摘要:

162 ABSTRACTS OF CHEMICAL PAPERS. M i n e r a l o g i c a l Chemistry. Brucite of Cogne, Val d’Aosta. By FRIEDEL (Gazzetta, 13, 278). --This mineral gave by analysis 67-06 per cent. MgO, 1.13 FeO, 29.48 HzO, and 2.13 silica and insoluble matter, total 99-80; or de- ducting the silica and insoluble portion: 68.53 MgO, 1.15 FeO, and 30.13 water = 99.31, agreeing nearly with the formula Mg0,H20 or Ng( 0 H)z, and showing that this mineral is identical with the brucites of other localities, and in particular with that of Hoboken. Like all other brucites, it is accompanied by serpentine. H. W. Chemical Composition of Apatites. By J. A. VOELCKER (Bey., 16, 2460--2464).-The formula 3Ca3(PO4)* + CaP , usually as- signed to apatite, does not appear to be founded on direct determina- tions of all the constituents, but to have been assumed on the strength of its isomorphism with pjromorphite, 3Pb3(P0J2 + PbC1,.In par- { CaC:MINERALOGICAL CHEMISTRY. 163 ' 90.93 l - 2 -38 3 -57 0 -20 0.24 0 -40 0 -92 0 -64 0 -18 0 -04 ticular, the fluorine seems not to have been estimated, but calculated from the excess of lime beyond that required for the phosphate and chloride. The author has determined all the constituents in several samples of apatite, and finds that the amount of fluoride and chloride is always considerably below that required by the above formula, but that there is an excess of calcium oxide present equivalent to the deficiency in the haloid salt, and that apatite must therefore be repre- seuted by the formula- CaCl,. 3Ca3(POJ2 + 1 CaF2. { CaO.The analyses were all made from crystals with completely smooth A and B are Canadian apatites, D, Ea, Eb, and and sharp faces. F Norwegian apatites containing no fluorine. 89-81 1 *42 4-36 0.22 1.67 1.04 0 -39 0.27 - - Ca,P,OB. ....... CaF, .......... CaC1,. ......... CaO .......... CaCO, ....... CaSO, ........ MgO .......... Fe,O,. ......... A1203 ......... Insoluble residue Water ........ 87 96 3.53 3.60 0.25 0-64 0.39 1.89 0.14 - - - Loss on ignition A. B. 1 D. 1 Ea. 1 E6. I F. 89 -36 4 *64 0-14 1 3'2 1 -95 0 -54 0 *19 0 *41 (2 -86 0 -15 0 *04 0 -25 90 -14 1.27 4 -98 0 *25 1 -62 0 *85 0 *34 } 0.44 - - - 90 -14 1 -42 4 -34 0 -22 1'57 1 -04 0 -24 0 -34 - - - ---- I A. J. G. Formation of Albite in the Wet Way. By C. FRIEDEL and E. SARASIN (Compt.r e d . , 97,290--294).-When solutions of sodium sili- catme and aluminium silicate in the proportions necessary to form albite are heated together in a, strong steel tube at about 400°, no albite is formed, but crystals and globules of analcime separate out in considerable quantity, a certain proportion of the sodium silicate and traces of the aluminium silicate remaining in solution. If, however, the sodium sili- cate is added in excess to the extent indicated bythis experiment,and the solution heated at about 500", crystals of albite are obtained identical in chemical composition and physical properties with the natural crystals. The crystals are sometimes slender needles, sometimes shorter and thicker prisms, and some of them show the usual albite twinning.When the solution of sodium and aluminium silicates is mixed with potassium chloride, the results are somewhat contradictory. I n the first experiment, no albite was formed, but crystals of quartz and a quantity of small crystals apparently belonging to the cubical system were obtained. In other experiments, however, both a1 bite and orthoclase were formed simultaneously, but the two minerals did164 ABSTRACTS OF CHEMICAL PAPERS. not crystallise together. Albite is formed even in liquids containing four times as much potassium as sodium, and sodium chloride even in large proportion is apparently without effkct on the formation of the mineral. C. H. B. Rhodonite from Vih. By V. FINO (Gazzetta, 13, 277).-Thi~ rhodonite is red, but is mixed with a black substance difficult to separate, probably ~t product of alteration.The rhodonite has a density of 3.65, hardness 5-5.6. It melts before the blowpipe, gives a brown bead with borax; with phosphorus salt a bead which is opaque when cold, and becomes red in the reducing flame. Its analysis gave- Loss by Si02. MnO. FeO. CaO. ignition. 44.31 48.77 1.53 4.44 1.25 = 100.30 44.34 48.64 1.48 4.57 1-25 = 100.16 agreeing nearly i n composition with the rhodoiiite of S. Marcel, in which Ebelman found 46.37 SiO,, 47-58 MnO, and 5.48 CaO. H. W. Artificial Production of Rhodonite and Zephroite. By A. GORGRU (Comnpt. retid., 97, 320--323).-When a current of hydro- gen and carbonic anhydride cliarged with aqueous vapour is passed overa mixture of 10 parts mnnganous chloride and 1 part precipitated silica fused at a cherry-red heat, the ruanganous chloride is partially decomposed, yielding hydrochloric acid and manganous oxide, which dissolves in the unaltered mangauous chloride and is thus brought into intimate contact with the silica.The first product is a bisilicate, which is obtained in small distinct rose-coloured crystals by treating that part of the fused mass which is insoluble in water with dilute hydrochloric acid (1 : 2). If the action of the moist gas is prolonged, and the residue after being washed with water is treated with very dilute hydrochloric acid (1 : 5 O ) , grey crystals of a norrnal silicate are obtained. I n these experiments, the aqueous rapour is the active agent, the hydrogen or carbonic anhydride simply preventing access of air and consequent formation of hausmannite.The rose-coloured crystals have the compositioii SiOz,MnO, and correspond in crystal- line form and other properties with rhodonite; the grey crystals have the composition Si02,2M n o , and correspond with tephro'ite. The presence of alkaline chlorides has no effect on the production of t,hese compounds. I n presence of the chlorides of iron, magnesium, and calcium, small quantities of these met*als are taken up, but the oxygen ratio remaiiis the same. The artificial crystals are about a degree softer than the natural crystals. Both compounds are anhy- drous, and do not appreciably oxidise in dry or moist air. They melt with difficulty a t a hright red heat, forming a brown enamel, and they dissolve in fused manganous chloride, and are deposited in definite crystals on cooling.The rose-coloured silicate when fused with man- ganous chloride in presence of aqueoiis vapour, is gradnally converted into the neutral silicate, and the latter, when fused with manganous chloride and silica out of contact with air and moisture, is convertedMINERALOGICAL CHEMISTRY. 165 into an acid silicate, insoluble in hydrochloric acid. Hydrochloric acid has little action on the rose-coloured silicate, but attacks the neutral salt even when very dilute ; sulphurous acid also has no action on the first compound, but dissolves the neutral salt. Chlorine water blackens and partly dissolves the grey crystals, but has little action on the acid salt. Saturated solutions of carbonic anhgdride and hydroqen snlphide respectively decompose the neutral salt, but have no action on the other.A 2.8 per cent. solution of sodium hydrogen carbonate has very little action on the rose-coloured salt at 40-60", but partially converts the grey silicate into carbonate. Natural rho- donite behaves in exactly the same way as the artificial product, and i t would appear probable from these reactions that the manganese carbonate, sulphide, and peroxide found in miueral veins have been formed by the alteration of tephroite rather than by that of the much more stable rhodonite. C. H. B. Meteoric Dust and Analysis of the SoiI of Sahara. By TACCHINT (Gazzstta, 13, 327).-An investigation as Lo the origin of the mins of sand and meteoric dust which fall in Italy,. and especially in Sicily, shows that the sand comes from Africa, being raised by cyclones, and carried into Sicily and Italy by the strong south-east and south-west currents.Tacchini and Macagno are comparing these powders with the soil from the Desert of Sahara. Analysis of the Brine-Spring of Stoke Prior, Worcestershire. By A. B. GRIFFITHS (Chenz. News, 48, 207).-This deposit of rock- salt is in the lias; the water is pumped from a depth of over 300 feet. The following are the results of analyses recently made by'the author, which are compared with results obtained by Northcote in 1854 :- C. E. G. Northcote (1854.) Per cent. Soda.. ............ 15.7779 Lime.. ............ 0.1075 Magnesia .......... 0.0165 Ferric oxide ........ trace Chlorine .......... 15.4697 Phosphoric acid ....trace Silicic acid ........ trace Lithium - Bromine .......... trace Potash.. .......... trace Sulphuric acid.. .... 0.4888 .......... Gri5ths (1883.) I. 11. Per cent. Per cent. 137741 13.7752 0.11 192 0,1085 0 0159 0.0173 trace trace 15.4620 15.4683 trace trace trace trace trace trace trace trace trace trace 0.4890 0.4892 1 T-L- It contains 25.49 per cent. sodium chloride, the brine is therefore a baturated solution; the sp. gr. is 1.2049 a t 24". D. A. L.162 ABSTRACTS OF CHEMICAL PAPERS.M i n e r a l o g i c a l Chemistry.Brucite of Cogne, Val d’Aosta. By FRIEDEL (Gazzetta, 13, 278).--This mineral gave by analysis 67-06 per cent. MgO, 1.13 FeO,29.48 HzO, and 2.13 silica and insoluble matter, total 99-80; or de-ducting the silica and insoluble portion: 68.53 MgO, 1.15 FeO, and30.13 water = 99.31, agreeing nearly with the formula Mg0,H20 orNg( 0 H)z, and showing that this mineral is identical with the brucitesof other localities, and in particular with that of Hoboken.Like allother brucites, it is accompanied by serpentine. H. W.Chemical Composition of Apatites. By J. A. VOELCKER (Bey.,16, 2460--2464).-The formula 3Ca3(PO4)* + CaP , usually as-signed to apatite, does not appear to be founded on direct determina-tions of all the constituents, but to have been assumed on the strengthof its isomorphism with pjromorphite, 3Pb3(P0J2 + PbC1,. In par-{ CaCMINERALOGICAL CHEMISTRY. 163' 90.93l -2 -383 -570 -200.240 -400 -920 -640 -180 -04ticular, the fluorine seems not to have been estimated, but calculatedfrom the excess of lime beyond that required for the phosphate andchloride.The author has determined all the constituents in several samplesof apatite, and finds that the amount of fluoride and chloride isalways considerably below that required by the above formula, butthat there is an excess of calcium oxide present equivalent to thedeficiency in the haloid salt, and that apatite must therefore be repre-seuted by the formula-CaCl,.3Ca3(POJ2 + 1 CaF2.{ CaO.The analyses were all made from crystals with completely smoothA and B are Canadian apatites, D, Ea, Eb, and and sharp faces.F Norwegian apatites containing no fluorine.89-811 *424-360.221.671.040 -390.27--Ca,P,OB........CaF, ..........CaC1,. .........CaO ..........CaCO, .......CaSO, ........MgO ..........Fe,O,. .........A1203 .........Insoluble residueWater ........87 963.533.600.250-640.391.890.14---Loss on ignitionA. B. 1 D. 1 Ea. 1 E6. I F.89 -364 *640-141 3'21 -950 -540 *190 *41(2 -860 -150 *040 -2590 -141.274 -980 *251 -620 *850 *34} 0.44---90 -141 -424 -340 -221'571 -040 -240 -34------- IA. J. G.Formation of Albite in the Wet Way. By C. FRIEDEL and E.SARASIN (Compt. r e d . , 97,290--294).-When solutions of sodium sili-catme and aluminium silicate in the proportions necessary to form albiteare heated together in a, strong steel tube at about 400°, no albite isformed, but crystals and globules of analcime separate out in considerablequantity, a certain proportion of the sodium silicate and traces of thealuminium silicate remaining in solution.If, however, the sodium sili-cate is added in excess to the extent indicated bythis experiment,and thesolution heated at about 500", crystals of albite are obtained identicalin chemical composition and physical properties with the naturalcrystals. The crystals are sometimes slender needles, sometimesshorter and thicker prisms, and some of them show the usual albitetwinning. When the solution of sodium and aluminium silicates ismixed with potassium chloride, the results are somewhat contradictory.I n the first experiment, no albite was formed, but crystals of quartzand a quantity of small crystals apparently belonging to the cubicalsystem were obtained.In other experiments, however, both a1 biteand orthoclase were formed simultaneously, but the two minerals di164 ABSTRACTS OF CHEMICAL PAPERS.not crystallise together. Albite is formed even in liquids containingfour times as much potassium as sodium, and sodium chloride even inlarge proportion is apparently without effkct on the formation of themineral. C. H. B.Rhodonite from Vih. By V. FINO (Gazzetta, 13, 277).-Thi~rhodonite is red, but is mixed with a black substance difficult toseparate, probably ~t product of alteration. The rhodonite has adensity of 3.65, hardness 5-5.6. It melts before the blowpipe, givesa brown bead with borax; with phosphorus salt a bead which isopaque when cold, and becomes red in the reducing flame. Its analysisgave-Loss bySi02.MnO. FeO. CaO. ignition.44.31 48.77 1.53 4.44 1.25 = 100.3044.34 48.64 1.48 4.57 1-25 = 100.16agreeing nearly i n composition with the rhodoiiite of S. Marcel, inwhich Ebelman found 46.37 SiO,, 47-58 MnO, and 5.48 CaO.H. W.Artificial Production of Rhodonite and Zephroite. ByA. GORGRU (Comnpt. retid., 97, 320--323).-When a current of hydro-gen and carbonic anhydride cliarged with aqueous vapour is passedovera mixture of 10 parts mnnganous chloride and 1 part precipitatedsilica fused at a cherry-red heat, the ruanganous chloride is partiallydecomposed, yielding hydrochloric acid and manganous oxide, whichdissolves in the unaltered mangauous chloride and is thus brought intointimate contact with the silica.The first product is a bisilicate,which is obtained in small distinct rose-coloured crystals by treatingthat part of the fused mass which is insoluble in water with dilutehydrochloric acid (1 : 2). If the action of the moist gas is prolonged,and the residue after being washed with water is treated with verydilute hydrochloric acid (1 : 5 O ) , grey crystals of a norrnal silicateare obtained. I n these experiments, the aqueous rapour is the activeagent, the hydrogen or carbonic anhydride simply preventing accessof air and consequent formation of hausmannite. The rose-colouredcrystals have the compositioii SiOz,MnO, and correspond in crystal-line form and other properties with rhodonite; the grey crystalshave the composition Si02,2M n o , and correspond with tephro'ite.The presence of alkaline chlorides has no effect on the production oft,hese compounds.I n presence of the chlorides of iron, magnesium,and calcium, small quantities of these met*als are taken up, but theoxygen ratio remaiiis the same. The artificial crystals are about adegree softer than the natural crystals. Both compounds are anhy-drous, and do not appreciably oxidise in dry or moist air. They meltwith difficulty a t a hright red heat, forming a brown enamel, and theydissolve in fused manganous chloride, and are deposited in definitecrystals on cooling. The rose-coloured silicate when fused with man-ganous chloride in presence of aqueoiis vapour, is gradnally convertedinto the neutral silicate, and the latter, when fused with manganouschloride and silica out of contact with air and moisture, is converteMINERALOGICAL CHEMISTRY.165into an acid silicate, insoluble in hydrochloric acid. Hydrochloricacid has little action on the rose-coloured silicate, but attacks theneutral salt even when very dilute ; sulphurous acid also has no actionon the first compound, but dissolves the neutral salt. Chlorine waterblackens and partly dissolves the grey crystals, but has little actionon the acid salt. Saturated solutions of carbonic anhgdride andhydroqen snlphide respectively decompose the neutral salt, but haveno action on the other. A 2.8 per cent. solution of sodium hydrogencarbonate has very little action on the rose-coloured salt at 40-60",but partially converts the grey silicate into carbonate.Natural rho-donite behaves in exactly the same way as the artificial product, andi t would appear probable from these reactions that the manganesecarbonate, sulphide, and peroxide found in miueral veins have beenformed by the alteration of tephroite rather than by that of the muchmore stable rhodonite. C. H. B.Meteoric Dust and Analysis of the SoiI of Sahara. ByTACCHINT (Gazzstta, 13, 327).-An investigation as Lo the origin of themins of sand and meteoric dust which fall in Italy,. and especially inSicily, shows that the sand comes from Africa, being raised bycyclones, and carried into Sicily and Italy by the strong south-eastand south-west currents. Tacchini and Macagno are comparing thesepowders with the soil from the Desert of Sahara.Analysis of the Brine-Spring of Stoke Prior, Worcestershire.By A. B. GRIFFITHS (Chenz. News, 48, 207).-This deposit of rock-salt is in the lias; the water is pumped from a depth of over 300 feet.The following are the results of analyses recently made by'the author,which are compared with results obtained by Northcote in 1854 :-C. E. G.Northcote (1854.)Per cent.Soda.. ............ 15.7779Lime.. ............ 0.1075Magnesia .......... 0.0165Ferric oxide ........ traceChlorine .......... 15.4697Phosphoric acid .... traceSilicic acid ........ traceLithium -Bromine .......... tracePotash.. .......... traceSulphuric acid.. .... 0.4888..........Gri5ths (1883.)I. 11.Per cent. Per cent.137741 13.77520.11 192 0,10850 0159 0.0173trace trace15.4620 15.4683trace tracetrace tracetrace tracetrace tracetrace trace0.4890 0.48921 T-L-It contains 25.49 per cent. sodium chloride, the brine is therefore abaturated solution; the sp. gr. is 1.2049 a t 24". D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600162

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

166 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Galician Petroleum. By B. LACHOWICZ (Annulen, 220, 188-206).-The volatile portion of the petroleum from Boryslaw, in Galicia,boiling between 30' and 125", contains the following hydrocarbons :-(1) Tsopentnne boiling at 30", which yields a chloride boiling a t 100"(sp. gr. 0.8703 at 20"); (2) normal pentane boiling at 37" (sp. gr.0.6267 at 14"), yielding two chlorides boiling a t 106" and 104";(3) a hexane boiling at 60" ; (4) hexane boiling a t 70" (sp. gr. 0.6985at 14") ; ( 5 ) heptane boiling at 99"; ( 6 ) nonane boiling a t 148"; and(7) decane boiling a t 152", and a decane boiling a t 16.2-163" (sp. gr.0.7324 a t 20") ; also benzene, toluene, xylene, and mesitylene. Thepetroleum does not contain any olefines.The author is of opinionthat olefines do not occur ready formed in petroleums, but that theyare produced in the process of distillation,The relatively high sp. gr. of certain portions of the distillate of thepetroleum, from which the hydrocarbons of the benzene series have beenremoved, leads the author to infer the presence of the hydrides of thearomatic hydrocarbons, e.g., hexahydrotoluene and hexahydro-iso-Some Paraffins and their Derivatives. By B. LACHOWICZ(Annulen, 220, 168--188).--Dia,myl, Cl,,H22, prepared by the actionof sodium ,on amyl bromide from commercial amyl alcohol, boils at157*1", and has the sp. gr. 0.72156 at 22". It is a tasteless liquid,having a, faint odour. It is soluble in 12 parts of acetic acid a t theordinary temperature, and is miscible with alcohol, ether, benzene,and chloroform in all proportions; it is not attacked by sulphuricor nitric acid.No bromide couldbe isolated by the action of bromine on diamyl, as the product splitsup into decylene and hydrobromic acid on distillation. Decylene(boiling at 161.5') has an aromatic odour.Normal decane, obtained by the action of sodium on a mixture ofoctyl and ethyl bromides diluted with benzene, is tasteless, and almostinodorous. It boils a t 169*5", and ignites at 55". Its sp. gr. at 18"is 0.73097. Dioctyl (melting a t 19-20") is-obtained as a bye-product.Secondary octyl bromide (sp. gr. 1,0989 a t 22"), boils at 188", withslight decomposition. Octglene boils a t 122.4".When sodium acts on a mixture of ethyl bromide and secondaryoctyl bromide, dioctyl and butane are formed, but decane is not pro-duced.Dioctyl is a thick colourless liquid?, boiling at 263" (sp. gr.0.80011 at 11').xylene. w. c. w.The hydrocarbon ignites at 53".The paraffins are almost devoid of smell. w. c. w.Butylene and its Derivatives. By E. PUCHOT (Ann. China. Phys.[ 5 ] , 28, 507-569) -Butglene is most conveniently prepared bywarming a mixture of fermentation butyl alcohol (24 pnrts), aulphuricacid (26 parts), plaster of Paris (4 parts), and potassium sulphatORGANIC CHEMlSTRY. 167(1 part). The gas is passed through two flasks containing milk of limeor soda ; it is then dried over quicklime, and condensed by a freezingmixture. At the ordinary temperature, water absorbs one-tenth itsvolume of the gas, alcohol 36 vols., and glacial acetic acid, 62 vols.Liquid butylene boils at -4".Butylbutyrate and isotribntylene are obtained in small quantities as bye-products in the preparation of butylene. They are also formed by theaction of phosphorus pentachloride on butyl alcohol, and hutylbutyrate is produced on heating but$ alcohol with phosphoric anhy-dride. Butylene is absorbed by sulphuric acid, yielding isotributy-lene boiling at E O " , and a mixture of isomeric bodies boiling between172" and 244'. Butylene iinites with bromine to form the dibromideC4H8Br2, a colonrless liquid boiling a t 153" (sp. gr. at 0" = 1.8053) ;with hydriodic acid it yields an iodide which boils with decompositiona t 100.25".Cold concentrated h-jdrochloric acid absorbs butylenewith formation of the tertiary chloride boiling a t 55" (sp. gr. 0.8658at 0"). In diffused daylight chlorine unites with butylene to formthe dichloride C,H,CI,, boiling a t 129". The product of the action ofalcoholic potash on this chloride contains oxygen. At the ordinarytemperature in direct sunlight, chlorine replaces 4 atoms of hydrogenin the chloride, yielding the compound C4&CI6. At a higher tem-perature, chlorine expels two more atoms of hydrogen and C4H2C16 isformed. The former compound is decomposed by alcoholic potash ;4 mols. of hydrochloric acid being eliminated, and C4C12 produced : itis an unstable liquid, which appears to boil above 200". Alcoholicpotash deconiposes the chloride CaHzC16, yielding a componnd having w.c. w.Some Reactions of Tertiary Alcoholic Iodides. By K. BAUER(Amalen, 220, 158--166).