimidoxalate, and ethylic cyan- imidocarhoLate are formed, the last named being convcrted by the alkali into ethylic imidocarbonate.On addiilg ethylic hrpochlorite to diliite alcoliolic potassiuni cyanide a t - 7", ethylic diimidoxalate is for M ed . Reiizer/ eazo-ir,/ idofor my Z cyanide, pu' PhX* (3 (N H) *C iN , is the ye1 lo m substance obtained by Gabriel (Abstr., 1880,41) 011 adding a solution of diazo benzene chloride to potassium cyanide dissolved in water, and which he regarded as having the formula NPIi:N*CiN + HCN on account of ihe readiness with which hydrogen cpnide is eliminated ; the product of this decomposition is diazolnenzene cjanide, NPli:N-C:K (compare Abstr., 1895, i, 34s). Ethylic eth?lli~~?idocl~Zoi.ociii.boiiate, NEt:CCl*OEt, is obtained by adding dry ethylic hypochlorite at -5' to ethjlic isocyauide at -10 to - 1 5 O , in molecular proportion, and maintaining the tempera- ture of the mixture below O", it boils a t GSo and 68" under pressures of 58 mm.and 100 mm. respectively, and at 126" under atmospheric pressure. The vnpour has a penetrating odour resembling that of alkjlic isocyanates, and vigorously attacks the eyes. Water and dilute hydrochloric acid slowly decompose ethjlic ethylimidochloro- carbonate, giving rise to carboriic anhydride, ethylic chloride, diethjl- carbamide, and much ethylurethane. Alcoholic sodium ethoxide converts it into etlrylic ethyli~zidocnrbonate, which boils a t 147", and ethyylic eth~Zimidocyn~zoca~bollnte is obtained when ethylic ethylimido- chlorocarbonate is added to a solution of potassium cyanide in dilute74 ABSTRACTS OF CHEMICAL PAPERS. alcohol ; it is all oil which boils at 7t3' under a pressure of 82 mm., and has a sweet, penetrating odour. Ethylimidoch1ol.o-j~rmyl cyanide, NEt:CCl*CiN, is obtained by alIowing a mixture of cyanogen chloride and ethylic isocyanide, in molecular proportion, to remain in contact for two days, and then raising the temperature f w a few minutes to 70"; the portion dis- tilling between 120' and 130" is agitated with very dilute hydro- chloric acid, washed, dried, and 18edistilled.It is a colourless oil which boils a t 126O, and has a peneti-ating odour. Trimolecdar benzoic cyanide, [COPh*CN],, is obtained by heating benzoic bromide (21 grams), absolute ether (150 c.c.), and silver cyanide (20 grams) for 10 hours in a reflux apparatus from which moisture is excluded, and which is heated on a water bath a t 60'.After removing the ethereal liquid, aqueous pctassium cyaiiide is added to the yesidue in order to remove silver bromide, and the pro- duct is then dissolved in chloroform ; it crystallises f ~ o m hot benzene in pale yellow needles, and melts a t 195'. The substance is insoluble in water and ether, but dissolves readily in chloroform and hot ben- zene ; when heated at 300°, it decomposes, yielding benzonitrile. It may also be obtained from ordinary beuzoic cyanide by passing hydrogen bromide into the solntion in absolute ether. Dimolecular benzoic cyanide was obtained by Wache on heating an ethereal solution of benzoic cyanide with sodium ; it is also fcrmed when benzoic chloride is agitated a t -5'with a solution of potas- sium cyanide i n dilute alcohol. It ciystallises from alcohol in colour- less needles, and melts at 99--100° (Wache observed 95') ; undei- a, pressure of 15 mm.i t boils a t 220'. Ordinary benzoic cyanide is formed when benzoic anhydride and potassium cyanide in molecular proportion are heated a t 190'. When ethjlic chlorocarbonate (28.5 grams) is heated with silver cyanide (36.4 grams) f o r six hours a t 130-140', :I mixture of ethylic cyanocarbon~te and ethylic isocpanocarbonate is formed. Ethylic chlorocarbonate (50 grams), when agitated with a solution of potassium cyanide (32 grams) iii water (96 grams) and alcohol (25 grams), cooled at -13', yields ethylic cyanocarbonate and a small quantity of ethylic carbonate ; i f action proceeds at ordinary temperatures, less ethylic cyanocarbonate is formed, a substance being produced which, in the presence of water o r alkalis, yields hydrogen cyanide, potassiiim chloride, carbonic ail hydride, and alcohol. On agitating a solution of potassinm cyanide in 6 parts of water cooled at - 10' or - 15' whilst carbonyl chloride is slowly added, an additive compound is formed which breaks up spontaneously into hydrogen cyanide, potassium chloride, and potassium carbonate.I n 1857 CloEz obtained from cyanogen chloride and alcoholic sodium ethoxide, an oil which he regarded HS ekhylic cyanate (Conyt. rend., 44, 482), and this result was confirmed by Hofmann and Olshausen (Be,.., 2870, 3, 269) ; subsequently Muldcr observed that the action of cyanogen bromide on sodium etlioxide in presence of water gave rise to urethane and the substalice isolated by Cloih, which, how- ever, has the composition OEt*CN,HOEt, and also a considerable quan- tity of ethylic cjannurate.Finally, Ponomarefi (Abstr., 1832, 937) re-ORGANIC CHEblISTRY. 75 corded the formation of an oil which distilled between 90" and 200", and had a basic odour which disappeared on heating the product in an open basin on the water bath. The author finds, in the first place, that pure cyanogen bromide is without action a t 50" on sodium ethoxide suspended in absolute ether and free from alcohol : cyanogen chloride is equally inert, but if alcoholic sodium ethoxide is added to cyanogell bromide or chloride a t -S' to -lo", a rise of temperature takes place, and the sole product is ethylic imidocsrbonate ; if the action proceeds a t ordinary temperatures, the yield of ethylic imido- carbonate is diminished, urethane and ethylic cyanurate being formed in small quantity.Ethylic imidocarbonate is produced with a small quantity of urethane when excess of caustic soda OY potash is added to a mixture of cyanogen chloride (or bromide), water ( 5 parts), and alcohol (2 parts) cooled to -5" or -lo", the temperature of the liquid being maintained below 0' ; these substances probably a&e from the decompositio~i by water or alcohol of the intermediate pro- duct NH:CCI*OEt. When hydrogen bromide is passed into a solution of cyanogen bromide in absolute ether, a yellowish-whit,e precipitate of imidocarbonyl bromide, NH:CBr2, or the hydrobromide, is formed ; i t is hsgroscopic, and fumes in air, yielding carbonic anhydride and ammonium bromide, whilst, in a dry atmosphere, hydrogen bromide is elimirinted atld cyanogen bromide formed.Phenylic ii,iidocurbonate, NH:C( OPh),, is obtained by adding a solution of phenol (80 grams) and caustic potash (48% grams) in 300 C.C. of water to a solution of c*yanogen bromide (46 grams) in 6500 C.C. of water at 20°, and crystallises from petroleum in colour- less needles melting at 54'; it is insoluble in water, but dissolves readily in organic solvents, excepting petroleum. Dilute hydrochloric acid converts it, into phenylic carbonate and animonium chloride, the action of alcoholic potash gives rise to potassium cyanate, and when heated alone in a dry tube, phenylic imidocarbonate yields phenol and phenylic cyanurate.The observation of Hofmann and Olshausen (loc. cit.), who passed cyttnogen chloride into alcol~olic sodium plienoxide and obtained phenylic cyanurate, is incorrect, neither t h i s substance nor phenylic cyanate being formed ; when an alcoholic solution of cyaiiogen chloride or bromide is treated with aqueous or alcoholic sodium pheiioxide, plienylic imidocarbonate is the chief product, eflzylic plzenylic indocnrtoizate being also formed ; the latter boils at 120" under a pressure of 18 min. The observa- tion of Hofmaiin and Olshansen originates in the fact that both this salt and also phenylic iniidocarbonate decompose into phenol and phenjlic cpnurate when heated a t 180". When cyanogen is passed into an ice-cold solution of potassium cyanide in dilute alcohol, ethylic cyaniniidocarbonate is formed together with n small quantity of ethylic diimidoxalate ; when passed into a solution of sodium et'lioxide in alcohol a t 0", ethylic diimid- oxalste is the sole product.The author has devised a method of obtaining hydrogen cyanide in the pure siate. The slightly itbnoi*mal vapour density of former preparations is probably due to the presence of about 2 per cent. of ammonium cyanide, and to remove this impurity, dry hydro-76 ABSTRACTS OF CHEMICAL PAPERS. gen cyanide obtained from potassium ferrocyanide a1.d sulphuric acid is distilled from phosphoric anhydride, and the rapour, after pa~siiig through a tube maintained at 40-50' containing a mix- ture of glass beads and pliosplior~c anhjdride, enters a long con- denser, the distillate being collected in a recciver and protected from moisture by a long tube containing cnlcinni chloride and pliosphoric anhydride.The product boils a t 25" {corr.), and melts a t -12O to -loo, undergoing no change when preserved for many months in closed vessels ; the purest specimen previously obtained boiled a t 26' (con.), and melted at -14" (Gautier). I n comparison with its salts and the alkylic isocyaaides, hydrogen cyanide is a very inert sub- stance ; it does not combiDe with chlorine or hydrogen chloride at lorn temperatures, and no action takes place when it remains in con- tact with ethylic hypochlorite for a protracted period a t -10". The want of harmony among the statements of prcvions investigators (Pinner, Abstr., 1883, 731 arid 1089 ; and 1895, i, 264 ; Lengfeld and Stieglitz, Abstr., 1895, i, 277 ; and Clnisen and Matthews, f j e y ., 188:3, 16, 311), has led the author to study the action of hydrogen chloride on hydrogen cyanide in presence of alcohol, with the result that the following observations hare been made. Imidoformyl chloride, NH:CHCI, is first formed, a2d unites with hydrogen cyaxide form- ing the compound NH:CH*C(NH)Cl, which takes up one or two inoleculai* proportions of hydrogen chloride ; in presence of alcohol, the product gives rise to the compound OEt-CH(NH2)*CCl(NH,)*OEt, which is present in the mixture of salts which Pinner obtained. The intermediate compound, NH:CH*C(NH)Cl, also yields ethylic diethoxyiniidoglyoxylate, CH (OEt),*CCl (SHH?) *OE t, and et hxlic diethox-~ortliamidoglyoxylate hydrochloride, CH(OEt)z-C (OEt)2*NH,,HCl.This brief 'summary is much expanded in the original paper, which contains a theoretical discussion of the results obtained. Imidofo~myl cyanide, NH:CH*C':N, is prepared in the following manner. Pinner's salt, ethylformimide hydrochloride (Zoc. cit.), ob- tained by passing hydrogen chloride into a mixture of alcohol with a solution of hydrogen cyanide in absolute er;her, is suspended in ether and treated with caustic soda; after remora1 of solid matter, and evaporation of the ether, an oil is deposited which is a mixture of irnidoformyl cyanide, the dialcoholate, and cthylic diethoxyorth- amidoglgoxylate. On distillation under reduced pressure the cyanide solidities in the condenser.Imidoformyl cyanide melts at 8 7 O , and boils at 120-125' without decomposing ; it is extremely volatile, and sublimes in closed vessels. The substance is clecomposeci by caus tic soda or dilute hydrochloric acid, yielding ammonia and formic acid, whilst an aqueous solution quick!y decomposes when heated in a sealed tube at looo, yielding formamidine formate and ammonium forniate ; agitation with caustic soda and benzoic cliloride gave rise to benzamide and dibenzoyl formamidine. The s i l v e ~ derivative of the hydrate of iniidoforniyl cyanide, AgC2N2H,H20, is formed on adding silver nitrate t o the concentrated aqueous solution ; i t is crj-stalline and colourless, becoming black when treated with boiling water.ORGANIC OHEMISTRY. 77 On heating hydrogen cyanide (10 grams) with acetic anhydride (37.4 grams) in a sealed tube for five hours a t 190--2OO", diacetjldi- cyanide is formed.When hydrogen cyanide (15 grams) remains in con- tact with acetic bromide (45.5 grams) for f o u ~ weeks a t the ordinary temperature, n hygroscopic substance is formed which decomposes on treatment with water into hydrogen cyanide, acetic acid, 2nd hydrogen bromide ; i t probably consists of pyruvimide bromide, NH:CBr*C OMe. The paper concludes with a theoretical discussion of the results described. M. 0. F. Compounds of Acetone with Polyhydric Alcohols. By AR'r HI: R s YE 1 E It (Bey., 1 &%, 28, 253 1-2 5 34) .-Dimetone- ery thrit ol, c4H604(c3H6)2, prepared by Fischer's method (Abstr., 1895, i, 441) from acetone and erythritol, has a bitter tast'e, melts at 56", and boils at 1O5-l0(io (pressure = 29 mm.). Diacetonearabitol, C5HE0,(C3F~,),, is a, colourless syrup with a bitter taste, and may be distilled under diminished pressure.Diacetone-adonitol is also a syrup which has a bitter taste, and boils at 150-155° (pressure = 1 7 mm.). Diacetone-dzdcifoZ, CsH,,Os( C3H6)*, crystallises in prisms, melts at 9so, aud boils a t 193-195" (pressure = 18 mm.). T~.iaceto?ae-so?.bitoZ, C6H80,( C3H,),, is a colourless, crystalline mass, which melts a t about 40°, and boils at 170-175° (pressure = 25 mm.). Friacetone-2- ylucoheptitol, C,H,,,0,(C3H6)3, is a thick, faintly yellow syrup, which has a bitter taste, and boils a t 200--201° (pressure = 24 mm.). Acetone is thus seen to react much more uniformly with the higher nlcoliols thau does benzaldehpde.A. H. Constitution of Pectins. By CHARLES F. CROSS (Ber., 1895, 28, 2609--2611).-According to Tromp do Haas and Tollens(this vol., i, 7), the atomic ratio of oxygen to hydrogen in the pectins is very nearly 1 to 2, and the percentage composition of nearly all the substances analysed is very similar t o that of the oxycellulose-cellulose series. One specimen of pectin had the composition of the typical limo- cellulose, jute fibre, and appears by its reactions to be a scliihle ligiiocellulose free froni the substances which usually bccompany lignncellulose and react with phloroglucinol and aniline salt.. l'lie pectins appear to be distillpished from ore another by differences which me quite analogous to those by means of which the various members of tile group of celluloses can be dislinguished.Preparation of Ethylamine from Aldehyde-Ammonia. BJ FERDIXAND JEAN ( B U Z Z . SOC. Chim., 1895, [ 3 ] , 13, 474; compare Cambiei- and Brochet, Abstr., 1895, i, 641, and this vol., i, 7).- Ethylaminc is readily obtained by reducing aldehyde-amnionia with zinc and hydrochloric acid by Trillat and Fayollat's method. The freshly prepared crystals (10 grams) are mixed with a little water and zinc dust (20 grams), and dilute hydrochloric acid (150 gixm5, 1 : 3) gradually added during 10 minutes; after the lapse of a further interval of 10 minutes, some concentrated acid (20 grams) is added, and the mixture kept cool at first, but after 45 minutes heated on a A. H.78 ABSTRACTS OF CHEMICAL PAPERS. water bath; the ethylamine is then liberated by adding sufficient caustic soda to redissolve the zinc hydroxide at first precipitated, and is separated by distillation with steam.The yield of the hSdrochloride is about 30 per cent. of the alde- hyde employed. As no appreciable amonnt of t,he amine is formed by the action of hydrochloric acid alone, the process seems to be pnrely one of reduction. JN. W. Hexamethylenetetramine Mercurochlorides and Mercur- iodide. By MARCEL DEL~PTNE (Bull. Soc. Chim., 1895, [3], 13, 49-97 ; compare Abstr., 1895, i, 444).-There are three mercurc- chlorides of hexamethylenetetramine. The first, CsH,,N4,2HgCI,,H,0, obtained by exactly precipitating the aqueous amine with aqueous mercuric chloride in the cold, forms silky, white needles, and is stable at loo", but at a higher temperature commences to decom- pose, finally melting at abont 208".It forms a yellowish, amor- phous additive compound xith 1 mol. of bromine a t the ordinary temperature. The second mercurochloride, C6Hl2Nd,HC1,2 HgC12,H20, resembles the first in appearance, and is formed in a similar manner from the hydrochloric acid solution of the amine ; it melts sharply at 165", but becomes solid ,again at a higher temperature, finally softening at about 210" to a yellowish-grey paste. T t also fornis an additive com- pound with bromine. The third naercurochlo~*ide, (C,H,,N,,'2HgC:,,H,O),,NH,CI,HgC 12,HZO, is prepared by adding a concentrated solutiou of mercuric chloride in ammonium chloride to a boiling solution of hexamethylene- tetramine containing ammonium chloride : a precipitate forms at first, but redissolves, and on cooling, the mercurochloride separates in hard, dense, colourless prisms. It is stable at loo", but commences to decompose a t about 168".All three mercurochiorides are hydrolysed by water at 100" into formaldehyde, mercuric oxide, and ammonium chloride, and the yellowish powder resulting from their decomposition a t a higher temperature consists chiefly of mercuric oxide. The mercuyiodide, C6H12N4,2Hg12,H20, is obtained by adding excess of a solution of potassium rnercuriodide in dilute acetic acid to the aqueous amine ; the solution is boiled until the precipitate redissolves, and the double salt separates in golden-yellow scales. It softens at 156", and melts at 165".JN. W. Compounds of Amidoguanidine with the Sugars. By HEINRICH WOWF (Uer., 1895, 28, 2613-2615 ; compare Abstr., 1894, i , 3 15) .-Gal a ctoseamidoguanidine ch lovide forms rho mbic cry stais, and is slightly dextrorotatory ; gulactoseamidoguanidine szrlphate also forms rhombic crystals, which are sparingly soluble in alcohol. Lactoseantidogz~anidiize sdphate crjstallises like the sulphate just described, and is dexti*orotatory ; the nitrate forms microscopicORGANIC CHEMISTRY. '79 needles, which melt and decompose at about 800'. obtained from the sulphates by means of baryta are amorphous. The free bases A. H. Thiamines. By FELIX LENGFELD and JUL~US STIEGLITZ (Be).., 1895, 28, 2742-2744 ; compare A bsti.., 1895, i, 864).-Thiethylirnine, (SXEt),, is prepared by the action of ethylamine (10 grams) dis- solved in light petroleum (150 grams) on recently prepared sulphur dichloride (7.5 grams) dissolved in light petroleum (20-30 grams). The solutions must be dry, as, in presence of moisture, dark-coloured compounds are formed ; the ethylanline li,ydrocLiloride is removed by filtration, aiid the light petroleum distilled under reduced pressure in it stream of nitrogen free from moistuiae, carbonic anhydride and oxygeii.The thioimitie is n pale-jellow, mobile oil, with an odoar recalling both those of carby lamine and mercaptans ; i t decomposes when heat,ed, and on stailding graclually darkens. Cryoscopic mole- cular weiglit deterriiinatiolis agree with the above formula. The l i g h t petroleum employed W'RS treated succesnively witli siilphur di- chloride, water, potash, dried wit 11 potassium Iiydroxide, and distilled, that portion boiling a t 39-40' being employed for the experiments ; unless these precnntions are adopted tlie petroleum yields a chloro- derivative in small quantity, which cannot be removed from the thio- i in i lie.J. B. T. Action of Hydroxylamine Hydrochloride on Isonitroso- acetone. By ILIiLoTtAD JOV~TSCH ITSCH (Ber., 1895,28,2673-2674) .-A yellow, amorphous mass is obtained when isonitrosoacetone (acetone- oxime) is warmed with an aqueous solution of hydroxylaaiine hydro- chloride ; when recrystallised from water, itl forms small, colourless needles, and melts and decomposes at 245-246'. It has the composi- tion CfiH9N303, is readily dissolved in alkalis yielding a yellow solu- tion, and gives precipitates with solutions of most of the heavj metals.When hydrolysed with 30 per cent. sulphuric acid at 140°, i t gives acetic acid, formic acid, r? hydroxylamine salt, and ammonia. The substance, C6H9N303, is identical with that obtained by Scholl (Abstr., 1891, 287), and tlie autlioi* has discoutinu2d his investigation. J. J. S. zxp-Trihalogen Butyric acids from the Geometrically Iso- meric a-Halogen Crotonic acids. By VICTOR VALENTIN (Bey., lS95, 28, 2661-2665).- Both a-cllorocrotnnic acids, when sus- pended in carbon irisulphide, readily absorb chlorine, and foim the ax/3-trichlorobu t.yric acid previously described by Kramer and Pinner ( B e y . , 3, 389), Judson (ibid., 785), and Garzat*olli-Thurnlakh (this .Journal, 1876, ii, 623).Wlien warmed, the sodium salt of this acid rapidly decomposes, evolving carbonic nnliydride, and giving Judson's aa-dichloropropylenc. axp-Tribromobutyvic acid may be obtained in a similar manner by the addition of 2 atoms of bromine to either of the a-bromocrotonic acids (Micliael a n d Pentlleton, Abstr., 1888, 1176) ; an aqueous solution of the sodium salt of tlie tribromo-acid readily evolves carbonic anliydride, and yields m-dibt.omopropyletie. When the latter is hentecl for I d lmnrs a t 150' with excess of alcoholic potash, i t is almost cntlreiy coriverted into alljlene. J. J. S .89 ABSTRACTS OF CHEMICAL PAPERS. a-Dimethylamidocaproic acid. By ?DOCARD T)L-VILLIEK (Bull. SOC. Chim., 1895, [3], 13, 484-4S7) .-a-Dimethglamidocaproic acid is formed by heating a-bromocapi*oic acid with aqueons dimethyl- amiiie (2 niols.) in a sealed vessel a t 100'.the liberated hydrobromic acid combining with the second molecule of the aniine ; the product is boiled with bargta water to expel the excess of the amine, and the acid obtained by decomposing its silver salt, or better, its copper salt with hydrogen snlphide. a-Dintrth ylrrnzidocapnic acid, CH,Pr-CH( NMe,)*COO H + 2H20. crpstallises in bundles of needles, and is freely soluble in water and alcohol, b u t insoluble in ether ; when hcated, it melts and sublimes, but at the same time decomposes; the melting point is not giren. The coppel. salt, with 2H20, cr~-st;illises in dai-k blue plates or scales, and melts a t ZLO", hut neither t!le zinc nor the cadmium salt seeins to be capable of existence.The pltztinocldoride forms sm:dl, clino- rhomhic, orange prisms, and melts a t 108", at the same time decom- posing slightly ; the azirochlomle resembles lead iodide in appearance, a i d a crystalline 1.ydrochZol-ide also appears to exist. Behaviour of the Alkali Salts of the Fatty Acids and of Soaps in presence of Water. By FI~IEDRICH KRAE'YT and H. \VIGI,OM (ller., 1895, 28, 256ti-2573, %73-2582).-11 I. The Soaps as C~ys- tnZloiJs.--When hot 1 per cent. aqueous solutions of sodium stearate, pa Imi tate, mjristnte, Iaurate, eh'iclwte, and oleate are allowed to cool, crjstals begin to form respectively at 60") 45", 31*5", ll", 35O, and O", that is, a t temperatures 9.2". 17', 23", 3P6", 16", and 14" below the melting points of the corresponding acids.The crystals consist of a mixture of the normal and acid salts ; when deposited fro171 more dilute solutions, the crystals co1lt:iin a smaller pi-oportion of sodiuni, whilst from x 5 pel- ceiit. solution of sodiuiii oleate, the neutral salt separates unchanged I If the hot aqueous solutions are satiiratcd with c;irboiiic anhydi*ide and allowed t o cool. the acid salts separate out ; for example, sodium h j drogeii palmitate, C16H: 10LNa,C16H3?02. 'I'he teniperature rtt \I hich any one of these separates lies above the melting l'oint of the ('orre- sponding acid, but below that of the sodiuiii IIFdrogen salt. 1V. The Socqx as Collozds.-'l'lic soaps Iiavt: keen examined n i t L respect to the extent to which they raisc the boiling point of water in Becknuann's appitratue.dodiuill wetate m d propionate act as if each molecule were dissol iated into two ; but, curiously enough the molecular weight, as cntculated from the observed rise of the boiling point, does not increase with iucreasing concentration, but actually diminishes With sodium capreate, a slight increase is oberl-cd ; but in very strong solutions the tl~ern~ometer actually begins to sink again, a i d the solution solidifies, on cooling, t o a gelatinous mass. Sodium iioiiylate and laurate are coiuparati vely little dissociated in ioodei ately dilute soliitions, and their inolecular weights incwase with increasing concentration to about double the theoretical. Sodium palmitate, stearatt), and oleate a t first produce n rise in tbe boiling point, but erentuall~-, a5 the solutions become more concentrated, the thermometer falls t o the boiling point of the JN.W.ORGANIC CEEMISTRY. 61 water used, and the solutions solidify on cooling to gelatinons masses. The soaps, then, iuider these circumstances, do not raise the boiling pDint of water in which they are dissolved, and, so far, exhibit the be!iaviour of collo'id substances such as gelatin and starch. C. F. B. Derivatives of p-Chlorocrotonic acid. By WL. SZENIC and R. TACGESELL (Ber., 1895, 28, 2665-2672).-Both Geuther's j3-chlorocrotonic acids (Zeit. fuy Chemie, 1871, 240), when dissolved in carbon bisulphide, readily absorb chlorine, and yield a&'3-trichloro- hittyric acid, which crystallises in rhombic plates, and melts at 51-5-52'.It is only sparingly solnble in water, but readily in alcohol, ether, bepzene, &c. If an aqueous solution of the tri- chlorinated acid is treated witb granulated zinc and leftJ for several weeks, a mixture of the zinc salts of ,@-chloroisocrotonic: acid and /3-chlor ocrotonic acid is formed. A solution of sodium trichloro- butyrate, when heated at loo', evolves carbonic anhydride and yields ~~-dichloropropylene ; the latter readily absorbs chlorine, and yields a tetrachloropropane which is ideutical with that obtained by Borsche and Fittig (A?mlnZen, 133, 114) by the action of phosphorus pents- chloride on unsymmetrical dichloracetone. By treating the a&3- trichlorobutyric acid with alcoholic potash, a mixture of two isomeric dichlorocrotonic acids is obtained ; the one which is formed in larger quantity melts at 75-5', and is the centric sym- metrical ap-dichlorocrotor& acid.The one formed in smaller quantity melts at. 92', and is identical with the ap-dichlorocrotonic acid obtained by the addition of two atoms of chlorine to tetrolic acid ; it must, therefore, be the plane symmetrical isomeride. The acid melting a t 92' is readily converted into tetrolic acid when treated with zinc, whereas the acid melting at 7.5" is not. J. J. S. Action of Hydroxylamine Hydrochloride on Ethylie Iso- nitrosoacetoacetate. By MILORAD JOVITSCHITSCH (Ber., 1895, 28, '2675-2683) .-By warming ethylic isonitrosoacetoacetate with hydroxylamine hydrochloride, the author has obtained a substance which crystallises in colourless, glistening plates, turns red at 120°, and is completely decomposed at 141-142' ; it is readily soluble in ethei- and in alcohol, sparingly in water, and quite insoluble in light petroleum.It dissolves in alkalis, yielding a deep red solution, but is decomposed when boiled with excess of potassium hydroxide, yielding hydrogen cFanide and the substance C8H9N3O3, this vol., i, 79. Aqueous sulphuric acid also decomposes the compound, yielding hydroxylamine and the compound CsHgN303. The author terms the substance oximidomethylisoxazololte, >C:N*OH, and thinks it is identical with the subst2ance previously described by Ceresole and Koeckert (Abstr., 1884, 1120) and by Nussberger (Abstr., 1892, 1175). The silver derivative is obtained as a red, crystalline precipitate on the addition of silver nitrate to the solution of the oxazolone or of its salts.The red precipitate usually contains YCMe 0--co82 ABSTRACTS OF CECEMLCAL PAPERS. more or less of a colourless silvei- salt mixed with it ; this colourless salt is more readily soluble in nitric acid than the red one, and the two may be separated by this means. The red salt is explosive, especially when previously heated for some time at 100'. The colourless salt is silver izormal diiso?zit?.o,~obutyl.ate ; i t readily explodes, and also turns black when heated with water. Wlien warmed with an alkali carbonate, the oximidomethylisoxazolone is rapidly converted into diisonitrosobutyric acid, tlie silver s a l t of which, when oxidised with nitric acid (sp.gr. 1*3), yields the peroxide of diisonitrosobutyric acid previously described by Angeli ( A hstr., 1893, i, 310). The silver salf crystallises in colourless plates, and is explosive ; the etltylic sulf may be obtained by oxidising ethylic diisonitrosobutyrate with nitric acid ; it is a thick, oily substance which boils a t 240-242'. When silver oximidomethylisoxazolone is oxidised with nitric acid, a small quantity of Angeli's acid is obtained, together with tlie silver salt of an isomeric acid. This silver salt crjstallises from water in silky needles. The corresponding acid, CdB4N2O4, differs from Angeli's acid in being only sparingly soluble in ether, in containing no watei of crystallisation, anti in the sweet taste of its sodium salt. The following formulze are given for tlie various acids :- Gale-- :COO€€ S.Me-1C;.(COOH) $Me*CH(KO2)*?0 N*OH 0H.K N.0-O-N N-- 0 Syn-diisonitrosobutpic Angeli'a pcroxidc acid. Xitroinethylisoxazolonc. J. J. S. acid. Preparation of Ethylic Isonitrosoacetoacetate and of an Isomeride from E thylic Acetoacet ate. By MIL o RA D JU v 11's c H IT s c II (Bey., 1895,28! 2683-2687 ; compare Abstr., 1878,396 ; 1882,949 and 1052).-The author recommends the following method for the prcpara- tion of ethylic isonitrosoacetoacetnte. Sodium nitrite (1 mol.) is inti- mately mixed with ethylic ecetoncetate (1 mol.), and to the well-cooled mixture 18 per cent. sulphiiric acid (+ mol.) is slowly run i l l ; after dilution with water, 'the solutioii is extracted with ether, the ether evaporated, aud the residue dissolved in light petroleum, this solution is then dried with anhydrous sodium sulphate, and, on evaporation, gives a 90 per cent.yield of the isoiiitroso-compound. When oxidiscd with nitric acid containing nitrous acid, it yields ethylic oxixnidonitroacetate (Abstr., 1895, i, 447), which can also be obtained in small quantities directly from ethylic acetoacetate by the action of nitric acid (sp. gr. 1.4) and a small quantity of sodium nitrite in the cold. The chief product of this action, however, is the componnd ?