-Tertiary pentyl iodide is decomposed bywater into hydriodic acid and ethyl dimet,hjl carbinol. It is also decom-posed by methyl alcohol at loo", yielding methyl iodide and tertiaryamyl alcohol. Under similar treatment tertiary butyl iodide yieldsmethyl iodide and trimethyl carbiuol. On heating a mixture of methylhcetate and tertiary butyl or amyl alcohol for several hours, methyliodide, acetic acid, and butylene or amylene are produced.Menthyl Chloride. By G. ARTH (Con~pt. rend., 97, 323-324).-When an ethereal soltition of menthene is treated with hydrochloricacid gas, or when menthene and a concentrated solution of hydrochloricacid are heated together in sealed tubes a t 120", menthene hydrochloride,C,,H,,,HCI, is obtained.It is an oily liquid, which burns with a green-edged flame, and cannot be dis.tilled without decomposition. Whenboiled with water, i t yields hydrochloric acid and menthene, and whenheated with silver acetate in a closed vessel, i t yields acetic acid, silverchloride, and mentbene, but no menthyl acet<ate. This compoundtherefore agrees in its properties with the menthyl chloride obtainedby Oppenheim by the action of coilcentrated hydrochloric acid onmenthol in a closed vessel, and the author considers that the two corn-pounds are identical, j nst as camphme hydrochloride and the chlorideobtained from borneol are identical.These last two compounds, how-Its sp. gr. a t -14.2' is 0.639.the composition (C4Cl&w. c. wL 68 ABSTRACTS OF CHEMICAL PAPERS.ever, apnear to be true hydrochloric ethers, whilst the derivatives ofmenthol have no analogy to the hydrochlorides of terebenthene.The menthene used by the author wa-s dextrogyrate, unlike that ofWalter, Oppenheim, and Moriya, which was inactive.Silver Nitrocyanide. By C. L. BLOXAM (Chew. News, 48, 154).-The author has examined the crystalline compound obtained by dis-solving pure silver cyanide in a nearly saturated boiling solution ofsilver nitrate. It is anhydrous, and is decomposed by water into silvercyanide and nitrate. Analysis gives 68.09 per cent. total silver, deter-mined in nitric acid solution of the compound ; 22.97 per cent.silveras qanide, determined in residue from decomposition with water ;45.64 per cent. silver as nitrate, determined in aqueous extract. Itsconstitution is therefore AgCy,2AgNOa, and not AgNOs,2AgCy, as isgenerally supposed. D. A. L.C. H. B.Reaction between Mercuric Cyanide and Silver Nitrate inPresence of Ammonia. %y C. L. BLOXAM (Chew. News, 48,161).-Wohler obtained a salt having the formula AgN0,,HgCy2 +2Aq, from which, according to Gmelin’s Hamibook, alkalis throwdown silver cyanide, a reaction incompatible with the above formula.Tlie author has iiivestigated the subject, and his results form thesubstance of this pr\per.When neutral solution^ of mercuric cyanide and silver nitrate aremixed together, the mixture becomes acid, indicating the formation ofmercuric nitrate, whilst it deposits a crystalline double salt.Thesame salt is formed when precipitated silver cyanide is dissolved in asolution of mercuric nitrate. The aqueous solution of the salt is pre-cipitated by ammonia and by hydrocyanic acid, which causes theseparation of silver cyanide, indicating the presence of silver nitratein the salt.If mercuric cyanide in solution is added hy degrees to an ammo-niacnl solution of silver nitrate, a white, opaque and silky crystallineprecipitate separates, The two precipitates have the same composi-tion, and t h e numbers from analysis, after corrections have beenmade for impurities, agree with those required by the forrnula2BgO,HgCy2,7AgCy :-4.Hg. CY-Calculated (for formula) . . 46.60 36.99 14.42Found .. .. .... .. .... .. .. 46.43 37.03 14.29The impurities found were 0.32 per cent. of ammonia and 2.11 percent. nitric acid. The silver was determined as chloride, the mercuryas sulphide, and the cyanogen by converting it into ammonium thio-cyanate, and subsequent precipitation with silver nitrat,e. Both pre-cipitates are anhydrous and explode when heated, the opaque onemore violently than the crystalline. The filtrate from these precipi-tates deposits silver cyanide, and the filtrate from this contains asmall quant)ity of silver and much mercury and cyanogen.The author is therefore of opinion that in the above experimentsthe mercuric cyanide and silver nitrate are conrerted, a t least parORGANIC CHEMISTRP, 169tially, into silver cyanide and mercuric nitrate, and the precipitateformed in the presence of ammonia is composed of silver cyanide andmercuric oxycyanide.D. A. L.Influence of Asymmetrical Carbon-atoms on the EthanesDerived from Active Amy1 Alcohol. By I?. JUST (Annalen, 220,146-157) .--In order to observe the influence of asymmetrical carbon-atoms on the optical activity of organic compounds, and to test theaccuracy of Le Bel's hypothesis (Bull. Xoc. Chim. [2], 22, 337) theauthor has examined a series of the derivatives of active amyl alcohol.The amyl alcohol was prepared from fuse1 oil by Le Bel's process.Repeated attempts to obtain the methylamyl described by Le Be1(ibid. [2], 25,545) proved unsuccessful, but the following compoundswere investigated.Isopentune, boiling a t 30", prepared by the actionof zinc and hydrochloric acid on an alcoholic solution of active amyliodide ; methylethy~ropylmethane, boiling at Yl", from amyl and ethyliodides, and dianayl which yielded the following results :-SP. gr. c.1.Amyl alcohol, C2H5.CHMe.CH2.0H .......... - - 2.82Amyl iodide, C2H5.CHMe.CH21 .............. 1,5425 at 16" + 2.43Ethyldimethylmethane, C2H5.CHMe2.. ........ 0.6375 at 13 0MethJ'lethJ'lpropJ'l- C2H,.CHNe.CH2.CH2Me. . 0.6895 a t 20 + 3.93Active diamyl, C2H5.CHMe.CHz.CHz.CHMe.C2H5 0.7463 at 22 + 8.69These results confirm the accuracy of Le Bel's hypothesis.P-Butyl Glycol.methane ...... 1w. c. w.By A. WURTZ (Cornpt.rend., 97, 473-475).-The action of sodium-amalgam on a cold dilute slightly acid solutionof aldol yields butyl glpcol, which forms a thick perfectly colourlessliquid boiling a t 207-208" under a pressure of 769 mm., and solublein all proportions i n water, alcohol, and ether ; sp. gr. a t 0" = 1,0259.It is violently attacked by phosphorus pentach loride, with formationof a small quantity of a chloride boiling at 130-135", and anotherproduct which cannot be distilled, but which contains both chlorineand phosphorus. Acetic chloride also reacts violently with butylglycol, forming hydrochloric acid and an acetin which cannot be purifiedfrom chlorine even by distillation with silver acetate. The same acetinis easily obtained by heating the glycol a t 100" in sealed tubes forseveral days with 6 or 8 times its weight of acetic anhydride. Itforms a colourless neutral liquid, insoluble in water, with a feebleacetic odour; sp.gr. a t 0" = 1.055. It has the compositionC4H,(zO),. When the butyl glycol is heated for some time with alarge excess of highly concentrated hydriodic acid it yields butylenedi-iodide, C4HsT2, probably CHMeI.CH,CHJ ; sp. gr, a t 0" = 2.291.That fraction of the crude butyl glycol which boils at 220-250"under ordinary pressure, contains a substance which boils a t 160-165" under a pressure of 15 mm. It has the same composition asdialdanic alcohol, C14H1603, and is probably an isomeride of thatbody. It yields an acetin. C. H. B.VOL. XLVI. 91 70 ABSTRACTS OF CHEMICAL PAPERS.Fermentation of Glycerol with the Bacteria from Ammo-nium Tartrate.By A. VIGNA (Gaazetta? 13, 293-296; Ber., 16,1438).-The glycerol (2,200 grams) mixed with a solution of potas-sium phosphate (22 grams) and ammonium tartrate (44 grams), isdiluted with water (40 litres), and a small portion of liquid containingthe bacteria of ammonium tartrate added ; this is easily obtained byadding to a solution of ammonium tartrate a small quantity of the saltsnecessary to nourish thebacteria, and exposing it to the air until theyhave developed. The glycerol mixture is allowed to ferment for twomonths at a temperature of 20-25", adding calcium carbonate fromtime to time to neutralise the paraffin acids as they are formed:hydrogen and carbonic anhydride are el-olved during the whole timethat the fermentation is going on ; when gas is no loiiger given off theliquid ie distilled with excess of calcium carbonate ; ethylic alcohol(72 grams), normal butylic alcohol (196 grams), and an insignificantquantity of the higher alcohols pass over with the aqueous vapour.The author has not as yet examined the residuum containing thecalcium salts.As the yield of normal butyl alcohol is 9 per cent. ofthe glycerol employed, it seems to be the most convenient process forpreparing that compound.Electrolysis of Glycerol with Electrodes of Carbon and Pla-tinum. By A. BARTOLI and G. PAPASOGLI (Gaazetta, 13, %37--293).-The authors have already published on this subject (Abstr., 1882,406).EZectroZysis with Gas-carbon Electrodes.-The glycerol diluted withan equal bulk of dilute sulphuric acid (1 : 5), was electrolysed, usingsi,x Bunsen's elements which were renewed every five days; thenegative electrode was of platinum, and the positive of gas-carbon ;hydrogen in abundance was evolved a t the negative pole, and but verylittle gas at the positive pole, which was rapidly disintegrated, bein?reduced to one-third of its weight after the action had continued fora month.An abundant black deposit of carbon mixed with mellogenformed at the bottom of the voltameter ; the liquid became dark, andthere was an intense, suffocating odour of acraldehyde.The liquid, filtered from the black deposit and neutralised withbarium carbonate, yielded a nearly colourless solution ; on distillingthis, water passed over, together with trioxymethylene which is leftin the crystalline state on evaporating the distillate over sulphuricacid (RQnard, Abstr., 1880, 25).It melts a t 155", is but sparinglysoluble in water, insoluble in alcohol, and reduces Fehling's solutionand nitrate of silver. When hydrogen sulphide is passed into itssolution a t 60°, a white precipitate of methylene oxysulphide,( CsH,S,0)2,H20, is obtained : this has a marked alliaaeous odour, andmelts at $0". If the aqueous solution of trioxymethylene is evapo-ratedon the water-batlh, taking care always to keep it strongly alkalinewith ammonia, a substance is obtained melting at 120-125", andhaving all the properties of Butlerow's kexamethylenamine, C,H,,N,.The solution of barium salts remaining in the retort was carefullyexamined and found to contain glyceric acid and a small quantity of a,saccharine substance, but no benzenecarboxylic acids ; much unclecorn-posed glycerol was also present.C.E. GORGANIC, CHEMISTRY. 171Electrolysis with Graphite Electrodes.-The electrolysis took placein much the same way as with the carbon electrodes, only that the solu-tion remained colourless, and the graphite (positive) electrode was butvery little disintegrated, the small quantity of black deposit formedconsisting of a mixture of unaltered graphite with graphitic oxide.The solution, when neutralised with barium carbonate and distilled,yielded trioxymethylene, and the residue in the retort was found tocontain, besides glycerol, formic acid and a substance having many ofthe characters of a glucose, but incapable of undergoing fermenta-tion ; with ammoniacal lead acetate this new compound yields a whiteprecipitate insoluble in water.The glucose solidifies over sulphuricacid, but is not crystallisable; it is soluble in alcohol, and easilyreduces Fehling's solution and ammoniacal silver nitrate,Electrolyfiis with Platinum Electrodes.-When both the etectrodmare of platinum, gas is evolved in abundance a t both poles ; there is apowerful odour of acraldehyde, and the liquid remains colourless.The solution when treated in the way previously described was foundto contain formic and glgceric acids and a minute quantity of a c.E. G.Maltose. By A. EERZFELD (AnnaZen, 220, 206--224.).--Therotatory power of a 5 per cent. solution of pure maltose was found t obe [a]= = 139", which agrees closely with Soxhlet's results [a]D =139*3", and differs considerably from that found by O'SuElivan,[aIn = 149.5". Maltose forms the following compounds with sodiumand calcium, C12H21Na011 and C12H&aOll + H20, and analogous coni-pounds with barium and strontium.The octacetic derivative, C12HICOI&6, crys Wises in thin prismswhich belong to the mcno- or tri-clinic system. The crystals meltwith decomposition a t 150-155". They are soluble in ether, waymalcohol, benzene, and acetic acid. For the solution in benzene [a]== 81.18".The reducing action of maltose on Fehling's solution is equal toabout two-thirds of that of glucose, but if the filtrate from thecuprous oxide is acidified with hydrochloric acid the solution slowlyacquires the power of reducing a further quantity of Fehling's solu-tions equal to about half the volume originally reduced.I n thisrespect maltose resembles lactose. A second point of analogy is thatneither of these sugars form double salts with borax, o r with potas-sium or sodium chlorides or bromides.Maltose is not a simple anhydride of glucose ; its molecular weightmust be a t least 3 times as great as that of diglucose.substance resembling a glucose.w. c. w.Saccharin. By C. SCHETBLER (Ber., 16, 24-34).-1n the pre-paration of saccharin by the action of the alkaline-earths on theglucoses, the author has observed that a vigorous absorption of oxygenfrom the air always occurs.He is working a t this subject and also atthe action of aqueous ammonia on the glucoses.By L. PRATESI (Gazaetta, 13, 313-315).-0n distilling a mixture of paraformaldehyde (trioxymethylene)with ethyl alcohol and bulphuric acid- continuing the distillalionA. J. G.Diethyl Methylene Ether.n 172 ABSTRACTS OF CHEMICAL PAPERS.until it becomes turbid on the addition of water,-a product is ob-tained which, when treated with water and calcium chloride, yieldsimpure diethyl methylene ether, CH,(OEt),. It may be purified bydigesting i t with potash, first in a flask furnished with a reflux con-denser, and then with fresh potash in a sealed tube heated a t 100".It boils a t 87-88', has a sp.gr. of 0.8504 a t O", and a vapour-density of 102 referred to hydrogen, C,H,,O, requiring 104. It is lesssoluble in warm water than in cold, requiring 11 vols. of water at 18"f o r t h a t purpose, and 15 ~01s. a t 30".The boiling point and solubility of the substance show that it isisomeric with Wiirtz's methylacetyl, so that there can be no doubtthe formida C,H,(OEt).OMe, assigned by Wurtz to the compoundobtained by the action of sulphuric acid and manganese dioxide on amixture of ethyl and methyl alcohols, is correct.Action of Ammonia on Propaldehyde. By A. WAAGE(Monatsh. Chem., 4, 708--732).-This paper gives a detailed accountof experiments, a preliminary notice of which has already beenpublished (Abstr., 1883, p.39). These experiments confirm theforma tion of parvoline, C9H13N, from the crystalline compoundC15H25N3 produced by the action of carbonic acid on propaldehyde-ammonia, C,H,O,NH, or CH,Me.CH(NH,) (OH), or from its mother-liquor or the crude product containing the two. When this crystal-line product is heated with dilute hydrochloric acid, propaldehyde andmethylethylacraldehyde, CGH,,O, distil over, and the residue distilledwith potash yields parvoline, together with a dark resinous residue :C. E. 0.2C15H29N3 + 6Hz0 = CgHJ? + CsHioO + 5C3HCO + 5NH3 + HZ.Parvoline thus obtained is a mobile, colourless, strongly refractiugliquid, boiling at 198-200", lighter than water, having a very strongaromatic odour like that of the ohher pyridine-bases, and an extremelybitter taste.It is not very soluble in water, but dissolves readily inalcohol and ether; forms white fumes with hydrochloric acid, andcolours pine-wood yellow. With picric acid, it forms a compound con-taining molecular proportions of its two constituents. This compoundforms crystalline lamin= having the colonr of picric acid, more solublein alcohol than in water, melting at 149". With tannin solution,parvoline forms st white flocculent precipitate, easily soluble in alcohol ;with phosphotungstic acid it forms a faint bluish-white body, whicliincreases on addition of hydrochloric acid and is insoluble in alcohol ;withpotassio-nzercuric iodide, a yellowish-white precipitate, easily solubl ein alcohol and in hydrochloric acid.Iodised solution of potassium iodideforms with it a brown flocculent precipitate soluble with violet colourin carbon sulphide. Potassio-bismuthous iodide forms a dark brownprecipitate soluble in hydrochloric acid, and coloured yellow by alcohol.Parvoline aurochloride crystallises in deliquescent yellow needles.The parvoline formed as above agrees with that which is obtainedfrom bituminous shale in all its properties except the boiling point,which the author finds to be 198-200", whereas shale parvoline boilsat 188'. The lower boiling point of the latter is probably due to theadmixture of lower homologuesORGANIC CHEMISTRY. 173The decomposition of the compound ClaHB,N, by hydrochloric acidyields also a small quantity of a lower base of the series, viz., C6H7N(composition determined by analysis of platinochloride), which distilsfor the most part a t 160", has a more pungent odour than parvoline,and appears to be identical with picoline.Oxidu,tion of ParvoZine.-This base oxidised with potassium perman-ganate is converted into a pyridine-dicarboxjlic acid, C7H,NOa =C,H,N(COOH),, which cq-stallises in crusts of chalky microscopicneedles melting a t 219".It gives a red coloration with ferrous sul-phate ; with lead acetate after a whiie a, white precipitate ins6lubIein excess; with silver nitrate a white flocculent precipitate, easilysoluble in ammonia and in nitric acid ; blue-green with cupric acetate.Its cadrrtium salt is obtained by precipitation, as a white crystallinebodj, C7H3NOdCd,4H20, which gives off half its water on prolongedstanding over sulphuric acid, or when heated to 1410".In most ofthese characters the acid in question agrees with lutidic acid (Moiiatsli.Chern., 1, 20) ; the latter however and its copper salt are described ascontaining crystal-water, whereas the pyridine-dicarboxylic aciddescribed above and its copper salt are anhydrous; lutidic acid isalso described as more soluble in water than Waage's acid. Thecalcium salt of the acid heated in a, tube with excess, of quicklimeyielded a distillate of pyridine. H. W.Tobacco Fat. By R. KISSLING (Ber., 16, 2432-2434).-Thevegetable wax occurring in tobacco, and usually termed " tobaccofat," has not previously been obtained in a state of purity.To pre-pare it, tobacco is extracted with ether, the extract, after the removalof the greater part, of the ether, mixed with alcohol and the pre-cipitated wax purified by repeated crystallisation from hot alcohol.The wax then forms a snow-white mass of satiny lustre, melts a t 63",and on analysis gave numbers agreeing with the formula C70H14002,but after removal of a small quantity of a substance insoluble in coldether, the result's agreed better with Cs,H,,,O2 (mellissyl-mellisate).Kentucky tobacco yielded 0.18 per cent. of wax.In the course of some investigations on the constituents of tobacco-smoke, a wax-like body was obtained, similar in appearance to tobacco-wax, melting a t 64.5", but appearing, from its analysis, to be a hydro-carbon containing C 84.7-85.5 per cent., and H 14.63-15.16 per cent.By A.RENARD (Compt. rend., 97,328 - 330). -When that portion of crude rosin-oil which boilsbetween 180" and 200" is treated repeatedly with sulphuric acid andcarefully distilled, i t yields a light oil which boils at 193-195", and isnot attacked by ordinary sulphuric acid. This liquid has the com-position CIIH,, ; Tapour-density, 5-37 ; sp. gr. at 19"'= 0.8588. It isan isomeride of laurene. It dissolves in fuming nitric acid withdevelopment of heat and evolution of nitrogen oxides, forming a heavyoily orange-coloured mononitro-derivative, C,,H,,N02. The hydro-carbon is only slightly attacked by ordinary nitric acid in the cold, butyields isophthaiic acid when boiled with it.It is, therefore, metaethyl-propylbenzene, C,H,EtPr [l : 31. On treating it with fuming sul-A. J. G.An Isomeride of Laurene174 ABSTRACTS OF CHEMICAL PAPERS.phuric acid, a sulphohic acid is formed. The barium salt is somewhatsoluble in boiling water, but only very slightly soluble in cold water.It forms brilliant white crystalline plates which, when dried a t IOO",have the composition ( C,,H,jSO,)zBa + HzO, but become anhydrousa t 175".The metaethylpropylbenzene contains a sniall quantity of a hydro-carbon which is not attacked by fuming sulphuric acid or by ordinarynitric acid. It is in all probability one of the higher members of theC.H,,-,H6 series. C. H. B.Chemical Nature of Phlorol. By V. OLIVER~ (Gazzetta, 13,263--269).