*N:?.CooEt (Cramer, Abstr., 1892, 699), which the author terms 0.N:C-COOEt ethylic perozydiisonitl.ososzLcci?zate. If, in the above reaction, a n excess of sodium nitrite is used, the product formed is a yellow oil, which does not crystallise and has the same percentage composition as ethylic isoilitrosoacetoacetate. It differs from its isomeride in the ease with which it is decomposed by dilute alkali, yielding a yellow solu tion.With hydroxylamine hydrochloride, it yields oxiniidomethyl-ORGANIC CHEMISTRY. 83 isoxazolone ; on oxidation, it gives the same products as ethylic iso- nitroaoacet&e, and, with phenylliydraziiie hydrochloride, it yields 4-oximido-3 : 1-methylphen~lpy~*azolone. The new isonieride can also be prepared by the action of nitrous acid on ordinary ethylic isoni t rosoacetoaceta te. The author considers the two compounds as s y n - and aiiki- isomerides accordiiig to Hantzscli's terminology. The new com- pound is ethglic syn-isonitroeortcetoacetate, arid the old cornpound is tile anti-isomeride.When treated with bromine (1 niol.), the two compounds yield the correspondiug monobroi~~o-der.ivatires ; these are both oils, but differ in their action with alkalis. J. J. S. Preparation of the Oxime of Ethylic Acetoacetate and its Derivatives. By ROBERT SCHIFF (Bes.., 1895, 28, 2731-2734).- Ethylic acetoacetate and aniline are dissolved a t the ordinary teni- perature in concentrated aqueous solution of hydroxylamine Iiydro- chloride (all in molecular proportion) ; when cool, the solution is extracted with ether, arid on evaporating the latter the oxinze remains as a reddish oil, which slowly changes into a ci.ystitlline condensation product melting a t 124.5-125'. If, instead of extracting with ether, the solution is saturated with sodium carboilate, acetoacetic aniiide oxime, NOH:CMe*CH2*CO*NHPh, is formed ; it has been receutly prepared by Know and Reuter (Abstr., 1894, i, 371). Etliylic EMe-fi*CooEt', is obtained by the action N*OH N*OH ace toacetate amphidioxime, of sulphuric acid (30 per cent.) and sodium nitrite O:I the monoxime ; contrary to the statement of Nussberger, it gives, with cupric acetate, a brown coloration and then a brox;n precipitate.NHPh*N:C - C0/O7 '' prepared by treating the solution of ethylic acetoacetate, aniline, and hydroxylamine hydrochloride, as above, with hydrochloric acid and sodium nitrite (compare Know and Reu ter, Zoc. cit.). Benzylitletbe- vMe:N>O, is obtained by any of the ketomethyl isozazolom, following methods : (1) simple mixing of the oxime and benz- aldehyde, (2) saturation of an ethereal solution of the oxime and aldehyde with hydrogen chloride, (3) addition of concentrated hydro- chloric acid to a mixture of the oxime and aldehyde, (4) addition of fuming hydrochloric acid to a mixture of the aldehyde and acetoacetic anilide oxime.The first method is the least, the third generally the most, satisfactory. The compound, whicli is deposited in pale yellow, lustrous crystals, softens a t 1 3 9 O , melts and in part decomposes at 14l0, and is extremely stable towards acids, being precipitated un- changed from concentrated sulphuric acid 011 dilution. I t is readily soluble in sodium carbonate solution, in potash, a i d in ammonia, and, if the solution has nol been unduly heated, it is reprecipitated OIL the addition of ail acid; if boiled with ammonia for a short time, however, the compound is conipletely decomposed, benxaldehgde being regenerated.Its solubility in alkalis suggests that in their presence the ?Me:N\ . Ketomethylisoxazolone phenylhydrazone, CHPh:C-CO84 ABSTRACTS OF CHEXlCAL PAPERS. isoxazolone ring is resolved, the acid N0H:CNe.C (CHPh)*COOH being formed. J. B. T. Crystallised Lactic acid of Constant Boiling Point. By FRIEDRICH K n a ~ ~ r and W. A. Dyes (Ber., 1895, 28, 2589-259i).- T h i s may be obtained by drying the commercial acid-best of sp. gr. 1.16-for a meek or two in a ('i vacuum) desiccator, and distilling it twice under apressure of 12.15 mm., obtained by means of the water pump, The distillation flask should have a capacity of 60-80 c.c., ancl should not be more than half filled ; the side tube should be wide and as low in the neck as possible, and the receiver should be kept at a temperature of 90-100° to prevent the condensation of water in i t ; the liquid is first heated in a water bath at '70" t,o drive off water, and then the residual acid is distilled as rapidly as possible, being heated by a small, rather smoky flame kept in motion under the flask.The product obtained in this way contains 99-99.5 per cent. of the acid; it boils at. about 122' under IA-15 mm., at 119-120" under 13-14 mm., and at 82-85' under 0.5-1 mm. pres- sure ; when cooled, it solidifies to white crystals which melt at about 1 8 O , and it is very hygroscopic. c'. F. B. Formation of Carbon Chains : Alkylation of Ethylic Malonate and Acetoacetate.By CARL A. BISCHOFF (Ber., 1895, 28, 2616- 2631).-The velocity of formation of the alkyl derivatives of ethylic malonate and acetoacetate cannot be deduced simply from the time which elapses before the reacting mixtnre of ethereal salt, sodium eth- oxide, and alkylic iodide,oT bromide assumes a neutral reaction, because several other reactions may occur which also lead to a condition of neutrality. Thus, the following may all take place : (1) hydrolysis of the original ethereal salt, (2) hydrolysis of the ethereal salt pro- duced, (3) production of an ether of the alkyl group, (4) elimination of the halogen combined with hydrogen, (5) exchange of the alkyl group of the et,hereal salt with that of the iodide added.It is there- fore necessary to determine experimentally in each case the amount of the " normal " product obtained. For the purposes of comparison, the author numbers the chain of atoms of the normal product in order, beginning with that carbon atom of the alkyl group which is most remote from the niethylene group of the original ethereal salt, and proceeding as shown in the accompanying scheme for ethylic isopropyl- malonate, 1 2 1 c yc c~c*o*co*c*co*o*c*c. 1 6 5 4 3 4 5 6 7 The course of the reaction is fouiid to depend on the presence of carbon atoms at the positions 1-5 and 1-6 ; the more carbon atoms there are in these positions, the less readily does the " normal " reac- tion proceed. Iu many cases, moreover, the iodide reacts more readily than the bromide.These results are in agreement with the author's " dynamical theory." Dericatires of ethylic: malonate ; the numbers express the percentage of the theoretical The following are t b e experimental details.ORGANIC CHEMISTRY. 85 amount which is experiment,ally obtained. Methyl-, 70-SO per cent., propyl-, 61--75 per cent. ; the bromide gives t h e better yield ; ethyl-, 73-80 per cent. ; isopropyl-, 77-83 per cent. ; butjl-, about 20 per cent. ; isobutyl-, 20-40 per cent. ; psendobutyl-, the " normal " pro- duct was not formed either from the chloride or iodide under the usual canditions ; traces were produced under R pressure of 5 atmos. ; isoamyl-, about 25 per cent. ; tertiary amyl-, the " normal " product, wag only formed in very small quantity ; allyl- good yield.Methjlic malonnte gives a yield of 75 per cent. of the methyl derivative. Derivatives of ethylic ucetoacctcite : Methyl-, 76 per cent. from the iodide, 46 per cent. from the bromide ; ethyl-, 60 per cent. ; propyl-, 72-78 per cent,. ; isopropyl-, the " normal " product is readllg formed from the iodide, but oiily in traces from the bromide; iso- butyl-, 66 per cent. from the iodide, only 6 per cent. from the bro- mide ; pseudobntyl-, the normal reaction does not occur when tlie chloride is used; isonmgl-, 75 per cent. ; tertiary amyl-, the normal reaction does not occur ; allyl-, 53-54 per cent. Action of Acetic Anhydride on the Acids of the Acetylene Series. By AR'rHUR MICEAEL and JOHX E. BUCHER (Be,.., 1895, 28, 2511-2512) .-Acetylenedicarboxylic acid is converted by acetic anhydride at 100" into acetoxymaleik anhydride, O A C * C < ~ ~ , ~ ~ , which melts at 89-91O ; alcohol converts this into ehhylic acetate and oxalacetate, whilst cold water produces tho corresponding acids.When cthylic dibromosuccinste, melting at 58O, is treated with sodium ethoxide, the product consists of about 80 per cent. of ethylic as-diethoxysuccinate, and 'LO per cent. of ethylic ethoxymaleate or ethoxyfnmamte. Both of these ethereal salts are converted by hydrolysis into the sodium salt of a diethoxyszsccinic acid, which loses the elements of ether when heated a t 100' or allowed to stand in a vaciium for some time, oxalacetic acid being formed. The same intermediate product is formed when Nef's ethylic ethoxy- fumarate (Abstr., 1893, i, 6%) is heated with alcoholic soda.Phenylpropiolic acid is converted by acetic anhydride i n t o a substance melting a t 'L53', which has the formula of phengl- propioliu anhjdride, but is probably the anhydride of a poly- meric dibasic acid. On reduction, this substance is converted into an acid which has the composition of the truxillic acids, bnt is not identical with any of the acids described by Liebermann. Action of Primary Aromatic Amines on Unsymmetrical Ketonic Compounds. By TAOUIS SIMON (Bdl. Soc. Chim., 1895, (3), 13, 474-484; compare Abstr, 1894, i, 509).-'l'he present instalment of the paper deals with the actioir of aniline on the alkglic pyruvates, including the ethylic, active amylic, isoamylic, allplic, and benzylic salts ; all these substances combine with aniline to form compounds of the type NPh:CMe*CO*CH2*C( COOR):NPh, A.H. co -0 COOH*CHz*C( OEt),*COOH, A. H. VOL. LXX. i. h86 ABSTRACTS OF CaENIOAL PAPERS. probably by condensation of two molecules of the nlkylic anilido- pyruvate, in a manner analogous to the condensation of aldehyde- aniline observed by von Miller and Plochl. Nthylic pyruvate is readily prepared by boiling the acid with alcohol in a reflux apparatus under ordinary pressure, and fractionat- ing the product under low pressure ; the yield is 90 per cent. of that indicated by theory, and the product particularly pure. Ethylic pyruvate is an almost colnurless liquid, resembling ethylic acetate in odour, and boiling a t 66" (18-20 mm.), and a t 155' nnder the ordinary pressure, in the latter case decomposing slightly ; the sp.gr. = 1.080 at 14" ; it is freely soluble in water, rapidly becoming hydroljsed into its proximate constituents. The hydrazone is identical with that prepared by Fischer from the hydrazone of pyruvic acid. The product of the condensation of ethylic pjruvate with aniline, CzoH2ONzO3, the molecular weight of which was determined by the cryoscopic method, is a white, crystalline solid, melting a t 146"; i t appears to foi-m two prodncts with phenylhydrazine, a white substaim melting at 55", and a yellowish-white substance melting at 119-120". Besides the more complex condensation product, some aniluvitonic acid (methylquinolinecarboxylic acid) is formed at the same time. Ethylic pyruvn te condenses with paratoluidine iri a similar manner, a stbbstance, C22HzJNZO3, being formed, which crystallises in colourless needles and melts a t 186' ; a t the same time, a second white crystal- line substance, melting at 140-14r3°, is produced.The condetzsation pyoduct of aniline with active amplic pyruvate melts at 110-1 I lo, and is unaccompanied by any other product. Issoamylic pyyuvate is prepared in the same way as the ethyIic salt ; i t is a limpid, yellowish liquid, having an odonr resembling t h a t of amylic acetate, and boiling at 86" (14 mm.), and at about 185' under the ordinary pressure ; sp. gr. = 0.978 at ISo. The phenylhydrazo~ce, which is very soluble in ether, melts at about 185-186". The product of the condensation of isoamylic pyruvate with aniline, C23Hz6Nz03, crystallises in well-defined needles, and melts at 126-127'.The condensation product with paratoluidine, C,,H,N,O,, melts at 1 4 0 O . Allylic pyruvate is prepared by passing hydrogen chloride into a mixture of the acid and the alcohol ; it is a colourless liquid, having a pungent odour, and boiling at 65" (14 mm.), and a t 165" under the ordinary pressure ; sp. gr. = 1.082 a t 17.5'. It unites with phenyl- hydrazine to form a yellow product melting at. l%", which does not appear to be the hydrazone. The co?tdensation p o d u c t with aniline, CZ4HZONZO3, melts at 136'. Benzylic pyruvafe is prepared diwctlg from its proximate consti- tuents; it is a liquid boiling at 103-104O (26 mm.), 107-108" (36 mm.), and at 207-208" under the ordinary pressure ; sp.gr. = 1.090 at 14O. The phenylhydrazone is a yellow substance melting at 150'. The co~tdensaticn product with aniline, CZJHZ2N2O3, melts at 173-174'; if kept, however, in the liquid in which it is formed, it is converted into a substance having a higher melting point and con- taining relatively more carbon. I n the prepaivation of benzylic pyruvate, a liquid is obtained, which, although closely resembling it, forms a compound with phenylhydra-ORGANIC CHEMISTRY. 87 zine containing a much larger percentage of carbon than the hydra- zone of the benzylic salt. Jx. W. Constitution of Tetric (a-Methyltetronic) acid. By LUDWIG WOLFF (Awzalcn, 189-5, 288, 1-37 ; compare Abstr., 1893, i, 689).- The author discusses the structure of tetric acid, which he regards CO - CHZ its having the constitution attributed to it by Michael, I >o; >O,a CHMe*CO YO*CH2 CH2 CO it is propofied to substitute thc name a-methyltehonic acid for tetric acid, it being a methyl derivative of tetronic acid, substance which will be deecyibed in a future communication.Pentic acid, therefore, will be called a-ethyltetronic acid. a-Methyltetronic acid (Demargay, Abstr., 1880,625) is obtained by brominating ethylic methylacetoacetate and heating the product for two hours at 180'; when heated with an aqueous solution of bnriuni hydroxide for 30 hours in a reflux apparatus, it yields glycollic and propionic acids, ethylketole being formed at the same time. E'thyZkeluEe, C2H5*C'O*CHP*OH, is obtained by heating a-methyl- tetronic acid (10 grams) with water (GO grams) in a sealed tube at, 200-210" ; it is a neutral, colourless oil which boils at 155-15tj0, and decomposes slightly under a pressure of 741 nim.It is readily soluble in wRter, alcohol, and ethei-, being precipitatcd from the aqueous solution by salts ; the substance reduces Fehlinp's solution and a silver solution, and is slowly decomposed by alkalis. Theyheuyl- hydrazoue crystallises from petroleum in yellowish prisms, and melts at 76-77' : the osazom crystailises in lustrous, yellow prisms, and melts a t 116". Carbonic anhydride and propionic acid are obtained on oxidising a-methyltetronic acid. >0, is obt.ained by treating the acid with boiling aniline, and pouring the product, into water ; i t crystallises in small, slender needles, and is resolved into its components by boiling, dilute hydrochloric acid.Its nitroso-derivative crystallises in yellow needles, and melts and evolves pas at 103-104". NH1'h.s- CH, CAfe*CO The nnilide of a-methyltetronic acid, U NHPh*yH- CH2 CHMeCO a-Methyl-&a ?iilidobz~tyrolactoiLe, >0, is formed when the anilide is reduced with sodium and amylic alcohol; it cqstallises from hot water in long needles, and melts at 92". The aqueous solution is neutral, and indifferent towards boiling dilute hydrochloric acid ; Fehling's solution is reduced by it when heated. The barium salt of the hydroxy-acid is obtained on treating the lactone with boiling aqueous barium hydroxide. The author has obtained the bromo-derivative of a-methjltetronic acid in long needles which sinter at 85' and melt a t 87-88"; the bromotetric acid prepared by Moscheles and Cornelius melted a t 75".The aqueous solntion is feebly acid, and after sonie time contains hydrobromic acid ; when heated a t loo', i t yields carbonic anhydride, diacehyl, and methyltetronic acid, a pungent oil which probably con- h 288 ABSTRACTS OF CHEMICAL PAPERS. sists of bromethylketole being formed at the saine time. Bromo- methyltetronic acid is immediately dissolved by ammonia and alkalis, and slowly by alkali carbonates, thc bromide of the metal being formed ; a concentrated Rqueous solution of sodium carbonate gives rise to methyl tetronic acid and cliacetyl. Methyltetronic acid is readily oxidised, yielding dirtcetyl, cnybonic anhydride, formic and propionic acids, and an oil which closely re- sembles ethvlketole.YO-CH, >0, is obtained by sus- NO* CNe *CO 2\Titr~60-~-~neth~ltetronic acid, pending a-methyltetronic acid in glacial acetic acid, cooling the liquid with ice, and submitting it to the action of a current of gas obtained from arsenious anhydride and nitric acid. On adding water to its solution in acetone, it crystallises out in minute prisms, aiid melts, evolving gas, at 130-13 1' ; i t is indift'erent towards cold water and hydrochloric acid, but yields nitrous acid and met hyltetroiiic acid with a small quantity of a-oximidopropionic acid when treated with the boiling agents. Cold aqueous ammonia gives rise to ammonium nitrite, methyltetronic acid, a-oximidopropionamide, and glycollic acid. a-OximidopropionyEgZycolZic acid, NOH:CMe*CO-O-CH,*COOH, is obtained when the gas from nitric acid and arsenious anhydride acts on methyltetronic acid in presence of water, and it is prepared ill the form of the sodium salt by dissolving the original substniice in concentrated aqueous sodium nitrite.It ci-ystallises from water in large, transparent prisms, and undergoes no chaiigct a t loo3: it melts a t 165O, slowly evolving gas, and is occasionally obtained in the form of needles containing water, which effloresce on exposure to air. The sodiwn salt cryfitallises in lustrous needles containing 1H,@ ; the siZz.ei* salt crystallises in needles which soon become prisms. The ncetyl derivative crysbllises from benzene ; i t sinters a t 1 0 2 O , and melts at 105'. Cold caustic soda, hydrochloric acid, and boiling water decompose a-oximidopropionylgl~collic acid, giving rise to a-oximidopropionic acid and glycollic acid ; the amide of thc former acid is produced by the action of ammonia, glycollic acid being formed ;it the same time.a-Oximidopropiouylgl~collic acid is obtained from nitrosomethyltartronic acid by treatins it with boiling solutions of sodium nitrite and sodium acetate, which, however, are without action when cold. The a i i h y d d e , which may have the constitution 0 C 0. CH, NGCMe - co>O, is obtained as a bye-product in preparing the acid from a-methyltetronic acid by means of sodium nitrite ; i t is an amor- phous, hygroscopic powder, which begins to decompose at iO", evolr- ing gas vigorously at 150'. It dissolves readily in alkalis and COA- centrated acids, and is converted into a-oximidopropionylglycollic acid on treatment with boiling watey.Dimethylvioluric acid and Dimethyldilituric acid. By RUDOLF ANDREASCH (Monatsh., 16, 773-788 ; compare Abstr., 1895, i, 336).-When dimethylvioluric acid is heated in a water bath with excess of potash, and the product acidified with acetic acid, carbonic anhydride, methylamine, and oximidomalonic acid are forined. If M. 0. F.ORGAN10 CHEMISTRY. 89 barium hydi-oxide solution be substitzted for the potash, carboiiic anhydride and oxinzidodinzethyZi,zaZoiza~~zide, HO*N:C( COmNHMe),, are obtained. The latter crystallises from water and from alcohol in needles, and melts a t 2%" (uncorr.). Xitrodimethylbarbiburic acid, if boiled with baryta water, or allowed to remain in contact with potash for several days, yields nitro&- methyZntalonamide, NO,*CH( COOH,)2, which crystallises from hot water in needles, nielts at 156" (uncorr.), and yields a barium salt, (CaH8X:104)2Ba + H,O, which crjstallises in drusy masses of prisms, a pofnssiiiin salt, which crystallises in white needles, and a copper salt, which is soluble in water, and crystallism in sky-blue octahedra.Nitro- dimethylmalonamide, when heated with hydrochloric acid in sealed tubes at l l O o , yields formic acid, carbonic anhydride, hydroxylamine, and methylamine. An aqueous solution is converted by chlorine and bromine into ch109'0iLit1.otliiizethylnzalonanzidc. and bro,,toiLitrodinzeth~L- mabonamide respectively ; the former crystallises in spear shaped needles and melts at 109" (uncorr.), the latter forms four-sided plates and melts a t 137-138' (uncorr.).These compounds do not yield salts, the halogen having become attached to the carhon atom bearing the nit1.o-group. Nitrodimethylbarbituric acid forms similarly consti- tuted compounds when timcated with chlorine water and bromine water respective1 y. Chlo~o~zitrodimetl~ylbal.hitu~ic acid, NO,*CCl: (CO*NMe),:CO, thus obtained, crystallises from chloroform in slender needles, and from alcohol in octahedra, and decomposes at 15G". Bromoizits.odi- methy lbarbitiiric acid, C6H6BrN305, closely resembles the corresponding chloro-compound, turns yellow a t 149", and melts partially a t 1 5 8 O . G. T. M. Methylethylhydantoin (Ethylpropiohydantoh) .By EDOUACD DUVILLlER (Bull. Soc. Chim., 1895, [3], 13, 487-490).-When Carl)- amide is heated with a-ethylamidopropionic acid, N HE t*C'HMe* C 0 OH, yHMe*NE t methylethylhydantoin (ethyllactylcarbamide), >CO, is GO--NH formed, the hydantoic acid appearing to condense a t once to the lactam. ,liletl~yEethyZhydnntoin crj-stallises in transparent, rhomboidal plates, and is very deliquescent ; it is stable towards boiling baryta water, so that the corresponding hydantoic acid cannot be formed by the action of this agent; the lactam is also formed instead of the acid by the action of potassium cyanate on ethylamidopropionic acid. It thus appears that this hydantoic acid is as unstable as the corresponding creatine, ;t ring compound being formed in both casea where an open chain compound might be expected.Thiohydantoi'n. By RUDOLF A ~ u i t e . 4 ~ ~ ~ (Monatsh., 1895, 16, 789-797 ; compare Abstr., 1888, 47) .-Thiohydantoinacetic acid, COOH*CHz<Co,NH> C:NH, is obtained on heating together at 1 0 5 O , ;t mixture of male'ic or fumaiaic acid (5 grams), thiocarbamide (3.3 JN. W. CH-S90 ABSTHACTS OF OHEMICAL PAPERS. grams), and water (4 c.c.). It is sparingly soluble in cold water, does not dissolve in alcohol, and ~ R S a powerful acid reaction (com- pare Tarnbach, Abstr., 1895, i, 13). When boiIed with barium hydpoxide, the acid is resolved into thiomalic acid, and probably cjanamide, although this was not identified, since from these two subst,ances thiohydantoinacetic acid can be directly synt,besised. On oxidation with barium chlorate in hydrochloric acid solution, thiohydanto'in- acetic acid yields carbamide and hydrothiosuccinic acid, COOH*CH,*CH( SH)*COOH.Diphen?llthiohydanto~~~acetic acid, obtained on heating a mixture of diphenylthiocarbamide and maleic acid for 14-2 hours at 140-144", crptallises from alcohol in yellowish, nodular masses, and melts a t 188' (compare Tambach, loc. cit.). G. T. N. Formation of 1 : 3 : 5-Trinitrobenzene and 1 : 4-Nitrophenol from Nitromalonic Aldehyde. By HENRY B. HILL and .TOSRPH TORRAY (Ber., 1895, 28, 2597-2599) .-The sodium derivative of nitromalonic aldehyde, N02*CNa(CH0)2, is formed whensodium nitrite acts on mucobromic acid. When its aqueous solution is treated with an equivalent quantity of hydrochloric acid and warmed, or simply allowed to remain, 1 : 3 : 5-trinitrobenzene and formic acid are formed.If its aqueous solution is treated with acetone (1 mol.), and soda is gradually added, 1 : 4-nitrophenol is formed. Preparation of Parethyltoluene and its Derivatives. BJ- GEORGE DEFRE?; (Rer., 1895, 28, 2648-2653).-The author has attempted to separate the mixture of ethyltolucnes, obtained by the action of ethylic chloride on toluene in the presence of alnmininni chloride, by a method similar to that used for the separation of the xylenes (Zeif. anal. Chew., 32, 243), but as it did not give good results he prepared parethyltoluene by Fittig's synthetical method, and obtained the following derivatives. Paret hy 1 toluenesuZphonic a cia, C6H3MeE t*S O,H + 1 4H,O, forms gI is- tening plates, melts a t 59-60', and is readily soluble in water. The bnrizm salt, ( C6H3&feEt*S03)2Ba + 2H20, crystallises from water in slender needles, and in the anhydrous form is insoluble in ether and in alcohol ; the sodiuna salt ci*ystallises with 1: H,O ; the sulphonic chloride is a yellowish, heavy oil, which solidifies when placed in a freezing mixture, and melts at 3' ; the sullphoiznmids is readily soluble in ether and in alcohol. PnrethzJltoluonitriZe, obtained by heating dry sodium ethylhluene- sulphonate with potassium cyanide, is a yellowish oil; i t begins to boil at 235O, but then rapidly undergoes decomposition, and cannot be hydrolysed by heating with concentrated hydrochloric acid at 200O.ChZoroparethyZtoZuei~e, obtained by chlorinating the hydrocarbon in the presence of iodine, is an oily liquid with an agreeable odour, and boils at 200" to 203' ; on further chlorination, it yields the dichloro.derivative, which boils a t 240-243". Orthobromcrparethyltolzlelze, obtained by the action of bromine on the C. F. B.ORGANIC CHEMISTRY. 9 1 hydrocarbon in presence of iodine, boils a t 22c)-222° (corr.), a t the same time undergoing slight decomposition ; the dibro?no-derivative [Me : E t : Br, = 1 : 4 : 2 ?] boils at 260-265O (uncorr.). Chloro~areth~ltolueiteszilphonic acid crystallises in glistening plates, which readily liquefy when 'exposed to the air. The barium salt crystallises with 4H20, the sodiziin salt is anhydrous, and the sdphonicl chloride is a yellow oil which does not become solid at -15'.Orthobromopareth~lfoliiei~esiLlplionic acid crystallises in thin plates, jields a ba&cm salt, (C6H,MeEtBr*S03),Ba + FiH,O, a sodium salt, C,H,MeEtBr*S03Na + €LO, an oily szilphonic chloride, and a sulplton- nruide which melts a t 143". J. J. S. Three Octochlorophenols. By XTIENN E BARRAL (Bztll. Sot. C'hiiri ., 1893, [3 3, 13, 490-492) .-Hexachlorophenol dichloride is the final product of the action of chlorine on phenol in presence of antimonic chloride, and exists in three modifications. The dark brown crystalline product is washed with dilute acid, and recrys- tnllised alternately from light petroleum and chloroform, yielding nltimately a white, crystalline mixture of the three isomerides, melting somewhat indefiuitely at 68-70". The separation is effected by hand, large and sufficiently characteristic crystals of the three varieties being obtained by slow evaporation of the ethereal solution in the cold. a-Hezachlorophenol dichloride, C,CI&, obtained in this manner is identical with that prepared by Benedikt and Schmidt by chlorinating pentachlorophenol in acetic acid solution, and it is also prepared by heating hexachlorophenol in sealed vessels a t above 210°, or a t R somewhat lower temperature in presence of bromine ; it crptallises in orthorhombic prisms, and melts at 103.5-104". ~-Hexachlompher~ol dichloridc crystallises in flat, orthorhombic prisms, and melts a t 89.5-90".It i; converted by fuming sulphuric acid into a hexac7Lloroquiizoize, which has a slight odour of camphor and melts a t $7.5-8S.5° ; this ketone is distinct from that of Zincke and Fuchs, and is converted by phosphorus pentachloride into hexa- chlorophenol and liexachlorobenzene dichlorides. yHexachloropheizo1 dichloride crystallises in monoclinic prisms, as broad as they are long, and melts at 88-89".The hexachloroph enol dichlorides are reduced to pentachloro- phenol by tin and hydrochloric acid, and are converted into t'he acetate of that substance by acetic anhydride ; they are decomposed a t temperatures somewhat above their melting points, into chlorine and products containing perchlorodioxyphenylene, but, on the whole, are much more stable than hexnchlorophenol, of which they are probably additive derivatives. JN. W. Formanilide and its Derivatives. By LUDWIG CLAISEN (Aiaitnleu, 1895, 287, 360--371).-0n a former occasion (Abstr., 1895, i, 62), the author traced an analogy between hydroxymethylene compounds, and formanilide, which he represented as hydroxymethy leneaniline, NPh:CH*OH, and this view has been accepted by Auwera (Abstr., 1895, ii, 41 ; compare also 1894, ii, 133) on the ground that in crjo-92 ABSTRACTS OF CHEMICAL PAPERS.scopic behnviour formyl deyivatires of primary bases differ fi-orn those of secondary bases. The author, however, no longer advocates his former conception of the constitution of formanilide on accouii t of the fact that, unlike the sodium derivatives of hydroxymethylenc compounds, sodium formauilide does not yield an alkyl ether when treated with alkylic iodides ; moreover, whilst hydroxymethylene compounds boil at a lower temperature than their alkyl ethers, formsnilide (h p.294") boils 82" higher than the ethyl ether. Detailed directions for preparing ethylforrnanilide (ethoxynaetlzyEeiw- aniline) from aniline and ethylic orthoformate are to be. found in the original paper (compare Cornstock and Clapp, Abstr., 1892, 708). I n preparing diphenylformamidine ())LethenyZb~.~anili?ze), there is 1 1 0 occasion to heat. aniline with ethylic orthofoririate in a sealed tube, as stated by Wichelhaus (BeT., 1869,2,116), the most coiivenient method being that adopted in preparing the foregaing substance, using the calculated quantities of material. When phenylhydrazine, dissolved in glacial acetic acid, is brought into contact with ethylic orthoformate at 0", formylphenylhydrazide and formazylhydride (Abstr., 1893, i, 83) are produced, the yield of the latter substance being larger than when ethylic formate is em- ploy ed.Sodium formanilide is conreniently prepared by heating in a reflux apparatus an ethereal solution of aniline containing sodium, and slowly adding the calculated amount of ethylic formate. Formjl- phenylhydrazide is obtained by heating sodiiim (23 grams), dissolved in alcohol (500 grams) with phenylhydrazine (108 grams) and ethylic formate (75 grams) for half an hour on the water bath ; one-third of the alcohol is distilled off, and the clear liquid obtained on pouring the residue on to melting ice is acidified with dilute acetic acid, wheii formylphenylhydrazide ( 108 grams) separates. Diazoperhaloyds. By ARTHUR R.HANTZSCH (Bey., 1895, 28, 275&2763).