-When barium phloretate is distilled over an open fire withlime and powdered glass, part of it is resolved into phlorol, C,H,,O,and carbonic acid: (CgHg03)2Ba + CaH,O, = 2C8H,,0 + COaBa +C03Ca, while a portion of the phlorol undergoes further decomposi-tion into ethylene and ordinary phenol : C,H,,O = C,H, +C6H60.The phlorol thus obtained is a colourless strongly refractive liquid,having the characteristic odour of the phenols, boiling a t 210-212",soluble in alcohol and ether, slightly soluble in water.I t s aqueoussolution gives a faint green coloration with ferric salts. Its potassiumsalt is easily decomposed by carbonic acid. The methyZic ether,C,H,,O = C,H,Et.MeO, prepared by digesting molecular proportionsof phlorol and potassium hydroxide dissolved in anhydrous methjlalcohol, is a heavy strongly refracting oil having a pleasant ethericodour, boiling a t 185", not oxidised by potassium permangannt,e.Ph ZoroZcarboxzJZic acid, C9H1,03 = H0.C6H3Et.COO~I, prepared byheating phlorol with sodium and carbonic anhydride, crystullises i nslender silky colourless needles, slightly soluble in cold water, verysoluble in alcohol and in ether, melting at 112".Its aqueous solutionis coloured violet by ferric chloride. I t s bnri?im salf,(€30. C6H3Et. COO)J3a,H20,crystallises in small scales. By fusing phlorol with potassium hydr-oxide, two acids are obtained, viz., salicylic acid melting at 156--158",and a small quantity of metahydroxybenzoic acid, a t 190-19.5".The phlorol prepared as above is identical with the ortho-ethyl-phenol, C6H4Et.0H, which Suida and Plhon obtained by the action ofiiitrous acid on amidethplbenzene (Abstr., 1881, 268), and Beil-stein and Ruhlherg by fusing potassium ethylbenzenesulphonate withpotassium hydroxide (Anrlderr, 156, S l l ) , the products formed inthese several processes agreeing in boiling point, in their behaviourwith fused potash, and with bromine-water, and in yielding carboxylicacids exhibiting similar properties.By G.SCHIAPARELLI and M. A BRT,LI (Gazzetta,13, 25 7) . - M o n o n i t r o d i b e i r z o r e s o r ~ ~ ~ ~ Z , C6H3 (NO,) ( O E ) 2, obtainedby heating dibenzoresorcinol (m. p. 117") with a mixture of Sdphuricand nitric acids, crystadlises in stellate groups of needles melting a t107", and is resolved by saponification into benzoic acid and mono-iiitroresorcinol melting at 115'.7'1.initrodibenzoresorcinoZ, C6H(N02),(O~)2, is formed on dissolvingdibznzoresorcinol in cold strong nitric acid (sp.gr. 1-5), and separatesH. W.NitroresorcinolsORGANIC CHEMlSTRY. 175on addition of water, as a faintly yellowish solid substance which,after crystallisation from methyl alcohol, melts a t 123". By saponi-fication with alcoholic potash, it is resolved into metanitrobenzoic acidand nitroresorcinol melting a t 115", ethyl metanitrobenzoate meltinga t 43" being formed at the same time. The separation of the m-nitro-benzoic acid and nitroresorcinol was effected by the differsnt solubili-ties of their copper-salts.On dissolving dincetylresorcinol in well cooled nitric acid of sp.gr.1.45 and adding water, a white or slightly yellowish substaiice aepa-rates, consisting of a mixture of dinitroresorcinol and styphnic acid,melt'ing a t 17.5". The dinitroresorcinol separated from this mixtureby fractional crystallisation, melts at 214.5'.Arbutin. By J. HABERMANN (Monatsh. Chem., 4,753-786) .-Thispaper gives a detailed description of a large number of experiments onthe composition of arbutin and its behaviour at high temperatures,tending to esta,blish the correctness of the formula C2sH3.1014, deducedby Hlasiwetz and Habermann for arbutin, from the occurrence ofinethylquinol, C,H80z, as a product of its decomposition (Rer., 14,302), in opposition to the view put forward by H.Schiff (Gazzetta, 11,99 ; and Abstr., 1881, 610) and Michael (Ber., 14, 2097 ; and Abstr.,1882, 174) that two different arbutins occur in nature, viz., arbutin,C12H1607, and methylarbutin, Cl3HI80,.Hydroxybromotoluquinone. By G. SPICA and 0. MAGNANIMI(Gazzetta, 13, 31&----313).-A paper by Spica and Canzoneri on somebrominated derivatives of toluquinone has been already published(Abstr., 1883, 330), in which i t is stated that the action of potassiumhydroxide on tribromotoluquinone gave rise to resinous productsfrom which nothing could be obtained in a state fit for analysis. Theauthors now find that on treating the tribromoquinone with a 5 percent. solution of potassium hydroxide in the cold, it dissolves, and onacidifying with hydrochloric acid a reddish flocculent precipitate isobtained.This is somewhat difficult to purify, but by repeated treat-ment with cold benzene the impurities are dissolved, and a reddiah-white substance is left; this may be purified by recrystallisation,first from dilute alcohol, and then by dissolving it in absolute alcoholand allowing i t to crgstnllise by spontaneous evaporation. It formspale rose-coloured crystals of the composition C6HMeBr,(OH) : 02",melting at 196-197'. The yield is very small, being only about5 per cent. of the tribromotoluquinone employed. When submittedto the reducing action of sodium amalgam it does not yield ahydroxytoluquinol, but the action goes further, and cresol is formed.From want of material the authors have not as yet been able to ascer-tain which cresol this is.C. E. G.H. W.H. W.Electrolysis of Pyrogallol. By E. ROTONDI (Gazzetta, 13, 279).-By electmlysing solutions of pyrogallol acidulated with sulphuric acid,the author has obtained, at the positive pole, mixed with other products,n crystalline substance, which after recrystallisation exhibits all theproperties of purpurogallin. From his electrolytic researches he is in176 ABSTRACTS OF CHEMICAL PAPERS.clined to think that purpurogallin is not a direct product of the oxida-tion of pyrogallol, but is derived from an intermediate compound.Pyr0~01l. By G. L. CIAMICLAN and P. SILBER (Qazzetta, 13, 320-322).-In a paper by Ciamician and Danesi (Abstr., 1882, 875), theydegcribed a compound of the formula C5CliN0, obtained by the actionof phosphorus pentachloride at 250" on perchloropyrocoll, whichevolved ammonia in abundance when boiled with potassium hydroxidesolution. This compound is decomposed when heated with water a t130" into ammonia, carbonic and hydrochloric acids, and an acid freefrom nitrogen, which may be extracted from the solution by meansof ether.It melts at 85-86", and has all the properties of the a-di-chloracrylic acid obtained from mucochloric acid by Bennet and Hill(Abstr., 1879, 616). The barium and silver salts also correspond withthose described by these chemists.It would seem, therefore, that the decomposition of the compoundC,HiNO takes place in the manner represented by the equationSynthesis of Acetylphenylparacoumaric and Phenylpsra-coumaric Acids- By A.OGLIALORO (Gazzetta, 13, 173).-The first ofthese acids is formed on heating parahydroxybenzoic acid aldehydewith acetic anhydride and sodium alphatoluate ; the second by boilingthe first with baryta-water. Acetylphenylparacoumaric acid melts a t1 70", phenylparacoumaric acid at 219".Synthesis of Phenylmelilotic Acid. By S. SARDO (Gazzetta,13, 273).-This acid, discovered by Oglialoro (Gazzettu, 9, 428 ; andAbstr., 1880, 164), is formed by the action of sodium amalgam onphenglcoumarin dissolved in dilute alcohol. On decanting the result-ing alkaline solution, filtering, and acidifying with hydrochloric acid,a viscid substance separates, from which, by fractional extraction withether, evaporation, treatment of the residue with water containing alittle alcohol, and fractional crystallisation, pheny lmelilofic acid,Clal103 = C9H9Ph03, is obtained in small prisms, melting at 120",slightly soluble in cold, more readily in boiling water, also in ether,alcohol, benzene, and chloroform.Its silver salt, C15H1303Ag, obtainedby precipitation, is white, alterable by light, slightly soluble in cold,somewhat more freely in boiling water, and crystdlisable.Electrolysis of Solutions of Ammonia and Ammoniacal Saltswith Carbon Electrodes. By A. BARTOLI and G. PAPASOGLI (Gnzxetta,Electrolysis of Solutions qf Ammonia with Electrodes of Gas-carbon07, Wood-charcuaZ.-Pure ammonia solution is electrolysed withdifficulty, requiring a powerful pile, but iE it is mixed with an alka-line salt the liquid conducts the current and is decomposed.Theauthors employed a saturated aqueous solution of ammonia mixed withhalf its volume of a solution of pure sodium chloride and a, pile offour to six Bunsens, which was allowed to act for periods varyingfrom a week to t w o months, the battery charges being renewed everyH. W.C5HiNO + 5H2O = C3ClZH20 + 3HC1 + NH, + 2C02.C. E. G.H. W.H. W.13, 281-286)ORGANIC OHEMISTRY. 177three or four days. The carbon used for the electrodes was purifiedby heating it to a very high temperature in a current of chlorine.The evolution of gas from the negative electrode was considerable,although but little was given off from the positive : the latter wasstrongly acted on, and a black powder was deposited at the bottom ofthe voltameter, whilst the supernatant liquid was almost colourless.The solution evolved abundance of carbonic anhydride when neutra-lised with hydrochloric acid, and the addition of barium chloride t,henproduced a precipitate from which mellic, pyromellic, and hydro-mellic acids were isolated and recognised ; the filtrate from the mixedbarium salts contained hydropyromellic acid.The black precipitate at the bottom of the voltameter, after beingwashed free from ammonia, was boiled for a long time with soda solu-tion, filtered, and the black filtrate precipitated with hydrochloricacid in excess: this precipitate is insoluble in water or acids.It isblack, uncrystallisable, neither melts nor volatilises, and containscarbon, hydrogen, oxygen, and nitrogen.Like mellogen, it yieldsbenzenecarboxylic acids when treated with oxidising agents, butdiffers from it in containing nitrogen.E lectrdysis of Ammoniacal S a Its with Carbon Electrodes.-Solutionsof ammoniacal salts when electrolysed in the manner above describedyield a precipitate containing mellogen free from nitrogen, but noappreciable quantity of benzenecarboxylic acids could be found in theclear solution.Electrolysis of Ammonia with Electrodes of Graphite.-The experi-ments were conducted in precisely the same manner as those first de-scribed, nsing, however, electrodes of purified graphite. Gas wasgiven off from both electrodes, but only in small quantity from thepositive.which became gradually disintegrated and formed a blackprecipitate. Mellic acid was detected in the clear Supernatant liquid,which also appeared to contain pyromellic, hydromellic, and hydro-pyromellic acids. The black precipitate was nothing but disintegratedgraphite.Electrolysis of Ammoniacat Salts with Electrodes of Graphite.-Afterpassing a strong current for 15 days, the clear liquid was examined,b u t no trace of benzenecarboxylic acids or any other carbon compoundcould be detected. The black precipitate was a mixture of unalteredgraphite with graphitic acid, and another substance analogous tographitic oxide, sparingly soluble in alkaline aud ammoniacal solu-tions ; the yellow liquid thus obtained deposited dark red flocks whenacidified.It will be seen from the above that when ammonia solution is elec-trolysed, using electrodes of gas-carbon or wood-charcoal, i t yieldsbenzenecarboxylic acids, as is the case with solutions of the fixedalkalis under similar conditions, but that the black powder formed bythe disintegration of the electrodes differs from mellogen in that itcontains nitrogen ; moreover, the authors have shown that this blacksubstance is essentially distinct from ulmic compounds, since it yieldsmellic acid when treated with oxidising agents, whilst ulmic COUI-pounds do not.C. E. G175 ABSTRACTS OF CHEMICAL PAPERS.Ethylic Dinitrophenylacetoacetate. By J. HECKMAWN (AmaZen,220, 123--146).-EthyZic orthoparctdinkts.o~henylacetucetate,is prepared by adding a slight excess of dinitrobromobenzene inalcoholic solution to a mixture of sodium ethylate and ethyl acetoace-tate in their molecular proportions.The liquid is kept at a tempera-ture of 20-25" for a week; a t the end of this time it will have lostits alkaline reaction, and on the addition of water ethylic dinitro-phenylacetacetate will he precipitated. If a higher temperature is em-ployed, a portion of the ethylic dinitrophenylacetoacetate is decomposed.The crude product is purified by recrystallisation from warm alcohol.Unaltered dinitrobromobenzene is removed by dissolving the crystalsin cold diliite potash, and rapidly reprecipitating with dilute hydro-cIiloric acid. The pure ethylic salt crystallises in amber-colouredprisms or plates, which appear to belong to the triclinic system.Thecrystals are soluble in warm alcohol, ether, benzene, and chloroform.They melt a t 94", and decompose a t a higher temperature with slightdetonation. On boiling with water containing 10 per cent. of sul-phuric acid, orth~~aradii~itrol?h enylncetic, carbonic, and acetic acids,and dinitrotoluene melting at 70" are formed. Dinitrophenylacetia acid,C6H3(NO&CH2.COOH [CH,.COOH : NO, : NO, = 1 : 2 : 41, crystal-lises in pale yellow needles melting at 160O. Ethylic dinitrophenyl-acetoace tate dissolves without decomposition in cold dilute alkalis,but on boiling with alcoholic potash the solution blackens and decom-position ensues, a black amorphous acid being produced, together witha white crystalline compound of the composition C24H,8N60,5, meltingat 105.5", which is sparingly soiuble in boiling alcohol.The crystal-line substance dissolves in dilute potash or soda, forming a blue solu-tion, and is reprecipitated by carbonic acid. On ahaking a solution ofthe substance in benzene with alcoholic potash, the compoundC2rH,6K,N,0,5 is obtained in golden plates, which explode whenheated.The black compound mentioned above is also formed by the actionof alcoholic potash on the preceding substance or on dinitrophenyl-acetic acid. It appears to have the composition C4,H,,N6OI9, and toyield a silver salt, CasH2,Ag3N,019, containing 3 mols. H,O.Azylines. By E. LIPPMANN and F. FLEISSNER. Third Memoir.(Monatsh.Chem., 4, 'i88--799).-The action of methyl iodide ondiethylanilinazyline is very different from that of ethyl iodide(Abstr., 1883, 868). On heating the azyliiie with 4 mols. methyliodide in a sealed tube a t loo", dissolving the resulting crystallinemass in wateia, evaporatiug to a syrup, repeatedly boiling with waterthe resinous substance which separates out, evaporating the solutionsthereby obtained t o the crystallising point, and repeatedly preci-pitating with alcohol, white shining four-sided needles are obtained,melting a t 218". and consisting of the di-iodomethylate of dimethyl-dieth yl-paraphenylenediami?~e, CI4H,,N,I2 = CeH4(NMe2) (NEQ ,2MeI,or rather perhaps tetmmethyl~iet~yl-par~phen~lammonium iodide,NMe,I.C6H4.NEt,MeT. This iodide dissolves very easily in water,C H,C 0.C H( C 0 OE t ) . Cc,H,( NO,) 2,The crystals are soluble in water, yielding a blue solution.w. c. wORGANIC CHEMlSTRY. 179sparingly in alcohol, and not a t all in ether. It is not attacked bystrong potash-lye, but silver oxide decomposes it immediately, formingthe corresponding hydroxide C laH26 Nz(O €3) ,.When diethy I-p-phenylenediamine is treated with methyl alcoholand hydrochloric acid at 200°, the contents of the tube precipitatedwith potash, and the separated oil dried and fractionated, diethyl-dimethyl-$7-phenylenediamine, NEk.C,H,.NMe,, is obtained, as afaintly yellow oil, which turns brown in the air, and exhibits a deepblue colonr with oxidising agents, e.g., copper sulphate, potassi urndichromate, iodine, bleaching powder, &c. This base, heated withmethyl iodide, is converted into the compound C1,HZ6N,T, abovedescribed.Oxidation.- Azylines a1.e but slightly attacked by weak oxidisingagents, undergoing no alteration on exposure to the air at ordinarytemperatures, and very little when heated above their melting points.Potassium permangannte acts on them but slowly in alkaline, veryquickly i n acid solntion.Chromic acid, manganese dioxide, and sul-phuric acid, as well as lead dioxide, act on them with violence. Withpotassium permangante, the chief products formed are acetic, carbonic,and oxnlic acids. With chromic acid 01- a mixture of potassium di-chromate and sulphuric acid, the liquid froths, emits a peculiar odourlike that of chlorine, and deposits a small quantity of yellow needles,easily volatile with water-vapour, very soluble in ether : probablyquinone.When diethylanilinazyline is slowly added to well-cooled red nitricacid of sp.gr. 1.5, it dissolves, and the solution diluted with waterdeposits shining red needles of dinitrorliethylaniline, C,H,(N0,),Et2N,contaminated with brown products. The same compound is, however,more easily and abundantly obtained by adding ordinary strong nitricacid to a well-cooled solut'ion of the azyline in glacial acetic acid, thenprecipitating with water, and crystallking from alcohol. The com-pound thus obtained forms orange-red needles melting a t 180", easilysoluble in hot alcohol, also in benzene and in ether, sparingly i n lightpetroleum.I n these and all its other characters it agrees with thedinitrodiethylaniline which von Romburgh obtained ( RRC. Trau. Uhim.,2, 35; Rer., 16, 1496) by the action of red nitric acid (sp. gr. 1-48>on diethylaniline dissolved in strong sulphuric acid. By boilingwith potash, i t is resolved into diethylamine and dinitrophenol :CsH,(N0,)2.NEt2 + KHO = NHEt, + C6H,(N0,)2.0K. The authorsfound that this decomposition is effected only by very strong potash-I?., and that it, is accompanied by the evolution of ammonia anddiethylamine. According to Rombnrgh, the dinitrophenol producedin this reaction is the ordinary modification OH : NO, : NO = 1 : 2 : 4 ;consequently the two nitro-groups i n the corresponding aniline deli-vatives must be similarly situated [NH, : NH,: NO, = 1 : 2 : 41.AZYLINES OF TERTIARY DIPHENTLAMINES.- These compounds areformed by passing nitrogen dioxide through an alcoholic solution of aI ertiary diphenylamine, the liquid then turning red, and yieldingafter some time R crystalline deposit of the azyline, mixed withcoloured secondary products, which greatly diminish the yield of thenzyline. They are weak bases, forming neither salts nor doubla corn180 ABSTRACTS OF CHEMICAL PAPERS.pounds.acid, a green coloration, both these reactions being very delicate.With hydrochloric acid they give a blue-violet, with aceticMeth yldip henylaminaxy line,C26HZd'N4= PhMeN.C6H4.N N.CsH4.NPh&fe,forms yellow crystals, melting at 150°, very slightly soluble in coldalcohol, freely in chloroform and benzene.Et h y ldip hen y laminaz y l ine,separates from alcoholic solution in large red monoclinic crptals,exhibiting the combination OP.P. mP and the opposite faces. Axialratio a : b : c = 0.206106 : 1 : 1.1826. Angle ac = 92" 29' 30". DoubleBy G- ROUSSEAU (Ann. Chim. Phys. [SIP28? 145--198).-0f the a- and @-naphthols, the latter alone yields 8hydroxyaldehyde when heated with chloroform and alcoho!ic potash(Reimer and Tiemann's reaction) ; but only one such compound is ob-tained, and not a mixture of two isomerides (comp. Ahstr., 1882, 735,1211, 1299). During t'he course of the reaction, large quantities ofresinous substances are formed, from which the aldehyde may be sepa-rated by steam distillation.The aldehyde crystallises in slenderrefractive needles, which melt a t 77". Its ethereal solution gives acrystalline magma with sodium hydrogen sulphite ; it combines alsowith aniline, yielding a yellow crystalline compound melting a t 90".The principal product, of the reaction is, however, an aromatic glycol,C,2H,2(OH)2, formed probably by the partial hydrogenation of thehy droxyaldehyde, two molecules of which combine together withelimination of two molecules of water. This glycol forms smallwhite crystals, which are with difficult,y separated from the adheringresins ; it is insoluble in alkalis, soluble in concentrated sulphuricacid, with production of a blood-red solution, from which red crystalsof an ethereal sulphate separate out.This glycol and its immediatederivatives are characterised by the readiness with which they aretransformed into the corresponding ether, C2,HI2O ; in this respect theglycol is analogous to the pinacones. The bromhydrin has beenalready described (Zoc. cit., 1299) ; it takes up a molecule of bromine,yielding the compound C,H12Br(OH) ,Br,, which crystallises in yellowleaflets resembling lead iodide, and decomposes a t 280" withoutmelting. The chlorhydrin, C,Hl,Cl(OHj.HC1,30H2, cryst allises inred needles. Both the brom- and chlor-hydrin, when dissolved inacetic acid, yield on evaporation of the solution a crystalline substance,consisting of a molecule of the halo'id ether and a molecule of aceticacid.The ether, C22H:120, can be obtained by the action of dehydrating orreducing agents on the glycol, or by boiling the ethereal derivativeswith alcohol ; it cryRtallises in pale yellow needles which melt at 198",insoluble in cold alcohol, readily soluble in acetic acid.By the actionof hydrogen, it is converted into the rnonohydrozy 1 akohol, C22H13,0H.The monethyl derivative of the glycol, C,,H,,(OH).OEt, preparedrefraction very Ptrong, H. w.An Aromatic GlycolORGANIC CHEMISTRT. i a iby decomposing the chlor-, brom-. or iod-hydrin with alcoholicpotash, forms small feathery crystals, which by solution in benzeneand subsequent evaporation is separable into two substances, the onemelting at 250°, and probably identical with the monhydroxyl alcohol,the other cr.ystallising in brilliant leaflets, melting at 144", or theethyl derivative.The amido-derivative, C,,H,2(0H).NH,, obtained by the action ofammonia on the bromhydri 11, crgstallises in slender colourless needles ;it acts as a weak base, combining with hydrochloric or hydrobromicacids to form crystalline salts, of which the hydrochloride yields aplatinochloride salt, crystallising in golden needles.Both the hydro-chloride and hydrobromide are converted into the ether when boiledwith alcohol.The monoatomic alcohol, C22H13011, alluded to above, is one of theproducts of the reaction of chloroform with alcoholic potash on&naphthol, but is best prepared by the action of reducing agents onthe chlor- or brom-hydrin. It crgstallises in silky needles, which de-compose at 260".When heated with the haloiId acids, it is probablyreti*ansformed into the halogen derivatives of the glycol.The glycol, when heated t o a red heat with soda-lime, is decomposedinto carbonic anhydride and a dinaphthyl, probably identical with thecompound obtained by Watson Smith by passing naphthalene vapourthrough a red-hot tube (eomp. Trans., 1879, 224-232).Colocynthin. By G. HENKE (Arch. Pharrn. [3], 21, 200--205).