--Nine of the 10 theoretically possible diazopei-haloids RN2X, can readily be obtained (R = an aromatic radicle; X = a halo'id atom) ; attempts to prepare the trichloride have hitherto failed. These compounds are probably constituted according t o the diazoninm type NiNRX3 ; they closely resemble the alkali trihaloids, such as K13, CsBr3? HIM3, &c., of which, in the case of the cmhnri derivatives, eight of the 10 possible are known, the trichloride and the chlorodiiodide not having been described. The resemblance extends to the colouis : the diazotriiotlides are bluish-black, have a metallic lustre, and are almost opaque ; the diiodobromides are dark reddish-brown, the dibromiodides cherry-colonred, the tribromides orange, and the chlorobromiodides dark yellow ; the remaining com- pounds are less intensely coloured, the dicblorobromides being qale yellow.The colour is also influenced by the presence of substitutmg groups in the benzene nucleus. The cornpounds are unstable, but less explosive than the diazonium monohaloYds ; they are sparingly soluble in water, and generally a portion is decomposed; this property being most marked in the case of the two diiodides, the dibrom- and dichlor-iodides and the ch lorobromiodide are much more M. 0: F.ORQANIC C HEXISTRY. 93 stable. Alcohol dissolves them more readily, and less decomposition takes place; in ether, they scarcely dissolve, and undergo slow decomposition. Uiazoparachlorobenzene cyanide, by the action of bromine, is con- rerted, not into the additive compound C,H,Cl*NBr*NBr*CN, but into the tribromide, which is also formed from parachlorobenzene- diazonium chloride; this does not readily accord with the usual diazo-formula.All attempts, by varying the experimental condi- tions, to prepare structural isomerides, sach as PhNBr*NClI and Ph*y'C1 respectively, hare been uu- aiid I.N*Cl B r*N-I PhNC1-NIBr, or successful, it, is possible that the diazonium radicle N:NPh- is linketl to the trihalo'id group as a wholc rather than to any single atom ; this would be similar to the hydrogen-nitrogen Iinkiug in the irnide group of pyrazole, tetrazole, and probably azoimide. Attempts to eliminate selected haloid atoms from the above coiiipoundsy. particu- larly in the absence OF solvents which could cause dissociation, were unsuccessful. No pentahaloyds corresponding with CsX, could be isolated, b a t evidence of their probable existence is afforded by thc fact that ail the trihaloi'ds combine with Eromine, iodine, bromine iodide, and chlorine iodide and triiodicle to form dark colonred un- stable oils.The haloids may be employed in considerable excess without t h e benzene nucleus being attackcd ; this is in marked con- trast with aniline and its derivatives ; dimethylaniline rapidly attacks bromine water ; tri~nethylphenylammonium salts, like the diazoniurn salts, are without action ; this also favours the diazonium constitm- tion. Most of the dixzoiodides are unstable, and are possibly syn- derivatives. Diazomesitylene iodide, which will be described later, is exceptional in this respect, and, with alcoholic solution of iodine, yields mesityldiaxoniuiir t?*iiodide, C6H2Me3N,13, which crystallises iii dark brown needles with a blue i-eflex, a n d decomposes at about 70".Benzenediazoiiiunz chlorodiiodide, PhN,ClI,, .prepared from the di- azoninm chloride and alcoholic iodine solution in molecular proportion, crptallises in dark violet, lustrous needles, melts at 67", is stable in dry air, but is quant itatirely decomposed by water. The dichloriodide, PhN2C121, is formed by the action of alcohol on the preceding com- pound and subsequent precipitation with ether ; the action takes place in two stagm, a portion of the diiodide is resolved into iodo- benzene, nitrogen, and iodine chloi.ide, this then combines with the remaining diiodide forming iodine and the dichloriodide ; the latter is also formed from benzenediazonium chloride and chloi*iodide, itt is stable, crjstallises from alcohol in yellow plates, and melts a t 86-87".The bronzodiiodide, PhK2Br12, is prepared like the pre- ceding compouncls, and crystallises in lustrous, brownish-red needles. The dibronziodide, PhN2Bi;I, is obtained in n similar manner to the dichloro-derivative, and also from benzeiiediazoniuni tribromide and iodine ; i t forms brown crystals, and decomposes a t f7". The chloro- dibromide, PbN,CIBr,, prepared by the action of benzenediazonium chloride and bromine in chloroform solution, is a reddish-yellow, crystalline powder ; i t melts at 6l0, and is comparat,ively unstable. The Zwomodichloriclc, PhN,Bi.CI,, is formed by the action of chlorine Ph*r*Br94 ABSTRAOTS OF CEEMICAL PAPERS.on the tribromide in chloroform solution ; it crptallises from alcohol in pale yellow needles, melts at 63", and is imtnediately decomposed by water. The chloi*obronziodide, PhN,ClBrl, is formed from the diazoninm chloride or bromide by the action of bromine iodide and chlorine iodide respectively ; it is heposited in golden needles melting a t 80--81°. Parahromobenzenediazoniunz bronaodiiodide, C6H4Br*N2BrI,, can only be prepared a t about -E0, and forms brownish-red plates melting at about 79'. The dibromiodide, C6HpBr*N2Br2T, is obtained, to- gether with parabromiodobenzene, by heating the preceding com- pound with alcohol or glacial acetic acid, and also from the diszonium bromide and bromine iodide or iodine; it crystallises in brownish- yellow needles, melts and decomposes at 106-107°.The chloro- bromiodide, C6H4Br*N2C1BrI, is comparatively stable, and crystallises in golden needles melting a t 111-112'. The paranitrobenzenediazonium trihaloids are much less stable than the above compounds ; attempts to prepare the chlorodiiodide were unsuccessful, its even at very low temperatures nitrogen is evolved and paranitroiodobenzene is formed. Paranitrobenzenediazonium di- chloriodide, NO2.C6H4*NpCI2I, melts and decomposes a t 106'. The chlorobromiodide, No2*C6H4*N2C1BrI, forms yellow crystals, melts at 93", and, with alcohol, yields bromoparanitrobenzene. p-Laetylphenylhydrazide : Phenylhydraeine Citrate and Tartrate. By HESRY J.l?. DE VRIES (Ber., 1895,28,26ll--ZGl2).- p- Lactylphenylhydrazide, NHPh*NH*CO*CHMe*OH, is formed when phenjlhydrazine and lactic acid are heated together at 130-140' ; it forms white crystals, which melt at 114.5'. Phenylhydrazine citrate melts at 102'. PhenyEhydrazim d-tartrate probably has the formula, (N2H3Ph),C,H6o6 + 3H20, and turns brown in the air. Phen ylazocarboxylamide and Phenylazocarboxylic acid. By JOHAN N ES TH I EL E (Be?.. , 1895, 2 8, 2599-260 1 ) .- P hen y lazocarbox yl- amide, NPh:N*CONH2 (Widman, Abstr., 1895, i, 603), when it is formed in presence of water., crystallises with 2H20 as an orange- yellow powder that melts a t 84" ; i t readily loses its water by deli- quescence, or when recrystallised from organic solvents, and then forms red needles melting at 114".Its (mono-) potassiu?n derivative forms dark red plates. Potassium phenylazocarbozylate, NPh:N*COOK, is obtained by the action of potash on phenylazocarboxylamide, or by the oxidation of phenylsemicarbazide in alkaline solution ; it c r p t a l - lises in orange-red needles, and is decomposed by water. p-Pv~aphthyZazocarbolcyZa?nide is obtained, though much less easily than the phenyl compound, by the oxidation of /%naphthylsemicar- bazide ; it forms orange-red crystals, and melts a t 137-138'. J . B. T. A. H. C. F. B. Ketones from Propenyl Compounds. By Owo WALLACH and F. J. POKD (Ber., 1895, 28, 2714-2728).--1 anethoil is converted into the dibromide, and the latter treated with sodium methoxide, an oil is formed which contains the componnd, OMe*C6H4-C(OMe):CH&fe;ORQANIC DEEMISTRY.95 if the crude product of the action is distilled with steam, eth?yZ nnisyl ketone, OMe*CsHA*CO*CH,Me, is obtained ; this rnelts at 26-27', and boils a t 136-139' under 12 nim. pressure, at 265-270° under atmo- spheric pressure ; the osirne melts a t 74", the senticarbazoize a t 172-173". When oxidised with permanganate, the ketone yields anisic acid and a ketonic acid, OMe*C,H,*CO*COOH, which melts at 75", and is very soluble in water. When it is heated with strong sniphuric acid at. 200", some propionic acid is formed. Tsosafrole, CH2:O2:CsH3*CH:CHMe, and ethylisoaugenol, OMe*CsH3( OE t) CH:CHMe, behave in exactly the same way, the ketone formed always contain- ing the carhonjl group directly attached to the benzene ring.The ketone, CH2:O2:C,H,*CO*CH?Me, me1 ts a t 39", and boils a t 15.3-154' under 13 mm. pressure; the oxinzc nielts at 104". It is probably identical with the ketone obtained by Angeli (Abstr., 1892, 119S), and perhaps also with another obtained by Tonnies (Abstr., 1888, 264) from anetho'il nitrite. The ketone, OMe*C6H3(0Et)*CO*CH2Me, melts a t 62", and boils at 155' under 13 mm. pressure ; the owime melts at 114", the semicarbazone a t 1 7 5 O . When oxidised, it jields two acids, one sparingly soluble in water and melting a t 190°, the other (? ketonic) easily soluble, and melting at 64-45". The ketone is doubtless identical with that obtained by Hell and Portmann (Abstr., 1895, i, 657). C. F. B. Etherification and Hydrolysis.By RUDOLF WEGSCHEIDER ( B e y . , 1895, 28, 2%35-2536 ; compare Abstr., 1895, i, 499).-The author, in reply to Meyer (Ber., 1895, 28, 1798), maintains his former criticism of Iteyer's theory of the etherification of substituted ethereal carb- oxylates. He also criticises Briihl's treatment (Ber., 1895, 28, 1913) of the same question. Dinitrobenzoic acids. By Ftr. GBELL (Bey., 1895, 28, 2564- 2565).--2 : 5-Dinitrobenzoic acid can be obtained by oxidising with nitric acid at 140-130" the 2 : 5-dinitrotoluene obtained by Sand- meyer's reaction from 5-nitro-orthotoluidine. I n t h e same way, 2 : 3-dinitrobenzoic arid can be obtained from 2 : 3-dinitrotoluene, the latter being obtained when 8-acetotoluidide is nitrated, and the resulting 3-nitro-derivative treated with nitrous acid and cuprous oxide ; the acid melts a t 201°, the bariwn salt crystallises with 4H20.By EUGEA- BAMBEHGER (A.nnnZr?c, 1895, 288, 134-138 ; compare Abstr., 1893, i, 592).-1n ordep to establish the identity of the acid obtained by oxidising dihydronap h- tho1 with potassium permmganate (Eoc. cit.), isocoumarincarboxy lic acid was reduced with sodium amalgam, the product being identical with dihydroisocoumarincarboxylic acid, as already described. When isocoumarincarboxylic acid is treated during one hour with boiling, aqueous caustic soda, orthotoluic acid is produced, oxalic acid being formed a t the same time. Other ketonic acids undergo analo- gous decomposition ; thus pyruvic acid and phthalonic acid, A. H. C. F. B. Isocoumarincarboxylic acid.96 ABSTRACTS OF CHEMICAL PAPERS.COOH-C,H4*CO*COOH, yield oxalic acid when treated with boiling, aqueous soda, but benzoylformic acid does not behave in this way. The Red Isomeride of Indigotin; Derivatives of Isatin. 1 3 ~ EDWARD MCHUKCR and LEO MARCHLEW~KI (Bey., 1895, 28, 2525- 2531 ; compare Abstr., 1895, i, 288).-The three substances which liave been described as red isomerides of indigotin have been proved by the authors to be identical ; this identity is further shown by tthe fact that they all yield the same substance when treaked with zinc dust in presence of acetic anhydride and dehpdrated sodium acetate. This product crystallises in faintly pink, lustrous needles melting at 2043. M. 0. E’. It appears to be ncetylhzdileiiciu, by the reduction of pararnethylisatin chloride.I t crystallises i n chocolate-brown needles, and closely resembles indirubin. Isscrtiirmethylphenyl h ydruzoue, NMeP h*N:C< OH)>^, C-,H, - crystallises in orange needles melting at 172-17P; i t is strictly analogous to isatinphenylhydrazone, and ii; is, therefore, probable that both of these substances are true hydrazoiies, and not azo-compounds, since the ‘‘ mobile” hydrogen of the hydrazone is replaced by methyl in the methylhydrazone. lsntiizacetylmethylplisnylhydrazo~~e forms yellow needles melting a t 145’. _Tsnfi.12-P-naphth2jlhydrazolLe crystnl- lises i n dark yellow needles melting at 234’. Isatin readily reacts with orthophenylenediamine, isatohydropheu- aziTe, C14HSNR, being obtained; it is as yet doubtful whether this substance is a derivative of isatin or of pseudo-isatin.It crystallises in yellow needles which melt at 285--887’, and can be sublimed ; it is stable towards acids aiid alkalis, and is insoluble in the latter. The silcer salt is rz reddish-bromii powder. The acetyl deri?;ative melts at ‘ L O d O . lMetnchZorisatoh ydrophenaziiLe, CI4H&1N3, is prepared f porn meta- chlorisatin and orthophenylenediamine, and crystallises in sparingly soluble, yellow needles. Its silver salt is an orange coloured pre- cipitate. The acettjl compound melts at 215’. A. H. Reduction Products of Azo-compounds. By PAUL JACOBSON (Bey., 1895, 28, 2541-2558 ; compare abstr., 1895, i, 26).-The main object of the following research was to experimentally determine whether ortho- and meta-methylazobenzene and metazotoluene undergo the normal reaction when converted into benzidine derira- tives; all the three compounds were found to yield derivatives of paradiamidodiphenyl.Many of the substances described have already formed the subjects of patents. I. With W. LIscHKE.-Ort,homethylazobenzene is a red oil which boils a t 180-18lo (cori-.) under 20 mm. pressure. The hydraxo-ORGANIC CHEMISTRY. 97 cornpound melts a t 101'. 3-JIethyZbenxidiiie [Me : (KH2)2 = 3 : 4 : 4'1 is a syrup which conld not he obtained crystnllised. Its dibeuzylideite d e r i m t ive, C H P h K C ,H ,* c1 H,Me*N : C I3 P h , forms ye 1 1 o mi s h tablets melting a t 134". 4 : 4'-DiioJo-3-~i~etliyZ~~~7ie~~~Z, C6H,I*C6H3&~cI, is obtained by means of the diazo-reaction from methylbenzidine.It forms rosettes of needles, and melts a t 109'. When it is distilled with zinc dust, it yields metaphengltoluece, identical with the hydrocarbon which has been described by Adam (Abstr., 1888, 959). It follows from this, that methylbenzidine has been formed from orthomethylhydrazo- benzene in the normal manner. IT. With A. w. N~~h.~~~A.-~~etaine~hylazobenzene is usually pre- pared (German Patent, KO. 54,599) by the elimination of the amido- group from the condensation product formed from diazobenzene chloride and orthotoluidine; it may also be obtained by the con- densation of metanitrotolueiie with aniline in the presence of alkalis. It crystallises ill prisms, melts a t 18-19', boils at 175' (pressure = 19 mm.), and h a s t,he sp. gr. 1.065 at 20°/4'.Metanzethylli ydrazobemvie, NHPh*lu'HC6H4Me, crjstallises in yellow- ish needles, and melts at 59-61". The corresponding 2-methylbenzidine (4 : 4-dianaido-2-nzetl~yZdi- pkeizyl) cannot be obtained in the crystalline form. The hydmhlorid:. forms long needles. The diacetyl derivative crystallises in pointed prisms which do not melt when heated to 300'. The dibenzylidew derivative crystallises in groups of small needles and melts a t 11 1 -1 12'. OH.C6HA*C H: N*C6H4* C6H3Me*N:C H*C6H4*OH, crystallises i n slender prisms which me1 t indefinitely at about 160'. 4 : 4'-Diioao-'L-,iaethyZdipheil.yi forms arborescent crystals melting at 114-116'. 4 : 4'-Diliydroxy-2-methyldiphelz?/E crystallises in lustroue plates melting at 155-157'. When the diiodo-derivative is distilled with zinc dust, i t yields orthophenyltoluene, identical with the hydrocarbon described by Odd0 and Curatolo (Abstr,, 1895, i, 606).The formation of the benzidine compound in this case is, therefore, normal. 111. With 0. FAerA~.-Metazotolnene, together with some of its derivatives, has already bcen described by Buchka and Schachte- beck (Abstr., 1889, 701 ). The dibenzylidem dcrivative of the corresponding tolidbe, C12H,91e2(N:CHPh), [= 2 : 2' : 4 : 4'1, crys- tallises in stellate groups of light yellow tablets melting at 17%--173", '1% e diort hohydro2.y bemy liclene derivative melts a t 198-1 96'. This tolidine was then conirerted into the diiodo-derivative, and this. without compIete purification, distilled with zinc dust. The hydrocarbon produced is conrerted by oxidation into diphenic acid, and is therefore ortlioditolyl.The conversion of the Iiydrazc- compound into tolicline has, therefore, also proceeded normally in this case. IV. With K. MICHAELIS, and A. W. NANNJN~A.--~ : 4-Dirnethyltrzo- Oewene, CGH3Me2*N2Ph, prepared from metaxylidinc and nitrobenzene, boils a t %05--215" (pressure = 50 rnrn.), and lias the sp. gr. 1.071 a t The tliortl~ol~ ydrozy bewylideue derivative,98 ABSTRACTS OF CHEMICAL PAPERS. 20°/40. The h ~ d r a z o - c o ~ ~ ~ p o ~ c n d cvystallises in white needles melting at 77-79". 4 : 3'-Dimethylazobenzene, C,H,Jle-N,*C6H,Me, which has been prc- viously obtained by Ziiicke and Lawson (Abstr., 1886, 795), ma.y also be prepared from paratoluidine and metanitrotoluene. It crystallises in red needles melting at 55".The corresponding hydruzo-compo~c~icZ crystallises in colourless six-sided tablets and melts at 74'. A. H. Isomeride of Hydroxydiphenylethylamine. By HENRYK G. SODER~AIJM (Be,.., 1895, 28, 2522-2524).-The author has obtained, in the prepayation of hydroxydiphenylethylamine, an isomeric sub- stance which appears to be identical with t h e compound obtaiued by Erleumeyer by the condensation of benzaldehyde with glycocine (Abstr., 1895, i, 596), and by Polonowska by the reduction of benzile- monoxime (Abstr., 1888, 485). It melts at 1 2 9 O , and forms a Jryd~o- chloride which at first separates as an amorphous mass, but changes into slender needles. The plati~zochtoride, 2CI4H uNO,H,PtCl,, is pnhydrous, and melts at 213'.A. H. Stilbene Dibromides and Monobromostilbenes. By JOHANNES WISLICEN'US and FELIX SEELER (Ber., 1895,28, 2693-2703).-When stilbene is treated with bromine in carbon bisulphide solution, two, doubtless geometi*icxlly isomeric, dibromides are formed ; the less soluble a-compound melts at 237", the more soluble p-(iso)com- pound at 110-110.5°. The a-compound is always the main product, and so would appear to be the normal additive product of ordinary ~tilbene, but if that be so, i t is remarkable that increase of tempera- ture or of light intensity during the operation causes a large:. .amount of i t to be formed; as a rule the amount of the abnormal product is increased thereby. Either of the two dibromides under- goes a partial conversion into the otlier when heated.Both yield monobromostilbenes, when treated with alcoholic potash ; the a-com- pound yields an oil, the /?-compound crystals melting at 31". These bromosbilbenes both yield tolane when treated with alcoholic potash, but the crystallised compound does this very much more readily than the uthei., and heuce has the hydrogen and bromiue a toms in corresponding positions. From this the stereocheniicnl formuloe of the other compounds mentioned can be deduced. S tilbene S tilbene. dibromides. YPhBrH Ph$*H P h*C*H CPhBrH Phi I e- a. m. p. 237' symmetrical. (Meso-tartaric). YPhBrH Ph$*H HC-Ph CHBrPh Central- B. m. p. 110' symmetrical. (Racemic). 3 3 Monobromo- stil benes. Tolane. Ph-G-H Br* C*Ph e Oil. Central- \ Cph / CPh symmet,rical. I l l * Ph*f?H Ph*C*Br M.p. 31". Plane- symmetrica I.ORGAN10 CHEnIISTRT. 99 The dibromides are thus represented as derived from isomeric stilbenes ; the authors were, however, unable to obtain satisfactoiy evidence that stilberie does exist in two configurations. By HG. PREY (Ber., 1895, 28, 2514-2521).-Sodium decomposes ethylic oxalate into etliylic carbonate and carbouic oxide. When a solution of ethylic oxalate and bromobenzene in ether is treated with sodium, a mixture of hydrogen and carbonic oxide is evolved and triphenylcarbinol is formed together with benzoic acid. It is probable that the bromo- benzene is first converted into benzaldehyde or benzophenone by the carbonic oxide and hydrogen in presence of sodium, aud that the tri- phenylcarbinol is obtain-ed from this. The product actually contains n small amount of henzaldehyde, and both this substance and benzo- phenone yield tyiphenylcarbinol when they are mixed with bromo- benzene in etheteal solution aiid treated with sodium. The yield obtained from benzophenone is almost quanhitative.The author has attempted to prepare the corresponding derivative from acetone and methylic iodide, but without success, isopropylic alcohol being the chief product. Parabrornmiline, moreover, does not yield pararosaiiiline when treated with sodium rtnd ethylic oxalate, although nitrogen compounds of high melting point are formed. Alicyclic Derivatives of Naphthalene. By EUG EN BAM RERGER, and WILHELM LODTER. [with BERNHARD DEICKE! ( A n n u l e n , 1895,288, 74-1 33 ; compare Abstr., 1893, i, 591, and 1894, i, 419).-1 he paper coutains a detailed account of the preparation and properties of those derivatives which have been already described (Eoc.cit.), aiid the follow- ing facts (obtained in conj~ziictiou with B. Deicke) are also recorded, The hydrochloride and picrate of 2-dimet hylamido-3-hydroxy- tetrahydronaphthalene, CSHA<~ H,.CH-T.OH , melt at 180-181° nnd 182" i*espectively ; the awochloride crystallises in lustrous, yellow needles, and the pZatinochZoride forms orange-red leaflets. The methiodide crgstallises from water in long, lushi~ous prisms, and melts at 201", and the benzoate crystallises in aggregates of needles ; the latter has powerful toxic properties. The hydrochloride and picrate of 2-diethylamido-3-hydroxytetra- hJdronaphthalene (diethyltetrahydronaphtbylalkine) melt at 167- 1'10" and 170.5-1 71" respectively ; the a w o c h h - i d e crystallises in yellow leaflets or needles, and the pZatinochZoriiZe is orange-red.The 7Izetltiodide crjstallkes in white leaflets and melts at 151.5', and the beuzoate separates from alcohol in reddish-yellow, lustrous needles ; the latter forms a picrate which crystallises in yellow needles. The auwxhloride of 2-piperidyI-3-hydroxytetraliydronaplithalene crystallises in yellow leaflets, and the platinochloride separates from water in orange-red crystals. C. P. B. Formation of Triphenylcarbinol. A. H. CH,*$lH*NM e, Trimethyl-3-hydroxytetrahydronaphthylammonium chloride, CH,*QH*NMe,Cl csH4<c Hs' CH.0 H '100 ABSTRACTS OF CKEMIOAL PAPERS. forms crystals belonging to the monoclinic system : a : b : c = 1.0854 : 1 : 0.5081 ; /3 = 67' 43'.Precipitates similar to those formed Is!- choline are produced when the chloride is treated with common reagents for the detection of a!kalo'ids. The platinochloride crystal- lises in orange needles and melts a t 222-2235' ; tlie airrochloride separates from water in lustrous, golden-yellow leaflets, arid melts a t 132-154'. The p'crale crystallises in flat needles, and melts at 161-162". The hydrochloride of bishydroxytekrahydronaphthylamine, NH,(CloH,,*OH)zCl [NH : OH = 2 : 31, scparates from alcohol on adding ether in lustrous, white needles. The platinochloride, which is only sparingly soluble in cold water, crystallises in light-orango needles which melt and decompose at 835" ; the aurichloride crystallises in lustrous, yellow leaflets.The platinochloride of 2 : 3-hydroxytetrahydronaphthy:amine cq-s- tallises in reddish-yellow prisms, and the auyichloride forms needles. The picrate dissolves in hot water, and crystallises in needles. M. 0. F. Tetralkyldiamidoazonaphthalenes. By PAur, COH x (Monatsh., 1895, 16, 798-8806).-TetramethyZdiamido-a-azonuphthnlene is ob- tained on passing nitric oxide for two or three weeks through an alcoholic solution of a-dimethylnaphtbylaminc (compare Lippmann and E'leissner, Abstr., 1883, 55, 184, 868, 1100). It separates from alcohol, in which i t is only'sparingly soluble, in brownish-red, dichroic crystals, sinters a t 140', and melts at 145' ; it. yields a yellowish-brcwn cry st d l i ti e picraf e, C2rHz4N4,2CsH2( N02),*OH, which is a1 most in- soluble in boiling orgmic solvents, and, on reduction with stannous chloride in hydrochloric acid solution, forms paradimethylamido- napbthylamine (compare Friedlander and Welmana, Abstr., 1189, 150).Tetreth yldia?iiido-2-azoiLaphf halcnc, obtained in a similar manner to that employed in preparing the tetramethyl compound, crystallises i n reddish-yellow, rhombic plates, gives, with hgdrochloric acid, a blue coloration, which.is destroyed on the addition of water, and melts a t 143' to a reddish-brown liquid ; it yields a p k r a t e , C2,H&N,,2CsH,( KO?)s*OH: which crrstallises in reddish-brown necdles, is spariiigly dissolved by ordinary solvents, and melts and decomposes a t 200'. Dipropyl-a-naplithylnmiiie, C16H21N, obtained on heating a mixtiire of a-naphthylamine, potash so111 tion, and normal propylic iodide under pressure at 180', boils at 300', has a specific gravity of 0.9935 at 20°, yields a hydrochloride, C16H21N,HCI,H20, which crystallises in white kedles, a hyd&dide, C16H21N,HI, which crystallises in yellow, felted needles, and a yellow platinocldoride, (C,,H21~)2,H2PtC16, which darkens a t 160", and melts and decomposes at 212'.No definite azo-compound could be obtained by the action of nitric oxide on d iproyyl- a-nap h t hy lami 11 e. G. T. M.ORGANIC CHEMISTRY. 101 Terpenes and Ethereal Oils. Phellandrene. By OTTO WAL- IACH and AD. HEIWIG (Annctlen, 189.3, 287, 371-3843 compare Abstr., 1887, 965 ; 1888, 1204).-The result of the author's investi- gation shows that reduction of phellandrene nitrite gives rise to optically active tetrahydrocxrvone, tetrahydrocarveole, and tetra- hydrocarvylamine, the inactive modifications of which have been already described (Abstr., 1894, i, 44) as arising from carvenone (Abstr., 1895, i, 622), on reducing it with sodium and alcohol ; on pre- paring racemic mixtures of the compounds from d- and I-phellandrene, inactive tetmhydro-derivatives of the carvone series are obtained.Phellandrene nitrite, which melts at 105", is prepared in the fol- lowing manner ; 100 grams of hydrocarbon, rich in phellandrene, are placed in a beaker surrounded by a freezing mixture, along with 400 grams of petroleum, and covered with dilute salphuric acid, prepared by mixing 37 grams of the coiiceritrated acid with twice its volume of water ; 230 grams of a 44 per cent.solution of sodium nitrite is then slowly added, the temperature being maintained below 4", and the liquid gently stirred from time to time. Eucalyptus oil was em- ployed as the source of I-phellandrene, bitter fennel oil being used when derivatives of d-phellandrene were required. When phellandrene nitrite is treated with alcoholic sodium ethoxide, i t becomes red, heat being generated and nitrous oxide liberated ; in this way, npale yellow oil is obtained, which boils a t 134-138', aud has a penetrating odour ; it is identical with the " nitrophellandrene " describefi by Pesci (Abstr., 1886, 1038). On reducing phellandrene nitrite, or the foregoing compound dissolved in absolute alcohol, with sodium, the ketone, CIOHIBO, the alcohol CloH200, and the base CloH19*W€Z, are obtaiiied.The ketone boils a t 90-100" under a pressure of 15 mm., and yields a dextrorotatory oxime, which crystallises in needles, a i d melts a t 97-98' ; the sernicarbazo?ae melts a t 185-187'. The alcohol (tetrahydrocarveole) is obtained on reducing the ketone wit.11 sodium and alcohol; it boils at 100-104°under a pressure of 12 mm. The base (tetrnhydl.ocarv?lIamine, Abstr., 1894, i, 44) boils at 210-212', and absorbs carbonic anhydride. The hydrochloride melts at 199--204", and the acefyl derivative :tt 158-159" ; the carbanride and phenylcarbamide melt at 201-203O and 185-186' respectively. When sodium nitrite is added to a feebly acid solution of the hydro- chloride, the alcohol is produced, and this substance, on oxidatioxi, yields the ketone.The authors discuss the constitution of phellnndrene. Pinole. M. 0. F. By Om0 WALLACH (Bey., 1895, 28, 2708--2713).--The anthor has modified the formula. he previously gave to pinole (Abstr., C H,* C H: CMe , CH as the most 1895, i, 59), and now regards CEI------CH2- probable, although it does not satisfactorily explain all the reactions ; in deducing it, regard was had to the fact that terpineole appears to have an hydroxyl group in a side chain. If pinole glycol is prepared from pirole by direct oxidation, a,nd also by means of the dibromide of the latter, the properties of the two samples are not qcite identical. VOJI. LXK i. i / 'CMez-- 0'102 ABSTRAGTS OF OHEMICAL PAPERS.The ketone, CIOHIBO, prepayed by reducing pinole tribromide (loc. cit.) in acid solution, has been obtained pure by means of its semicsrbazone; it boils a t 214-217'; a t 20' its sp. gr. = 0.916, and index of refraction ?zD = 1.46603; the semicarbazone melts a t 158"; the oxime boils a t 150" under 15 mm. pressure, and can be reduced to a base C10Hl,*NH2, the hydrochloride of which can be transformed into a carbamide, CloH17.NH*CO*NH2, melting a t 188O. The ketone probably contains one ethylene linking, possibly in a'side chain in which it is probable that the oxygen atom also is contained. The alcohol, CloH180, obtained by reducing the pure ketone, boils at 108" under 15 mm. pressure, has sp. gr. = 0.913, and index of refrac- tion ?aD = 1.47292 at 18". If pinole tribromide is treated with silver acetate in the cold, a compound, CloHl,Br,O*OAc is formed ; if heat is employed, an acetate containing no bromine is obtained, the semicarb- azoiie of which melts a t 177-178". By OTTO WALLACH (Ber., 1895, 28, 2703-2707) .