-The bitter principle of colocynth, or Citrullus colocynthus, was obtainedby Walz in the following manner :-The colocynth was exhausted withalcohol (sp. gr. 0.40) and the residue from the evaporation of thealcoholic solution dissolved in cold water, and precipitated with leadacetate. The lead was removed from the filtrate by sulphuric acid,and the liquid precipitated with tannic acid.This precipitate, afterbeing dried, was dissolved in alcohol, and the tannic acid precipitatedby lead acetate ; the lead was then removed from the filtrate, and thesolution digested for some time with animal charcoal. The -filtratefrom this solution evaporated to dryness and extracted with ether,left, a residue of colocynthin. This was subsequently slowly depositedfrom a solution in alcohol in yellowish-white tufts of crystals. Itsformula was found to be C56H12023. It was soluble in 8 parts of coldand 6 parts of hot water. By treatiiient with acids, colocynthin wassaid to yield a sugar having the foi*mula C,,Hl,,O,o, and colocyntheh,C.ilH32C)13, which is soluble in ether.The author attempted to extractcolocynthin by a similar process, with the difference that the tannateof colocyn thin was decomposed by evaporation with freshly precipitatedlead carbonate, and the colocynthin extracted from the dry residuewith absolute alcohol. The colocynthin obtained by this method is inthe form of a light yellow powder, which could not be crystallised.It is without action on litmus, insoluble in chloroform, ether, benzene,carbon bisulphide, and light petroleum, but soluble in 20 parts of coldand 16 parts of hot water. It is also soluble in alcohol, and is repre-cipitated in white flocks on adding ether. Concentrated sulphuricacid dissolves it in the cold, producing a deep red solution; the colo-V. H.V182 ABSTRACTS OF CHEMICAL PAPERS.cynthin is carbonised by heating this solution. Dilute sulphuric acidhas no action. The aqueous solution of colocynthin easily reducesFehling's solution. Concentrated hydrochloric and nitric acids bothdissolve colocynthin, forming coloured solutions, and on boiling thehydrochloric acid solution a dark green greasy substance is precipi-tated, which after being dried over sulphuric acid, is only partlydissolved by ether. The hydrochloric acid solution from which thissubstance was obtained reduces Fehling's solution. The author con-siders that these experiments, as far as they go, fail to confirm theresults previously obtained by Wale.Laserpitin. By R. K ~ L Z (Arch. Pharm. [3], 21, 161-175).-The author has made an investigation to determine the nature of thebitter principle Zaoelpitin, which is contained in the root of Lnserpitiu?~,Eut<foZiurn, or white gentian root, and to discover the connection (Ifany) which obtains between this substance and the bitter principlescontained in ot-her umbelliferous plants.Laserpitin.-The finely sliced root was extracted by boiling withlight petroleum, and on evaporating the solution 2rserpiti.tz was depo-sited in crystals belonging to the monoclinic system.These werepurified by recl;ystallisation from light petroleurn, and were found tocontain no water of crjstallisatiou. Laserpitin melts at 118", is inso-luble in dilute acids o r alkalis, but is easily soluble in chloro-form, ether, benzene, and carbon bisulphide.Concentrated acidsdecompose it, sulphuric acid dissolving it with the production of adeep red colour. This same colour is observed when Zaserpitirz isboiled with concentrated hydrochloric acid, or with alcoholic potash.A series of combustions of the pure laserpitin gave numbers point-ing to the formula CI5H2,O4. No chloride or bromide of laserpitincould be obtained, but an acetate, C15H2?04,&OH, crystallised insilky needles from a solution in acetic acid ; even this salt was unstable.Several derivatives of laserpitin were obtained. An attempt to Fro-duce an acetyl derivative by the direct action of acetic chloride o racetic anhydride gave negative results.When laserpitin is distilled with zinc-dust o r soda-lime, no benzeneor other aromatic hydrocarbon is obtained, from which the authorconcludes that the molecule of laserpitin contains no compound con-stituted on the type of the closed carbon-ring.The action of concentrated hydrochloric acid on an alcoholic solu-tion of laserpitin gives rise to methylcrotonic acid, and the action ofconcentrated sul phuric acid yields angelic acid.* When laserpitinis heated with dilute nitric acid, oxalic acid is one of the products.Ebullition with alcoholic potash yields angelic acid, and fusion withpotassia m hydroxide, me thy lcrotonic acid.Monucetyl Zaserpitin, C&,&04, may be obtained by the action ofacetic anhydride on laserpitin in presence of anhydrous sodiumacetate.It crystallises in colourless needles melting a t 1 1 3 O , and* I n another place the author mentions the production of angelic acid by theaction of hydrochloric acid, and of metliylcrotonic acid bv tlie action of sulphuricacid on laserpitin, but from internal evidence this is probably a mis-statement.-W.R. D.W. R. DORGANIC CHEMlSTRY. 183soluble in glacial acetic acid, alcohol, ether, and chloroform, but inso-luble in water.Dirzitrolaserpitin, CI5H,,( N0z)20,7H20, is obtained as an amorphousmass by the action of nitric acid on Zasel-pitin. It melts at 115", andis insoluble in water, but soluble in alcohol, ether, chloroform, andglacial acetic acid.Bronzolaserpitin, C30H,,Br,0,, obtained by the action of bromine ona solution of laserpitin in chloroform, crystallises in rosettes, whichare soluble in ether, alcohol, chloroform, and glacial acetic acid ; theymelt at 90".Luzeriw, C20H3005, is a resinom substance (called by t9he authorZaxerol) which is produced when concentrated acids o r alkalis act onlaserpitin.It is insoluble in acids, but is dissolved by ether, alcohol,chloroform, and glacial acetic acid. Its production, together withangelic acid or methylcrotonic acid, by the action of sulphuric o rhydrochloric acids on laserpitin, is symbolised by the equation2CisHyzOa + HzO = CzoH,oOti + 2csHgoz.Attempts to produce derivatives of this body were unsuccessful. Frointhese results, the author infers that laserpitin is chemically differentfrom peucedanin, ostruthin, and athamantin, bitter principles whichhave been found in other umbelliferous plants.W. R. D.Quinaldine Bases. By 0. DOEBNER and W. v. MILLER (Rer., 16,2464-2472) .--Several methods for the preparation of quinaldine havebeen already described (Abstr., 1882,868; 1883, 602; and Ber., 16,165,and 1835), but it is most simply effected by heating on the water-batha mixture of If parts paraldehyde, 1 part aniline, and 2 parts hydro-chloric acid; in all probability the aldehyde is first converted intoaldol by the hydrochloric acid, but whether this reacts directly on theaniline, or is first converted into crotonaldehyde, remains an openquestion. The hydrochloric acid may be replaced by ohher eoncen-trated acids, but the yield is not so good.Tetrahydroquiiaiildi.lle, CloH13N, is readily obtained by the action oftin and hydrochloric acid on quinaldine ; it forms a colourless liquidof agreeable odour, boil8 at 246--248", a t 709 mm.pressure, issparingly soluble in water, readily soluble in alcohol, ether, and ben-zene. Its salts crystallise well, are generally readily soluble in water,and are characterised by the blood-red coloration produced in theiraqueous solution by oxidising agents. The ylatinochloride formsclear yellow needles. Nitrous acid gives a yellow nitroso-compound ;from this, hydroquinaldirie must be a secondary base, standing toquinaldine in the same relation as piperidine does to pyridine, and. A base of this formula having the constitution C6Hhas been obtained by Jackson (Abstr., 1881, 742) from methylphenylethjl ketone, which from its properties appears to be identical withtetrahydroquinoline.Methyl hydropuirbaldine, CloHlzNMe, obtained by the action ofNH.CH.CH3 /4\CH,.AH184 ABSTRACTS OF CHEMICAL PAPERS.methyl iodide on hydroquinaldine. is a colourless liquid boiling at245-248" at 708 mm. pressure. The platinochloride,is sparingly soluble in water. Other alkyl derivatives have beenobtained ; they are all characterised by yielding green colouringmatters when heated with benzotrichlot-ide and zinc chloride.QuinaZdin,e methiodide, CIoH,N,MeI, is obtained by the direct uniorrof methyl iodide and quinaldine ; it crystallises in long citron-yellowneedles, melts at 195", is readily soluble in water and hot alcohol,insoluble in ether. When heated with concentrated potash, it yieldsa very small quantity of a carmine colouring matter.MethylquinaZdirLes.-On treating the isomeric toliiidine i n a mannersimilar to that already described in the case of aniline, three methyl-quinaldines are obtained.OrthornethyZq~innZc~, CloHpMeN [ 1 : 21, is a colourless liquid,which soon turns brown on exposure to air, boils at 252", is sparinglysoluble in water, readily soluble in alcohol and ether ; its odour closelyresembles that of quinaldine.The dichromate, (CllHllN)2,Cr207H2,crptaJlises in orange-yellow needles, readily soluble in water. ThepZatinochZoride, (C11HllN)Z,HZPtC16, forms bright yellow needles,sparingly soluble in water. IIydro-orthomethyZqu/inaZdine, C,,Hl,MeN,is a colourless liquid of agreeable odour ; it boils at 260--262", and iscbaracterised by the sparing solubility of its hydrochloride in hydro-chloric acid. The platinochloride forms round nodules of concen-trically grouped brownish-red needles.The hydro-base gives a blood-red coloration with ferric chIoride, and on treatment with methyliodide, yields a liquid methyl derivative, CI1HI4NMe.Paramethy ZrluinaZdine, CloH,MeN [ 1 : 41, forms large colourlessrhombic prisms, melts at 60", arid boils at 266-267". It has an odourlike that of aniseed, is sparingly soluble in hot water, readily in alcohol,ether, and benzene. The dichrornate, ( C1lH,lN)Z, Cr20,H2, forms longyellow needles, sparingly soluble in cold water. The pZuttinochZoride,(ClIH,,N)2,HZPtC16,crystnllises in nearly colourless slender needles, and is sparingIysoluble in hot water.H~droparameth~ZquinaZdii~e, Cl0H,,MeN, formsa colourless, mobile liquid, boils at 267", is sparingly soluble in water,readily in alcohol and ether. Solutions of its salts give a red colora-tion with ferric chloride.Metamethy ZpzLinaZdine, C,,H,SleN [ 1. : 31, crystallises in colourlessneedles, melts at 61", and boils at 264-265" ; is sparingly soluble inwater, readily soluble in alcohol, ether, and benzene. It has a faintquinaldine-like odour. The dichrorzzate, ( Cl~HllN)2,Cr207H2, crystal-lises in long -orange-red needles, nearly insoluble in water. Theplatinochloride, (C11HllN)2,H2PtC16, forms tufts of small yellow needles,sparingly soluble in water.All pri-mary amines of the aromatic series appear to react withaldehyde to form quinaldine-like bases, several of which are beinginvestigated by the authors. A.J. GORGANIC CHEMISTRY. 185Quinaldic Acid (a-Quinolinecarboxylic Acid). By 0. DOEBNERand W. v. MILLER (Ber., 16, 2472--2476).--In their earlier experi-ments on the oxidation of quinaldine (Abstr., 1883, 602), the authorswere unable to confine the oxidation to the methyl-group ; they havenow accomplished this by dissolving 10 grams of the base in sulphuricacid (1 : 5), adding a solution of 28 grams of chromic acid and 40grams of sulphuric acid in 100 C.C. of water, and heating on thewater-bath until the chromic acid is completely reduced. Quinaldicacid, C6H/ I , so obtained, crystallises with 2 mols.H,O in colourless asbestos-li ke needles, sparingly soluble in cold,readily in hot water.Quinaldicacid yields salts with both acids and bases, of which those with acidscrystallise the best. The sulphate is readily soluble in water; thenitrate crystallises in prisms and is sparingly soluble in water contain-ing nitric acid ; the hydrochloride, CloH7N02,HC1 + H,O, forms largetables sparingly soluble in water.( C ~ O H ~ ~ ~ Z ) ~ ~ H ~ C ~ Z ~ ~ ,forms red crystals sparingly soluble in cold water. The picrate crgs-tallises in tufts of long yellow needles readily soluble in hot waterand alcohol. The platinochZoride, ( CloH7N02) ,Hd?tC16 + 2H,O,forms tabular crystals sparingly soluble in cold, readily soluble in hotwater.The quinaZdates of the alkalis are readily soluble in water.CaZciumquirzaZdate, Ca( G,oR6N02)z, is obtained as a white precipitate sparinglysoluble in water. The copper salt, CU(CIOH~NOZ), + 2H@, forms amicrocrystalline bluish-green precipitate. The silver salt is obtainedas an amorphous precipitate, not decomposed by light ; it dissolves inhot concentrated solution of silver nitrate ; on cooling a double COM-pound of the formula CloH6NOzAg + CJ&N02,N03H .t H,Oseparates in silky needles.On heating quinaldic acid to a little above its melting point, it isquantitatively decomposed into carbonic anhydride and quinolines.This acid completes the series of quinolinecarboxylic acids inwhich the carboxyl is considered to. be attached t o the pyridinenucleus, and from its formation from quinaldine must be the a-acid.p-Quinolinecarboxylic acid was obtained by Riedel from P-ethylquino-line (Ber., 16, 1613), whilst the quinolinecarboxylic acid obtained byGraebe and Caro (Abstr., 1880, 338) must have the carboxyl-groupin the yposition.Caffeine and its Salts.By EL BIEDERMANN (Arch. Pharm. [S],21, 175--18Ci).-The author has examined caffe'ine and its principalsalts, as the existence of many of these has recently been denied byseveral authors. Caffeine, C8HloN,0z,H20, melts at 230.5" ; the auro-chloride of caffeyne has the formula, C8H,oN402,HCl,AuC13 + 2Hz0,and the platinochloride the formula (CsH,,Na0~)2,HzPtC16. Caffeinehydrochloride, C8H10N402,HC1 + 2Hz0 ; hydrobromide,N=C. CO OH\CH=CHThe anhydrous acid melts at 156".The dichromate,A.J. G.C8H,,N4O2,HBr + 2H20 ;VOL. XLVI. 18 6 ABSTRACTS OF CHEMICAL PAPERS.nitrate, C8H10N402,HN03 + H20 ; sulphate, CsH~oN40z,HzS04 ; for-mate, C8Hl0N4O2,H2CO2 ; acetate, C8H,,,N,0,, (ZHO)? ; benzoate,CsHl,,N40z,C4H,02 ; and valerate, C8H10~402,C5Hlo02, were all obtainedin the crystalline state by dissolving caffeine in the appropriateacid, and evaporating the solution over potash. All these salts areunstable, and cannot be crystallised from alcohol o r water ; at 100'they are either wholly o r partially decomposed. Anhydrous chlorideshaving the formuIae C8HloN402,4HC1 and C8H,oN402,MCl, were obtainedby the action of dry hydrochloric acid gas on caffe'ine. A normalsulphate was also obtained which crystallised with 1 mol.H20. Whencaffeine is dissolGed in a strong solution of hydriodic acid and thesolution evaporated over potash, the normal hydriodide is not aloneobtained, but a periodide, (C8H,oN40z,HI,12)z + 3H20, and also amixture of the normal hydriodide, C8HloN40z,HI, and the hydriodide,C8H10N402, 2HI. W. R. D.Papaverine. By G. GOLDSCHMIEDT (Mondsh. Chew., 4,704- 707).-The oxidation of papaverhe with potassium permanganate yieldsnothing but uncrystallisable products. On boiling this base with asomewhat dilute solution of potassium permanganate, ammonia isgiven off, and an uncrystallisable acid is formed which decomposescarbonates and forms amorphous salts.Papaverine fused with potassium hydroxide yields protocatechuicacid and an alkaline distillate containing papaverine, methylamine,and dimethylhomocatechol, boiling a t 218" and convertible by oxida-tion into protocatechudimethylet heric acid.The same two volatileproducts, dimethylhomocatechol and methylamine, are formed in thedry distillation of papaverine, and apparently also in the distillationof that base with lime or zinc-dust.Baryta-water acts very slowly on papaverine, with evolution ofammoniacal vapours, and formation of a very small quantity of a,greasy substance smelling like guaiacol. Sodium-amalgam slowlyconverts papaverine in alcoholic solution into a thick oil whichdeposits crystals after long standing. With acetic anhydride andsodium acetate, papaverine does not yield an acetyl-derivative, whenceit may be inferred that this base does not contain an acetyl-group.Papaverine, heated with hydrochloric acid in a sealed tube a t B O " ,yields a gas which burns with a green flame (probably methyl chlo-ride) and a solution, the evaporated residue of which forms a thickbrown oil which, in dilute aqueous or alcoholic solution, gives withferric chloride a deep emerald-green coloration, changed by sodiumcarbonate to red-a reaction probably due to homocatechol.Withpotash-lye, the oil forms a dark brown liquid. Sodium carbonateadded to the aqueous solution of the oil, throws down a white floccu-lent precipitate which soon resinises after filtration, and turns greenin contact with the air. These reactions point to the presence ofapomorphine.H. WCompound of Quinine with Chloral. By G. MAZZARA(Gazzetta, 13, 269-272).-This compound, chZoraZ-quinine, is formedon adding to a solution of quinine in chloroform dried at 120" aORGANIC CHEMlSTRY. 187equivalent quantity of chloral (5.5 g. anhydrous chloral to 10 g.quinine). On evaporating the liquid in a dry atmosphere, a yellowishtransparent gelatinous mass is left, which dissolkes in cold ether; andon exposing the solution to a gentle heat, a white mammellary crys-talline substance separates which soon pervades the whole liquid,converting it into a. pulp. The same result is more quickly obtainedon adding the calculated quantity of chloral to a solution of quininein chloroform diluted with anhydrous ether, and heating the liquid.The precipitate, after washing with ether and drying over sulphuricacid, forms an apparently amorphous, perfectly white and very lightmass, having it slightly bitter taste, melting and blackening at 149",not perceptibly altering in dry air.This body has the compositionCmH2aN202,CCI,.COH. It is insoluble in benzene, sparingly solublein cold, more soluble in hot alcohol, from which it separates on evapo-ration as a gelatinous mass. The solution, on addition of water,deposits a white precipitate consisting of a mixture of quinine andchloral- quinine.Chloral-quinine dissolves in water slightly acidulated with sulphuric,acetic acid, &c., forming solutions which exhibit a fluorescence similarta that of quinine salts, and react like the latter with chlorine andpotassium ferricyanide.The acetic acid solution yields with sodiumbicarbonate a precipitate nearly free from chlorine. These reactionsshow that chloral-quinine is decomposed partially by water, completelyby acids.Phenols, as is well known, do not form addition-products withchloral, but in presence of dehydrating agents they yield condensa-tion-products with elimination of water-phenol and thymol forexample, forming respectively dihydroxyphenyl- and dihydroxythy-myl- trichlorethane. The author has also succeeded in obtainingaddition-products by the action of chloral paracresol and thy mol,without the aid of sulphuric acid.Paracresol-chlord, C6H4Me( OH) ,CC17.COH, crystallises in smallneedles melting a t 52-56'. Thymol-cliloral,melts a t 130-134".H. W.C6H4.Me(C3H7) (OH) ,CCla.COH,Solubility of Strychnine and Preparation of some of its Salts.By P. CRESPI (Gazzetta, 13, 175)..-The author has determilied thcsoliibility of strychnine at ordinary temperatures and at 56", 78", and98.5" in various solvents. He finds that 1 pt. of water a t 14.5" dis-solves 0.025 pt. of strychnine ; that 1 pt. absolute alcohol dissolvesfrom 0,302 to 0.325 at 8-25' and 10.75" ; 0.975 at 56" and 1.846 a t78" ; that amyl alcohol, one of the best solvents, dissolves 0.525 a t11*75", and 4.262 a t 98.5" ; that its solubilit<y in dilute alcohol increaseswith the proportion of water up t'o 85" of Gaj-Lussac's areornetel.,and diminishes a t greater dilution.The salts described are the normal succinate, CaHI04Str2,6~H20 ;normal malate, C4H605Str,,3$,H,0 ; normal pyrotartrate,and the phthslate which has not been analysed.C5HSOaS tr,,5+H20,H.W.0 188 ABSTRACTS OF CaEMICAL PAPERS.Behaviour of Strychnine in the Animal Organism; and aProduct of the Action of Potassium Permanganate on Strych-nine. By PLDGGE (Chew. News, 48, 207).-The contention as towhether alkalo’ids do or do not undergo decomposition in the animalorganism has never been definitely settled. Kerner (P’iiger’s Archiv.. 2,20 ; 3, 30) proved that quinine in paxt reappears unchanged in theurine, whilst another portion becomes oxidised into dihydroxyquinine, asubstance which is also obtained by the action of potassium perman-ganate on quinine. The author has made similar experiments withstrychnine. Strychnine was given to animals ; and the blood, tissues,and urine were examined. The results obtained indicate that thestrychnine is decomposed in the organism, but the investigation isincomplete.By the action of potassium perrnanganate on strychnine, a yellowish-brown or light grey amorphous substance is obtained. It is sparinglysoluble in cold water, ether, and chloroform, more freely in hot water,from which it is partially deposited on cooling; readily soluble inalcohol, and very readily in dilute aqueous alkaline solutions, fromwhich it is incompletely reprecipitated by adding hydrochloric acid.The substance is neither bitter nor poisonous, and is not precipitatedby the usual alkalo’id reagents. Treated with chromic mixture, itgives a red-violet coloration without the preliminary blue-violet, as isthe case with strychnine. The author regards this strychnine-derivative as strychnic acid, to which he assigns the formulaCIlHlINOs,H20 for the present. D. A. L.Alkaloids of Buxus sempervirens. By G. A. BARRAGLIA(Gazzetta, 13,249-257) .-The author has extracted from the leavesand twigs of the box tree, a substance which he regards as a newalkalo’id, and designates by the name Buzidine. He denies the exist-ence of the base called Buaeiize described by Alessandri (0. J., 1882,Abstr., 745) as existing in the same plant. His results however arenot very definite. H. W.Acid Products of the Bacterial Fermentation of Albuminoids.By A. GAUTIER and A. ETARD (Clornpt. rend., 97, 325--328).-Whenthe products of putrefaction are distilled to dryness in a vacuup, andthe residue extracted with ether, the principal constituent of the solu-tion (this vol., p. 89) is palmitic acid. Neither stearic nor oleic acidis present, and all traces of the original fatty bodies, and all the cor-responding glycerol, have completely disappeared. Stearic acid is,however, represented by a small quantity of amidostearic acid (Zoc.cit.). The acid products of the putrefaction of albumino’ids are-(I.) Fatty series . . . . . . Formic: acid. . Very small quantity.Acetic ,, . . Doubtful.Butyric ,, . . Large proportion.Valeric ,, . . Smaller proportion.Palmitic ,, . . Abundant.Crotonic ,, . . Considerable proportion.(11.) Acrylic series . . . . Acrylic ,, . . Small quantityPHYSIOLOGICAL CHEMISTRY. 189(111.) Lactic series. ... . . . Glycollic acid Moderate quantity.Lactic(ord.) ,, Small quantity.Valerolactic ,, Doubtf ral.Succinic ,, Large quantity.Carbonic ,, Large quantity.(V.) Nitrogenous acids. . CSH,,NO4.. . . . .Amidostearic acid Small quantity.Leucines and Abundant.(IV.) Oxalic series . . . . Oxalic ,, Trace.Moderate quantity.luce’ines. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8844600166