-When dihydrocarvone is oxidised, two ketones are formed, in addition to various acids, including oxalic acid and a a acid that melts a t 205-204", and contains 59.43 and 8-33 per cent. of carbon and hydrogen respectively.The ketone formed i n larger quantity melts at 115-120°, and boils a t about 200" under 100 mm. pressure; it is a ketoglycol, CIOH1803, the oxime of which, C,,H,,O,:NOH, melts at 202", and the seinicarbazone a t 187"; when boiled for a long time with dilute sulphuric acid, it yields a ketone, boiling at 220', the semicarbarone of which melts a t 206'. The second of the two original ketones boils at about 130" under 10 mm.pressure, and solidifies in a freezing mixture ; i t is a diketone, C9HI4O2 ; its oxime and sernicarbazone melt at 195' and 203-204' respectively ; it can be obtained from the ketoglycol by further oxidation. By ARNOLD HESS (Bey., 1895, 28, 2687- 2693).-Pure camphoronic acid, G9H1406, melts at 148-150" when it is placed i n a bath at 136O, and the latter rapidly heated. When it is slowly heated, starting from the ordinary temperature, it is con- verted for the most part into the anhydride. It yields a triethylic, together with the diethylic, salt when it8 solution in absolnte alcohol is saturated with gaseous hydrogen chloride ; it boils at 295-300'.When the diethylic salt is treated with alcoholic ammonia, it yields ammonium ethylic camphoronamate, melting a t 144--145O; this can also be obtained by the action of ammonia on eth ylic anhydrocamphoronate, 0: C20 I:C6H,l*COOEt. When boiled with aqueous alkalis, it yields camphoronimic acid, NH:C2O2:C6Hl,-COOH, melting at 210". When the above-mentioned diethylic salt is heated at 120-130' with alcoholic ammonia, OF when a benzene solution of anhydrocamphoronic acid is saturated with ammonia and then heated a t 140°, ammonium cumphoronimate, NH:CzO2:C6Hll-COONH~, melting at 175O, is formed ; this only loses half of its nitrogen when boiled with aqueous alkalis. By heating C. F. B. Oxidation Products of Dihydrocarvone. C. F. B. Camphoronic acid.NH2*CO0C6Hl1 (CO OE t)*CO ONHI,ORGANIC OHEMISTRY. 103 triethylic camphoronate with alcoholic ammonia a t 1 7O-l9OG, a €ew crystals, melting a.t 210-218', were obtained ; these were possibly camphoronimic amide, NH:C20,:C6Hl ,*C 0 NH,. C. F. B. Compounds from Lichens. Atranoric acid and Substances accompanying it. By WIramM ZOPF (Annalen, 1895,288,38-74 ; compare Abstr., 1895, i, 297).-Atranoric acid is the substance first isolated from Lecaitora a t m (Hudson) by Paternb and Oglialoro (this Journal, 1877, ii, 986) ; its presence in Cladonia miigiforniis (Schaerer) and Stereocadon ceszccianum (Pers.) has been since observed by Paternb, and its existence in the dissimilar groups, to which the first-named lichen and the last two belong, has led the author to conduct a systematic search for atranoric acid among 33 different varieties. The investigation has revealed the presence of this acid in the lichens Stereocaulon nlpinum (Laurel.), S.coyalloicles (Fries), X. incrustatum (Florke), S. denudaturn (Florke), xnr. geiauinum (Fries), 8. fonzentosum (Fries), X. pileaticm (Acharins). S. condensatirm (Hoffmannj, S. paschale (L. and Fries), S. virgatum (Ach.), forina pTiinaria (Wainio), 8. Tarnulosum (Ach.), Physcicc cwia (Hoff mann), 2'. pulvemlenta (Schreber), var. P-pityrett (Ach.), P. endo- coccina (Korber), P. fenella (Ach.), P. aipolia (Ach.), Anaptychia ciliaris (L.) , A . speciosa (Wulf), Parmelin encausta (Sommerfelt), P. pertusa (Schrk.), Parmeliopsis hypempta (Ach, and Nyl.), Hceiircc- tomma coccineuni (Dickson) , Placodiwna saxicol m a (Poll.), and P.i)ielnnaspis (Ach. and Fries), in addition t o those already mentioned. The cortex of the thallus i s stained yellow by alkalis in the case of those species which contain an appreciable amount of atranoric acid, the coloration being very feeble when the acid is present in small quantity; the test, however, is not trustworthy, as a yellow stain with alkalis may arise from the presence of evernic 01' thamnolic acids. The lichens Ecenzatoninta centosum ( L.), Placodiunt o.adiosurn (Hoffmann), Cladonia comztta (Ach.), C. gracilis (L.) f o r a a chorduIis (Florke), c'. g., formn mpem, C. ntacilenta (Ehrb.), C. furcatn (Hudson) forma polyphylln (Florke), and C. spmmosa (Hoffmann), do not con- tain atranoric acid, and Placodizmz crassum (Hudson), ider?tical with Psoyoma Crassuwi, caT.cwspitosuni (Schaerer), contains oniy n trace of it. Atranoric acid, Cl9Hl6O8, has been already described by Paternb and Oglialoro (loc. cit.) ; it separates from chlorofoi-m in crystals several millimetres in length, and melts a t 195-197'. The crystals belong to the rhorubic system ; a : b : c = 0.7773 : I : 1.2808. A h - noric acid yields with alkalis R yellow solution, from which it is pre- cipitated by carbonic anhydride ; a yellow coloration is developed on dissolving the substance iri conceiitrated sulphuric acid, and the alco- holic solution becomes purple-red with ferric chloride. Hcematonmic acid, Cll€T1205, is obtained by heating atranoric acid (1 gram) with absolute alcohol (40 c.c.) in a sealed tube at 150' for oue hour; it crystallises from dilute dcohol in snow-white, silky needles, and melts st 113--114".It is exceedingly soluble in hot alcohol, and also dissolves in cold ethei-, chloroform, aud benzene, whilst cold alcohol and light petroleum dissolve it b u t sparingly ; the substance dissolves in alkalis and alkali carbonates, formicg a yellow104 ABSTRACTS OF CHEMICAL PAPERS. solution, from which it is precipitated by carbonic anhydride, and the alcoholic solution develops a purple-brown coloration with ferric chloride. When an alcoholic solution of atrnnoric acid is boiled for mahy hours in a reflux apparatus, h3ernatommic acid is produced ; it is, therefore, undesirable to employ boiling alcohol in recrystallising atranoric acid, and prolonged treatment of the lichens with boiling alcohol is to be avoided.Hsmatommic acid has been isolated from the lichens Hmntatomma coccineurn and Physcia ccesia. Hematonzmenic acid, C21H22010, is obtained by heating atranoric acid (9.5 grams) with methylio alcohol (20 c.c.) in a sealed tube at 150' for one hour ; it crystallises from a mixture of methylic alcohol and chloroform in thread-li ke aggregates of colouyless needles, and melts a t 146-14'i0. The solution in alkalis and alkali carbonates is yellowish-green, and the acid is precipitated by carbonic anhydride. Omrnatic acid is formed when atranoric acid is heated with propylic alcohol in a sealed tube at 150" for one hour; it melts at 75', and dissolves in alkalis and alkali carbonat'es, forming a Fellow solution.In addition to the lichens already mentioned (Abstr., 1895, i, 298), Lecanom (Zeora) scrdida, Hamatornma C O C C ~ ~ L ~ ~ L ~ L , and Placodlzcm saxicolzim contain zeorin, which crys tallises from chloroform or abso- lute alcohol in hexagonal double pyramids ; it melts a t 247-252", and is insoluble in hot alkalis. When treated with boiling alcohol and hydrochloric acid, it yields zeorinii~, which c~ystal lises in colour- less, lustrous leaflets, and melts at 182--284O; tbis is insoluble in alkalis, and dissolves in concentrated sulp huric acid with develop- ment of a yellow coloration. Usnic acid has been isolatsd from Hcematonzmn coccinezim and H. ventosuin, whilst the lichens i3te~eocaulorL comlloades, S. incrustaizcm, S.' vesuvianicin, and S.denudatum contain psoromic acid. Placodiit is a copper-red substance obtained from Placodiurn naeka- naspis (Ach. and Fries), identical with 1'. iiijlatunz (Korber) ; it crystallises from absolute alcohol in thin, pleochro'ic plates, and melts and decomposes at 245". It dissolves with difficulty in ether and chloroform, and is nearly insoluble i n benzene ; the solut.ion in caustic soda is violet-brown, and concentrated nitric acid dissolves it with development of a yellow coloration. S;'tc;.eocaulic acid is isolated from Stereocuulon, akinzcm and Lepra chlorina, and crystallises from alcohol in white needles melting at 200-201"; it d'ssolves with difficulty in alcohol, ether, benzene? and chloroform, and carbonic anhydride does not precipitate the acid from its solution in sodium carboilate, which is yellow-.The alco- holic solution develops a violet coloration with ferric chloride. 31. 0. F. Nitro-derivatives of Pyridine. Bg HUGO WEIDEL and ERNST MURMANN (Moizatsh., 1895, 16, 749--759).-The authors obtain pyridine-p-sulphonic acid, in the exceptionally high yield of from 45 to 65 per cent., by the sulphonation of pyridine in presence of anhydrous aluminium sulphate with 33 per cent. anhj-dro-sulphuric acid at 330-350'. The sulphonic acid is first converted into P-hydroxg- pyridine (m. p. lag"), nd asubsequently into its acetyl derivative,ORGANIC CHEMISTRY. 105 and the latter is nitrated by the addition of nitric acid to an ice-cold solution in acetic anhydride ; the action is then completed a t the ordi- nary temperature, the acetic anhydride removed by distillation under diminished pressure, and the residue hydrolysed with sodium hydr- oxide. OD adding hydrochloric acid to the product, a precipitate i s obtained which, ou exhaustion with boiling water, leave9 an insoluhle nitro-/3-hydrozypyridine. This crystal lises f roin alco h ol i 11 du 11, yello \v needles, and melts and decomposes at 295-298" (uncorr.).The aqneoiis solution, on exhaustion with ether, yields a ~iiaitro-/3-hytl?.ox2/pyridilLc! which crystallises from the ethereal solution in dull, yellow needles, and melts a t 133" (uncorr.). A second ?litl.o-P-h!/d,.o,rypyridine crystal- liaes from the aqueous solution in pale, lemon-yellow plates, aiid melts at 210-211° (uncorr.). G. 1'. 31. Direct Introduction of Hydroxyl-groups into Hydroxy - quinolines.By JULIUS DIAMANT (Afonat.sh., 1895, 16, 760-772).- When 1-hydroxyquinoline is heated a t 380°, with 10 times its weight of caustic soda and a little water, hydrogen escapes, and 1 : 2'-dL'- 7/ydroz?lqz~i72oZine, C9HiN02, is formed ; this crystall ises from water i n scales, melts with partial decomposition and sublimation at. a tempera- ture above 260°, andgives a dirty green coloration with ferric chlo- ride. The hydrochloride, CgH7N02, HCl+ H,O, crystallises in yellow- ish-white needles 01' scales, and is very unstable. The acefyl dprimtice, CgHsNOaAc, foibms crystdline scales, and melts :it %44+-247". On oxidation with potassium permnnganate in alkaline solution, the dihydroxyquinoline yields 6-hydroxyquinolinic acid, thus showing that the second hydroxgl-group is in the 2' position. Trih-jdroxyquinoline, C,H,NO,[(OH), = 1 : 2' : ?I, obtained on further heating the above-described dihydroxyquinoline with excess of caustic soda at 380°, crystallises in long, colourless needles ; it is almost insoluble in ordinary solvents, but dissolves i l l borax solution and in alkalis, has an intensely sweet taste, and gives with ferric chloride a dirty green solution, which is turned brown by sodium carbonate.Trihydroxyyuinoline may also be obhined by long-con- tinned heating of hydroxyquinoline with excess of potash. G. T. M. Formation of Thiazole Derivatives from Uric acid. By HUG( I WEIEEL and LADISLAUS NIKIIILOWJCZ (Monatsh., 1895,16, 721-748).- When uric acid (2.5 grams) and ammonium hydrosulphide (15 C.C.of a solution obhained by adding 1 vol. of commercial ammonia to 2 vols. previously saturated with hydrogen sulphide) are heated together for four hours at 1 8 5 O , 3-amidourncyl Zhydrosulphide, is formed. It crystallises from dilute acetic acid and from strong hydrochloric acid in slender needles, which do not melt a t 300°, forms an unstable anhydrous ammonia compound having the composi- tion C4H5N,SO2,NH,, and on the addition of bromine yields uranil, iso- barbituric acid, and other substances. On heating with a large excess i 2106 ABSTRACTS OF CHEMICAL PAPERS. oE acetic anhydride? amidouracrl hydrosulphide yields the crystalli tie metyl derivative, CAH7N3SO3, which is soluble in water, amylic alcohol and acetic acid, with partial decomposition, and melts and deuoni- poses a t a hemperatwe above 300'.On treatment with water, O Y better, with a dilute alkaline solution, the acetyi compound jields the 1i ,.eide of p-met h y 1 - f i - o ~ y th iazole- a-ca r b ox y 1 ic acid, which crystallises in felted masses of small needles, is soluble i n water containing acids and alkalis, dissolves sparingly in alcohol and ethylic acetate, and gives the following salts. An ammonium salt, C,H,N,SO,,RH,*OH, crystallising in hair-like needles ; a sodium s d t , with 2H20, crystallising in colourless needles ; a bariiLrn salt, and an anhydrous crystalline silrer salt, C6H,N3S02Ag. When the ureide 01' its acetyl derivative is boiled with acetic anhydride and sodium acetate until no more carbonic anhydride escapes, and the excess of acetic anhydride is distilled off, the residue contains P-acefyl- nmido-~L-nieth2/lthintole-~-ca~.boxylonit~le.This is insoluble in cold chloroform, but dissolves in the boiling solvent, from which it crystallises on cooling in long needles, and, when quickly heated, me1 t s at 280--285O, undergoing partial sublimation. The residue also occasionally contains the p-acety1a.mido-pL-methylthiazo1e-u-cn,.- Aoxylacetylanzide, which dissolves in cold chloroform and in water, melts at 176-178" (uncorr.), and, on further treatment with acetic acid and sodium acetate, gives the nitrile C,H,N3S0. Each of these products from the residue is converted by dilute hydrochloric acid inbo /3-amido- p- meth y 1 t hiazol e-a- car boxy 1 anzide, C5H,N3S 0 + d H 2 0 , which crystallises in yellowish-white, monoclinic plates, [a : b : c = 2.783 : 1 : 1.2781, is only sparingly soluble in cold watey, melts with decomposition a t a temperature above 300°, and, on fusion with potassium hydroxide a t 260-280", yields a crystalline mixture from which two substances were isolated, one soluble in alcohol and the other insoluble.The insoluble substance, formed only in small quantity, It is ,(3-am~do-~-~~aethy~t~~iazo~e-u-cu~boxy1ac acid, CMe< S *g*NH, 'N-C*COOH' crvstallises from water, in which it is fairlv soluble, in scales. and dgcomposes a t '200". The soluble portion i9' apparently the hydro- c h l o d e of /3-amido-p-methylthiazole, CMeGN.8 ~ , which is S *C*NH2 readily dissolved by water, the solution giving an intense cherry-red coloration with ferric chloride, crystallises in scales, and decomposes at 250'. Azimido-~~-nzet~Lylthiazole-a-ca~bolcylic acid, which crystallises iu yellow scales and decomposes a t 270-280", is obtained on dissolving &amidomethyIthiazolecarboxylamide in hydrochloric acid, adding the requisite quantity of potassium nitrite,ORGAN10 OEEMISTRY.107 bailing tlie solution, evaporating in a vacuum, and finally extracting \v i th alcohol. G.. T. M. Tetrazole Derivatives. By JOHANN vs THIELE arid HARRY 1wi,il: (,hza/eu, 1895, 287, 233-265 ; compare Abstr., 1892, 1295, and 159:3, i, 440).--AmidotetrazoZe is the name by which the authors now refer to arnidotetrazotic acid (Zoc. cit.), which has the constitution, N-x I I The cyanate is obtained by adding potassium cyanate N*NH to an 9.queous solution of the hydrochloride ; it melts above 2.50G, aiid dissolves in dilute hydrochloric acid with liberation of carbonic.anhydride, having the odour of cysnic acid. Boiling water decom- poses the cyanate, giving rise to carbonic anhydride, ammonia, and amidotetrazole ; an alcoholic solution of aniline yields phenyl- carbamide. ZZei~~oyZaPnidotetra=ole dissolves readily in alkalis, and melts and deccmposes above 250” ; the ncetyl derivative crystallises in white leaflets melting a t 2Gg0, and has a strongly acidic reaction. k’uming hydrochloric acid does not attack amidotetrazole at 160-170”, but at 200--210° carbonic anhydride, ammonia, nitrogen, and hy- drazinc are formed, the last-named being produced in theoretical quantity.In preparing beiizylidenetetrazylhydmzine (Zoc. cit.), an improved yield is obtained by regulating the quantity of hydrochloric acid in such a manner that at the conclusion of the operation excess of this agent is a minimum. I I , crystallises froin glacial acetic acid, and sinters at 140-150°, melting at 192”; it is strongly acidic, and does not develop a red coloration with ferric chloride. Acetophenonetetrnzylhydruzone is obtained fi*om aqueous tetrazylhydrazine hydrochloride and alcoholic acetophenone ; it melts at 235O, and dissolves readily in alkali carbonates. Acetow- tet,.ctzyZl~yd/.cczo?~e is prepared from tetrazylhydrazine hydrochloride and acetone in presence of sodium acetate ; it crystallises from water.. and melts at. 181.5O.Tetrnzylsenzicarbazide is formed on mixiug warm, aqueous solutions of potassium cyansta and tetrazylhydraziiie hydrochloride; it melts a t 211’ if slowly heated, a t 218’ when the temperature rises rapidly. The semicarbazide is acidic and stionglly reducing, and is sparingly soluble in cold water ; an alkaline solution of potassium permanganate oxidises i t to tetrazolazocarboxylic acid, of which the sodium derivative was precipitated, ammonia being liberated at the same time. Tetrazylazoimide (diazotetrnzolei~t~ide), I I >CON< I I , is obtained by adding 5 C.C. of concentrated hydrochloric acid mixed with ice to an ice-cold solution of tetrazylhydrazine (2.3 grams) and sodium nitrite (2 grams); it crystallises from benzene in beautiful white needles.When rubbed slightly, or on heating gently, it explodes with greater violence than silver azoimide ; it dissolves readily in water and acetone, but is insoluble in petroleum or ether, >C*NH,. N--N NH*N l’r.iacetyZtet,.azllZhydrnzine, NAc2*NAc*C< N-N N N*NH N108 ABSTRAOTS OF CHEMICAL PAPERS. and yields azoiniide when treated for seveml hours with boiling coii- centrated potash. The silver derivative is insoluble in cold, dilute. nitric acid, and explodes violently in the moist state : the derivative is a, white powder, obtained on passing dry ammonia into a solution of tetrazylazoimide in benzene, and does not explode with greater violence than gunpowder. The ammonium salt is very solnble in water and methylic alcohol, but dissolves less readily in benzene.Fuming nitric acid decomposes tetrazylhydraz ine at 1 W , giving rise to hydrazine, carbonic anhydride, and nitrogen. Dihyd,.obenzyZidenetetraz~lhydl.a~int: is obtained by reducing beii- zylidenetetrazylhydrazine with sodium amdgnm ; it crystallises f t v n i alcohol, and melts and decomposes at 187-191'. The sodium derivn- tive is colourless, and crystallises from dilute alcohol. The dihydro- derivative differs from benzglidenetetrazylhydrnzine in dissolving i i i dilute mineral acids, and forming a sdphate which is sparingly solnl~lc in cold water; it is, moreover, readily osidised by mercuric oxide or an arnmoiiiacal silver solution, whilst these agents attack benzylideiie- tetrazylhydrazine slowly when heated. When the dihydro-compound is treated with boiling hydrochloric o r sulphuric acid, a small quati- tity of benzaldehyde is formed, but a t 1603 hydrochloric acid gives rise to benzylidene chloride and hydrazine.Acetonetetrazylhydrazoiie is indifferent towards sodium amalgam. When sodium diazotetrazolate (Zoc. cit.) is reduced with alcohol, tetrazole is produced ; this crystallises from ethylic acetate in aggre- gates of needles or leaflets, and melts at 156' (compare Bladin, Abstr., 1892, 1009). On heating tet,razole with hydrochloric acid for threc. hours at 200°, animonium chloride is formed, but no hydrazine ; it is completely decomposed by hot, concentrated sulphuiic acid, yielding nitrogen and carbonic oxide. The sodium derivative of tetrazole contains lH20, and crystallises in thin prisms, which dissolve very readily in water.The barium derivative contains 3iH20, and crys- tallises in large, transparent prisms, which become nearly anhydroni; in the exsiccator ; it belongs to the rhombic system, and has a : b : c = .0*5689 : 1 : 0.7217. The conductivity constants of tetrazole, of thr. sodium derivative, and of amidotetrazole have been determined. N-N NMe*N 1.1 :is obtained by heat- MethylamidonzethlJZtetl.azole, NHilIe*C< ing anhydrous amidotetrazole (1 0 grams) with methylic iodide for three hours at 160-165" ; it crystallises from ethylic acetate in leaflets, and begins to decompose at 80'. The substance is very hygroscopic, m d its solution is strongly alkaline. The hydrochloride crys tallises from alcohol in white needles, and melts and decomposes at 241"; the picrate melts and decomposes a t 20.3".The awochloride cry stallises from water in large plates, and melts at 164"; the platinoddoridti crystallises from alcohol in golden-yellow needles, and from water in large prisms, melting at 200". The nifrosamine forms yellow needles, and yields nitrous acid under the influence of dilute mineral acids, nitrogen being evolved on treating it with potash. Methylamidotetruzole crystallises from water in white needles, and me1t.s at 218-220" ; the aqueous solution is neutid. Eth$laiii/&-ORGANIC CEEMISTRP. 109 ethyltetyazole hydrochloride is very soluble in water and alcoliol, and forms white needles melting a t 232-233'. a-BemyZamidotetrmole is obtained by boiling benzylic chloride ( 2 mols.) with amidotetrazole (2 mols.), sodium carbonate (1 mol.), water, and alcohol, until the odour of benzjlic chloride is no longer perceptible ; it melts a t 191-192", and is neutral.P-Be?,z!ylarzlido- tetrazole, CH2Ph.NH*C< I I , is formed on heating amidotetrazole (10 grams) with benzylic chloride (40 grams), caustic potash (50 grams), and dilute alcohol, for six hours ; it melt,s a t 181", and dissolves in alkalis. N-- N NH*N Benzy~a?nidobenzyZtetrazole, N--- N:y N*NCHzPh' fi or CH2Ph*NE*C< N(CH,Ph) N ' C B ,Ph*NH* C< arises from the action of boiling benzylic chloride on anhydrous amido- tetrazole, and is also obtained :is a bye-product in the preparation of a-benzylamidotetrazole ; i t separates from alcohol arid ether in lus- trous crystals, and melts at 88.5". The substance has an alkaline rcaction.The hiydrochloride crystallises in needles, and melts H t !208-209', and the nitrafe at, 122'; the latter salt and the sdphate, which melts a t 173", are sparingly eoluble, and the mh*ite crystallises from ether and melts a t 108". The nitrosarnine crystallises in yellow needles melting at 105", nnd when treated with boiling water yields lrenzyZoxllhenzyItelrazole, which crystallises from alcohol in small needles, and melts a t 106'. P-AmidodiBenzylfetl.nzoZe is most conveniently prepared by heating amidotetrasole (5 grams), with caustic potash (IS grams), benzylic chloride (30 grams), and dilute alcohol in a reflux apparatus for two hours, adding a further qnantity of caustic potash (10 grams), and again heating for two hours, or until the odour of benzylic chloride is no longer perceptible ; it is also formed in the preparation of a- and p-benzylamidotetrazole.It ciytallises from alcohol in lustrous needles, and melts at 169-1iO" ; i t is a neutral substance, arid when oxidised in acid solution with potassium permanpanate yield3 benz- aldehyde. The ~iit/-osarnine crystallises from alcoliol in lustrous, yellow plates, and nielts a t 97-98'. Benz~lben~lllidenebenzy ltetrazylhydruzi~~e, C €3 P h:ru'*N (CHZP h ) * CN4.C HzPh , is obtained by reducing the nitrosamine of benzylaniidobenzyltetrazole in alcoholic solution with zinc dust and glacial acetic acid, and treating the base with alcoholic benzaldehyde ; it, is also formed when benzyl- idenetetrazJ-lhydrazine is treated with boiling benzylic chloride.The substance is insoluble in water, and melts a t 98". Ilenzljlidene-p-di- b e ~ ~ z ~ Z t e t ~ a t y l h ~ d r a z ;ne, C H Ph :N*N*CN4( C H,Ph) *, is ob tai ncd by heat- ing a solution of beiizglidenetetrazylhydraeine in caust ic soda with benzylic chloride for several hours ; it crystallises fi*om alcohol in lustrous leaflets, and melts a t 132-133", yielding benzaldehyde when treated with boiling dilute sillphuric acid. a-Reizzylideizebenzyltetritzylhlldrazi?ze crystallises Pro111 alcoh01, and110 ABSTRACTS OF CHENICAL PAPERS. melts at 161" ; the hydroc7iZo~ide, FvIiicli melts a t 246O, is obtained a8 st bye-product in preparing benzylbenzylidenebenzjltetrnzylhydrazine. a-BenzyltetrazyllL?/drazi?~e is obtained by eliminating benzaldehyde Irom the benzylidene derivative by means of boiling hydrochloric acid ; it crystnllises from water in lustrous leaflets, and melts a t 123".The aqueous solution has a strongly reducing action, and yields the benzylidene derivative when treated wi t,h benzaldchyde. The hydyo- chloride crystallises in long needles, and melts and decomposes at 200". p- Benzylidenebenzyltetrazylhydrazzhe is prepared by heating ben- zylidenetetrazylhydrazine (2 grams) with sodium carbonate ( 1 gram), benzylic chloride (1.3 gram), and a small quantity of water and alcohol; it crystallises from alcohol and melts a t 199'. Boiling mineral acids resolve the substance in to benznldehyde and P-benzyl- t et.razy1 hydrazin e. a - T ~ i b e n z y l t e t ~ a z ~ l l i ~ d m r i ~ ~ e is a bye-product in the formation of Benzylidene-~-dibenzyltetrazylhydrazine, and also arises from treat- ment of tetrazylhydrazine in alkaline solubion with benzylic chloride ; i t crystallises from ethylic acetate in white needles melticg a t 1 5 3 O , and is indifferent towards boiling dilute sulphuric acid.p-l'ribenzyltetrazylIrycE,.aziiLe ia obtained by heating benzglidenetetr- azylhydrazine (2 grams) with benzylic chloride ( 5 grams) and a 25 per cent. solution of caustic soda (10 c.c.), benzaldebyde being elimi- nated. It melts at 121", and is insoluble in acids and alkalis, under- going no change when heated with these agents, 31. 0. F. Effect of Light on Diastase. By JOSEPH R. GREEN (Ann. Agron., 1895, 21, 442-443; from Annals of Bot., 1894, 8, 370).- Sunlight and electric light destroy diastase, the violet rays of the spectrum having thc grcatest eflect, whilst on the other hand, the less refrangible rays have a slightly favourable effect ; the colouring matter of the covering of barley thus protects the diastase from injury by light.Diastase which has been exposed to light, and afterwards kept in darkness, gradually loses its power, the destructive action induced by light continuing. Maltase and the Alcoholic Fermentation of Maltose. By E a m r ; : BOURQUELOT (J. Pharnz., 1895, [GI, 2, 97-103) .-The question whether the enzyme, by which maltose is hydrolysed into glucose, is R chemical individual distinct from the known enzymes, such as dias- tase and invertase, has not j e t been decided. It certainly has not been obtained in a state of purity, for the various preparations that have been made, although possessing the common propevty of hydro- lysing maltose, differ in their powers of hydrolysing other carbohy- drates ; but it is hardly likely, as E.Fischer seems to suppose, that there are many inaltohydrolytic enzymes differing in their powers of hydrolysing other carbohydrates, for all the well-known enzymes of this class are characterised by the limitation of their powers t o the hydrolysis of single carbohydrates. It is now fully established that there is a inaltohydrolytic enzjme in the pancreas and small intestine of various animals, but the ques- N. H. J. &I.ORGANIC CHEMISTRY, 111 tion of the presence of such an enzyme in plants has not hitherto been investigated.The author finds that when the colninoii moulds, Aspe,*gilZus )tiger and PeiiiciZZizirn ghucurn, are cultivatcd in a n aqueous medium containing maltose, with tartaric acid and the usual salts, a, considerable amount of the maltose is hydroljsed into glucose; and by .grinding the moulds with sand, and extracting them with water, liquids can be obtained, from which a maltohydrolytic enzymc is precipitated by alcohol. The lactic fermentation of maltose, like the alcoholic fermentation, is preceded by its hydrolysis ; Fischer’s isolation of glncosazone in the latter case is conclusive, and the author has proved the presence of glucose indirectly in the former case. When chloroform is added t o x solution of maltose, OY of a mixture of maltose and levulose, in alcoholic fermentation, the reducing power of the liquid continues t o increase, whilst the rotatory power diminishes, and this can only be due to the continued formation of glucose by the hydrolytic action of an enzyme, during the suspension of the activity of the yeast. With regard to the presence of a similw enzyme in blood, Dubourg (Inazcg. L h s . , Paris, 1889) has proved that the blood of rabbits kept on an amylaceous diet has the power of hydrolysing maltose. It is thus clear that the assimilation of maltose in animals is always pre- ceded by its hydrolysis into glucose. The author inclines to the opinion that the maltohydrolytic enzyme, maltasc, is a chemical individnal distinct from the other well-known enzymes. JN. W. Preparation of Crystalline Bile acids and their Relation- ship t o Colouring Matters. By RICHTER (Chem. Centr., 1895, i, 282-283; from Deut. Med. Woch., 1894, 21; Vereinsbeilnge, i, 2-3). -Ox bile (250 c.c.) is treated with concenti*ated ferric chloride solution (10-15 c.c.), .and the precipitate dissolved in sulphuric acid (60 per cent.) ; the residue consists chiefly of glycocholic acid; the solution, which contains the taurocholic acid, is f’reed from iron by means of ammonia, the filtrate diluted, sulphuric acid (10 per cent.) added until a precipitate is formed, and then shaken with ether, after 24 hours, crystals of practically pure glycocholic (Y taurocholic) acid are deposited. The two acids may be separated by dissolving them in soda, and acidifying with sulphuric acid ; glycocholic acid is first precipitated, and the taurocholic acid is then deposited as an oil wliicli erystallises after some time. VJhen these acids are treated by Hoppe- S2yler’s method mi th ammol;ia and concentrated sulphuric acid, and the fluorescent product exposed to air, shaken with chloroform, and water added, a violet colour is produced ; this, on fnrther dilution, becomes deep blue, and then changes spontaneously to green. The colours are stable in the dark, but are affected by light., and theii. spectra resemble those of bile pigments. Human bile, and that of an ox suffering from jaundice, gave similar results, but. the glyco- cholic acid appears to be absent. Constitution of Vegetable Proteids. BY € ~ L E C. A. FLGURENT (Compt. rend., 1895, 121, 216--219).-Vegetable proteids can be J. B. T.112 ABSTRACTS OF CHEMICAL PAPERS. divided into two groups, namelg, those, such as gluten, case'in, and vegetable fibrin, in which the ratio of ammoniacal nitrogen estimated to that calculated is greater than uuity, and those, such as legumin and vegetable albumia, in which the ratio is less than unity. The fixed residue from gluten, after boiling with barium hydroxide solu- tioii (Abstr., 1894, i, 214), consists mainly of tryrosine, the caproic leucine, and the leucine, C4H7N02, whilst the fixed residue from legurnin is a mixture of tryrosine, alanine, butalanine, and the diffe- i*ent glucoproteins. I n both animal and vegetable proteids, the water necessary for hydrolysis combines pa,rtly with special groups yielding ammonia, and carbonic, oxalic, and acetic acids, and partly with a special nucleus, yielding a fixed residue. The formula of the fixed residue from vegetable prote'ids, expressed in the simplest general terms, is C,rI12rrN'LOb, whilst that from animal proteids is C,,H211N204. The nucleus of all the vegetable prote'ids examined can be represented by the genernl formula C,lH2,,-dN203, wbilst Schiitzen- berger found for the nucleus o i egg albumin and its congeners the formula CnH2,r--4N202. There is therefore a difference of an atom of oxygen. Ir, both cases, as many molecules of water are necessary to I~ydrolysis as there a1.e atoms of nitrogen present ; in both cases also, liydrolysis takes place in two stages, and it follows that the nucleus of vegetable proteids is a mixture of imido-compounds, which are converted by hrdrolysis into amido-acids. Gluten, case'in, and vege- table fibrin contain a glutamine group, whilst legurnin a.nd vegetable albumin contain an asparagine group (Abstr., 1894, i, 571), and to these respectively is due the departure from unity of the ratios between the found and calculated quant'ities of ammoniacnl nitrogen. The glutamine and asparagine groups do not exist in animal proteids, and Schiitxenberger has found that the quantities of ammoniacal iiitrogen found and calculated aye identical. These groups are the tirst to undergo hydrolysis, and give rise to the ammonia which is obtained by boiling gluten or legumin with alkali solutions under ordinary pressure. C. H. B. Albumoses. By H U G O SCHRij'I'TER (Il.lb?~atsh., 1895, 16, 609-618 ; compare Abstr., 1894, i, 2ll).-The method of distinguishing albu- inoses and peptones proposed by Kuhne is valueless, since these substances and their respective salts all give precipitates with an aqueous solution of ammonium sulphate. Albumoses, however, are perfectly differentiated from peptones by their large percenbage oE nitrogen, by their high molecular weight, and by the still morc important fact that they contain sulphur, whiIst peptones contain none. The generally accepted view, that by the action of ferments or acids, albumin is first of all converted into albumoses, and finally into true peptones, is incorrect. As a matter of fact, when albumin is heated with an acid, a direct conversion into peptones, without the formation of albumoses, takes place, and this is con6rmed by the filct that dburnos?s, when tyeated with an acid, are in a great measure decomposed, and give rise to no peptones. G. T. &I.

ISSN:0368-1769    

DOI:10.1039/CA8967000069

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

70 Analg t i c a l Chemistry. New Forms of Gas Burettes. By 0. BLEIER (Bw., 1895, 28, 2423-2427).--Tn order to avoid inaccuracy in measuring the original volume of gas taken, the burette is made to contain exactly 100 C.C. under the conditions of experiment. The burette is filled with water, and the gas introduced through a tap at the top by allowing the water to run out by a tap at the bottom of the burette. If the gas is readily soluble in water, i t must be passed through the burette for a certain time, in no case more than 30 seconds, in order to saturate the moisture adhering to the walls. A. H. Inertness of Oxidising and Reducing Agents in Analyses in the Wet Way. By XARCELLIN BERTHELOT (Ann. Chim. Phys., 1895, [7], 4, 429432).-The author calls attention to the fact that in the titrstion of persulphuric acid with ferrous sulphate and sul- phuric acid, a discoloration of the liquid often occurs, and the final point is difficult to detect.This leads to erroneous results, and the muse is, probably, that an intermediate compound of persulphuric acid with ferrous sulphate is formed ; this has a most decided colour, is unstable, but is not instantaueouslg reduced. I n cases of tit,ration of persulphuric acid, it is, therefore, better to at once add an excess of ferrous sulphate, and then to titrate back again with permsn- gttnate. Titrations of oxalic acid with potassium permanganate in similar manner, proceed very slowly in the cold, but, in order to complete the reduction quickly, it is merely necessary to add a trace of manganese sulphate.A similar observation has also been mado by Engel (Abstr., 1892, 277). These resultts may be due to the temporary formation of a manganic salt, or to the union of permanganic acid with a manga- iiese salt. J. J. S. Estimation of Water in Commercial Ammonium Sulphate. By JOHN HUGHES (C'hem. News, 1895, 72, 6).-The author calls attention to the importance of always estimating the moisture, and also the free sulphuric acid, in the samples. The water should be estimated by drying at looo, and this shouId be done first in the original sample, and then be repeated after the salt has been finely ground for the purpose of analysis, as the moisture lost during the preparation of the sample may occasionally amount tc! 1 per cent. The analytical results are afterwards calculated into the state of the sample as received.L. DE K. Detection of Chlorine, Bromine, and Iodine in Organic Compounds. By P. N. RAIKOW (Ohem. Zeit., 1895, 19, 902-903). -A fragment of silver nitrate is for it moment gently heated with a little sulphuric acid in a teat tube. After cooling, the substance to be tested is added, and the mixture is again gently heated. If iodine isANA LTTICAL OHEhllSTRY. ‘I1 present, part of it escaps, but some of i t forms a yellow precipitate of silver iodide, which, however, gradually disappears on boiling. Chlorine will be detected by a temporarv white precipitate ; bro- mino by a temporary pale yellow deposit. The process is applicable t o all organic compounds containing halojids. Electrolytic Estimation of the Halogens.By GEORG VORT- MANN (Monatsh., 1895, 16, 674-683) .-The author has previously described a method for the electrolytic estimation of iodine (Abstr., 1894, ii, d26), and now calls attention to several important improve- ments in the process. An anode of pure silver, shaped like a clock- glass, a cathode of platinum or‘ copper, aiid a current which does not exceed 2 volts in the case of cold solutions containing no alka.li t.artrate, or 1.3 volts when $he Bolution is warm and contains alkali tartrates, are employed. The electrolysis is continued until the solu- tion no longer gives the iodine reaction or until a new anode placed i n the solution does not gain in weight. Undor these conditions, no silver is dissolved from the anode, which retains on its surface the whole of the iodine in the form of silver iodide.L. DE K. G. T. M. Estimation of Iodine in Organic Substances. By M. C. SCHUYTEN (Chem. Zeit., 1895, l9,1143).-The author’s method is applicable to members of the fatty series only. The substancc is introduced into a 15-cm. test tube, and mixed with finely powdered, previously fused, potassium dichromste. After covering the mixture with anothey 5-6 cm. layer of the chromate, the tube is drawn out t o a bent capillary. While the latter is kept cool with a wet piece of cloth, the contents of the tube are heated, commencing at the top, until no further sublimation of iodine takes place. The tube is cut in two, the part containing the iodine is rinsed with cz solution of potassium iodide, and the iodine is then titrizted as usual; or the iodine may be weighed.I n the latter case, the cupil- lary part containing the iodine is connected with a calcium chloride t,ube containing also a fewlpieces of soda-lime ; when a magnifying glass no longer shows the presence of water, the tube is weighed. After gently heating to volatilise the iodine, the glass is re-weighed. Estimation of Sulphur in Pyrites. By ALEXAXDEE vos ASB~TH (Chern. Zeit., 1895, 19, 598--599).-The author .has investi- gated the processes recommended by Johuson (reduction of the ferric salt by means of sodium hypophosphite before precipitating with barinm chloride), Xoehnel and Glaser (fusion with sodium carbonate and sodium peroxide), and Fresenius (fusion with sodium carbonate and potassium nitrate).The second method is, in the author’s opinion, the best, but it is necessary to evaporate the aqueous solution to dryness with addition of bromine and hydrochloric acid so as to ensure the complete oxida- Detection of Sulphates, Sulphites, and Thiosulphates in Presence of each other. By R. GREW SMITH (Cheitz. ATe~~s, 1895, L. DE K. tion of the sulphur and the removal of any silica. L. DE I(.72 ABSTRACTS OF CHEMICAL PAPERS. 72, 39-40) .-Excess of barium chloride and pleni,y of ammonium chloi-ide are added to the solution, which is made dilute when thio- sulphates are present; hydrochloric acid is then dropped in until barium sulphate alone remains undiasolved. The filtered solution is next rendered permanently yellow with iodine, when a turbidity or precipitate indicates the presence of sulphite, which has been oxidised to sulphate, whilst any t.hiosulphate is converted into tetra- thionate ; this in its turn is oxidised to sulphate on adding bromine water to the clear solution.Hydrogen sulphide mould interfere with these reactions, and is removed at the start by means oE a current of carbonic anhydride. D. A. L. Qualitative Analysis of a Mixture of Hydric Sulphide, Polysulphid e, Thiosnlphate, Sulphite, and Sulphate. Bg W. POPPLEWELL BLOXAM (Chem. News, lb95,72,63-64).-The solation is precipitated with an animoniacal solution of zinc, cadmium, and am- monium chlorides. The filtrate is divided into two portions; one of these is tested for sulphites and thiosulphates by Fresenius’s pro- cess, which consists in neut.ralising part of the liquid with acetic acid and adding a trace of sodium nitroprusside and, if necessary, some potassiumferrocyanide, which gives a red coloration with sulphites.Thiosulphates ape tested for by adding hydrochloric acid. The other half is tested for sulphates as follows. After adding a little sodium hydrogen carbonate, the liquid is placed in a flask fitted with a trebly perforated cork ; through an inlet tube, a current, of carbonic anhydride is admitted, and an outlet tube is provided dipping below the surface of water, whilst through the third hole, a small stoppered separating funnel is passed, the tube reaching nearly to the bottom of the flask. While the gas is passing, the liquid is gradually raised to boiling, and, after all the air is expelled, hydrochloric acid is slowly admitted through the funnel until i t is in excess; the liqnid is then boiled down to one-fift)h of its original bulk, t,he current of carbonic anhy- dride still being maintained. After filtering off the separated mlphur, the liquid is tested for snlphates as usual.L. DE K. Estimation of Organic Nitrogen by the Kjeldahl Process. By HENRI E. CAUSSE (J. Pharm., 189!5, [ 6 ] , 1, 543-549; compare Dyer, Trans., 1895, 81 l).-The ordinary modification of the Kjeldahl process yields satisfactory results with substances, such as guano, con- taining less than 5 per cent. of nitrogen, but with more highly nitro- genous substances, such as wool and leather, it gives results as much as 2 per cent. too low. The addition of mercuric oxide, recommended by the American Committee, is either unnecessary or objectionable, for, although the time required to effect the decoloriaation of the liquid may be considerably diminished by using sufficient oxide, the clear product then contains unreduced nitrogeu.A sample of dried wool, for instance, which yielded about 12.5 per cent. of nitrogen by the soda-lime method, and also by the American method when a small amount of the oxide (0.2-0-3 gram to 0*3-0*35 gram of wool) was used, gave only 10.5 per cent., or even less, wberi the amountANALP TICAL CHEMISTRY. 73 of the oxide (2-4 grams) was such as to effect decolorisation in an hour. Neither is the result improved by the addition o€ sodium snlphic?e to the alkaline liquid before distillation, and t.he deficiency is there- fore not due to the retention of ammonia in mercuric combination ; the addition of permnnganate is equally inefficacious, as nitrogen ring compounds are stable towards that agent.The author recommends the substitution of copper sulphate for the mercury or mercuric oxide. The substance (0-3-0.8 gram) is boiled in a round-bottomed flask with concentrated sulphuric acid (20 c.c.), and a small amount (0.3 gram) of the sulphat,e, until n clear solution is obtained ; the operation requires about three hours, but does not need attention if the flask is surrounded by a metal jacket. The product is diluted (to 300 c.c.), rendered alkaline with caustic soda, and distilled into standard sulphuric acid in the usual way. The copper remains in the solution, which is at first blue, and finally colonr- less, provided the caustic soda is free from carbonate, b u t if carbonate is present Eopper is precipitated, and a portion of the ammonia re- tained.The specimen analyses quoted agree well with duplicates made by the soda-lime method. J-r. W. Estimation Gf Phosphoric acid by the Molybdenum Method. By HUGO NEUBAUER (Zeit. anorg. Chem., 1895, 10, 60-65).-1n the estimation of phosphoric acid by means of molybdic acid, the precipi- tate obtained is usually not more than 0.27 gram Mg.,P207. %'he author has determined the correction necessary to compensate for the volatilisation of phosphoric acid. With 0.07 gram Mg2P207, the volatile P,O, = 0 ; with 0.35 gram Mg2P207 the volatile P20a cal- culated as Mg2P,0, = 0.006 gram.Whence the following equation is obtained for the correction number 2. When n = the MgzP207 found in milligrams, z = (n - 70) . 0.021. The author recommends the use of a crucible lid coated with mag- nesium oxide to prevent loss of phosphoric acid, especially when larger quantities of phosphoric acid are being estimated. The follow- ing directions must be closely followed in order to obtain trustworthy resnlts by the molybdic acid method. The yellow precipitate is dis- solved in 100 c . ~ . of tL$ per cent. ammonia. The precipitation with the magnesia mixture must be performed slowly, with stirring. When the volatile phosphoric anhydride is determined directly by means of a crucible lid coated with magnesia, the filter is burned at the lowest possible temperature, and the lid put on directly the teni- perature is raised, the precipitate beiiig heated for one hour over R strong Terquem- or Teclu-burner, in such a way that the whole crucible is at a full red heat.Care must be taken to determine if the magnesia coated lid gains in weight under the influence of the burning gas. The author recommends a spirit burner instead of gas, especially when the gas coutains any quantity of sulphur compounds. E. C. R.74 ABSTRACTS OF CHEMICAL PAPERS. Analysis of Artificial Manures. By VON GRUEBER (Zeit. angw. Chein., 1895, 504--516).-An elaborate article, dealing with the practical analysis of manures in the way proposed by the society of G winan manure manuf~cturers. The methods present, on the whole, no novel features, but., by strictly adhering to them, analytical differ- ences will, no doubt, be to a great extent obviated.L. DE K. Gravimetric Estimation of Arsenic. By CARL FRIEDHEIM and I’AUL MICHAELIS (Zeit. anal. Chem., 1895, 34, 505-545) .-I. The am- monium magnesium arseiiate method.-The authors, combining the most advantageons features of the proposals of Puller, Wood, Fresenius, and others, proceed as follows :-About 0.3 gram of arsenic acid in 100 C.C. is mixed with 10 C.C. of ammonia (sp. gr. 0*96), 20 C.C. of magnesia mixture (made from magnesium chloride), and about 45 C.C. of alcohol; after.48 hours, the precipitate is collected and washed with a, mixture of 2 vols. alcohol, 1 vol. ammonia, and 3 vols. water until frce from chlorine. The filtrate contains only unweighable trac2s of arsenic, so that Puller’s cori%cction of 1 milligram per 16 C.C.is not required. The use of the Gooch crucible, with a filter-bed of asbestos, is strongly recommended, since, with paper filters, a loss of ai-senic is inevitable. The precipitate is ignited in oxygen, a t first by ;L single burner, then by a multiple one for 15-30 miiiutes, until a constant weight is attained ; the blowpipe should not be used, for, a t the temperature which it gives, decomposition of the pyroarsenate and loss of arsenic occur, moreover, the crucible should stand in a small porcelain capsule to protect its contents from the flame. The precipitate undergoes partial decomposit.ion when heated with water, hence attempts to ascertain its weight by rinsing it into a crucible and eyapcrating the water results in serious loss.Bunsen’s method of dissolving in nitric acid and evaporating is also unsatisfactory, but cxperiments conducted as above did not in any case deviate more than 0.0007 gram of As,03 from the amount taken. 11. Estimation as Trisu@hide.-Here, also, the employment of the Gooch crucible avoids the inconveniences attending the use of dried paper filters. The chief dif€iculty in this process is the tendency of the precipitate to contain more sulphur than corresponds with t>he formula AS& ; part, a t least, of this excess, is shown to exist in the form of arsenious hydrosulphide, which compound is not decomposed by expelling the dissolved hydrogen sulphide by a current of carbonic anhydride, and is only very slowly decomposed, with partial oxidation and separation of sulphur, when the precipitate is dried at 100-103”.Hence, all attempts to dissolve out the excess of sulphur by carbon disulphide, fail to remove it completely. For the same reason, also, the method of Classen and Ludwig (Abstr., 1885, 932) does not give correct results. Mobr’s method of dissolving in ammonia and evapo- rating t’he solution is also untrustworthy, as, in consequence of the large surhce exposed, oxidation of sulphur and loss of weight occur dui ing the drying. Rose’s method of oxidising the precipitate, determining the total sulphur as barium sulphate, a n d estimating the arsenic from the difference, seems to be free from sources of error. A customary niethod is to oxidise the precipitate by nitric acid andANALYTICAL CHEMISTRY.75 thyow down the arsenic acid as ammonium magnesium arsenate, but the presence of the sulphuric acid resnl ting from the oxidation, entails thc co-precipitation of some basic magnesium sulphate, and renders a double precipitation necessary. In this second precipitation, too much dilution must be avoided ; 30 C.C. of solution for 0.1 gram of Asz& is an appropriate proportion; a little magnesia mixtiire should be added, and 3 vol. of alcohol, or the precipitation will be incomplete. Backstrom has proposed (Abstr., 1893, ii, 299) t o separate the sul- phuric acid from ihe arsenic acid in the oxidised precipitate by simply heating until the former is expelled, but the authors show that how- ever carefully the heat is applied, a loss of arsenic acid occurs before :dl the sulphuric acid is driven off.Arsenious acid, intended for precipitation as sulphide, is kest dis- solved in potassium hydrogen carbonate, as its solution in an alkali hydroxide oxidises gradually to arsenate on exposure to air. Before precipitating, it muot be acidified with a quarter to one-half its volume of hydrochloric acid of 1.12 sp. gr. ; passing hydrogen sul- phide for half an hour suffices for compIete precipitation, but one hour is recommended. Subsequent expulsion of the dissolved hydro- gen sulphide, either by warming or by carbonic anhydride, is neither necessary nor desirable, and since arsenious sulphide is not soluble in hydrogen sulphide water, moreover, the passage of carbonic anhydride does not diminish the excess of snlphiir in the precipitate if filti+aticn is commenced within 10 minutes of stopping the current of hydrogen sulphide, but, on the other hand, dissolves traces of arsenic from the precipitate, in consequence of the reaction As,S3 + 3H,0 = As,03 + 3H2S.One and a-half hours drying a t 105-110° suffices to give a constant weight, ; in an atmosphere of carbonic anhydride, no loss of weight takes place a t 140". Boric acid. By A. VILLIERS and M. FAYOLLE (J. Pharm., 1895, [6J, 2, 241--244).-The ordinary tests f o r boric acid leare much to be desired. Those founded on the turmeric reaction a1.e unsatisfac- kory, because the colour change is not sufficiently characteristic. Those based on the flame coloration, on the one hand, if applied directly t o t'he solid substance, are liable to give misleading indications if copper be present, as is often the case in wine ash, and to be masked by the more intense colorations due to sodium, &c.; and, on the oiher hand, if applied to the alcoholic distillate, they are open to the objec- tion that the delicacy 01 the test is very variable, the intensity of the coloration depending on the stage of the distillation at which it is observed, as well as on the amount of boric acid present. I n testing for boric acid in wines, the authors recommend the repeated distillation of the ash (from 25 c.c.) with small quantities of mefhylic alcohol (3 c.c., three times), after moistening i t with cowen- trated sulphuric acid (1 c.c.). The whole of the boric acid passes over, and its amount may be estimated colorirnetrically with fair accuracy, by comparison of the flame with those given by standard solutions of the acid.Quantities from 0.5 to 0.1 milligram may be detected in this way. A number of natural wines which werc examined by this process M. J. S.76 ABSTRACTS OF CHEMICAL PAPERS. did not contain a tlrace of boric acid. The marked quantities found by other authors must, therefore, either be aktributed to the mesence 01 copper, or to the iutrodaction of boric acid i n fining tde wines. JN. W. Estimation of Boric acid. By HENRI JAY and DCPASQUIER {Compt. reitd., 1895, 121, 260--262).-1n order to estimate boric acid by converting it into methylic borate, the substance is very slightly acidified with hydrochloric or sulphnric acid, mixed with 25 to 30 C.C.of methylic alcohol, and placed in a flask, which is connected with another flask containing a normal alkali hydroxide solution free from carbonates, and also with a condenser, i n such a way that the methylic borate formed in the first flask passes through the alkali solntion in the second flask, whilst the methylic alcohol, which is again set frec, is condensed, and falls back into the first flask. After boiling for about an hour and a half, the alkali solution is heated to expel methylic aleohol, very slightly acidified with dilute hydrochloric acid, again heated to expel carbonic anhydride, and titrated with decinormal alkali until neutral to litmus paper. Two drops of an aqueous solution of the blue C.4.B. are added, and the addition of alkali is continued until the first colour-change begins.The second quantity of alkali, less 0.2 to 0.3 c.c., according to the volume of the liquid, gives the quantity of boric acid present. I n order to obtain accurate results, the temperature and volume of the liquid operated on must be constant, and methylic alcohol and carbonic anhydride must be expelled. Pure wines contain from 0.0105 to 0.022 gram of boric anhydride per Iitre; cider and perry 0.011 t o 0.017; urine, 0.008 to 0.017. The acid was not f o n d in the bone or flesh of an ox. The accuracy of the estimation is slightly affected by the presence of fluorides, bnt not by that of other salts. C. H. B. Estimation of Carbonic Oxide in Air. By JOHN S. HALDAXE ( J . Physiol., 1895, 18,463-469).-The method described depends on fhe fact that when a hmmoglobin solution is shaken with air con- taining carbonic oxide, the proportion of the pigment which finally combines with the gas varies with the percentage of carbonic oxide in the air.This proportion is determined by a colorimetric method, standard carmine solution being added to a standard solution of diluted blood till it becomes as pink as that which has been shaken with the air containing the poisonous gas. The details of the method, which yields delicate rather than accurate results, are described in full. W. D. H. Gold and Silver in Copper and Copper Matte. By ERNEST A. SMITH (Chem. News, 1895, 72, 76--77).-Cornmenting on the discrepancies that often occur in the results obtained by different assayers working on the same sample, it is suggested that neglect to take notice of the silver in the test-lead, use of one acid only, and that probably strong, for parting, and bad balances are the most frequent causes of the differences alluded to.D. A. L.ANALYTICAL CBEMISTRY. ‘77 Detection and Estimation of Mercury in Urine. B y ADOLI’ ,JOI,LES (Monafsh., 1895, 16, 684--692).--From 100 to 300 C.C. of urine, according to the amount of mercur.7 supposed to be present,, is treated with stannous chloride and free hydrochloric acid i n presence of about 2 grams of granular gold. The precipitated mercury amal- gamates with the gold, which is afterwards washed by decantation and treated with hot coiicentrated nitric acid, whereby the mercury is dissolved. The solution thus obtained is diluted with water, and, 011 the addition of stannous chloride, yields a precipitate even when only a minute trace of mercary is present.To determine the mercury quantitatively, the amalgam of gold obtained as above is washed with water, alcohol, and ether, weighed in a hard glass tube, and the mercury distilled off. The loss in xeight gives directly the amount of mercury present. G. T. M. Volumetric Estimation of Platinochlorides ; Estimation of Potassium, Ammonium, Nitrogen, and Platinum. By LUCIEX L. DE KONIKCK (Chem. Zeit., 1895, 19, 901-902).-The platino- chlorides of potassium or ammonium obtained during an analysis, rimy, instead of being weighed, be volumetrically treated by apply- ing t h e reduction principle of Correnwinder atid Contamina.The precipitate is dissolred in boiling water and heated for some time with calcium formate, which soon removes the platinurn, leaving potassium 01- ammonigm and calcium chloyides, also free hydrochloric acid in solution. The mixture is neutralised by means of calcium carbonate suspended in water, and, after filtering, the chlorine is estimated as usual by rneans of silver nitrate. Six atoms of chlorine represent 2 atoms of l~otassium, ammonium, or nitrogen, and 1 atom of platinum. The calcium carbonate is made from calcium nitlaate and sodium carbon- ate. L. ~ l i : K. Quantitative Separation of Benzene from Light Petroleum. By HOBERT HFNRIQUYS (Chem. Zeit., 1895,18, 958-959).-5-7 C.C. of the mixture is introduced into a 25-C.C. glass stoppered cylinder, divided to 0.2 c.c., and shaken with twice its volume of sulphuric acid containing 5 per cent.of added sulphurio anhydride, uiitil notliing more is dissolved. Ti Le benzenes soon become sulphonated and dissolve, whilst the light petrolenm is scarcely attacked, and floats on the surface of the acid ; its volume may then be read off. Analysis of the Cyanide Solutions used in the Extraction of Gold. By GEORGE A. GOYDER (Chew. News, 1895, 72, 80-82).--- S?e this vol., ii, 28). Estimation of Glycerol in Fermented Liquors. By J. LLABORDE ( J . Yhccrm., 1895, [6], 1, 568-57O).-The liquor (50 c.c.) is boiled neai-ly to dryness (1 c.c.) in a flask containing zt quantity of lead shot (100 grams). The glycerol, which is retained in combination with the acid of the wine, is liberated from the residue by the addi- tion of finely powdered, slaked lime, with which i t is incorporated L.DE I(.i 8 ABSTRACTS OF OHEMIUAL PAPERS. into a stiff paste by agitation with the shot. If sugar is present,, the lime is previously moistened with alcohol, and a larger quantity is used. The liberated glycerol is extracted from the paste by repeatedly shaking with alcohol-ether, and the extract having been a9idifieci with sulphuric acid (10-15 drops), the solvent is as far as possible distilled off, and the residual alcohol removed by repeatedly boiling with water; the acid aqueous solution thus obtained is evaporated to dryness and carbonised, and the amount of glycerol calculated from that of the carbon obtained. Trial analyses of wine and beer, to which various amounts of glycerol were added, are stated to have been satisfactory.The ratio of alcohol to glycerol in red wines appears to vary within the limits 1 : 10 and 1 : 16. JN. W. Estimation of Glycerol in Wine and Beer. By ALFRED PAI~THE~L ( A ~ c h . Pliarm., 1895, 233, 391-398).-The liquid under examination (50 c.c.) is mixed with calcium carbonate and concen- trated to 10-15 C.C. ; it is then filtered into a tubulated retort, a, of 100 C.C. capacity, fitted at the tubulus with a bored cork, which is closed with a glass rod; the retort is heated in an air bath, b, thc bottom being of sheeh iron, the sides and top of asbestos paper, fastened by means of water-glass. The bath is heated at 120°, and when the contents oE the retort have been distilled almost to dryness, the bath is cooled to 60’, the apparatus exhausted, and the distillatiou coii- tinued at 180’ (25-30 mm.) ; this requires 1.5 hours.The apparatus is allowed to cool, the pressure restored, water (10 c.c.) added to the retort, and the distillation repeated at 120’. All the glycerol will be found in the receiver, d ; should i t be coloured, it must be distilled Again under similar conditions. The glycerol is determined by Uaumert and Schaumann’a method (Abstr., 1892, 1529). The con- tents of the receiver and condenser, e, are washed into an ErlenmeyerANALYTICAL CHEJIISTRY. 