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a l Chemistry. 189 Chemistry of Perspiration. By ST. CAPRANICA (Gazzefta, 13, 171).-To establish the analogy between the kidneys and sudorific glands, the author has endeavoured to ascertain whether creatinine, which is known to be a normal constituent of urine, exists also in the perspiration. On evaporating 450 C.C. perspiration in a vacuum to one-fifth of its bulk, precipitating with absolute alcohol, filtering, evaporating, and testing the residue by Will's process, he succeeded in demonstrating the presence of creatinine. On the other hand, he does not think that any such relation exists between uric acid and sudoric acid, C1,H,6N,0,3, but he regards the latter as a product of the oxidation of glutamic acid (2C&l9NO4 + 0 6 = H20 + CloH&2Ol3), and as probably identical with the cryptophanic acid which Thudichum found in urine.H. W. Substitute Values of the Chief Organic Alimentary Prin- ciples in the Animal Body. By M. RUBNER (Zeitschr. BioZ., 19, 313-496).-Previous investigations on this subject by Pettenkofer and Voit (Zeitschr. BioZ., 7, 433 ; and 9, 1 and 435) formed the start- ing point of the author's researches. His experiments were carried out similarly on the dog. He employs the term &dynamic in connec- tion with those principles which are capab€e of replacing one another, as being more precise than the expression epuivalent, which has a wider application, Alimentary fat is isodynamic in equal weight with the body fat. On feeding with fat, loss of weight in fat is arrested by exactly the same amount as food which would otherwise have been consumed as body fat.Alimentary fat, when of the same composition as that of the animal body, is transformed into the lather with facility. Muscle- flesh food (circulating albumin) is isodynamic in equal weight with the albumino'id material of the body, which upon insuficient supply of albumin in food becomes consumed (disintegrated organic albumin). During starvation, when the fat of the body disappears, the organic190 ABSTRACTS OF CHEMICAL PAPERS. albumin becomes disintegrated in amount, corresponding with the calorificient value of the previously consumed fat. The actual value in respect of capacity for heat-production of un- organised or dead albumin and living or organised albumin, is the same.Hence it is extremely probable that the formation of the latter from the former takes place without any accumulation of potential energy. Fats and carbohydrates, as regards force-producing value, differ for equal weights, 100 parts of fat corresponding on the average with 240 parts of carbohydrate. The isodynamic values for albumin and carbohydrates map be determined from those of fat and albumin on the one hand, and fat and carbohydrates on the other, from which it appears that 100 parts of dried albumin are isodynarnic with 110 parts of cane-sugar or 122 parts of grape-sugar. The limits within which a replacement or substitution of one principle for another may take place are very wide. Hitherto it has been accepted that the alimentary principles replace one another according to definite chemical proportions.The present investigation places beyond doubt that the isodynamic value of these is the expression of equal intrinsic energy. In the following table, in which the calorificient values of alimen- t'ary substances is given after the statements of Danilewaky and Rechenberg, it will he seen tha,t the individual isodynamic values of these differ to an unimportant extent from the results of direct calorimetric determinations. 100 parts of fat corresponding with :- ---- 1 Albumin .................. Starch.. .................. Cane -sugar Anhydrous grape-sugar Ordinary grape-sugar ....... ................ i .... By direct experiment on the animal. 211 232 234 256 282 Ey calorimetric de- termination.201 221 231 243 271 The results of experiments in the animal are somewhat higher than those calculated, the difference being due to several causes, such as, in the case of albumin and starch, putrefactive and fermentative changes in the intestine, whereby a loss of potential energy is occasioned, whilst in the case of carbohydrates, the work done by the muscles of respiration being increased, the excretion of COz is also increased, and proportionately to a greater degree than in the case of fat itself, thereby accounting for the somewhat lower value of each of the carbohydrates in comparison with fat. Assuming that the suhstitution of alimentary principles was effected according to the amount of oxygen which these required for their oxidation, it is of interest to consider how the isodynamic values as determined in the animal, compare with the values which would thus be obtained.PHYSIOLOGICAL CITEhfISTRP.This is shown in the following table:- 100 parts of fat correspond with- According to oxygen con- sumed. According to experiment in the animal. Albumin.. ......... Starch ............. Cane-sugar ......... Grape-sugar ........ 193 240 249 263 21 1 232 234 266 191 According to calorimetric determination, 201 22 1 231 2 $3 Excepting albumin, the alimentary principles exhibit lower values than that obtained by calculating the oxygen required for combustion. As the conditions of direct experiment t,end rather to yield higher values than otherwise, it is apparent that the capacity of those principles for equivalent amounts of oxygen is not a measure of their capacity for substituting or replacing each other.Whilst the experiments show this replacement or substitut'ion of one alimentary principle for another, according to the amount of heat- production which is afforded by their combustion in the body, it is not implied that they replace each other because they yield the same amount of heat. The heat-production is only a measure of the total potential energy of the principle, and the isodynamic values indicate only alimentary principles of equal potent,ial energy. A knowledge of these isodynamic values allows of measurement of any given kind of tissue change, and by adding together the calorifacient values of t,he disintegrated tissues, a numerical expression for the whole is obtained.This expression may take the form of so much albumin, fat, or a carbohydrate, but more appropriately of heat-units, as best corresponding to the essence of the process itself. The greatest part of all these processes, included under the defini- tion of tissue-change, is in effect an exchange of energy. Within a small fraction of the total disintegration, it is quite indif- ferent as to what alimentary principles we introduce into the body. As regards albumin, only a trifling amount is incapable of being replaced by isodynamic quantities of other principles. To this amount the addition of albumin cannot be dispensed with, for there is a constant loss going on of epidermis and hair from the surface, of blood corpuscles, of epithelium in the intestine, and of nitrogenous secretions from the glands.For the renovation of such, processes of growth and maintenance are necessary, while i t is easy to show that these processes participate only to an insignificant extent in the total interchange of energy. What takes place in the organism as a whole may be regarded as taking place in each of its component cells, and that in the individual cell element, one alimentary principle substitutes another according to the proportion of its potential energy. Albumin is to be regarded as the most readily deaomposible prin- ciple, a fact which has already been established by the experiments of192 ABSTRACTS OF CHEMICAL PAPERS. Pettenkofer and Voit, although in apparent contradiction to observa- tions as to its comportment outside the body, which tended to show the more difficult disintegration of albumin in comparison with fats and carbohydrates.I n the body, the Iabter exhibit a different relation, the fats being more difficultly oxidisable than the carbo- hydrates ; of course it may be assumed that there is no essential dis- tinction of this kind, which may be mounted for by the readier solubility of the carbohydrates in the juices, whereby in simultaneous feeding with both principles, these are the first to be subjected to dis- integration. D. P. On the Digestion of Cows’ Milk, and on the Substances which increase its Digestibility. By J. UFFELMANN (Bied. Ceiatr., 1883, 315-319).-The points considered were-( 1) behaviour of milk with hydrochloric acid, lactic acid, and artificial gastric juice ; (2) behaviour in the alimentary canal; (3) digestibility of boiled milk and buttermilk; (4) methods of rendering milk more easily digestible.The precipitate formed by a fL per cent. solution of hydro- chloric acid in milk assumes either a fine or heavy flocculent con- dition, or also cheesy, according to the conditions of mixing, which are, however, not readily ascertained, as variations in the form of the precipitate occur, the reason for which is not apparent. The action of lactic acid is similar to that of hydrochloric acid. The lumpy condi- tion of the curd which is produced by 4 parts acid (2 per cent.) to 5 milk is not readily digested by pepsin, and if an insufficiency of acid produces no curd iu the cold, then the addition of pepsin to the warm liquid causes the production of firm and compact curd.Small quantities of lactic acid have no influence on the digestion, but large quantities retard the action of pepsin. The digestive coefficients of milk in the bodiea of adults and infants are as follows :-- Adults. Infants. Dry matter.. .. 90-91.7 90-94 Albumin. ..... 98.4-99-2 98.2-99.4 Fat .......... 93-4--95* 6 92%--94m9 Sugar.. ...... 100 100 S a1 ts ........ 44.2-56-6 45-4-47 Of the calcium salts only 25-30 per cent. are digested, whereas in human milk the percentage is 75-80. By boiling milk all the gases are removed, as well as some odorous substance ; when the boiling is conducted in an open vessel a skin is formed; this skin is not all casein, but has the following constitution :- In 1.506 grams. Fat........ 0.617 0-283 Albumin . . 0.820 0.751 Sugar.. .... 0.062 0.046 Salts ...... 0.007 0.006 In 1.086 grams. The author does not find boiled to be more digestible than unboiled milk. From buttermilk a curd i u formed by hydrochloric acid, whichPHYSIOLOGICAL CHEMISTRY. 193 is readily dissolved by gastric juice, Of the additions generally made to milk, such as arrowroot, yolk of eggs, &c., to render it more digestible, barley-water is the best, and experimentally it has been shown that the coefficient for albumin is raised to 99.75 by its use. Relative Absorption of Neutral Salts in the Human Stomach. By W. JAWORSKI (Zeitschr. Biol., 19, 397445).-These experiments were carried out under normal physiological conditions in a healthy man who drank the solutions (500 c.c.) of chemically pure salts and remained at rest until the residual fluid was recovered from the stomach by means of an aspirating pump specially devised for the purpose.This was then submitted to analysis, and the changes in the percentage of the salts determined. These investigations showed that in the human stomach the absorp- tion of individual salts is different, and dependent upon their chemical composition. The acid carbonates (magnesium and sodium) underwent the greatest, the chlorides (magnesium, potassium, sodium, and ferric) the least absorption, and the sulphates (sodium and magnesium) between these extremes. The difference in the absorption of two salts is the greater the longer the solution is present in the stomach. The presence of acids in the stomach hastens absorption, and the difference in the absorption of individual salts becomes more pro- nounced.Carbonic acid especially accelerates absorption, which, oq the other hand, is hindered by alkalinity of the contcents of the stomach. The presence of common salt neither accelerates absorption nor iccreases the gastric secretion; the action is negative in both direc- tions. The secretion of chlorine is greater in proportion to the alkalinity of the saline solution and the length of time the latter remains in the stomach. Acid sodium carbonate excites the secretion of the gastric mucous membrane less than the neutral carbonate. When distilled water is introduced into the stomach, secretion of acid contents (hydrochloric acid,) ensues, and that in proportiou to the lowness of its temperature.Should II salt undergo dissociation of its acid and base in the stomach, these are not absorbed in the ratio of their combining pro- portions. Saline solutions may be found on aspiration still present in the stomach an hour after their introduction, whereas the same quan- tity of distilled water disappears almost entirely within half an hour afterwards. Prom these results certain practical suggestions of clinical importance may be derived. . In the first place the administration of salts in the form of acid carbonates, as with an excess of carbonic acid, is advantageous, for absorption takes place more quickly, and with a more rapid emptying of the stomach there is less irritation of its mucous membrane.The author observed the action of GO, and of the acid carbonates, as also of CaH2CO3 in a aeries of experiments with acidulous mineral waters. E. W. P.194 ABSTRACTS OF CHEMICAL PAPERS. Alkaline fluids, on the other hand, delay absorption and the evacuation of the stomach, and the gastric walls are stimulated to secretion more strongly than by other solutions. Acids favour absorption and rapid evacuation of the gastric contents. The presence of common salt in the stomach does not appear to offer the advantages in regard to digestion which have heretofore been ascribed to it, neither stimulating to greater excretion of the gastric acid (this remark may perhaps not apply to pepsin) nor to evacuation of its contents. In the moderation of the activity of the gastric walls by alkaline agents may probably be found an explana- tion of the therapeutic resulks of certain remedies, such as magnesium carbonate, sodium carbonate, and certain metallic oxides, in relieving the pain of cardialgia.The introduction of salts in the form of chlorides in neutral solution is, as regards gastric absorption, not advantageous, and still less so in the case of neutral carbonates, which are absorbed only in proportion as their transformation into chlorides takes place. The difficult absorptivity of ferrous chloride is especially to be noted from a medical point of view, and considering the facility of absorption of acid carbonates, i t may be assumed that an acid ferrous carbonate would prove the most absorbable of all iron preparation9.D. P. Basic Phosphate of Lime as an Addition to Cattle Fodder. By COHN ( B i d Centr., 1883, 428).-The author has reviewed several experiments in this direction, and thinks that the addition of the substance, not only to medicines for cattle hut to their ordinary fodder, would be very beneficial. He recommends for lambs and young pigs 8.12 grams, for calves and foals 12.20 grams, for oxen and COWS 20.25 grams per head per day. Influence of Distillers’ Waste on Milk Secretion. By M. SCHMOEGER and 0. NEUBERT (Bied. Centr., 1883, 312--.314).-The full details of the experiments are given, and the results were that distillers’ waste (maize) greatly increased the yield of milk, but hardly affected the percentage of fat present. It is consequentlv a more remunerative food than brewers’ grains.J. F. E. W. P. Colouring-matters of the so-called Bile of Invertebrates, and of the Bile of Vertebrates, and some unusual Urine Pigments, &c. By C. A. MACMUNN ( P ~ o c . Roy. STOC., 35, 370-403). -The author’s observations lead him to conclude t,hat; the liver of Invertebrates discharges other functions besides those of a pancreas, which biologists generally regard it. The colouring-matter of the bile in vertebrates does not occur in invertebrata, with the single exception of hEmochromogen, which is found in Astacus$u,z7iatiZis and the pulmoniferous molluscs. Hoppe-Seyler had failed to detect bile pigments and bile acids in invertebrates. In the present instance, the animals submitted to investigation were taken from the sub-kingdoms, Mollusca, Arthro- pods, and Echinodermata.The most striking result of this examina- tion has been the discovery of a chlorophyll pigment in Mollusca andPHYSIOLOGICAL CHEMISTRY. 195 some Art,hropoda, and amongst echinoderms in the radial appendages or ceca of starfishes. This pigment, occurring i n the appendages of the enteron, has been termed enterochZorophyZZ by the author, in pre- ference to zoochlorophyll, as more precisely defining the location of t h e chlorophyll which has been found in the mantle or integument of certain invertebrates. Enterochlorophyll was not discovered in Lumbricus, Hirudo, or Aphrodite, amongst Vermes. I n this inquir7 reliance as to the identity of the pigment under consideration with that occurring in plants has been placed on spec- troscopic and chemical tests, the author accepting the dictum of Vogel and Rundt, that i f colouring-matters dissolved in the same medium yield identical spectra, and present identical changes of spectra when acted on by the same reagent, the colouring-matters are themselves identical. As a standard of reference for the spectral bands obtained from the pigment of invertebrates, the measurements of the bands of the 6 r p t half of the spectrum yielded by the ch1oroph;yll of the leaves of Primula are given.An alcohol-ether extract gave four bands :- 1st band X 674 -643 3rd ,, X 590.5-567 2nd ,, X 622.5-602 4th ,, X 548 -530 The residue left by this extract on evaporation and dissolved in rectified spirit, gave a series of five bands :- 1st band X 684 - 6 3 4 2nd ,, X618 -598 3rd ,, X 586 -570 4th ,, X 546.5-534 :,th ,, X 484 -465 and this solution treated with nitric acid yielded- 1st band X 661-646 2nd ,, X 608-592 3rd ,, X 576-561 4th ,, X 539-521 5th ,, h 5 0 2 4 8 4 ? With this latter series of five bands the spectrum yielded by the bile-colouring matters of the lamellibranchiate mollusca, examined under similar conditions of solution in alcohol and treatment with nitric acid, was identical.The molluscs included in this part of the investigation were the common oyster, mussel, and cockle, also Anodon and Unio. Hence it is concluded that the chlorophyll of leafgreen and their bile pigments are identical. It was proved that the colouring matter of the molluscan liver was not due to the presence of parasitic algs.Negative resiilts were obtained on treating the extracts with ammonium sulphide, showing hamoglobin to be absent.196 ABSTRACTS OF CHERUOAL PAPERS. Of Cephalopoda, the common squid, Octopus vulgaris, only was examined. The results were essentially the same, the five-banded spectrum being yielded by the colouring-matter of the liver on treat- ment with nitric acid. Some slight differences observable appear to the author to be due to the presence of the pigment in a more highly oxidised state than in other cases, perhaps as an acid enterochlorophyll. Among gasteropod mollusca, species of whelk were examined, includ- ing Buccinunt undatutn, Fusus antipuus, Purpura Lapillus, and Litorina litorea, with corresponding results. In the case of Purpura Lapillus, which possesses the well-known purple-producing glands, it was noted tchat there was no peculiarity of the colouring-mattcr obtained from the liver, which yielded enterochlorophyll alone.The investigation of the pulmoniferous mollusca embraced several species of snail, HeZix aspersa, H, pornatia, and others ; also of slugs, Lirnax $avus, and Planorbis. I n these, with the exception of Planorbis, which contains abundance of haemoglobin, haemochromogen (reduced haematin) was invariably present, in addition to chlorophyll, the author thereby confirming the previous observations of Sorby, who did not, however, notice the latter pigment. The spectrum of haemochromogen was yielded by the bile, both with and without treatment with ammoriium sulphide. Its presence may be dependent upon akial respiration, and this resem- blance of molluscan t o mammalian bile in respect of the presence cd haemochromogen is of interest.The respective bands of the two colouring-matters extended generally, the reduced haematin first band, X 570-566, second X 539--526, and the enterochlorophyll X. 678-661. The bands of reduced hrematin are not always in quite the same position. Of Arthropoda, some species of crab, and the common lobster, Homams vulgaris, were examined. Enterochlorophyll was less satis- factorily found, although present in most instances, than in the instance of the mollusca. In Carcinus mcenas its presence was, how- ever, exceptional, while that of a lutein pigment appeared to be con- stant. The common crayfish, Astacu8 JEuviatiZis, alone yielded evidence of the presence of haematin in the bile, and this in considerable amount. No other crustacean showed evidence of its presence.On treatment with ammonium snlphide, the two bands appeared, intensified, a s in the case of the pulmonate mollusca, by caustic soda. The first band alone was easily read ; it extended from X 568.3-539.5. The presence of enterochlorophyll, on the other hand, could not be detected. In the sub-kingdom, Echinodermata, certain starfishes and sea- urchins were examined. These yielded the usual five-banded spec- trum of chlorophyll on addition of nitric acid to the alcoholic extract of the intestinal appendages. The presence of these pigments, lute'in and tetronerythrin, was likewise indicated in the course of the examination of specimens of starfish. The latter pigment was found in the integument, and had also been found in the shells of the crustaceans previously referred to.The author conclpdes from these observations that the existence ofPHYSIOLOGICAL CHEMISTRY. 3 97 enterochlorophyll in the liver or other appendages of the intestine of the animals examined is definitely established. The bile of the pnl- monate mollusca and of crayfish contains in addition haemochromogen, which would appear to be a respiratory pi,gment, enabling intestinal respiration to be carried on, as in certain crabs, and Cobitis.fossiZis. The so-called liver of these invertebrates in addition to the pre- paration of a digestive ferment, discharges the function of a pigment- storing and pigment-producing organ in connection with surface coloration.In some additional Observations on the absorption-spectra of bile- pigments in vertebrate animals, the author alludes to his previously published observations, which appear to refer certain bands seen in bile to the presence of altered haematins (Proc. Roy. Xoc., 31, 26). He has since proved that urobilin is absent in the bile of reptiles during hybernation. It was detected in the liver of Xuhmundra mcrculntu in larger quantity than could be accounted for on the sup- position of its presence in the blood-vessels of that organ, hence its probable formation there. Concerning the origin of the colouring-matter of bile, proof of the transformation of haemoglobin into biliverdin was afforded by a pathological fluid derived from the tunica vaginuZis testis in a case of chronic epididymitis, when tapping had been previously resorted to for removal of the effusion.The fluid without any treatment showed the presence of a haemoglobin derivative, and the pigment was proved by the action of oxidising and reducing agents to be biliverdin. Experiments made on the colouring-matters of sheep- and ox-bile, although not completed, tend so far to show that chlorophyll as such cannot be present, inasmuch as the position of the band in red is altogether different, and the spectrum of acid chlorophyll was not obtained with nitric acid. Contrary to the statement of Hoppe-Seyler, the author, by direct experiment, finds that the pigments produced from bilirubin by oxidising agents and those of sheep- or ox-bile are not identical, Referring next to urinary pigments, the author finds that febrile urobilin is not ident,ical with hydrobilirubin or stwcobilin, an alcoholic solution of the former, when acted on by caustic soda, yielding no bands at C and D, as in the case of similarly prepared solutions of the two latter.Harley’s “urohaematin ” is shown to be a mixture of several decomposition-products of chromogens under the influence of heat and acids. The urohaematin described by the author has been met with in four cases of acute rheumatism, and in a case of “ idiopathic ” pericarditis, its presence in the urine indicating insuffi- cient oxidation of bodies with which it is associated, the normal oxidation of haemoglobin to urobilin not taking place.Its occurrence in rheumatic fever wonld further seem to point to an acid fermentn- t’ion, accompanied by destruction of haemoglobin and production pro- bably of lactic acid. The presence of urohaematin in urine can be easily detected, without preliminary isolation, by its characteristic spectra, those of acid and neutral urohaematin, which are distinguish- able from those of methsemoglobin or haematin, by the use of ammonium sulphide, which does not affect urohzmatin.198 ABSTRACTS OF CHEMICAL PAPERS. Spectroscopic Detection of Indican.-Indican when present in the urine may be detected by its spectrum when Jaffe’s test fails. The urine, mixed with its own bulk of hydrochloric acid, is boiled, and after cooling, shaken, but not violently, with chloroform.The chloroform layer, if indican be present, is more or less violet, and shows a band before D, and generally one after it. I t is noted that the reddening of normal urine when boiled with hydrochloric acid, is not due to the oxidation of indican, and only partly to the oxidation of urobilin chromogen. The author agrees with the view that this reddening is due to urobilin, and that this and indigo-red are two different colouring-matters. He has noticed a band half way between D and E, and extending nearly to E, X 558-534, in most cases in which indican has been detected by the method described ; and treat- meut with reagents pointed to its being due to some other colouring matter, although in some way connected with the presence of indican. Uroerythrin, obtained in alcoholic extract from pink urates, gives a double absorption-band of hazy outline from about three-fourths the distance between D and E to beyond F.No connection could be established between it and indican or nrobilin. It often accompanies urohsematin. In conclusion, the author refers to the existence of a red colouring- matter in pale urine, which becomes visible on adding a mineral acid, but which, as its spectrum showed, is neither indigo-red nor urrhodin. It was also not due to the oxidation of the chromogen of urobilin. From lack of material, the study of this pigment had to be left incomplete. D. P. Albuminolds of the Vitreous Humour of the Human Eye, By P. GJACOSA (Gazzetta, 13, 171).-In this liquid, the author has detected mucin, a globulin, and an albuminous substance analogous to serum albumin.Considering the small proportion of albuminoids existing in this liquid, the author regards its viscidity as due to an excess of salts over the albuminoids. H. W. Chemical Composition of the Egg and its Envelopes in the Common Frog. By P. GIACOSA (Gazzetta, 13, 1’71).-To isolate the envelope, the author placed the eggs for some hours in lime-water, whereupon the envelope dissolved, while the yolk settled down to the bottom. The filtered solution, treated with acetic acid of 10 per cent., yielded a flocculent precipitate, which, after repeated washing with acetic acid and with pure water, gave by analysis 52.71 per cent. C, 7.1 H, 9.33 N, 1.32 S, and 0.62 ash, whence the author infers the presence of a mucin. This substance resists putrefaction, and does not reduce copper salts till after boiling with dilute sul- phuric acid.The author intends to study the products of this decom- position, but as he has not been able to detect the presence of any other bodies, he concludes that the enveloping membrane of frogs’ eggs consists of pure mucin. From the oviduct of the frog he also succeeded in extracting a mucin, which, though differing from thePHYSIOLOGICAL CHEMISTRY. 199 preceding in centesimal composition, nevertheless agrees with it in all other characters. H. W. Localisation of Arsenic in a Case of Poisoning. By J. GUARESCHI (Gazzetta, 13, 176) .-From the experiments of Scolosuboff, it would result that arsenic accumulates chiefly in the nervous system, whereas, according to Johnson and Chittenden (Bmer.Chen2. J., 2, 332; Abstr., 1881, 1082), it is localised chiefly in the kidneys and liver, and according to Ludwig (Schmidt's Jalzrbiicher, 1881, p. lS9), it accumulates chiefly in the liver, and is found also in the bones. The author, having carefully examined the viscera of an individual who died of arsenical poisoning, found that, out of 100 parts of arsenic, the stomach contained 0.0165, the liver 0.00105, the large intestine 0.00133, the lungs and heart 0.006, the muscles O.CO011, and the brain only traces, whence it appears that arsenic tends to accu- mulate chiefly in the liver, and is likewise found in notable quantity Physiological Action of Paraldehyde and Contribution to the Study of Chloral Hydrate. By V. CERCELLO (Gazzetta, 13, li2).-The action of this substance is hypnotic and similar to that of chloral, excepting that it does not diminish the pressure of the blood, unless administered in large doses.The sleep which it produces is calm, and not accompanied or followed by disturbances ; in fact, it is similar to normal sleep. Paraldehyde is absorbed by the stomach, rectum, and subcutaneous tissue. The author supposes that it acts on the cerebral hemispheres, and then on the rneduZZn oblongata and spinal marrow. He recommends it for medical use as an excellent substitute for chloral. H. W. in the lungs and kidneys. H. w. Supposed Toxic Action of Aqueous Solutions obtained from Fresh Animal Organs. By E. DI MATTEI (Gazzetta, 13, 172).- The author shows by numerous experiments that the symptoms of poisoning consequent on injection of the aqueous extracts of fresh organs (under the skin, into the veins, or into the peritoneal cavity) are due, not to any special toxic principle contained in these organs, as might be inferred from the experiments of Pellicani, but to a purely infective process, determined by the action and decomposition of insoluble but decomposed and alterable materials held in suspension by the injected liquids.I n fact, when the turbid juice is freed from solid matters, either by filtration or by evaporation, and only the liquid portion is injected, death does not supervene. Another mode of experimenting consists in injecting beneath the skin of an animal the fresh juice of an organ reduced to a pulp, but not filtered, and, after a time more than sufficient to ensure the complete absorption of the liquid portion, making a wide incision in the skin a t the point of injection, and washing with water containing phenol, in order to remove the solid matters remaining beneath the skin. Operating in this manner, death does not occur.H. W.PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a l Chemistry.189Chemistry of Perspiration. By ST. CAPRANICA (Gazzefta, 13,171).-To establish the analogy between the kidneys and sudorificglands, the author has endeavoured to ascertain whether creatinine,which is known to be a normal constituent of urine, exists also in theperspiration. On evaporating 450 C.C. perspiration in a vacuum toone-fifth of its bulk, precipitating with absolute alcohol, filtering,evaporating, and testing the residue by Will's process, he succeededin demonstrating the presence of creatinine.On the other hand, hedoes not think that any such relation exists between uric acid andsudoric acid, C1,H,6N,0,3, but he regards the latter as a product of theoxidation of glutamic acid (2C&l9NO4 + 0 6 = H20 + CloH&2Ol3),and as probably identical with the cryptophanic acid which Thudichumfound in urine. H. W.Substitute Values of the Chief Organic Alimentary Prin-ciples in the Animal Body. By M. RUBNER (Zeitschr. BioZ., 19,313-496).-Previous investigations on this subject by Pettenkoferand Voit (Zeitschr. BioZ., 7, 433 ; and 9, 1 and 435) formed the start-ing point of the author's researches.His experiments were carriedout similarly on the dog. He employs the term &dynamic in connec-tion with those principles which are capab€e of replacing one another,as being more precise than the expression epuivalent, which has awider application,Alimentary fat is isodynamic in equal weight with the body fat.On feeding with fat, loss of weight in fat is arrested by exactly thesame amount as food which would otherwise have been consumed asbody fat. Alimentary fat, when of the same composition as that ofthe animal body, is transformed into the lather with facility. Muscle-flesh food (circulating albumin) is isodynamic in equal weight withthe albumino'id material of the body, which upon insuficient supply ofalbumin in food becomes consumed (disintegrated organic albumin).During starvation, when the fat of the body disappears, the organi190 ABSTRACTS OF CHEMICAL PAPERS.albumin becomes disintegrated in amount, corresponding with thecalorificient value of the previously consumed fat.The actual value in respect of capacity for heat-production of un-organised or dead albumin and living or organised albumin, is thesame.Hence it is extremely probable that the formation of the latterfrom the former takes place without any accumulation of potentialenergy.Fats and carbohydrates, as regards force-producing value, differfor equal weights, 100 parts of fat corresponding on the average with240 parts of carbohydrate. The isodynamic values for albumin andcarbohydrates map be determined from those of fat and albumin onthe one hand, and fat and carbohydrates on the other, from which itappears that 100 parts of dried albumin are isodynarnic with 110 partsof cane-sugar or 122 parts of grape-sugar. The limits within which areplacement or substitution of one principle for another may takeplace are very wide.Hitherto it has been accepted that the alimentary principles replaceone another according to definite chemical proportions. The presentinvestigation places beyond doubt that the isodynamic value of theseis the expression of equal intrinsic energy.In the following table, in which the calorificient values of alimen-t'ary substances is given after the statements of Danilewaky andRechenberg, it will he seen tha,t the individual isodynamic values ofthese differ to an unimportant extent from the results of directcalorimetric determinations.100 parts of fat corresponding with :----- 1 Albumin ..................Starch....................Cane -sugarAnhydrous grape-sugarOrdinary grape-sugar ....................... i ....By directexperiment on theanimal.211232234256282Ey calorimetric de-termination.201221231243271The results of experiments in the animal are somewhat higher thanthose calculated, the difference being due to several causes, such as,in the case of albumin and starch, putrefactive and fermentativechanges in the intestine, whereby a loss of potential energy isoccasioned, whilst in the case of carbohydrates, the work done by themuscles of respiration being increased, the excretion of COz is alsoincreased, and proportionately to a greater degree than in the case offat itself, thereby accounting for the somewhat lower value of each ofthe carbohydrates in comparison with fat.Assuming that the suhstitution of alimentary principles was effectedaccording to the amount of oxygen which these required for theiroxidation, it is of interest to consider how the isodynamic values asdetermined in the animal, compare with the values which would thusbe obtainedPHYSIOLOGICAL CITEhfISTRP.This is shown in the following table:-100 parts of fat correspond with-Accordingto oxygen con-sumed.According toexperiment in theanimal.Albumin...........Starch .............Cane-sugar .........Grape-sugar ........19324024926321 1232234266191According tocalorimetricdetermination,20122 12312 $3Excepting albumin, the alimentary principles exhibit lower valuesthan that obtained by calculating the oxygen required for combustion.As the conditions of direct experiment t,end rather to yield highervalues than otherwise, it is apparent that the capacity of thoseprinciples for equivalent amounts of oxygen is not a measure of theircapacity for substituting or replacing each other.Whilst the experiments show this replacement or substitut'ion ofone alimentary principle for another, according to the amount of heat-production which is afforded by their combustion in the body, it is notimplied that they replace each other because they yield the sameamount of heat.The heat-production is only a measure of the totalpotential energy of the principle, and the isodynamic values indicateonly alimentary principles of equal potent,ial energy. A knowledgeof these isodynamic values allows of measurement of any given kindof tissue change, and by adding together the calorifacient values oft,he disintegrated tissues, a numerical expression for the whole isobtained. This expression may take the form of so much albumin,fat, or a carbohydrate, but more appropriately of heat-units, as bestcorresponding to the essence of the process itself.The greatest part of all these processes, included under the defini-tion of tissue-change, is in effect an exchange of energy.Within a small fraction of the total disintegration, it is quite indif-ferent as to what alimentary principles we introduce into the body.As regards albumin, only a trifling amount is incapable of beingreplaced by isodynamic quantities of other principles.To this amountthe addition of albumin cannot be dispensed with, for there is aconstant loss going on of epidermis and hair from the surface, ofblood corpuscles, of epithelium in the intestine, and of nitrogenoussecretions from the glands. For the renovation of such, processes ofgrowth and maintenance are necessary, while i t is easy to show thatthese processes participate only to an insignificant extent in the totalinterchange of energy.What takes place in the organism as a whole may be regarded astaking place in each of its component cells, and that in the individualcell element, one alimentary principle substitutes another according tothe proportion of its potential energy.Albumin is to be regarded as the most readily deaomposible prin-ciple, a fact which has already been established by the experiments o192 ABSTRACTS OF CHEMICAL PAPERS.Pettenkofer and Voit, although in apparent contradiction to observa-tions as to its comportment outside the body, which tended to showthe more difficult disintegration of albumin in comparison withfats and carbohydrates.I n the body, the Iabter exhibit a differentrelation, the fats being more difficultly oxidisable than the carbo-hydrates ; of course it may be assumed that there is no essential dis-tinction of this kind, which may be mounted for by the readiersolubility of the carbohydrates in the juices, whereby in simultaneousfeeding with both principles, these are the first to be subjected to dis-integration.D. P.On the Digestion of Cows’ Milk, and on the Substanceswhich increase its Digestibility. By J. UFFELMANN (Bied. Ceiatr.,1883, 315-319).-The points considered were-( 1) behaviour ofmilk with hydrochloric acid, lactic acid, and artificial gastric juice ;(2) behaviour in the alimentary canal; (3) digestibility of boiledmilk and buttermilk; (4) methods of rendering milk more easilydigestible. The precipitate formed by a fL per cent. solution of hydro-chloric acid in milk assumes either a fine or heavy flocculent con-dition, or also cheesy, according to the conditions of mixing, whichare, however, not readily ascertained, as variations in the form of theprecipitate occur, the reason for which is not apparent.The action oflactic acid is similar to that of hydrochloric acid. The lumpy condi-tion of the curd which is produced by 4 parts acid (2 per cent.) to5 milk is not readily digested by pepsin, and if an insufficiency of acidproduces no curd iu the cold, then the addition of pepsin to the warmliquid causes the production of firm and compact curd. Smallquantities of lactic acid have no influence on the digestion, but largequantities retard the action of pepsin. The digestive coefficients ofmilk in the bodiea of adults and infants are as follows :--Adults.Infants.Dry matter.. .. 