79 flask, diluted t o about 200 c.c., sodium hydroxide (8-10 grams) added, and then potassium pernianganate solution ( 5 per cent.), until the liquid remains bluish-black ; it is next heated on the water bath for an hour, decolorised by means of sulphurous anhydride, acidified with glacial a c e h acid (20 c.c.), and evaporated until free from sulphurous anhydride.The residue is diluted to about 200 c.c., and calcium chloride added in excess, the mixed precipihate of calcium oxalate and calcium sulphate being collected on an asbestos filter, and washed until, the liquid ceases to affect potassium permanganate solution ; it is then dissolved in dilute sulphiiric acid, and the oxalic acid estimated in t'he usual manner by means of standard potassium permangnnate solution (about 5 : 1000). Under the above conditions, 1 mol. glycerol yields 1 mol. oxalic acid, and the analyses given of wine, beer, and aqueous glycerol solutions agree closely with thc theoretical.In tbc sketch, In is the manometer, and r a tube and valve to prevent the back flow of water from the pump. If the pressure in the apparatus is reduced without previously cooling, in the manner described by von Torring, loss of glycerol always occurs. Estimation of Pentoses and Pentosans in Diffusion Cuttings, Sugar Beet, and some Food Stuffs. By A. Smw (Chenz. Cenfr., 1895, i, 4 4 8 4 4 9 ; from 0sterr.-ung. Zeit. Zucker-Ind., 23,925-933). -The substance under examination (2-5-5.0 grams), together with hydrochloric acid, ~ p . gr. = 1.06 (100 c.c.), is placed in a fl:~& (300 C.C. capacity), which is fitked with a funnel and heated b y means of a bath of fusible metal; after distilling during lO-1h minutes, when 30 C.C.should have passed over, hydrochloric acid (30 c.c.) is added, the distillation continiied, and these operations repeated until the production of furfuraldehyde ceases. The distil- late is treated exactly in the manner described by Tollens. The whole analysis requires 5i-6 hours ; it presents no special difficul- ties, and afYord3 valuable information as to the relative worth of the most varied food stuffs. J. B. T. Relative Proportion of Glucose and Levulose in Sweet Wines. By F. JOSEF KONIG (C'henz. Zeit., 1895, 19, 999-lOOO).- The relative proportion of glucose and levulose in sweet wines may be calculated from the copper-reducing power? coupled with a polan- metric ohservation. The colouring and tannin matters are best removed by means of basic lead acetate, as the use of animal charcoal causes a slight loss of sugar.If there is a large excess of levulose present, it may be concluded that the wine has been prepared by fermenting a concentrated juice, and then suddenly stopping the fermentation by adding alcohol or by other means ; whilst, if the dextrose is largely i n excess, its wilful addition may be suspected. If both are pretlent in about equal amounts, with perhaps a slight excess of levulose, no particular con- clusion can be drawn; the relation of the dextrose to the levulose will not decide the question whether the grape-juice has, from the commencement, been fortified with cane or starch sugar. On the J. B. T.80 ABSTRACTS OF OEIlhlICAL PAPERS. whole tlie analysis of sweet wines is stiil in a somewhat nnsatisfac- Estimation of Glycogen in Liver and Muscle.By WLADIMIR A. I<ISTIAKOFFSKY (C/iem. Centr., 1895, i, 449 ; from Pharnz. Zd. EZLSS., 34, 25).-The use of 0.1-0.3 per cent. solutions of alkali instead of 2 per cent., for the extraction of glycogen, is recommended by Brucke ; but glycogen may also be obtained by extracting the finely divided substance 5-6 times with boiling water, and pressing the residue. In addition to the glycogen, the liquid contains alkali albuminates, glutin, and traces of peptone; these are removed by precipitation with potassio- mercuric iodide after the liquid has been concentrated and acidified with hydrochloric acid ; the glycogen is precipitated from the filtrate by means of alcohol (compare Huizinga, this vol., i, 6). Estimation of Glycogen.Detection of Albumoses in Presence of Glycogen. By D. HUIZINGA (PJliiger’s Archiv, 1895, 61, 32--38).--See this vol., i, 6 . Estimation of Formic acid. By FRANZ FREYER (Chew. Zed.. 1595, 19, 1184--1185).-The author’s process has been invented for the purpose of estimating calcium formate in the presence of acetate. The mixture having been distilled with dilute sulphuric acid i n a current of steam until the distillate is no longer acid, the total acidity is estimated in an aliquot part of the distillate by means of standard soda, and another portion of the liquid is neutralised with aqueous hoda and concentratled to a small bulk. I t is then boiled with a mix- tnre of dilute salphuric acid and potaesium dichromate, which is withoufi any action on the acetic acid, but rapidly and completely oxidises the formic acid to carbonic anhydride and water.The strength of the dichromate must, of course, be accurately known, and t h e excess is afterwards determined as usual by means of potassium iodide and sodium thiosulphate. To better see the change in colour, The Resorcinol Test for Tartaric acid. By GEORGES DENIG~S ( J . Yharnz., 1895, [6], 1, 556-589 ; compare Mohler, Abstr., 1891, 867).-Mohler’s test, which consists in the addition of tlie substance to be tested to a dilute solution of resorcinol in concentrated sulphuric acid at 120°, with the consequent production, if a tartrate is present, of a violet coloration, is open to the objections t h a t the reagent is perish- able, that the test is applicable only t o solid substnrices, thus necessi- tating the evaporation of so!utions to dryness, and that the violet coloration, or one closely resembling it, is produced by various oxidising agents.The author has modified the process in a manner to obviate these defects. A solution of pure, white reeorcinol (2 grams) in very dilute sul- phuric acid (-$ C.C. to 100 C.C. water) is quite stable, and, by adding a portion of this to about 20 vols. of concentrated acid a t the time of testing (2 or 3 drops to 2 c.c.), a solution is obtained equivalent to Mohler’s reagent. A small quantity of the liquid to be tested (1 or 2 drops) is added to the reagent, and the mixture gradually tory condition. L. DE K. J. B. T. a little metaphosphoric acid may be added. L. DE K.ANALYTICAL OEEMISTRP.81 warmed to 115"-140°, when, if tartaric acid is present, the charac- teristic piolet-red colour is developed. It is due to t,he preRence of a broad absorption band in the spectrum, extending from X = 510 to x = 545, and best seen with solutions diluted with conceut'rated snlphcric or acetic acids. If the coloration appears before heating, i t is due to the presence of an oxidising agent in the liquid, and this must be previously removed by reduction with copper-zinc and dilute sulphuric acid ( 5 C.C. of solution to be tested, 5-6 drops copper sulyhate solution, 2 grams of zinc, and 1 C.C. of acid), Tartaric acid can in this way be detected in a few drops of a 1 per cent. solution containing, in addition, 10 per cent. each of sodium nitrite? and potassium nitrate, chromate, and chlorate.Substances suvli as cane sugar, which are blackened by sulphuric acid, are best eliminated by Mohler's method of precipitating the acid ae lead salt, and washing the latter with dilute nitric acid before decomposing it and making the test. By VIKTOR VEDRODI (Chem. Zeit., 1895, 19,600-601).-The autjhor calls attention to the enormous difference in composition of various commercial brands of fish oil, particularly as regards their acidity and percentage of unsaponifiable matter. The acidity was fcund to yary from 0.74 to 38.9 per cent., and the nn- saponifiable matter from 0.6 to 82 per cent. No sample should be used for tanning purposes unless tho acidity and the unsaponifiable matter do not exceed 15 and 4 per cent.Examination of Fats by Means of the Refractometer. By HhINKlCH B~crtUrtI's arid H. HEILER (Arch. Yharm., 1895, 233, 423--428).--The objects of this invest.igat>ion were the determin- ation (1) of the influence of temperature on the refractive power of various fats and oils, and (2) the relationship, if any, between the refractive power, the percentage of volatile acids, and tho iodine additive capacity : the experiments were conducted with a Zeiss' refractometer. The increase in the refractive power in scale divi- bions, for a rise of lo, is as follows :-Butter = 0.54-0.58 ; olive oil = 0% ; cotton seed oil = 0.5-0.6 ; ground nut oil = 0-6-0.7 ; oil o€ apricots = 0.4-0.6 ; sun-flower seed oil = 0.5-0 6 ; sesame oil = 0.6-0.7 ; almond oil = 0.5-0.6 ; oil of peaches = 0%.No relation- ship was observed between the refractive power of butter and of deer fat and their iodine absorption value, hut high i*efractive power is accompanied by a relatively great additive power for iodine in the case of tho above oils, and also in the following : poppy oil, cocoa nut oil, palm oil, butter (?), tallow, lard, margarine. Nothing is said directly of the volatile fatty acids. By HEINRICH BECKURTS and F. OELZE (Arch. Pharm., 1895, 233,429-430).-Deer fat melts a t 49-49.5" and solidifies at 48", the corresponding values for tallow and beef fat are 44-45.5'and 32-36', and 43-44.5" and 37" respeztively. The fatty acids of JN. W. Analysis of Fish Oils. re spec tively . L. DE K. J. B. T. Deer Fat. VOL. I Y Y . ii. 782 ABSTRACTS OF CHEAIIOAL PAPERS.deer fat melt a t 49*5O, of tallow at 45--47O of beef f;tt a t 44*546° ; the iodine absoi*ption values are 19.8-21, 32.7-46-2, and 85.4-44 respectively. The refractive powers (Zeise' refractometer) at 40" are 44 5, 46, and 45. J. B. T. Lard Analysis. By A. GOSEE (Chem. Zeit., 1895,19,1043-1045). -The author recommends crystallising the sample from ether a t temperature of 12-13'. With a little practice, it will be found com- paratively easy to distinguish microscopically between tallow-stearin and any lard-stearin which, however, does not readily crystallise. When applying the silver test, the author uses the original Bechi test as approved by the Italian C'omiuittee. The test gains in delicacy if the lard is first pressed a t a temperature of 26-30', aud the reaction applied to the expressed oil.L. DE K. Examination of Pepper. By WALTER BUSSE (Zeit. anat. Chem., 1895, 34, 638-643 ; from Arbeiten I<. Geszcndlzeitsanzte, 9, 509).- The methods of estimating moisture, ash, sand, and total alcoholic extract are described. The estimation of the colouring mat (em, which occur only in the huak, i R considered important; these are extracted from the residue insoluble in alcohol by digesting it with hot sodium hydroxide solution, and are precipitated by lead acetate from the extract a,fter acidifying with acetic acid. The amount of lead so precipitated is called the "lead number," and seldom exceeds 0.122 gram per gram of pepper. M. J. S. Nutmeg. By WALTER BUSSF; (Zed. anal. Chem., 1895, 34, 643- 644 ; froin Arbeiten K.Gesuirdhei/samte, 11, 390j.--The total ash should not exceed 5 per cent., nor the amoiint insoluble in hydro- chloric acid (sa.nd) 0.5 per cent. For estimating the fat, 2 grams of the grated powder is extracted with ether for eight hours, then dried, rubbed down with qumtx sand, and again extracted for four hours; after evaporating the ether, the f a t is absorbed by 8 grams of ignited sand, arid dried a t 100" for five liours only, to avoid oxidation. The amount varies from 30 to 40 per cent. M. J. S. Margarine Cheese and its Analysis. By M. KUHX (Erper. Stat. Becord, 1895, 7, 158 ; from Molk. Zeit., 1895,9, 185--187).--The percentage ccjmposition of the cheese is said to be valuelew in dis- tinguishing it from natural cheese. The following determinatims are recommended to be made in the ether extract: sp.gr. at 100" by means of a Westphal balance and Konig's butter areometer; in- soluble fatky acids (Hehner's method) ; rolatile fatty acids [Reichert-Meissl-Wollnyj Kottesdorfer saponification equivalent,; angle of refraction in the Zeisa-Wollny butter refractometer. A number of results obtained with difterent cheeses are given in the original paper. Composition of Meat Extract. By F. JOSEF KijNIG and A. BOMER ( Z e i t . a n d Chern., 1895, 34, 548-562).-1t has hitherto N. H. J. M.ANALYTICAL CHEMISTRY. 83 been accepted that mcat extmcts contain gelatin and other protei’ds. Thus, C. Karmrodt found 10.4 per cent. of gelatin in Liebig’s extract, Kemmerich (Sbstr., 1894, ii, 150) 33.23 per cent. of proteids, and Stutzer (Abstr., 1853,146) 20.5 to 22.6 per cent.of peptone. The num- bers obtained by Kemmerich were deduced from the results of fractional precipitation by alcohol, on the assumption that. gelatin is precipitated by 60 per cent. alcohol, albumoses by 80 per cent., and peptones only by 90 per cent. The authors have repeated Kernruerich’s work, but employing Kjeldahl’s process, instead of weighing the precipitates, as was done by Keinmerich (a metliotl to wliicli they take exc:eption), have obtained numbers for gela t’in and rllbu- moses which are less than one-third of Kernmerich’s. 111 Liebig’s extract, the mode of manufacture would seem to exclude the pos- sibility of more than traces of gelatin being present. The usual mode of estimating peptone, namely, precipitation by phospho- molybdic acid, is erroneous, since this reagent gradually (in the course of 5-7 days) throws down the flesh bases also, about 90 per cent.of the total nitrogeu being precipitable. The absence of peptone may be shown qualitatively, as after precipitating with ammo~iinm sulphate to ensure the absence of albumoses, the tilt~ate does not give the biuret, reaction. In thecases of Kemmerich’s meat peptone, and Cibils’ meat extract obtained by means of the digestive ferment of Ca~ica Papaya, the filtrate is pale enough f o r the detec- tion of traces. The filtrates from Liebig’s and Kemmerich’s meat extracts are darker, but the colour is incompetent to mask the reac- tion if as much as 2-3 per cent. of peptone is present (see, how- ever, Stutzsr, loc.c i t . ) . Stutzer’s statement as to the presence of ammonia is confirmed, but no evidence could be obtained of the presence of amido- or acid amido-compounds. A1 bumose (prccipit- able by ammonium sulphate or zinc sulphate; see next abstract) is the oiily proteiid present in notable quantity, but the flesh bases constitute by far the largest portion of the total nitrogenous con- stituen ts. M. J. S. Precipitation of Albumoses by Zinc Sulphate. By A. ROMER (Zeit. anal. Chem., 1895, 34, 362--567).-Zinc sulphate possesses many advantages over ammonium sulphate for the separation of albuniose from peptone. The precilitation is equally complete, comparative estimations by means of the two reagents haviiig given identical numbers in the four meat extracts examined by the autlior and J.Koniq (preceding abstract), whilst the tiltrates in all cases gave no indication of the presence of a prote‘id by the biuret reaction. The presence of zinc gulphate in no way disturbs tlre Kjeldahl process, so that the nitrogem in the precipitate can be estimated without the need of applying any coi~ection. The filtrate is ac once suitable for precipitation by phosphomolybdic acid, eit’her for the purpose of testing the completeness of the washing or (nf’ter strongly acidifying with an equal volume of dilute sulphuric acid, 1 : 4) for t’he estimation of peptone, flesh bases, $c. Since phos- phates give a precipitate with zinc sulphate, it is desirable to slightly acidify the solution Kith sulphuric acid; 1 C.C. of acid (1 : 4) is84 ABSTRAOTS OF CHEMICAL PAPERS.therefwe to be added to 50 C.C. of solution containing 1-2 grams of the extract, and previously freed from insoliible a d coagulable substances; the liquid is tlien saturated in the cold with ;I small excess of finely powdered zinc salphatc, and the precipitate washed with a cold saturated solution of the same salt. Although meat extracts contain ammonia, and ammonia forms with zinc sulpha'te a sparingly soluble double salt, in no case was ammonia found in the albumose precipitate, but, on the contrary, the whole of the ammonia of the origiiial substance was obtained when the filtrate from the zinc precipitate was distilled with sufficient magnesia to precipitate all the zinc present and leave the liquid strongly alkaline. Estimation of Gelatin in Meat Extracts and Commercial Peptones. By ALBERT S w t z E R (Zeit. anal. (Jltem., 1895, 34, 568- 370).--The following is the exact method of carrying out the estima- tion ot wbich the outline was previously given (Abstr., 1895, ii, 543). Sand, previously ignited and freed from fine dust by a sieve, is used instsend of asbestos for absorbing the solution in the tinfoil capsule. After complete drJ-ing at looo, the contents of the capsule are pow- dered, and, with the cut up capsule, placed in a beaker, where they are extracted four times with absolute alcohol, filtering the extracts through an asbestos filter, but leaving as far as possible the insoluble mather in the beaker. The beaker (marked 4) together. with four others (t, c, (a, e) are then plunged into crushed ice, as also a flask contailling ;t niixturc of 100 C.C. of alcohol, 300 grams of ice, arid cold water to 1 kilogram. Of this mixture, the temperature of which must not exceed 5O, about 100 C.C. is poured on the sand, stirred therewith for two minutes, aid decanted into beaker b ; the second ducantate is poured into c, and so on, until the last washing is colourless, a frag- ment of ice being added to each as soon as it is poured off. Three funnels are then arranged with filter beds of long-fibred asbestos sup- ported by perforated porcelain plates, and connected with a pump by which getitlc and gradually increasing suction can be applied. The contents of beaker a are tiltered through the first., finally transferring ttie sand to the fuiinel, b is poured into the second, and c and d iIito the third. The three filters, as well as that through which the absolute alcohol extract had been filtered, are then thoroughly washed with the ice cold dilute alcohol, transferred to a basin, and repeatedly extracted by boiling with water. The aqueous extract, alter fiitration, is concentrated and submitted to Kjeldahl's process for the estimation of the gelatin. ln the process given in Abstr., 1893. 146, the albumose (line 2 from bottom of page) must be cor- rected for any coagulable albumin present in the meat extract. M. J. S. M. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8967005070

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

General and Physical Chemistry. Dissociation of Optically Active Salts in Solution. By PH~L~PPE A. GUYE and B. ROSS (Bull. Xoc. Chim., 18!J5, [3], 13, 464-469).-1t is well known that the specific rotatory powers of the salts of optically active monobasic acids, at sufficiently low concentra- tions, are identical with those of the acids themselves, whilst those calculated from the rotatory powers of more concentrated solutions are usually divergent. Although this is accounted for in a general manner by the theory of electrolytic dissociation, the optically active acids being, as a rule, comparatively little dissociated, and having approximately normal cryoscopic constants and electrolytic conduc- tivities at temperatures at which their salts are almost completely dissociated ; yet a complete examination of an individual case has not hitherto been made.The authors have, therefore, determined the rotatory powers of various inorganic and organic salts of active valeric acid, a substance which was chosen on account of the comparative simplicity of its constitution due t o the absence of alcoholic hydroxyl. The specific rotatory power of the aqueous solution of the acid is [:ID = + 17*3O, whilst that of the pure acid is +13*64O; but this difference may be due as much tso molecular association as to electro- lytic dissociation. The specific rotatory powers of the lithium, sodium, potassium, and rubidium salts at concentrations corresponding with 2.46 grams of the acid i n 100 c.c., and calculated on the amounts of the salts actually present, are respectively [a]D = +€POo, + 7.2O, +6*4O, and +5.4' ; whilst those calculated on the amounts of acid present, on the sup- position that the salts are conipletely dissociated into their ions, are respectively + 8*5O, + 9*8O, + 8*9", and + 10.1O.The approximate identity of the rotatory powers of the salts of metals differing so widely in atomic weight, is noteworthy, considering the great dif- ference between those of the alkylic valerates ; the lithium, potassium, and rubidium salts are the most dissociated, the mean rotatory power of the three being approximately half that of the acid at the same concentration. As might be expected from theory, the specific rotatory powers of aqueous solutions of valeric acid me diminished alike by dilutiori and by rise of temperature. The rotatory power, [aJD = + 12*02O, of an acid somewhat less active than that used in the foregoing determinations, became +14.6" in an aqueous solution containing 3-732 grams per litre, but was diminished to +14*4', when the concentration was reduced to 1-239 gram per litre, and was rednced in the two cases to +14*36O and +14*2', when the temperature was raised from 18" to 25O. The rotatory powers of aniline, pyridine, and diethylamine valerates in aqueous solutions of the same concentration of acid as those of the alkali salts, and calculated on the amounts of the salts actually present, are [a]= = +6*30°, +6*36O, and +4*99O respectively, whilst YOL.LXX. ii. 886 ABSTRACTS OF CHEMICAL PAPERS. those calculated on the amounts present on the hypothesis of complete dissociation are + L2.4', +11.26', and +8*77O.These results are in harmony with the cryoscopic constants of the bases. The specific rotatory powers of alcoholic solutions of the foregoing salts and of those of dimethy laniline, quinoline, and phenylhydraaine containing the same amounts of acid as before, are practically identical with that of an alcoholic solution of the acid of the same concentration, except in the case of the diethylamine salt, the activity of which is some 50 per cent. less. With this exceptioc,. therefore, these salts are completely dissociated in alcoholic soluticin, a conclusion similai. to that arrived a t by Ghira from a study of the cryoscopic properties of benzene soliitiona of the corresponding acet'ates.It is thus useless to determine the optical activity of solutions of the organic salts of optically active substances in organic solvents ; and where organic solvents are used, investigation must, in future, be limited to inorganic salts. Colour Change of Dilute Solutions of Potassium Chromox- alate. By FRIEDRICH HAMBURGER (Ann. Phys. Cheni., 1895, [el, 56, 173--174).-A dilute solutiofi of potassium chromosalate, K3Cr(C2O&, when placed in a cylindrical vessel was found to exhibit in general a green colour by transmitted daylight, hut showed purple streaks a t the edges and in the centre. By artificial light, the solution appesred only purple. An examination of the absorption spectrum was there- fore made, and showed a, wide absorption band between the wave- lengths 630 and 530, and complete absorption at the wave-length 4iO.Hence the yellow, orange, blue, and violet rays are absorbed from the spectrum, only red and iudigo remaining ; the colour resulting from these two is dependent on the proportion in which they are present in the incident light rays. Emission of Light by Organic Substances in the Gaseous, Liquid, and Solid Condition. By EILHARD WIEDEMANN and G. C. SCHMIDT (Ann. Plys. Chew., 1895, [2], 56, 18--26).-The authors find by numerous experiments that many organic compounds exhibit fluorescence in the gaseous condition; this fluorescence is blue or violet with retene, phenanthreae, anthracene, anthraquinone, chrjsene, indigo, and naphthalene, and a magnificent reddish-brown with napht.hazarin. 1 he absorption spectra of solutions of the hydro- carbons in this list, all lie in the extreme violet or ultra-violet, and, therefore, a s in the case of benzene and toluene, the absorption of the gaseous hydrocarbons probably lies still further towards the ultra- violet end of the spectrum. Anthrnquinone also absorbs violet rags, and nsphthamrin, i n alcoholic solution, green, blue, and violet rays.The emission spectra lie, therefore, in accordance with Stokes' rule, nearer the less refrangible end of the spectrum than the absorption spectra, and the spectra of organic vapours are fluorescence spectra in the nsnal sense of the term. Many organic compounds in the gaseous state yield characteriatic spectra under tahe influence of electrical discharges, but the spectra, obtained in this way do not correspond with the absorption spectra.In JN. W. H. C.GENERAL AND PECYSICAL CHEMISTRY. 57 the liquid state many organic compounds become luminous under the influence of the cathode discharge, and the colour in this case is the same a s that of the vapour. Solid organic compounds also frequently exhibit cathode-luminosity, but the colour is not in all cases identical with that of the liquid. By L. HOLBORN and W. WIEN (Ann. Phys. Chem., 1895, [2], 56, 360-396).-The Le Chatelier thermo-couple of platinum and a platinum-rhodium alloy containing 10 per cent. of rhodium, has been compared by the authors with the air thermometer up to the temperature 1450'. This instru- ment gives very constant readings i f protected from the possible action of carbon.Its use in high temperature measurements is, there- fore, to be preferred to that of employing the change of resistance of a platinurn wire, for with the latter, even if between each measure- ment the temperature coefficient between 0" and 100' is redetermined, this affords no guarantee for the behaviour at high temperatures. The authors find, also, that Callendar's formula for the change of resistance with change of temperature is not sufficiently exact to admit of a far reaching extrapolation. A comparison with the air thermometer can be most readily effected with the thermo-couple, as it can be directly introduced into the air vessel, and must in this way acquire the same temperature as that of the expanding air. The following melting points were measured :- H.C. Measurement of High Temperatures. Silver.. .......... 971' . Nickel. .......... 1484' Gold ............ 1072 Palladium.. ...... 1587 Copper. .......... 1082 Platinum . . . . . . 1780 H. C. i Some Melting and Boiling Points. By HENRI LE CHATELIER (Compt. reihd., 1895, 121, 32&-326).-Nxperiments made with ft thermoelectric couple protected by a thin film of glass and graduated up to the boiliug point of zinc (930') give 1050'to 1060' as the melting point of gold. Experiments made with another couple, taking the melting point of silver as 954', show that the meltiug point of gold is 1O55-1O6O0. The author concludes that the melting point of gold as given by Violle, 1045O, is too lorn, but that the error is certainly noh more than 20°, that none of the more recent estimations of t h i s melting point are sufficiently accurate t o warrant their sabstitution for Violle's number, and that it is very desirable to retain the scale of high tern- peratureR at present actually in use until new and more exact experi- ments made by direct comparison with the air thermometer shall give the true melting point of gold to within a very few degrees (compare Heycock and Neville, Trans., 1895, 1064).Explosion of Endothermic Gases. By LEON MAQUENNE (COW@. rend., 1895, 121, 4 2 G 4 2 i ) .-When a small quantity of mercuric fulminate is exploded in contact with nitrous oxide, the latter is de- compolred with a violent explosion. Acetylene under similar condi- tions only begins to decompose, about 95 per cent. of the gas remaining unaltered, and the explosive wave is not propagat,ed through the masB of the gas.With a larger quantity of fulminate C. H. B. 8-218 ABSTRACTS OF CHEMICAL PAPERS. (about 1 gram) the acetylene is decomposed, and the explosive wave travels through a distance which depends on the diameter of the tubes and the conditions under which the explosion takes place. Nitro-substitutions. By CAMILLE MATIGSON and DELIGNP (Conzpt- C. H. B. rend., 1895, 121, 422-424).- Ecat of cornbustion. Const. volume. Orthonitrophenol . . . . . . 688.6 Paranitrophenol ... .... 689.5 Orthonitrobenzoic acid . 731.1 Metanitrobenzoic acid.. 727.7 Paranitrobenzoic acid . . 729.6 Paranitroacetanilide.. . . 969.2 Nitrobenzaldehyde . . . . . 801.2 I Const. pressure. 688.2 689.1 730.4 727-0 728.8 968.9 800.3 Difference from parent compound.44.3 43.4 44.0 47.4 45.5 47.9 41.4 The third column gives the difference between the heats of com- bustion, at constant pressure, of the nitro-derivative and the parent substance. The position-isomerides have practically the same heats of combustion. With the exception of nitrobemaldehyde, the difference is practically constant and is about 45, whatever the function of the compound in which substitution takes place. The equation deduced from this difference is ihe thermal disturbance being indentical with that found by Berthelot in the case of the hydrocarbons benzene, toluene, naph- thalene, &c. C. H. E. Combination of Mercuric Cyanide with Bromides. By RAOCL VARET (Compt. rend., 1895, 121, 398400).-In the following table, column I, gives the heat of dissolution of the salt, column I1 the heat developed by the interaction of solutions of mercuric cyanide and the particular bromide, aud column TI1 the heat of formation of the solid salt from its proximate constituents, the salts being regarded as solid and the water as liquid. RCH + HNO, liq.= RCNO, + H20 liq. develops +36*7 Cnl. 2Hg( CN)2,2NaBr,4Hz0.. . 2Hg(CN),,2LiBr,7H20 . . . 