90-91.7 90-94Albumin. ..... 98.4-99-2 98.2-99.4Fat .......... 93-4--95* 6 92%--94m9Sugar.. ...... 100 100S a1 ts ........ 44.2-56-6 45-4-47Of the calcium salts only 25-30 per cent. are digested, whereas inhuman milk the percentage is 75-80. By boiling milk all the gasesare removed, as well as some odorous substance ; when the boiling isconducted in an open vessel a skin is formed; this skin is not allcasein, but has the following constitution :-In 1.506 grams.Fat.. ...... 0.617 0-283Albumin . . 0.820 0.751Sugar.. .... 0.062 0.046Salts ...... 0.007 0.006In 1.086 grams.The author does not find boiled to be more digestible than unboiledmilk. From buttermilk a curd i u formed by hydrochloric acid, whicPHYSIOLOGICAL CHEMISTRY.193is readily dissolved by gastric juice, Of the additions generally madeto milk, such as arrowroot, yolk of eggs, &c., to render it moredigestible, barley-water is the best, and experimentally it has beenshown that the coefficient for albumin is raised to 99.75 by its use.Relative Absorption of Neutral Salts in the HumanStomach. By W. JAWORSKI (Zeitschr. Biol., 19, 397445).-Theseexperiments were carried out under normal physiological conditionsin a healthy man who drank the solutions (500 c.c.) of chemicallypure salts and remained at rest until the residual fluid was recoveredfrom the stomach by means of an aspirating pump specially devisedfor the purpose. This was then submitted to analysis, and thechanges in the percentage of the salts determined.These investigations showed that in the human stomach the absorp-tion of individual salts is different, and dependent upon their chemicalcomposition.The acid carbonates (magnesium and sodium) underwent thegreatest, the chlorides (magnesium, potassium, sodium, and ferric)the least absorption, and the sulphates (sodium and magnesium)between these extremes.The difference in the absorption of two salts is the greater thelonger the solution is present in the stomach.The presence of acids in the stomach hastens absorption, and thedifference in the absorption of individual salts becomes more pro-nounced. Carbonic acid especially accelerates absorption, which, oqthe other hand, is hindered by alkalinity of the contcents of thestomach.The presence of common salt neither accelerates absorption noriccreases the gastric secretion; the action is negative in both direc-tions.The secretion of chlorine is greater in proportion to the alkalinityof the saline solution and the length of time the latter remains in thestomach.Acid sodium carbonate excites the secretion of the gastricmucous membrane less than the neutral carbonate.When distilled water is introduced into the stomach, secretion ofacid contents (hydrochloric acid,) ensues, and that in proportiou to thelowness of its temperature.Should II salt undergo dissociation of its acid and base in thestomach, these are not absorbed in the ratio of their combining pro-portions. Saline solutions may be found on aspiration still present inthe stomach an hour after their introduction, whereas the same quan-tity of distilled water disappears almost entirely within half an hourafterwards.Prom these results certain practical suggestions ofclinical importance may be derived. .In the first place the administration of salts in the form of acidcarbonates, as with an excess of carbonic acid, is advantageous, forabsorption takes place more quickly, and with a more rapid emptyingof the stomach there is less irritation of its mucous membrane. Theauthor observed the action of GO, and of the acid carbonates, as alsoof CaH2CO3 in a aeries of experiments with acidulous mineralwaters.E. W. P194 ABSTRACTS OF CHEMICAL PAPERS.Alkaline fluids, on the other hand, delay absorption and theevacuation of the stomach, and the gastric walls are stimulated tosecretion more strongly than by other solutions.Acids favourabsorption and rapid evacuation of the gastric contents.The presence of common salt in the stomach does not appear tooffer the advantages in regard to digestion which have heretoforebeen ascribed to it, neither stimulating to greater excretion of thegastric acid (this remark may perhaps not apply to pepsin) nor toevacuation of its contents. In the moderation of the activity of thegastric walls by alkaline agents may probably be found an explana-tion of the therapeutic resulks of certain remedies, such as magnesiumcarbonate, sodium carbonate, and certain metallic oxides, in relievingthe pain of cardialgia.The introduction of salts in the form of chlorides in neutralsolution is, as regards gastric absorption, not advantageous, and stillless so in the case of neutral carbonates, which are absorbed only inproportion as their transformation into chlorides takes place.The difficult absorptivity of ferrous chloride is especially to benoted from a medical point of view, and considering the facility ofabsorption of acid carbonates, i t may be assumed that an acid ferrouscarbonate would prove the most absorbable of all iron preparation9.D.P.Basic Phosphate of Lime as an Addition to Cattle Fodder.By COHN ( B i d Centr., 1883, 428).-The author has reviewed severalexperiments in this direction, and thinks that the addition of thesubstance, not only to medicines for cattle hut to their ordinary fodder,would be very beneficial.He recommends for lambs and young pigs8.12 grams, for calves and foals 12.20 grams, for oxen and COWS20.25 grams per head per day.Influence of Distillers’ Waste on Milk Secretion. By M.SCHMOEGER and 0. NEUBERT (Bied. Centr., 1883, 312--.314).-Thefull details of the experiments are given, and the results were thatdistillers’ waste (maize) greatly increased the yield of milk, buthardly affected the percentage of fat present. It is consequentlv amore remunerative food than brewers’ grains.J. F.E. W. P.Colouring-matters of the so-called Bile of Invertebrates,and of the Bile of Vertebrates, and some unusual UrinePigments, &c.By C. A. MACMUNN ( P ~ o c . Roy. STOC., 35, 370-403).-The author’s observations lead him to conclude t,hat; the liver ofInvertebrates discharges other functions besides those of a pancreas,which biologists generally regard it.The colouring-matter of the bile in vertebrates does not occur ininvertebrata, with the single exception of hEmochromogen, which isfound in Astacus$u,z7iatiZis and the pulmoniferous molluscs.Hoppe-Seyler had failed to detect bile pigments and bile acids ininvertebrates. In the present instance, the animals submitted toinvestigation were taken from the sub-kingdoms, Mollusca, Arthro-pods, and Echinodermata. The most striking result of this examina-tion has been the discovery of a chlorophyll pigment in Mollusca anPHYSIOLOGICAL CHEMISTRY. 195some Art,hropoda, and amongst echinoderms in the radial appendagesor ceca of starfishes.This pigment, occurring i n the appendages ofthe enteron, has been termed enterochZorophyZZ by the author, in pre-ference to zoochlorophyll, as more precisely defining the location oft h e chlorophyll which has been found in the mantle or integument ofcertain invertebrates.Enterochlorophyll was not discovered in Lumbricus, Hirudo, orAphrodite, amongst Vermes.I n this inquir7 reliance as to the identity of the pigment underconsideration with that occurring in plants has been placed on spec-troscopic and chemical tests, the author accepting the dictum of Vogeland Rundt, that i f colouring-matters dissolved in the same mediumyield identical spectra, and present identical changes of spectra whenacted on by the same reagent, the colouring-matters are themselvesidentical.As a standard of reference for the spectral bands obtained from thepigment of invertebrates, the measurements of the bands of the 6 r p thalf of the spectrum yielded by the ch1oroph;yll of the leaves ofPrimula are given.An alcohol-ether extract gave four bands :-1st band X 674 -6433rd ,, X 590.5-5672nd ,, X 622.5-6024th ,, X 548 -530The residue left by this extract on evaporation and dissolved inrectified spirit, gave a series of five bands :-1st band X 684 - 6 3 42nd ,, X618 -5983rd ,, X 586 -5704th ,, X 546.5-534:,th ,, X 484 -465and this solution treated with nitric acid yielded-1st band X 661-6462nd ,, X 608-5923rd ,, X 576-5614th ,, X 539-5215th ,, h 5 0 2 4 8 4 ?With this latter series of five bands the spectrum yielded by thebile-colouring matters of the lamellibranchiate mollusca, examinedunder similar conditions of solution in alcohol and treatment withnitric acid, was identical.The molluscs included in this part of theinvestigation were the common oyster, mussel, and cockle, also Anodonand Unio. Hence it is concluded that the chlorophyll of leafgreen andtheir bile pigments are identical. It was proved that the colouringmatter of the molluscan liver was not due to the presence of parasiticalgs. Negative resiilts were obtained on treating the extracts withammonium sulphide, showing hamoglobin to be absent196 ABSTRACTS OF CHERUOAL PAPERS.Of Cephalopoda, the common squid, Octopus vulgaris, only wasexamined.The results were essentially the same, the five-bandedspectrum being yielded by the colouring-matter of the liver on treat-ment with nitric acid. Some slight differences observable appear tothe author to be due to the presence of the pigment in a more highlyoxidised state than in other cases, perhaps as an acid enterochlorophyll.Among gasteropod mollusca, species of whelk were examined, includ-ing Buccinunt undatutn, Fusus antipuus, Purpura Lapillus, and Litorinalitorea, with corresponding results. In the case of Purpura Lapillus,which possesses the well-known purple-producing glands, it was notedtchat there was no peculiarity of the colouring-mattcr obtained fromthe liver, which yielded enterochlorophyll alone.The investigation of the pulmoniferous mollusca embraced severalspecies of snail, HeZix aspersa, H, pornatia, and others ; also of slugs,Lirnax $avus, and Planorbis.I n these, with the exception of Planorbis, which contains abundanceof haemoglobin, haemochromogen (reduced haematin) was invariablypresent, in addition to chlorophyll, the author thereby confirming theprevious observations of Sorby, who did not, however, notice the latterpigment.The spectrum of haemochromogen was yielded by the bile,both with and without treatment with ammoriium sulphide. Itspresence may be dependent upon akial respiration, and this resem-blance of molluscan t o mammalian bile in respect of the presence cdhaemochromogen is of interest. The respective bands of the twocolouring-matters extended generally, the reduced haematin first band,X 570-566, second X 539--526, and the enterochlorophyll X.678-661.The bands of reduced hrematin are not always in quite the sameposition.Of Arthropoda, some species of crab, and the common lobster,Homams vulgaris, were examined. Enterochlorophyll was less satis-factorily found, although present in most instances, than in theinstance of the mollusca. In Carcinus mcenas its presence was, how-ever, exceptional, while that of a lutein pigment appeared to be con-stant.The common crayfish, Astacu8 JEuviatiZis, alone yielded evidence ofthe presence of haematin in the bile, and this in considerable amount.No other crustacean showed evidence of its presence. On treatmentwith ammonium snlphide, the two bands appeared, intensified, a s in thecase of the pulmonate mollusca, by caustic soda.The first band alonewas easily read ; it extended from X 568.3-539.5. The presence ofenterochlorophyll, on the other hand, could not be detected.In the sub-kingdom, Echinodermata, certain starfishes and sea-urchins were examined. These yielded the usual five-banded spec-trum of chlorophyll on addition of nitric acid to the alcoholic extractof the intestinal appendages.The presence of these pigments, lute'in and tetronerythrin, waslikewise indicated in the course of the examination of specimens ofstarfish. The latter pigment was found in the integument, and hadalso been found in the shells of the crustaceans previously referredto.The author conclpdes from these observations that the existence oPHYSIOLOGICAL CHEMISTRY.3 97enterochlorophyll in the liver or other appendages of the intestine ofthe animals examined is definitely established. The bile of the pnl-monate mollusca and of crayfish contains in addition haemochromogen,which would appear to be a respiratory pi,gment, enabling intestinalrespiration to be carried on, as in certain crabs, and Cobitis.fossiZis.The so-called liver of these invertebrates in addition to the pre-paration of a digestive ferment, discharges the function of a pigment-storing and pigment-producing organ in connection with surfacecoloration.In some additional Observations on the absorption-spectra of bile-pigments in vertebrate animals, the author alludes to his previouslypublished observations, which appear to refer certain bands seen inbile to the presence of altered haematins (Proc.Roy. Xoc., 31, 26).He has since proved that urobilin is absent in the bile of reptilesduring hybernation. It was detected in the liver of Xuhmundramcrculntu in larger quantity than could be accounted for on the sup-position of its presence in the blood-vessels of that organ, hence itsprobable formation there.Concerning the origin of the colouring-matter of bile, proof of thetransformation of haemoglobin into biliverdin was afforded by apathological fluid derived from the tunica vaginuZis testis in a case ofchronic epididymitis, when tapping had been previously resorted tofor removal of the effusion.The fluid without any treatment showedthe presence of a haemoglobin derivative, and the pigment was provedby the action of oxidising and reducing agents to be biliverdin.Experiments made on the colouring-matters of sheep- and ox-bile,although not completed, tend so far to show that chlorophyll as suchcannot be present, inasmuch as the position of the band in red isaltogether different, and the spectrum of acid chlorophyll was notobtained with nitric acid. Contrary to the statement of Hoppe-Seyler,the author, by direct experiment, finds that the pigments producedfrom bilirubin by oxidising agents and those of sheep- or ox-bile arenot identical,Referring next to urinary pigments, the author finds that febrileurobilin is not ident,ical with hydrobilirubin or stwcobilin, an alcoholicsolution of the former, when acted on by caustic soda, yielding nobands at C and D, as in the case of similarly prepared solutions of thetwo latter.Harley’s “urohaematin ” is shown to be a mixture ofseveral decomposition-products of chromogens under the influence ofheat and acids. The urohaematin described by the author has beenmet with in four cases of acute rheumatism, and in a case of“ idiopathic ” pericarditis, its presence in the urine indicating insuffi-cient oxidation of bodies with which it is associated, the normaloxidation of haemoglobin to urobilin not taking place. Its occurrencein rheumatic fever wonld further seem to point to an acid fermentn-t’ion, accompanied by destruction of haemoglobin and production pro-bably of lactic acid.The presence of urohaematin in urine can beeasily detected, without preliminary isolation, by its characteristicspectra, those of acid and neutral urohaematin, which are distinguish-able from those of methsemoglobin or haematin, by the use of ammoniumsulphide, which does not affect urohzmatin198 ABSTRACTS OF CHEMICAL PAPERS.Spectroscopic Detection of Indican.-Indican when present in theurine may be detected by its spectrum when Jaffe’s test fails.The urine, mixed with its own bulk of hydrochloric acid, is boiled,and after cooling, shaken, but not violently, with chloroform. Thechloroform layer, if indican be present, is more or less violet, andshows a band before D, and generally one after it.I t is noted thatthe reddening of normal urine when boiled with hydrochloric acid, isnot due to the oxidation of indican, and only partly to the oxidationof urobilin chromogen. The author agrees with the view that thisreddening is due to urobilin, and that this and indigo-red are twodifferent colouring-matters. He has noticed a band half way betweenD and E, and extending nearly to E, X 558-534, in most cases inwhich indican has been detected by the method described ; and treat-meut with reagents pointed to its being due to some other colouringmatter, although in some way connected with the presence ofindican.Uroerythrin, obtained in alcoholic extract from pink urates, gives adouble absorption-band of hazy outline from about three-fourthsthe distance between D and E to beyond F.No connection could beestablished between it and indican or nrobilin. It often accompaniesurohsematin.In conclusion, the author refers to the existence of a red colouring-matter in pale urine, which becomes visible on adding a mineralacid, but which, as its spectrum showed, is neither indigo-red norurrhodin. It was also not due to the oxidation of the chromogen ofurobilin. From lack of material, the study of this pigment had to beleft incomplete. D. P.Albuminolds of the Vitreous Humour of the Human Eye,By P. GJACOSA (Gazzetta, 13, 171).-In this liquid, the author hasdetected mucin, a globulin, and an albuminous substance analogous toserum albumin.Considering the small proportion of albuminoidsexisting in this liquid, the author regards its viscidity as due to anexcess of salts over the albuminoids. H. W.Chemical Composition of the Egg and its Envelopes inthe Common Frog. By P. GIACOSA (Gazzetta, 13, 1’71).-To isolatethe envelope, the author placed the eggs for some hours in lime-water,whereupon the envelope dissolved, while the yolk settled down to thebottom. The filtered solution, treated with acetic acid of 10 percent., yielded a flocculent precipitate, which, after repeated washingwith acetic acid and with pure water, gave by analysis 52.71 percent. C, 7.1 H, 9.33 N, 1.32 S, and 0.62 ash, whence the authorinfers the presence of a mucin.This substance resists putrefaction,and does not reduce copper salts till after boiling with dilute sul-phuric acid. The author intends to study the products of this decom-position, but as he has not been able to detect the presence of anyother bodies, he concludes that the enveloping membrane of frogs’eggs consists of pure mucin. From the oviduct of the frog he alsosucceeded in extracting a mucin, which, though differing from thPHYSIOLOGICAL CHEMISTRY. 199preceding in centesimal composition, nevertheless agrees with it in allother characters. H. W.Localisation of Arsenic in a Case of Poisoning. By J.GUARESCHI (Gazzetta, 13, 176) .-From the experiments of Scolosuboff,it would result that arsenic accumulates chiefly in the nervous system,whereas, according to Johnson and Chittenden (Bmer. Chen2. J., 2,332; Abstr., 1881, 1082), it is localised chiefly in the kidneys andliver, and according to Ludwig (Schmidt's Jalzrbiicher, 1881, p. lS9),it accumulates chiefly in the liver, and is found also in the bones.The author, having carefully examined the viscera of an individualwho died of arsenical poisoning, found that, out of 100 parts ofarsenic, the stomach contained 0.0165, the liver 0.00105, the largeintestine 0.00133, the lungs and heart 0.006, the muscles O.CO011, andthe brain only traces, whence it appears that arsenic tends to accu-mulate chiefly in the liver, and is likewise found in notable quantityPhysiological Action of Paraldehyde and Contribution tothe Study of Chloral Hydrate. By V. CERCELLO (Gazzetta, 13,li2).-The action of this substance is hypnotic and similar to that ofchloral, excepting that it does not diminish the pressure of the blood,unless administered in large doses. The sleep which it producesis calm, and not accompanied or followed by disturbances ; in fact, itis similar to normal sleep. Paraldehyde is absorbed by the stomach,rectum, and subcutaneous tissue. The author supposes that it actson the cerebral hemispheres, and then on the rneduZZn oblongata andspinal marrow. He recommends it for medical use as an excellentsubstitute for chloral. H. W.in the lungs and kidneys. H. w.Supposed Toxic Action of Aqueous Solutions obtained fromFresh Animal Organs. By E. DI MATTEI (Gazzetta, 13, 172).-The author shows by numerous experiments that the symptoms ofpoisoning consequent on injection of the aqueous extracts of freshorgans (under the skin, into the veins, or into the peritoneal cavity)are due, not to any special toxic principle contained in these organs,as might be inferred from the experiments of Pellicani, but to apurely infective process, determined by the action and decompositionof insoluble but decomposed and alterable materials held in suspensionby the injected liquids. I n fact, when the turbid juice is freed fromsolid matters, either by filtration or by evaporation, and only theliquid portion is injected, death does not supervene. Another modeof experimenting consists in injecting beneath the skin of an animalthe fresh juice of an organ reduced to a pulp, but not filtered, and,after a time more than sufficient to ensure the complete absorption ofthe liquid portion, making a wide incision in the skin a t the point ofinjection, and washing with water containing phenol, in order toremove the solid matters remaining beneath the skin. Operating inthis manner, death does not occur. H. W