2Hg(CN)z,BaBr,,7Hz0 . . . ‘LHg(CN)2,SrBrz,6H,0 . . . 2Hg(CN)2,CnBrz,7H20 . . 2Hg(CN)2,ZnBrz,8H,0. . . Hg(CN)2,CdBr,,3H20.. . . 2 Hg (CN) 2,2NH4Br,2 H2O. . 28g(CN)2,MgR~~,8€320. . . I. -20.97 ,, -18.31 ,, -20.98 ,, -18.60 ,, -19.82 ,, -15.97 ,, -20.82 ,, -12.5 ?, -24.14 Cal. IT. 111. f0.98 Ca.1. + 18.52 Cal. +125 ,, +36*26 ,, +1.29 ,, +20.27 ,, +1.24 ,, +29*84 ..f l . 2 5 ,, +40*47 ,, +1*44 ,, +54*71 .. +133 ,, +31.15 ,, +0%6 ,, +10.5 ?, +1*06 ,, + 7.23 ,, At the ordinary temperature, the solutions are slightly alkaline to litmus, and slowly give the isopurpurate reaction with a picrate of the same base as is combined with the bromine. It follows that whilst; almost all the mercury is in combination with cyanogen, aGENERAL AND PHYSICAL CHEMISTRY. 89 small quantity is in combination with the bi-omine. of the latter increases as the temperature rises. accord with the thermochemicnl data. The proportion These result,s are in C. H. B. Distillations with an Automatic Mercury Pump. By FRIEDRICH KRAFFT and W. A. DYES (Ber., 1895, 28, 2583-2589).- The paper contains a description of an air pump devised some 16 years ago by v.Babo. It consists of a Sprengel mercury pump which works in the vacuum of a water suction-pump and so need not be more than 30-40 cm. long ; the mercury, which falls down the short Sprengel tube, is carried up again to the top of the apparatus by a current of air drawn in by the water-pump, aud the apparatus is thus automatic and continuous in its action. It is comparatively small in size, so that it can be placed, by moans of clamps and a retort-stand, on the laboratory bench, and it does not require more than 600-650 grams of mercury ; a vacuum of less than 1 inm. is attainable by its means. By means of this pump the boiling- or sublimation-points of several substances were determined. Manni to1 boils at. 276-280' under about 1 mm., at 285' under 2.5 mm., and at 290-293' under 3-3.5 mm.pressure. Dulcitol boils at 275-280', 287-288', and 290-295' under the same pressures. a-Hydroxybutyric acid boils at 84" under 1.5 mm. pressure. Succinic acid sublimes at 156-157' under 2.2 mm., at 160-165' under 2.5-3 mm. pressure ; fumaric acid at 163' under 1.7 mm., mesaconic acid at 139-141' under 1.5 mm., at 14.3-145' under 2 mm., and itaconic acid at 140-141' under 1-5 mm. pressure ; mnleic and citraconic acids do not sublime without forming some anhydride. Wood's metal was used to heat the distillation flasks; the temperature of the bath need not be more than a few degrees above the boiling-point oE the liquid, but if the substance does not boil, but sublimes, a much greater difference of temperature, 40-60' above the sublimation point, was found to be necessary.Density Determinations of Extremely Dilute Solutions. By FRIEDRICH KOHLRAUSCH (Ann. Phys. C'hem., 1895, [S], 56, 185-200). --The author has further improved the method of determining the density of very dilute solutions, which he had formerly employed in conjunction with Hallwachs (Abstr., 1894, ii, 441). The size of the ball of glass used was greatly increased, the suspension from the balance being effected by means of a thin platinum wire which was first coated electrolytically with platinum and afterwards ignited. The rough surface thus produced, satisfactorily removes the difficul- ties and irregularities observed when a smooth wire is employed. As very slight variations of temperature exercise a very disturbing influence on the results, owing to the unequal expansion of the soh- tion and of the glass ball, it was necessary to confine the observations within limits of temperature between which this inflnence is at a minimum, the limits within which a variation of a few thousandths of a degree may be allowed, being from 4' to 8'.A limiting error of lo-' has thus been reached in the determinations. Observations were made with solutions of cane sugar, magnesium C. F. B.90 ABSTRACTS OF UHEMICAL PAPERS. phste. A = 60.23. I A = 60'00. sulphate, acetic acid, and sulphuric acid. On the assumption that the water undergoes no contraction in volume, the molecular volumes @ of the dissolved substances are calculated by means of the formula s - 1 m c) = A - 1000 - , where A is the weight of the equivalent, m the number of gram- equivalents per libre in the solution, and s is the density. The resnlts are given in the following table, arid for the purpose of com- parison, t.he results formerly obtained with Hallwachs a.t the higher temperature of 18" are included.A = 49 -04. - m. -- 0 -0002 0 -0006 0 -001 0 *002 0.005 0 *01 0 *03 0.05 0.1 1 5 - - - - 50.7 50.88 51.0 51-04 51.10 51.34 52.14 Sugar. A = 341 '1. (6 '1) ( 5 . 5 ) (65:;) 6.92 7.71 9.75 10.75 12-03 I 15.54 17-57 6 '0". 207 '0 207 *3 207 -32 207 *41 207 48 207 *56 207 -70 207 -8 208 -0 203 *9 - 18". - - 209 -0 209 *O 209 -5 209 -69 299 -71 209 -57 209 -89 211 -5' 215 -9 6 *3". -4.5 -4.5 -4.6 -4.6 -4'14 -3 *91 -3 '37 -3 -03 '-2 -45 + 0 . 9 + 6 *o - - - -3 *4 - 3 '21 - 2 '65 -2 a15 -1.74 -1 *21 + 1 *68 + 6 *58 (51 '3) (49 '8) (50 -0) 49 -61 49 *69 49 '72 49 -85 49 '88 49 '93 50 *21 51 *05 18". -- - -.- 6 -9 7 '94 9.32 11 -80 12 -77 14 '05 16 -96 18-52 It will be seen that the continual increase in the molecular volumes with rising concentration is to be observed in these as in the former determinations. The only exceptions occur in very dilute solutions of acetic and sulphuric acids; here a complicated behaviour or disturbance occurs similar to that noticed in couduc- tivity determinations, the molecular contraction increasing only up to a certain degree of dilution, and then decreasing. It is probable that the explanation of this peculiarity may be found in the traces of impurities present in the water used, as these undoubtedly affect the density determinations in these extremely dilute solutions in a marked manner.The molecula,r volumes are throughout one to two units greater at 18' than at 6". H. C. Influence of Hydrochloric acid and Chlorides on the Photo- chemical Decomposition of Chlorine Water. By EUTHYM E KLIMENKO (Ber., 1895, 28, 2558-2564).-Norrnal solutions of hydro- chloric acid and of various chlorides were diluted with equal volumes of chlorine water and exposed in sealed tubes to sunlight, together with some tubes containing chlorine water only. When the chlorine in the latter had completely disappeared, the other tubes wereQENEHXL AND PHYSICAL, CHEMISTRY. 91 opened, and the amount of chlorine still remaining in them was estimated. It was found that the hyclrocliloric acid had most retarded the disappearance of the chlorine, very little chlorine having disappeared in this case ; if the amount left in the hydrochloric acid tube be taken as 1, then the amounts left in the tubes containing the chlorides aye represented by the following numbers : LiCl 0.308, NaCl 0.173, KCl 0.090, MgCI, 0.530, CaCl, 0.390, SrC1, 0.302, BnCI, 0.285, ZnC1, 0.200, CdCI, 0.042.The different metals group themselves in the same order as in the periodic system. The action of chlorine on water is said to result in the formation, first of hydrochloric and hypochlorous, and finally of hydrochloric and chloric, acids. The retarding action of hydrochloric acid is ascribed to its reconverting the hypochlorous acid formed into chlo- rine. It is further suggested that metallic chlorides are partly con- verted into chlorates by the chloric acid formed, and that the hydro- chloric acid thus liberated reacts with hypochlorous acid to reform chlorine, owing t o which circumstance the metallic chlorides retard the disappearance of the chlorine.C. F. B. Heating Apparatus for Drying Ovens. By JOHANNES THJELE (Uer., 1895, 28, 2601--260'L).-The tubes which carry the rows of small jets used in heating drjing ovens are usually clamped to the legs of the stand by means of screws ; these screws become so hot that it is generally impossible to touch them, and consequently diffi- cult to regulate the temperature of the oven. The author has devised a stand, figured in the paper, in which the tube of jets is carried by a rail that slides up and down between two of the legs, and is pressed against these by a spring, so that it is held fixed in any position. To alter the position, it is merely necessary to press two handles together ; these act as levers, and release the pressure of the spring ; they are, moreover, fairly long and have wooden ends, so that they do not get too hot to touch. . A Modified Condenser. By J. J . L. VAN RJJN (Ber., 1895, 28, 2388).-The modification consists in bending the inner tube so that the whole condenser can be rotated, without being removed from the vessel to which it is attached, in such a manner that it can be used eifher as an ordinary condenser or it reflux condenser. It appears from the drawing which is appended, that the modified condenser could not be used in connection with any vessel with a, narrow aperture. A. H. C. F. B. Modification of Liebig's Condenser. By HUGO MICHAELIS (Bey., 1895, 28,2615).-The author brought forward the modification recently described by van Rijn (preceding abstract) about 10 years a.go (Chem. Zeit., 1886, 1556). A. H.

ISSN:0368-1769    

DOI:10.1039/CA8967005085

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

92 In organic C h e m i s t r g. Decomposition of Hydrogen Peroxide. By WALTH~RE SPRING (Zeit. anoyg. Chem., 1895,10, 161--176).-When a 38 per cent. soln- tion of hydrogen peroxide is heated at 60' in a platinum dish which has been previously polished, no decomposition takes place; at a higher temperature small bubbles of gas are formed. When, how- ever, the inside of the dish is scratched with a needle, small gas bubbles are formed at the scratch, even at the ordinary tempera- ture, and on raising the temperature a brisk evolution of gas takes place. A 70 per cent. solution of hydrogen peroxide contained in a glass flask is only slowly decomposed when a current of air from a wide tube is passed through i t ; if, however, a capillary tube is used, brisk decomposition takes place.The author has examined the decomposition of hydrogen peroxide when mixed with various solutions. Five C.C. of a 36 per cent, hydrogen peroxide solution is mixed with 5 grams of each solution, and allowed to remain for a given time at 65' in a thermostat, and the remaining hydrogen peroxide titrated in acid solution with per- manganate ; the solutions employed contain 1 gram mol. of dry salt to 38.5 gram mols. of water. Rydrochloric and nitric acids decom- pose the peroxide quickly, but sulphuric and phosphoric acids have a preservative action. The decomposing action of salt solutions is more energetic the feebler the base they contain and the more readily the acid they contain is oxidised or reduced by hydrogen peroxide ; thus, lithium and sodium snlphates produce only a slight decomposition, magnesium chloride about double, and aluminium chloride about treble this decomposition, whilst sodium and potas- sium carbonates entirely decompose hydrogen peroxide.This decom- position is due to t'he acid function which hydrogen peroxide evinces towards some salts. If a solution of hydrogen peroxide is gradu- ally added to a solution of an alkali carbonate, pure oxygen ifi evolved ; if, however, the carbonate is added to an excess of hydro- gen peroxide, it is completely converted into alkali dioxide and carbonic anhydride. The ratio of the concentration of two solutions of st salt is not equal to the ratio of their decomposing action on hydrogen peroxide. E. C. R. Action of Hydrogen Peroxide on Ammoniacal Copper Compounds : Preparation of Oxygen.By DIOSCORIDE VITALI (L' Orosi, 1895, 1-5) .-When hydrogen peroxide is added to ammoniaca.1 copper sulphate, a brisk effervescence takes place in the cold, and oxygen is evolved in abundance, the copper salt remaining unchanged; and as an indefinite amount of the peroxide can be decomposed by means of the same portion of the metallic compound, pure oxygen may be very conveniently prepared by allowing the ordinary aqueous peroxide (3-4 per cent.) to flow steadily from a tap-funnel into a saturated solution of ammoniacal copper sulphatelNORGANIC CHEMISTRY. 9 3 (20-30 c.c.) contained in a fairly capacious Woulff's bottle. The gas is dried and purified from ammonia by means of sulphuric acid. The mechanism of the action appears to be analogous to that of the decomposition of potassium chlorate in presence of manganese dioxide ; the cupric compound reacts with the peroxide, yielding a cuprous salt and free oxygen, and the cnprous compound is then re- oxidised by another portion of the peroxide.The same action occurs to a limited extent with copper hydroxide alone, and to a varying extent with ammoniacal solutions of other metallic salts, but in no case is it continuous as with copper; mer- curic oxide and mercurocs nitrate, for instance, are visibly reduced, and the action ceases as soon 3,s tho reduction is complete. The method is not applicable to the estimation of hydrogen per- oxide in aqueous solution, as the whole of the oxygen is not evolved, part being employed in oxidising ammonia to nitrous and nitric acids, which may be detected in the solution at the end of the operation.JN. W. Formation of Ozone. By OTTO BRUNCK (Zeit. anorg. Ciiem., 1895, 10, 222-247 ; see also Abstr., 1893: ii, 454)-The anthor has already proved that the intense odour of the oxygen prepared from a mixture of potassium chlorate and manganese dioxide is chiefly due to the presence of ozone. A fui*ther examination of the gas shows that only a very minute trace of chlorine is evolved, equal in Rmount to that evolved in the decomposition of pure potassium chlorate alone. If the mixture is heated at 400" and above, at which temperature the dioxide commences to decompose, then more chlorine is evolved. It has already been shown that oxygen is ozonised when passed over heated manganese dioxide or certain other metallic oxides, and this action has been further examined.The ozone is estimated as follows : the gas is passed through a neutral solution of potassium iodide, which is then acidified with dilute sulphuric acid, and titrated with N/100 sodium thiosulphate solution. The action of ozone on an acidified potassium iodide solution takes place according to the equation 0 3 + 2KI = 21 + K,O + 0,; when, however, ozonised oxygen is passed through a neutral solution of potassium iodide, athe action takes place according to the equations O3 + 2KI = 21 + K2O + 0, and 61 + 3K20 = KI03 + 5KI. The second reac- tion does not take place quantitatively, and there remains free iodine and potassium hydroxide in the solution; the latter is partially converted by the ozone into potassium dioxide, so that finally the solution contains potassium iodate,.potassium hydroxide, and potas- sium dioxide. Hydrogen peroxide 1s not formed. When the solution is acidified, a third part of the iodine, equivalent to the ozone, is liberated at once, whilst the reaction with the hydrogen peroxide liberated from the potassium dioxide is only complete after 1-2 hours. Manganese dioxide when heated in a current of carbonic auhydride at 400°, and to an incipient red heat, does not yield ozone. In a current of oxygen at 400°, 6.5 grams of the dioxide gave in one hour 9.57 milligrams of ozone ; at an incipient red heat, it gave 7-46 milli- The gas examined was evolved at a temperature of 320'.94 ABSTRACTS OF CHEMICAL PAPERS.grams. The forrriation of ozone from a mixture of potassium chlo- rate and manganese dioxide increases with the amount of manganese dioxide ; manganous oxide acts i n a similar way to the dioxide, but much less ozone is formed. Cobalt oxide, Co203, behaves in a similar way to manganese dioxide, but in the presence of nascent oxygen the amount of ozone formed is greater in proportion to the amount of cobalt oxide employed. The compound K2Co,0,,, prepared by fusing cobalt carbonate with potassium hydroxide, when heated at 200° gives off three atoms of oxygen, but no ozone is formed. Nickel oxide behaves in a similar way to the above; apparently, it is not; altered by heating i n oxygen, and after heating some time still evolves chlorine when treated with hydrochloric acid, and ozone when again heated in oxygen. The reaction with potassium chlor- ate takes place violently at 300°, and less ozone is formed than in the case of cobalt.Silver oxide, when heated in a current of carbonic anhydride at 350', gives only a slight trace of ozone, which is probably due to the action of the oxygen formed on nndecornposed oxide; in a current of oxygen a t 280°, it forms ozone. Silver peroxide was prepared by the electrolysis of silver nitrate ; 1.22 gram heated at 300' gave 7.68 milligrams of ozone. Only a very small quantity of oxygen is evolved from a mixture of silver oxide and potassium chlorate a t 360° ; above 400°, the chlorate decomposes slowly without the formation of ozone. Mercuric oxide when heated at 400" does not give off ozone, but when heated in n current of oxygen, a small quantity of ozone is formed ; probably the greater part of the ozone is destroyed by the metallic mercury.With potassium chlorate, it behaves in a similar way to silrer oxide. Lead peroxide yields ozone when heated either in a current of carbonic anhydride or of oxygen, but with potassium chlorate at 320-350', only n very small quantity of ozone is formed, and the peroxide is reduced to red lead and litharge. When heated to redness in a current of oxygen, red lead and litharge yield small quantities of ozone. Cbromic anhydride (3.39 grams), when heated a t 260-280°, yields ozcne (1.52 milligram). Chromium oxide heated at 400' in a current of oxygen, yields small quantities of ozone. Uranimn trioxide does not yield ozone in an atmosphere of carbonic anhydride ; in oxygen, small quantities of ozone are formed.When heated with potassium chlora'te, i t yields potassium uranate and chlorine. The hydrate of the tetroxide, when heated at 150" in a current of carbonic anhydride, yields water and oxygen, but no ozone is formed, as probably hydroxyl groups are eliminated, which decompose irit o water and oxygen. The author was unabie to detect, the formation of ozone from platinum oxide, as the compound always contains chlorine, which is evolved on heating. Gold oxide was prepared by precipitation of gold chloride with potassium hydroxide; the mixture is acidified with sulphuric acid, and the precipitate dissolved in nitric acid,IKORGANIC CHEllllSTRP. 95 reprecipitated by dilution with water, and dried at 150’; 1.44 grams of the oxide heated in a curreiit of carbonic a.nhydride at 830-280O gaTe 21 milligrams of ozone, and 1.85 grams heated in oxygen gave 54.4 milligrams of ozone.E. C. R,. The so-called Oxysulphazotic acid or Nitrosodisulphonic acid. By ARTHUR R. HANTZSCH and WILLTAM SEMPLE (Bey., 1895, 28, ‘L744--2751).-Potassium nitrosodisulphonate, ON(SO,K),, pre- pared by the oxidation of potassium liydroxylaminedisulphonate by means of lead peroxide, has, according to Raschig, the formula (S03K),N- /o\ -N(S03K),; to this the authors make the following ‘O/ objections: (1) The group :NE‘N: has never previously been ‘O/ observed, and it3 chroniophoric character Las not been proved ; (2) the acidic character of two linked pentavalent nitrogen atoms is unique; (3) the difliculty of explaining the change of colour from orange-yellow t o deep violet-blue which takes place when the salt is dissolved; (4) when reduced, no hydrazine derivatives are formed. The authors regard the compound as a derivative of nitric peroxide with the simple formula ON(S03K),, the oxidation of nitrous acid to nitric peroxide, and of potassium hydroxylaminedi- snlphonate to potassium nitrosodisulphonate being analogous, the relationship between the yellow solid salt and the blue solution is similar to that between colourless solid N204 and coloured NOz.Cryoscopic: molecular weight determinations failed to give satisfac- tory results on account of the instability of the compound. I f the oxidation of the hyclroxyiamine derivative is incomplete, blue crystals axe formed ; these are also obtained by mixing solutions, saturated a t 40°, of potassium hrdroxylaminedisulphonate (3.5-4 parts) and potassium nitrosodisnlphonate (1 part), and consist of solid solutions containing 1-4 per cent.of the latter in the former. The colour of the crystals varies, according to the composition, from ultramarine to sky blue, they are comparatiwly stable, and the content of nitroso- disulphonate may be determined by means of potassium iodide and acetic acid, titrating the liberated iodine with potassium thiosul- phate. Raschig’s potassium nitrosotrisulphonate, (SO,K),N< g>N (SO.,K),, formed by the action of water on potassium nitrosodisulphonate, is also regarded as monomolecular ON (SO,K), ; crSoscopic molecular weight determinations were unsatisfactory, and the electrolytic con- ductivity of its solution does not follow Ostwald’s rule, but it is similar to “ dibenzsulphhydroxamic acid,” ON(S02Ph),, the mole- cular weight of which agrees with the formula.Raschig’s objection to the simpler formu!a for potassium nitrosotrisulp~ion~t~ was based on its non- formation by the oxidation of potassium azotriaulphonate,$6 ABSTRACTS OF CHEMICAL PAPERS. N(S03K)3; but this has little weight since tertiary ammonium de- rivatives do not yield amiiie oxides, ONR3, when oxidised. Dinitrososulphonic acid (Nitroxysulphurous acid). By ARTHUR R. HANTZSCH (Ber., 1895, 28, 2751-2754) .-The author replies to Divers and Haga’s criticisms (Trans., 189.5, 452) of his previous paper on this subject (Abstr., 2895, ii, 75).Their state- ment that he believes in the existence of two potassium nitroxysul- phites is based on a misapprehension, as reference t o his paper shows, and he takes exception to their formula OK*N:NO-SO,K on the following grounds : (1) The salt, being similar to nitrosylsulphuric acid, O:N*O*SO,H, should be readily hydrolysed to sulphuric acid and hyponitrous acid; actually it is, in alkaiine solution, very stable. (2) Until decomposed it does not give the reactions of the sulphates as might be expected. (3) Their general remarks on acids and bases are in conflict with the theory of dissociation. (4) The fact that alkyl hydrogen sulphates are not directly precipitated by barium chloride is explained by the fact that all alkyl derivatives are non- electrolytes.The above objections do not apply to the author’s formula O< “OK I with which Raschig’s ON.N(OK)*SO& may be tautomeric (compare Divers and Haga, Trans., 1895, 1098). J. B. T. NS03K’ J. B. T. Formation of Hydrogen Selenide. By H. ‘PELABON (Compf. rend., 1895, 121, 401-404 ; compare Abstr., 1894, ii, 135 and 447).-- In order to avoid any error that may arise from the fact that when selenium is heated in a mixture of hydrogen and hydrogen selenide, it absorbs a certain quantity of the latter, which is partially liberated on cooling, the author has determined by Ditte’s method the composi- tion of the gas obtained by heating hydrcjgen at various tempera- tures in presence of the smallest possible excess of selenium.The relation pl/p2 of the partial pressure of the hydrogen to that of. the hydrogen selenide was determined for each temperature, and the results are expresscd with great accuracy by the equation of Gibbs and Duhem, log (p!/p2) = M/T + N log T + Z, in which M, N, and Z are constants, ‘I’ is the absolute temperature of the experiment, and the logs are Napierian logs. Experiments at 350°, 440°, and 510° give 13170.3, 15.53, and 119-88 respectively for the values of M, N, and Z . I t follows from the equation that the ratio r = pz/pl + p2 should have 8 maximum value at the temperature t when t = M/N -273. With the values already given for M and N, t = 575O, and this de- duction is confirmed by experiment. I t also follows from Duhem’s equations and the values found for M and N that the heat of forma- tion of hydrogen selenidc should be -17380 minor calories, whereas Fabre’s experiments gave the ralue -18000.C. H. B. Tellurium. By LUDWIG STAUDENMAIER (Zeit. anorg. Chem., 1895, 10, 189--221).-‘l‘elluric acid is most easily obtained by dissolving tellurium in an excess of dilute nitric acid and then adding a slight excess of chromic acid. The solution is evaporated to crystallisation andINORGANIC OHEMISTRP . 97 tlie crystals mashed with nitric acid and dissolved in a small quantity of water. The solution is treated with a few drops of alcohol to reduce any chromic acid remaining, and precipitated by the addition of nitric acid. Finally, the product is dissolved in water and eva- porated t o dryness on the water bath.Telluric acid separates from water at the ordinary temperature in crystals, with 2H20, belonging to the irregular system; these are stable in the air, and are not hygroscopic. When precipitated from its aqueous solution with nitric acid, regular crystals resembling lead nitrate are obtained, together with tho ordinary modification ; these also contain 2H,O. From solutions at O", it crystallises with 6H20 in large, tetragonal crystals resembling monopotassium phosphate ; these crystals effloresce at the warmth of the hand, and are converted into the ordinary modification. When dried over phosphoric acid, they do not decompose even in a vacuum. Pure tellurium compounds are obtained from the crude Hungarian tellurium as follows. The finely powdered substance is dissolved in dilute nitric acid, the solution evaporated with strong hydro- cliloric acid, and filtered ; the tellurium is then precipitated from t h e filtrate with sulpliurous acid, and after being washed with hydrochloric acid and water, it is dissolved in nitric acid, oxidised with chromic acid, and the telluric acid treated as described above.The atomic weight of tellurium was determined in accordance with the following equations H2TeO4,2H,O = Te02 + 0 + 3H20 o r Te + 3 0 + 3H20 and Te02 = Te + 0,. The Erst decomposition is brought about by heating in a glass flask. The reduction in the second and third decomposition is performed as follows. The telluric acid o r dioxide is mixed with finely divided silver and pure silica, and the mixture contained in a platinum or porcelain boat, cGvered with a layer of finely divided silver.The admixture with silver prevents the slightest trace of tellurium from volatilising. The mixture is first heated in a glass tube until the telluric acid i s dehydrated, then in a current of hydrogen, while the temperature is gradually raised from 250' to 400°, and finally for a short time at a, dull red heat. The results of all the experiments (number of experi- ments not stated) agree closely with 127.6 (0 = 16) for the atomic weight of tellurium. Experiments on the fractionai crystallisation of telluric acid are described, which show tliat all fractions give the same atomic weight. The author discusses a t length the work of Brauner (Trtms., 1889. 382 ; 1895, 549) and of Retgers (Zeit.physika1.Chem., lk93,12; 596): E. C. R.. A Hydrate of Arsenic Trisulphide and its Decomposition by Pressure. By WALTH~RE SPRING (Zeit. anorg. Chem., 1895, 10, 185-188) .-The hydrate, As2& + 6H20, is obtained by precipitating a solution of arsenic trichloride containing hydrochloric acid with hydrogen sulphide, and drying the precipitate in a current of air having a relative humidity of 70 per cent. at the ordinary tempera-. tnre. It has a somewhat lighter yellow colour than ordinary arsenic trisulphide, and easily loses its water when warmed. The sp. gr. = 1.8806 at 25*Cio, and the specific volume = 53.174,; whereas the98 -4BSTRAOTY OF CHEMICAL PAPERS. specific volume of the sum of its constituents As,S, and 6H,O is 50.626, therefore, accordiig to the author's theory, i t must decompose when submitted to pressure. It is, in fact, decomposed quantitatively into water and anhydrous trisulphide when submitted to a pressure of 6000-7000 atmospheres.If the density o€ ice is taken for thc calculation of the specific volume of the hydrate, the number S2-662 is obtained, which shows that the water is present in the solid form. The Compounds of Arsenic with Selenium and of Arsenic, Selenium, and Sulphur. By EMERKH SZARVASP (Bey., 1895,28,2654 -2661 ; compare Clever and Muthmann, this vol., ii, 18).--A~senic pentaselenide, AsLSe5, was prepared by heating the two constituents in the requisite proportion in sealed tubes filled with nitrogen ; it forms a black, lustrous, brittle mass, and may be purified by fractional distil- lation under diminished pressure.It is not readily acted on by the ordinary solvents, but fuming nitric acid oxidises it to selenious and arsenic acids. Alkaline hydroxides and hydrosulphides readily dis- solve it, but the resulting yellow solutions decompose when exposed to the air, and, when acidified with the mineral acids, yield the penta- selenide in the form of a reddish-hrown, fiocculent precipitate. Vapour density determinations made a t 750-800° show that the molecule of As,Se, has undergone decomposition, probably into As,Se, and Se,; at still higher temperatures (1050-1100') the vapour density shows that the molecule of As,Se5 has split up into three simpler molecules. Sodium monosdenoarsenate, Na3As0,Se + 1!2H,O, is one of the compounds formed on dissolving arsenic pen taselenide in sodium lijdroxide, but as the solution readily decomposes when exposed to the air, it is necessary to work in an atmosphere of hydrogen.The salt may be obtained as colourless crystals on the addition of methylic alcohol to the aqueous solution; the crystals, when left exposed to the air, lose their water of crystallisation arid turu red, owing to the liberation of selenium. Sodium selenoarsennte, Na&Se4 + 9Hz0, obtained together with the preceding compound K hen arsenic pentaselenide is dissolved in sodium hydroxide, ci-ystallises in rub y-red needles, which rapidly :ose their water of ciytallisation when exposed to the air; it is readily soluble in water, and the aolutiou readily undergoes decomposi- tion, selenium being deposited. Mineral acids tlirow down the penta- selenide from its alkaline solutions i n the form of a reddish-brown flocculent precipitate.Arsenic triselenobisulphide, As,Se3Sz, is obtained when arsenic bi- sulphide and selenium are heated together in the requisite propor- tions in an atmosphere of nitrogen; it is best purified by repeated distillation under low pressure, and then forms ablack, highly glistening substance which, in thin plates, has a purple-red colour. Tn chemical properties it resembles arsenic pentaselenide ; it is soluble in alkalis, and is precipitated unaltered on the addition of' an acid. Vapour densi- ties taken at 550-600' indicated that dissociation had taken place. Arsenic diselenotersu/phide, As,SepS2, may bc obtained in a similar manner from arsenic tersulphide and selenium.It differs from the E. C. R.INORQANlO CHEMISTRY. 99 preceding compound in being ruby-red in thin plates. density at 750’ indicates that dissociation has taken place. The vttpour J. J. S. Atomic Weight of Helium. By N. A. LANGLET (Zeit. anorg. Chew,., 1895, 10, 289-29d).-The helium was prepared as follows. A hard glass tube, 1 metre long, is filled first with a column (10 cm. long) of manganese carbonate, then with a mixture of powdered cleveite (3 parts) and potassium pyrosulphate (2 parts), and then with a column (10 cm. long) of copper oxide. The air is expelled from the tube by carbonic anhydride, the copper oxide heated to redness, and the tube then heated, as in the case of an organic analysis.The gas produced is collected over 50 per cent. potassium hydroxide, and finally passed through a tube containing layers of copper oxide, phosphoric anhydride, and magnesium powder, the copper oxide and magnesium being heated to redness. The gas so prepared, when examiiieii spectroscopically in a Giessler’s tube, was found t o be free from nitrogen, hydrogen, and argon. The density was determined by weighing 100 C.C. in a glass balloon, and was found to be 0.139 (air = 1) or 2-00 (H = 1). The velocity of sound in the gas was then determined, and from this the ratio of the specific heats at con- stant pressure and at constant volume. The ratio. obtained = 1.B7, whence the molecule of helium contains only one atom, and the atomic weight = 4. Combination of Magnesium with Argon and with Helium.By LOUIS J. TROOST and L ~ O N V. R. OUVRARD (Compt. reiad., 1895,121, 394--395).-It is not indispensable to pass a mixture of argon and helium with nitrogen over red-hot magnesium or lithium before intro- ducing it into the spectrum tubes. The tubes are furnished with mag- nesium wires, and a RuhmkorE coil is used which has a Marcel-Deprez contact breaker. The dry gas is introduced, and a powerful current is passed. At first the nitrogen is slowly absorbed, but when the pressure is reduced to a certain point, the magnesium wires become very hot, and the nitrogen combines with the metal very rapidly. The nitrogen spectrum disappears, and that of helium or argon, 01’ both, becomes visible. If a powerful discharge is continued for some time, the argon and helium disappear, seemingly because they combine with the vupou~ of the magnesium.Platinum under similar conditions seems likewise to volatilise and combine with argon. E. C. R. C. H. B. Argon, a New Constituent of the Atmosphere. By LORD RAYLEIGH and WI LLraM R.AMSAY (PhiE. Tram., 1895, 186, 187-241). -It has been shown by Rayleigh that nitrogen extracted from chemical compounds is about 4 per cent. lighter than “atmospheric nitrogen ” (Abstr., 1895, ii, 444j, the chemically prepared nitrogen pre- viously used having been obtained from nitric oxide, from nitrous oxide, find from ammonium nitrite by the use ot: hot iron. As i t appeared desirable to show that the agreement of numbers obtained for chemical nitrogen does not depend on the use of no red heat in the process of purification, experiments were tried with nitrogen liberated from100 ABSTRAOTS OF GHEMfCAL PAPERS. carbamide by tho action of sodium hypobromite, which gas it \\-as hoped would require no further purification than drying.But the gas so obtained was obviously contaminated, attacked vigorously the mercury of the T6pler pump, and was desci-ibed as smelling like a dead rat. Its weight proved to be in excess even oE the weight of atmospheric nitrogen, and it was only after passing the gas over hot metals that the corrosion of the mercury and the evil small were in great degree obviated, and the weight was found to correspond with that of the chemical nitrogen previously examined. Nitrogen can, however, be prepared from ammonium nitrite without the employ- merit of hot tubes, which, in spite of a slight nitrous smell, shows no appreciable difference in density from that prepared by treatment with hot metals.To the above list may be added nitrogen, prepared in yet another manner, whose weight was determined subsequently to the isolation of the new dense constituent of the atmosphere ; in this case the nitrogen was actually extracted from air by means of magnesium. The nitro- gen thus separated was then converted into ammonia by the action of water on the magnesium nitride, and afterwards liberated in the free state by means of calcium hypochlorite. The purification was con- ducted in the usual way, and included in one case passage over red- hot copper and copper oxide, but this was subsequently omitted.With or without exposure to red-hot copper, the " chemical " nitro- gen derived from " atmospheric " nitrogen possesses the usual density. Experiments were also made to prove that the ammonia produced from the magnesium nitride is identical with ordinary ammonia, and contains no other compound of a basic character. For this purpose, the ammonia was converted into ammonium chloride and the percent- age of chlorine determined by titration with a solution of silver nitrate, which had been standardised with pure sublimed ammonium chloride. It was found that ammonium chloride prepared from mag- nesium nitride obtained by passing atmospheric nitrogen over red-hot magnesium contains practically the same percentage of chlorine as pure ammonium chloride. It may be concluded, therefore, that red- hot magnesium withdraws from atmospheric nitrogen no substance other than nitrogen capable of forming a basic compound with hydrogen.That the discrepancy between the weights of chemical and atmo- spheric nitrogen cannot be due to the presence of known impurities has already been proved (Zoc. c i t . ) . I t was thought that the lightness of the gas extracted from chemical compounds might be explained by partial dissociation of nitrogen molecules N2 into detached atoms. But as the silent electric discharge has no effect on the density of either kind of gas, and as the density of a sample of chemically pre- pared nitrogen showed no sign oi' increase after storage of the gas for eight months, this view had to be abandoned.Regarding it a s established that one or other of the gasetl must be a mixture, the simplest assumption, in view of the above facts, was to admit the existence of a second ingredient in air, from which oxygen, moisture, and carbonic anhydride had already been removed. If the density of the supposed gas were double that of nitrogen, Q per cent. only byINORGANIC CHEMISTRY. 101 volume would be needed, or, if the density were but half as much again as that of nitrogen, then 1 per cent. would still suffice. The positive evidence i n favcur of the prevalent doctrine that the inert residue from air after withdrawal of oxygen, water, and car- bonic anhydride is all of one kind appears to be derived from the experiments of Cavendish (Phil. Trans., 1785,75,372). By sparking a mixture of air and oxygen in the presence of alkali for the absorp- tion of the acid product of the reaction, and subsequent removal of the excess of oxygen by a solution of liver of sulphur, Cavendish found that only a small biibble of air remained unabsorbed, “ which certainly was not more than 1/120th of the bulk of the ” nitrogen “ let up into the tube,” and therefore concluded “that if there is any part of the ” nitrogen “ of our atmosphere which differs from the rest, and cannot be reduced to nitrous acid, we may safely conclude that i t is not more than 1/120th part of the whole.” Cavendish was satisfied with this result, and does not decide whether the small residue was genuine, but the experiment8 hereafter described render i t not improbable that his residue was really of a different kind from the main bulk of the nitrogen, and contained the gas now called argon.With a, view of isolating, if possible, the unknown and overlooked constituent, or, i t might be, constituents, the existence of which in atmospheric nitrogen had thus been rendered probable, this gas waR submitted to examination. The earliest attempts to isolate the suspected gas were made by the method of Cavendish, using a Ruhmkorff coil of medium size actuated by a battery of fire Grove cells. When the mixed gases were in the right proportion, a rate of absorption of about 30 C.C. per hour could be attained. In a particular instance, starting with 50 C.C. of air and <gradually adding oxygen, the volume was a t length reduced to 1 C.C.On treatment with alkaline pyrogallol, the gas shrank to 0.38 C.C. That this small residue could not be nitrogen was argued from the fact that it had withstood the prolonged action of the spark, although mixed with oxygen in nearly the most favourable proportion. To this residue another 50 C.C. of air was added, and the whole worked up with oxygen as before. The residue was now 2.2 c.c., and after removal of oxygen 0.76 C.C. In another case, a mixture of 5 C.C. of air with 7 C.C. of oxygen was sparked for one hour and a quarter, the residue was 0.47 c.c., and, after removal of oxygen, 0.06 C.C. Several repetitions giving similar results, it became clear t h a t the final residue did not depend on anything that might happen when sparks passed through a greatly reduced volume, but was ilz proportion to the amount of air operated on.I3ifficulty was experienced in accumulating a sufficient quantity for examination of the residue which refused to be oxidised, owing, as was proved later on, to the solubilityof the gas in water. At length, however, a sufficiency was collected to allow of sparking in a specially constructed tube, when a comparison with the air spectrum, taken under similar conditions, proved that, a t any rate, the gas was not nitrogen. Since nitrogen, at a bright red heat, is easily absorbed by ma& nesium, best in the form of turnings, an attempt was successfully VOL. LXX. ii. 9102 ABSTRACTS OF CHEMICAL PAPERS made to remove that gas from the residue left after eliminating oxygen from air by means of red-hot copper.In zt preliminary experiment, i n which a quantity of atmospheric nitrogen was admitted into contact with red-hot magnesium, pumped off, and then treated again with fresh magnesium, the original volume of LO94 C.C. was reduced to 50 c.c., which resisted rapid absorption. It still contained nitrogen, however, judging by the diminution of volume which it experieneed when allowed to remain in contact with red-hot mag- nesium. Its density was, nevertheless, determined by weighing a small bulb of about 40 C.C. capacity, first with air and afterwards with the gas. The density found was 18-88, and the gas, therefore, was heavier than air. An arrangement was then adopted by means of which a quantityof atmospheric nitrogen could be brought repeatedly into contact with fresh quantities of magnesium heated to redness.About 10 litres of gas were taken and treated in this manner, until the volume was reduced to 200 C.C. Unfortunately some of the nitrogen was lost by leakage, so that exact measurements could not be taken. The density of this residual gas was found to be 16.10, but as i t appeared advisable to continue the absorption of nitrogen, it was again treated with fresh magnesium. The volume was thus reduced to a little over 100 c.c., and the density was now found to be 19.086 (0 = 16). A portion of the gas was then mixed with oxygen, and submitted to a rapid discharge of sparks for four hours in presence of caustic potash. It contracted, and on absorbing the excess of oxygen with alkaline pyrogallol, the contraction amounted to 15.4 per cent.of the original volume. If the gas contained 15.4 per cent. of nitrogen of density 14.014, and 84.6 per cent. of other gas, the density of the mixture being 19.086, calculation leads to the number 20.0 for the density of this other gas. A vacuum-tube was filled with a specimen of the gas of density 19.086, and it could not be doubted that it contained nitrogen, the bands of which were distinctly visible. It was probable, therefore, that the density of the pure gas lay not far from 20 times that of hydrogen. At the same time many lines were seen which could not be recognised as belonging to the spectrum of any known substance. If atmospheric nitrogen contains two gases of different density, it should be possible to obtain direct evidence of the fact by the method of atmolysis, and experiments were made with this object.The atmolyser was prepared by combining a number of churchwarden tobacco pipes ; eight pipes connected in simple series, and placed in a large glass tube, closed in such a way that a partial vacuum could be maintained in the space outside the pipes by a water-pump, giqing the best results t'lius obtained. One end of the combination of pipes was connected with the interior OE an open bottle containing sticks of caustic alkali, the object being mainly t o dry the air. The other end of the cornbination was connected to a bottle aspirator, initially full of water, and so arranged as to draw about 2 per cent. of the air which entered the far end of the pipes. The air thus obtained was treated exactly as ordinary air had been treated in determinations of the density of atmospheric nitrogen.The density of the gas from theINORQANIC CHEMlSTRY. 103 above prepared air was in every case greater than that from unpre- pared air, and to an extent much beyond the possible errors of ex- periment. The conclusion seems inevitable that " atmospheric nitrogen " is a mixture and not a simple body. To complete the verification, negative experiments were made to prove that argon is not derived from nitrogen or from chemical sources. In one case 3 litres, alrd in another case about 59 litres of chemical nitrogen, prepared from ammonium nitrite, were treated with oxygen i n precisely tho manner in which atmospheric nitrogen had been found to yield argon.The final residue was in neithercasa more than 3.5 c.c., and this consisted mainly of argon, the source of which is to be found in the water used for the manipulation of the large quantities of gas employed. If atmospheric nitrogen had been used, the final residue should have been about 10 times the above amount. A similar set of experiments was carried out with magne- sium, and led to the same conclusion. A description is given of the methbds adopted for the separation of argon on a large scale, both by the oxygeu and the magnesium process. In the latter case, a quantitative experiment was carried out on a large scale, the amount of argon from 100 litres of '' atmo- spheric " nitrogen, measured at Z O O , being collected after treatment with magnesium, and measured at 12'.An accident led to the loss of about 4 litres of nitrogen during the process, and the total residue, after absorption of the nitrogen, being 921 c.c., the yield is therefore 0.986 per cent. It may be concluded, wibh probability, if allowance be made for the solubility of the argon in the water over which i t was collected, that argon forms approximately 1 per cent. of the atmospheric nitrogen. This result is confirmed by determinations in which the oxygen method of absorption was used, two independent observations giving 1.04 aud 1.03 as the percentage of argon in atmospheric nitrogen. Determinations of the density of argon prepared by means of oxy- gen, and of argon prepared by means of magnesium were made, A single determination of the gas obtained by the first method gave 19.7, and the mean of three results obtained with gas prepared by the second process was 19.88.The spectmm of argon has been examined by Crookes, and forms the subject of a separate communication. Seen in a vacuum tube of about 3 mm. pressure, it consists of a great number of lines, dis- tributed over almost tbe whole visible field. Two lines are specially characteristic ; they are less refrangible than the red lines of hydrogen or lithium, and serve well to identify the gas when examined in this way. The wave lengths of these lines are 696.56 and 705.64 x loR6 mm. Besides these red lines, a bright yellow line, more refrangible than the sodium line, occurs at 603.84. A group of five green lines occurs next, of which the second is perhaps the most brilliant, and has the wave length 561.00.There is next a blue line of wave length 470.2, and then five strong violet lines of which the fourth is the most brilliant, and has the wave length 420.0. When the current is passed from the induction coil in one direction, that end of the capillary tube next the positive pole appears of a redder, 9-2104 ABSTRACTS OF CHEMICAL PAPERS. Temp. and that next the negative of R bluer hue. There are, in effect, two spectra, which Crookes has succeeded in separating to R considerable extent. A phenomeuon of this order has been attributed to the presence of two gases, and the conclusion would follow that argon is in reality a mixture of two gases, which have as yet not been sepa- rated. This conclusion is, if true, of great importance, and experiments are i n progress to test it by other physical methods. Crookes and also Schuster have proved the identity of the chief lines of t'he spectrum of gas separated from air-nitrogen by aid of magnesium with that remaining after sparking air-nitrogen with oxygen, in presence of caustic soda solution. The solubility of argon in water bas been already alluded to, and special experiments were tried to determine the degree of solubility.The course marked out by Bunsen was followed. The solubility of the gas isolated by means of oxygen was found to be 3.94 per 100 of water at 1 2 O , and argon prepared by means of magnesium gave a result of 4.05 per 100 of water. The solubility is therefore about 2& times that of nitrogen. The fact that the gas is more soluble than nitrogen led to the expectation of finding it in increased proportion i n the dissolved gases of rain water, an anticipation which experiment con6rmed. The behaviour of the gas at low temperatures was examined by Olszewski, whose results are published separately.The following tables are given for convenience of reference. Vupour PTessures. Pressure. I Temp. I Pressure. Temp. I--- -- Pressure. - 186' 9' - 139 *1 -138.3 744) -5 mm. 23 -7 atms. 25'3 ,, -134-4 1 29-8 ,, -121.0 Gas i 60.6 ,, i I --- Critical Boiling Freezing Freezing teE$:" pressure. ' I point. , point. 1 pressure. Density I Density Of liquid Coloar of inn of gas. at liquid. point. Nitrogen, N3 ...... Carbonic oxide, co .................. Argon, A, .........Oxygen, O2 ......... Nitric oxide, NO.. ---!-- -'---- atms. mm. O ? O -121'0 50'6 -186'9 -189'6 -118'8 50'8 -18'2.7 ? - 81.8 54-9 -164'0 -1185.8 , - 93'5 1 71'2 1-153.6 -167.0 In order to decide regarding the elementary 01- compound nature of argon, experiments were made on the velocity of sound i n it. From these the ratio of the specific heat at constant pressure to that at constant volume was deduced in the well-known manner. The accuracy of the apparatus used was tested by preliminary observa-INORO ANIC CHEMISTRY. 105 tions with air, carbonic anhydride, and hydrogen, which gave results in agreement with those of other observers. Five series of ineasure- ments were then made with a sample of gas of density 19.86, and the ratio C,/C, of the specific heats found was 1.644.This is practically the theoretical ratio, 1.66, for a monatomic gas, that is, a gas in which all energy imparted to i t at constant volume is expended in effecting translational motion. The only other gas of which the ratio of specific heats has been found to fulfil this condition is mercury at a high temperature. A great number of attempts were made to induce chemical com- bination with the argon obtained by use of magnesium, but without any positive result. The following substances were tried under different conditions, but without effect :-(a) Oxygen in presence of caustic alkali, ( b ) hydrogen, ( c ) chlorine, ( d ) phosphorus, (e) sul- phur, (f) tellurium, (9) sodium, (h) fused and red-hot caustic soda, (i) soda-lime at a red heat, ( j ) fused potassium nitrate, (k) sodium peroxide, ( I ) persulphides of sodium and calcium, (m) nitro-hydro- chloric acid, (n) bromine water, (0) a mixture of potassium perman- ganate and hydrochloric acid, ( p ) argon is not absorbed by platinum- black.Argon is, therefore, most astonishingly indifferent, inasmuch as it is not attacked by elements of very opposite character ranging from sodium and magnesium on the one hand, to oxygen, chlorine, and sulphur on the other. It will be necessary to try whether tho inability of argon t o combine a t ordinary or at high temperatures is due to the instability of its possible compounds, except when cold. Mercury vapour at 800" mould present a similar instance of passive behaviour. The authors finally discuss the probable nature of the gas or gases which they have succeeded in separating from atmospheric air, and which has been provisionally named argon.It has been shown that argon is present in the atmosphere, and is not manufactured during the process of separation, and it is practically certain that the argon prepared by means of electric sparking with oxygen is identi- cal with argon prepared by means of magnesium. That argon is an element or mixture of elements, may be inferred from the obssrva- tions on the ratio of the two specific heats. For if argon molocules are di- or polyatomic, the atoms acquire no relative motion, even of: rotation, a conclusion improbable in itself and one postulating the sphericity of such complex groups of atoms. But a monatomic gas can be only an element., or a mixture of elements; and hence it follows tbat argon is not of a compound nature.Argon is approxi- mately 20 tinies as heavy as hydrogen, that is, its molecular weight is 20 times as great as that of hydrogen, or 40. But its molecule is monatomic, hence its atomic weight, or, if it be a mixture, the mean of the atomic weights of the elements in that mixture, taken for the proportion in which they are present, must be 40. There is evi- dence both for and against the hypothesis that argon is a mixture ; for the present, however, the balance of evidence seems to point to simplicity. If argon is a single element of the atomic weight 40, no vacant place can be assigned to it in the periodic system, and there is then106 ABSTRAOTS OF OBEMICAL PAPERS.reason to doubt whether the periodic classification of the elements is complete ; whether, in fact, elements may not exist which cannot be fitted among those of which i t is composed. On the other hand, if argon is a mixture of two elements, they might find R place in the eighth group, one after chlorine and one after bromine. It would be difficult, however, in this case to account for the heavier element having escaped detection. If it be supposed that argon belongs to the eighth group, then its properbies would fit, fairly well with what might be anticipated. For the series which contains might be expected to elid with an element of monatomic molecules of no valency, that is, incapable of forming a compound, or if forming one, being an octad ; and it would form a possible transition to potas- sium, with its monovalence, on the other hand. As for the physical condition of argon, that of a gas, we possess no knowledge why carbon, with its low atomic weight, should be a solid, while nitrogen is a gas, except i n so far as we ascribe mole- cular complexity to the former and comparative molecular simplicity to the latter.Argon, with its comparatively low density and its molecular simplicity, might well be expected t o rank among the gases. And its inertness, which has suggested its name, sufficiently explains why it has not previously been discovered as a constituent of compound bodies. Assuming provisionally that it is not ;t mixture, the symbol A is suggested for this element. In addenda by Ramsay, further determinations of the density of argon are given, the general mean being 19.900.The value of R in the gas equation R = p v / T , has been determined between -89" and +248O. The numbers show that argon nndergoes no molecular change within these limits of temperature. Further determinations of the ratio of the two specific heats were also made, the general mean being 1.643. H. C. A Singular Case of Metallic Precipitation. By J. B. SEN- DERENS (Bzill. SOC. Chim., 1894, [3], 11, 424-426; compare Abstr., 1895, ii, 315).-When bright lead is immersed in a solution of lead nitrate containing from 10 to 400 grams per litre, and protected from access of air, metallic lead is gradually precipit'ated on it in well- defined crjstals, just as on iron or zinc. A certain amount of lead nitrite is produced a t the same time, and in weaker solutions forms the exclusive product, being deposited in yellow crystals in place of those of the metal.The lead crystals form plates from 1 to 4 mm. in diameter, and are chemically pure, but they rapidly oxidise in air to the hydroxide, so that a ci-ystallographic examination is impracticable. When kept undisturbed in the original liquid, the metallic crgstnls are gradually converted into a basic nitrate, which crystallises in large, white tufts of silky needles as much as 2 cm. in length. The precipitation of the lead is not due to local electrolytic action set up by metallic impurities, for precisely the same result is ob-INORQAKIC CHEMISTRY. 107 tained with pure lead made by reducing, by means of sugar-charcoal, litharge prepwed from the pure nitrate (compare, however, Zoc.cit.) ; moreover, the precipitation does not occur in solutions of lead acetate, as would be tbe case i f it were due to this cause. JN. W. Double Halogen Salts of Ammonium and Copper. By HORACE L. WELLS and E. B. HURLBURT ( Z e i t . nno~g. Chem., 1895, 10, 157-lGO, and Amey. J. Sci., 1895, [3], 50,390--393).-The chloride, 4NH4C1,Cu,Cl,, is obtained by cooling a mixed solution of its com- ponent salts containing hydrochloric acid, copper wire being placed in the liquid ; a large excess of ammonium chloride must be used ; it crystallises in colourless pIisms, which, on exposure to air, quickly turn brown and then green. The chloride, 4NH4C1,3Cu,C12, is obtained when its component salts are dissolved in the proper proportions in dilute hydrochloric acid ; it crystallises in lustrous, colourless dodecahedra, and is fairly stable on exposure to air, but gradually turns green. The byomide, 4NH4Br,Cu2Br2, obtained in a similar way to the cor- responding chloride, crystallises in long, colourless prisms, and is much more stable than the corresponding chloride; on exposure t o air, it gradually turns green. The bromide, 2NH4Br,Cu,Brz + HzO, is obtained if an excess of cuprous bromide is present ; it crystallises in lustrous, colourless rhombohedra, and is more stable than the pre- cediug salt.The iodide, 2NH4I,CuzI2, is the only salt obtained even when the Components are employed in very diff ereat proportions. E. C . H. Formation of Nickel Carbonyl. By HG. PREY (Bey., 1895, 28, 2512-2514) .-Sodium decomposes ethylic oxalate into ethylic car- bonate and carbonic oxide. When ethylic oxalate is added to finely divided nickel chloride and sodium, suspended in light petroleum, traces of nickel carbonyl are found in the gas which is evolved, but the amount present is so small that no liquid can be obtained. Ferric chloride, when treated in the same way, gave no trace of iron carbonyl. A. H. Double Salts of CEesium Chloride with Chromium Tri- chloride and Uranyl Chloride. By HORACE L. WELLS and B. B BOLTWOOD ( Z e i t . nnorg. Chem., 1895, 10, 181-184 ; also Amer. J. Sci., 1895, [3], 50,254-258).-The chloride, 2CsCI,CrCl, 1- H20, is obtained by saturating warm solutions of its component salts with hjdrogcn chloride, and corresponds with the double chlorides prepared b j Neumann (Abstr., 1888, 655). It crystallises in aggregates of small, reddish-violet crystals, is stable on exposure to air, does not give up its water of crystallisation at loo", and dissolves slowly in water form- ing a green solution. The chloride, 2CsC1,CrCl3 + 4H20, is obtained from a cold solution of its components by sa-turating it with hydrogen chloride, or by evaporation over sulphuric acid; it crystallises i n green, monoclinic crystals, is somew hat hygroscopic, very easily soluble in water, and when heated at 110" loses 3H20, and is converted into the abore violet salt. The aiithors point out that wheraas green chromium sulphate contains less water than the Fiolet modificatior ,108 ABSTRACTS OF CHEMIOAL PAPERS. the reverse is t,he case with the double czsium salts, and that there- fore probably the green colour of the salts is not due t o the formation of basic salts and free acid, or of acid salts. The chloride, 2CsC1,U02CI,, prepared in a similar way to the above, corresponds with the double salts already described ; it crystallises in beautiful yellow, rhombic leaflets. JL C. R. Chemical Behaviour of Pyrites and Mareasite. By AMOS P. BROWN (Proc. Amer. Phil. Soc., 1894, 33, 225-243). See Abstr., 1895, ii, 316.-The constitution here deduced for marcasite is the same at3 that given by Loczka (Abstr., 1895, ii, 20) for pyrites, namely, ,-4 Fe<$ L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8967005092

出版商:RSC    

年代:1896

数据来源: RSC