ISSN:0368-1769    

DOI:10.1039/CA8844600189

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

200 ABSTRACTS OF CHEMICAL PAPERS. :::::) --.- Normal . . . 1.76 Bprouted.. 1.17 Chemistry of Vegetable Physiology and Agriculture. Other Nitrogen Dextrin. Dextrose. Maltose. soluble 2::;. in dry matter. matter. ------ ---- 1.1 0 0 3.12 5.64 64.10 1.90 0.0 492 7-32 5-23 53-98 2.045 Valuation of Seeds. By A. MAYER and others (Bied. Centr., 1883, 324--325).-Mayer employs as a germinator a glass fla& 15 cm. high and 6 cm. broad, having an opening close to the bottom, which allows of the free circulation of air, and removal of excess water. The seeds are laid on blotting paper o r cotton stuff placed iaside t<lie flask. When compared with Nobbe’s germinator, it was found that Mayer’s was best for clover, whilst Nobhe’s was best for most grass seeds. The reports of germinative power of a sample are made thus : , (2) percentage of foreign (1) Value = seeds, which are divided into harmful and harmless.As regards the influence of light, the author finds that the germination of Poa pra- tensis and Dactylis glomerqta is accelerated, whilst the admission of air has no effect on Pinus silvestris, Loliwrn perenne, Festzcca oZiina, and F. dwriuscula. Nobbe considers that germination should be tried in his germinator, on paper, in sand and in mould, before a satisfactory report can be made. A previous soaking for 6-12 hours is recommended f o r hard seeds, as also to remove the mucilage from the seeds of Limm, Camelina, C‘ydonia, &c., so its to admit oxygen more readily to the embrj-o. E. W. P. purity x germinative power. 100 --. Normal. .. . . Sprouted.. . . Nitrogen ‘ Nitrogen Nitrogen Nitrogen xitrogen nitrates. amide. ammonia. albumin. albumin. as. t t S as as soluble asinsoluble --- --- -- -- trace 0’028 0.045 0.087 1.740 trace 0’454 0044 0.036 1.511 1 I I I IVEGETABLE PHYSIOLOGY AND AGRICULTURE. 201 Robus found that in wheat, under similar circumstances, the nitro- genous matter was most affected, the gluten being reduced by 20-25 per cent. E. W. P. Function of Silica in the Vegetation of maize. By V. JODIN (Cow@ rend., 97, 344--346).-A grain of maize cultivated in a suitable solution of inorganic salts will develop and form a plant of normal appearance without assimilating any notable proportion of silica. This deprivation of silica produces no physiological degene- ration in the plant, which can be cultivated in a similar manner through several generations.Under somewhat similar conditions a maize plant will develop and attain full maturity, although retaining in its tissues only one-quarter the normal amount of phosphoric acid and one-half the normal amount of potassium. By cultivating in well moistened vegetable soil, a grain from a plant of the fourth generation cultivated in water free from silica, a strong and vigorous plant is obtained which contains only one-sixth the normal amount of potassium. These facts confirm DBh&ain’s srqyosition that the ash of a plant contains an amount of inorganic salts greatly in excess of that actually required for the proper development of the plant. The accumulation of this excesa in the tissues of the plant is due to the purely physical forces, diff nsion and evaporation.C. H. B. Constant Production of Oxygen by the Action of Sunlight on u Protococcus pluvialis.” By T. L. PHIPSON (Chem. News, 48, 205-206) .-In the summer Zygnema and Conferca may frequently be seen borne to the surface of pools of stagnant water by innumerable minute bubbles of oxygen-gas. Some of the simplest of the unicel- lular algce, e.g., Protococcus yhcvialis and P . palustris, exhibit this peculiarity to a remarkable degree. The author has cultivated some of the last-mentioned plmts by exposing pump-water t o air and light for some weeks, and, as soon as good growth was obtained, small dead branches of poplar were put in the water ; the protococ- cus developed rapidly upon them.The branches can then be put in flasks full of water and the production of oxygen observed; this takes place immediately the flasks are exposed to the sun’s rays ; the oxygen comes off in the minutest bubbles, but in such great numbers as t o form a froth on the surface ; in some higher plants, e.g., Achillea millifolium, the gas collects at the ends of the leaves and comes to the surface in large bubbles. If the flask is inverted the evolution of gas continues €or about three days; the introduction of a minute quantity of caustic soda stops it on the first day by depriving the plant of carbonic anhydride. On renewing the water, after three days, the evolution recommences, and so by keeping up a constant supply of pump-water, the production of oxygen may be kept up to all appearance indefinitely. The author has devised a simple appa- ratus for this purpose-a wide-mouthed bottle with tubulure near the bottom is fitted with a gas delivery tube and a tube with tap connected with a water supply ; the water must neither be boiled nor distilled, nor must, it be in the slightest degree alkaline.A tap is put in the VOL. XIAVI. P202 ABSTRACTS OF CHEMICAL PAPERS. tubulure and is used to empty the bottle. Some of the working poplar branches are placed in the bottle, water is run in, and the bottle exposed to sunlight ; the oxygen can be collected in a gas- holder. After three days the old water is run out of the bottle and fresh waterrun in. The author suggests that by employing graduated vessels, &c., the apparatus might be used as an actinometer.The gas produced contains about 98 per cent. oxygen. The author remarks incidentally that carbonic anhydride in presence of sunlight is not decomposed by plants, but simply absorbed, water and hydrogen dioxide being equally essential for the product'ion of oxygen, and the gas being evolved from the tissue as a consequence of the absorption. Aldehydic Nature of Protoplasm. By A. B. GRIFFITHS (Chem. News, 48, 179--18O)=--After reference to the work of Loew and Bokorny (Abstr,, 1883, 546, 447, and 882), of Reinke (ibid., 243 and 13121, of Mori (Chem. Centr. [3], 13, 565), of Beyer, of Kretzschmar ( B i d Centr., 1882,830), and to his own comninnication to this Journal (Trans., 1883, 195), the author proceeds to describe his new experi- ments.He has examined the protoplasm of living and dead cells of Spirogyra, and finds that it reduces alkaline solutions of cupric salts ; that crystals are formed in it by treatment with weak sodium chloride, and that the addition of ahsolute alcohol to the cells of the Spirogyra causes the deposition of crystals of anhydrous dextrose. It is there- fore probable that the reducing properties of protoplasm are due t o this glucose, and that the crystals formed with sodium chloride are C,H,@,,NaC1 + HzO. This view is supported by the following ex- periments:-Albumin (white of fresh egg) mixed with a small quantity of a very dilute solution of dextrose, when treated as above described, behaves in a manner precisely similar to the spirogyra cells. Moreover, if the living plant is kept in the dark for a couple of days and is then examined, none of these reactions are observed.This is evidently,due to the dextrose being used up in the dark to nourish the cell-walls and tissues, for after a short exposure to sun- light the dextrose reappears and the usual phenomena are to be observed in the plant cells. The author concludes with some remarks on the aldehydic nature of dextrose, on the assimilation of carbon by plants, and on the importance of researches on albumin. By P. MALERBA (Gaxzetta; 13, 173).--l)ry chestnuts contain at least 3 per cent. of fatty matters, for the most part liquid and of oily aspect, while the smaller portion is solid, the proportion of fatty matter increasing with age, and fatty acids being formed a t the same time.Cocoa and Chocolate. By BOTJSSINGAULT (Ann. Chim. PAYS. [ 5 ] , 28, 433-456) .-The cacao plant rarely flowers before it is 30 months old, but the first flowers are generally destroyed, as the planters do not permit the plants t o bear fruit before they are four years old ; 100 kilos. of fresh fruit yield from 45 to 30 kilos. of dry cocoa. In Venezuela, after a plant is seven years old, it yields 0.75 kilo. annually. In Magdalena a tree yields 2 kilos. of dry cocoa per annum. The D. A. L. D. A. L. Fatty Constituents of Common Chestnuts. H. W.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 203 kernel of the species 1M0,itaraz contains : Butter, 53.3 ; albumin, 12.9 ; theobromine, 2.4 ; gum and tartaric acid, 6.7 ; cellulose, lignose, starch, 9.1 ; ash, 4.0 ; water, 11% per cent.The ash consists chiefly of phosphate of calcium, magnesium, and potassium ; it also contains silica, carbonic and sulphuric acids. The husk has the following percentage composition :-Butter, 3.9 ; nitrogenous matter, 14.25, containing 2.8 N ; gum, 12.12 ; tartaric acid and tannin, 5-05 ; ash, 6.89 ; water, 12.18 ; lignose, cellulose, and other compounds not esti- mated, 45.61. The process of decortication is generally accomplished by means of gentle heat. The following table shows the composition of Trinidad cocoa, decorticated A by heat, B without heating :- A. 13 utter ............ 54.0 Starch and glucose . . 2.5 Theobromine ........ 3.6 Asparagine ........ trace Albumin .......... 11.8 Gum .............. 2.5 Tartaric acid.. ...... 3.7 Tannin ............0.2 Soluble cellulose .... 11.5 Ash .............. 4-4 Water - Not estimated ...... 5.8 ............ B. 49.9 2.4 3-3 trace 10.9 2.4 3.4 0.2 10.6 4-0 7.6 5.3 Cocoa butter is a white solid which melts at 30" and solidifies at 23". The gum resembles gum arabic in appearance, and also yields mucic acid when treated with nitric acid. It is powerfully dextrogy- rate. Chocolate, prepared by grinding together sugar and gently roasted cocoa, contains varying amounts of sugar. Spanish chocolate contains from 40.6 to 54 per cent. of sugar, and French chocolate cont,ains from 56 to 59 per cent. The relative value of chocolate and milk as food is seen from the following analysis of equal weights of milk and an emulsion contain- ing 20 per cent. of chocolate :- Chocolat,e emulsion.Milk. Albumin ........ 3.0 13% Fats ............ 14.0 15.0 Sugar.. .......... 32.0 15.0 Salts ............ 1.0 2.7 The large proportion of sugar in chocolate diminishes its nutritive Analysis of some Cider Apples. By R. LEZB (Ann. Agronomipues, 9, 105).-The fruits were exhibited a t the Apple Congress of St. LB, November, 1882, and analysed by the author a t the end of Decem- ber :- power. w. c. w.204 ABSTRACTS OF CHEMICAL PAPERS. Variety. Haut griset. ........... Avoine. ............... Doux lozon. .......... Aufriche tardive ....... Cartigny gros .......... A iru .................. Petit rouget ........... Frkquin. .............. Water. 80 *96 83 -38 80 -64 82 '02 81 *08 84 *02 83 -90 84 *90 - Sugar. 7 -64 9 -19 9 -22 8 -59 10 -41 6 -08 8 -50 7 .a - - Ash.0-52 0 '37 0 -36 0 -46 0 -34 0 -28 0 *36 0 -32 - Tannin. -- 0 *50 0 -21 0 -19 0 -35 0 -57 0 -72 0 -23 0 -27 Cellulose, albuminolds, &c. 10 -38 6 -85 9 -59 8 -58 7 *60 8 *90 7.01 7 -11 The variety Frequin is well known as yielding good cider, which will keep well. J. M. H. M. Poisonous Properties of Edible Fungi. By G. DUPETIT (BieJ. Centr., 1883, 356).-The physiological action of the juices of many fungi on animals is detailed in this paper. The poisonous principle is soluble in water, but insoluble in ether, chloroform, carbon bisulphide, and alcohol ; it is precipitated from its solutions by alcohol, tannin, lead acetate, and hydroxide ; it therefore less resembles the alkaloids than the soluble ferments, and its action is destroyed at 100". I n BoEetus two non-poisonous alkaloids have been found, the one resem- bling neurine, the other the ptoma'ines.E. w. P. Report on Experimental Plots at Grignon in 1882. By P. P. D ~ H ~ R A L N (Ann. Agronomiques, 9,106-124).-The crops grown in 1882 were wheat, oats, green maize, sugar-beet, and sainfoin. The yield of oats was under average, and that of wheat very poor, 35 hec- tolitres per hectare against 50 harvested in 1880. The author attributes the difference, not to the rainfall, which was less and more equally distributed in 1882 than in 1880, but to the difference in tem- perature, the monthly mean from March to September being from 1.3" to 5%" (July) less in 1882 than in 1880. For the same reason the vintage of 1882 was a bad one, as the grapes never ripened perfectly .Wheat.-All the plots carried potatoes from 1875-1879, and wheat 1880-1882 ; since 1879 no nitrogenous manure has been used. The best yield (27-30 hectolitres) was on those plots which had received dressings of farmyard manure from 1875-1879 ; plots dressed with sodium nitrate during the same period gave no more grain than the plot unmanured since 1875, although the straw was slightly heavier ; and plots which received ammonium snlphate, 1875-1877, yielded less of both grain and straw than the plot unmanured since 1875. The entire wheat crop of the neighbourhood suffered much from rust in June; 10 grams of wheat from one of the plots contained 128 well developed grains weighing 6.12 grams, and 132 stunted badly filled grains weighing 3.88 grams.The two lots were analysed and found to be almost identical in composition. Outs.-The harvest from the experimental plots was worse than theVEGETABLE PHYSIOLOGY AND AGRICULTURE. 205 :werage of the four years 1878-1881, but better than 1881; the deficiency was most marked in the grain, and the author attributes the falling off to the difficulty of cleaning land carrying the same cereal crop so many years in succession. Oats have been grown on all the plots for the last eight years, and in 1882 the yield from most of the manured plots wad3 actually less than that on the two plots receiving no manure, owing to the encouragement afforded by the manures to &he growth of weeds. Green $Iuize.-The seventh consecutive year of this crop has yielded results similar to those of the preceding years.The yield, favoured by a, wet season, has shown no falling off: and farmyard manure in quan- tities up to 29,000 kilos. per hectare, has proved by far the most efficaci- ous and remunerative dressing; with 40,000 kilos. instead of 20,000, the increased yield is nof sufficient t o cover the extra cost of the manure. A moderate dressing of farmyard manure each year has given better aggregate results than the same total quantity distributed over the three years 1875-1877. Partial or complete substitution of sodium nitrate for farmyard manure has resulted in diminished crops. Sugur-beet.-l'his crop has been grown in 1881 aad 1882 on six plots which carried green maize for the six previous years ; the previous dressings on half the plots having been farmyard manure, and on the others ammonium snlphate.The results of 1881 were so decidedly worse on the ammonium sulphate plots, that in 1882 an atcempt was made to restore their fertility by new dressings of farmyard manure alone or with artificials : '20,000 kilos. farmyard manure, together with 200 kilos. each of sodium nitrate, superphosphate, and potassium chloride, was the only application which raised the produce of the ammonium sulphate plots t o a level with the plots which received no manure in 1881 or 1882, but had been dressed with farmyard manure in 1878, ' i 9 , '80. The sugar in average samples of roots from each plot was determined by the polariscope, the percentage varying from 12-04! to 13.73 (the variety grown was Vilmorin's betterave CLU collet rose).The results confirm the author's previoiis conclusions that the richness in sugar is lowered by nitrogenous manures, and is not sensibly raised eitber by potassium salts or superphosphate. The most remarkable fact in this series of experiments is the decreased crops on the plots which formerly received ammonium sulphate, a result which the author attributes to the injurious action of this salt on the physical properties of the soil. Sainfoirz.--The sainfoin grown in 1879 had become replaced by grasses at the end of 1881 ; a new sowing was therefore made in 1882, and a satisfactory crop obtained, the best plots being those which were heavily dressed with farmyard manure from 1875-1878. Analyses of the soil and subsoil, made in the four years preceding 1879, during which the plots carried sugar-beet and green maize, showed a slight progressive diminution in the percentage of nitrogen, even in those plots which received large dressings of farmyard manure ; since the occupation of the ground by sainfoin, however, the percentage of nitrogen has remained stationary or has slightly increased. No ilgures are given on this point.J. M. H. M.206 ABSTRACTS OF CHEMICAL PAPERS. Influence of Rainfall on the Wheat Crop. (Bid. Cen,tr., 1883, 291-294.)-A table of the rainfall and temperature in England during July and August, in the years 1846-1876, is given, and this is divided into four groups; comparing this table with the wheat crops, it appears that when the average temperature of July and August is above the mean, the crop is above average: rain during warm seasons does not lower the quantity although the quality may be deteriorated ; however good a season may be in June, no good crop is obtained-that is one above the average-if the average tempera- ture in July and August is below the mean ; even if the weather in those months be fine, the quality only is good.If during July and August there is both wet and cold, the yield is always low and the quality poor. E. W. P. Comparative Feeding Value of Barley, Malt, and Peas. By A. VOELCHER (Jour. Roy. Agri. Soc., 1883, 422).-These experi- ments were conducted at Woburn. The barley an2 malt were used in the proportion shown in the malt'ing operation, 140 lbs. of barley yielding 11'7 lbs. of malt and malt-dust.Three pens, each of ten sheep (10 months old), received throughout the same quantity of swedes, with hay and straw chaff. During the first period of eight weeks, each sheep had in addition 4 lh. of linseed cake per day; pen 1, 4 lb. of barley meal ; pen 2, the equivalent in malt-meal and malt-dust; pen 3, 4 lb. of pea-meal. In the second period of two weeks the additional foods were increased to .$ lb. per head per day. In the third period of two weeks they were raised to 2 lb. In the fourth period of two weeks they were raised to 1 lb. The gain in live-weight of the sheep of each pen was as follows :- Pen I. Barley. I Pen 11. Malt. I Pen 111. Peas. lbs. lbs. lbs. First eight weeks.. . .. . . Following six weeks . . . . Total fourteen weeks.. . . 1 293k I 301P 1 3413 The feeding values of the barley, and of its equivalent in malt, were thus practically equal, whilst that of the peas was distinctly greater. The maximum rations were continued for two weeks longer; during this time the sheep of pen 1 refused a part of their barley, the results therefore ceased to be comparative.Composition and Digestibility of Serradella at various Ages. By H. WEISKE, G. KENNEPOEL, and B. SCHULZE (Bied. Cewtr., 1883, 307--309).-The seed was sown in the middle of April on two plots, from the first of which a crop was taken on July 22, and from the latter on October 2, also an aftermath was taken from the first plot on October 2. R. W. The composition of the crops was as follows :-VEGETABLE PHYSIOLOGY AND AGRICULTURE. 207 I Plot 1.1 July 22. Yield - Fresh. .......... Dry.. ........... A lb \ imin ........ Fat, &c. ........ Fibre. .......... Cellulose, &c. . , . . Ash ............ Containing- 110 *O kilos. 13.83 ,) 22 -62 p.c. 5.2 ,3 29.65 ,, 30.89 ,, 11.64 ,, October 2. -- 4 ~345 kilos. 0.577 ), 24.75 p.c. 5-12 ,, 27 -11 ), 34.33 ,) 8.69 ,, Plot 2. October 2. 85 -00 kilos. 17-15 ), 19-13 p . ~ ; 3.95 ,, 35-71 *, 32-39 ,, 8-82 ,, Feeding experiments showed that the younger plant was more easily digested than the older. Analyses of Heather (Erica vulgaris), Braken (Pteris aqui- lina), and Broom (Genista pilosa). By A. PETERMANN (Am. Agronomiques, 9,251-255).-Vast tracts of poor soil in the Ardennes (derived from schists and quartzose schists) ars covered with a thick vegetation of heather, broom, and fern, which is useful to the inhabi- tants in many ways.The dense mass of vegetation assists in the dis- integration of the rock, and acts as a sponge in storing up and gradually giving out the rainfall. Sheep and horses readily eat the young shoots of broom and heather, and the ashes of these plants, burnt on the spot, are found to be a good manure for oats. Cut with the scythe, air-dried, and stacked, these plants furnish fuel in the winter aud litter for cattle.* Sometimes they are, ploughed in as green manure, and frequently broom in flower is made into a com- post with soil and refuse. The analyses in the subjoined tables were made on the air-dried plants, including stems, leaves,. and flowers :-- E. W. P. Water ..................+Organic matter ......... Mineral matter .......... +Containing nitrogen ..... Fern. 1 Htather. 1 Broom. 12 -70 12 -30 85 *06 84.79 2.24 1 , 2.91 * Fern litter is also extensively used in the New Borest.-J. M. H. M.208 ABSTRACTS OF CHEMICAL PAPERS. Heather. Composition of the Ash after Deducting Carbon, Sand, and Carbonic Anhydride. Brcom. -.- --- Potash.. ............................. Soda ............................... Lime.. ............................. Oxide of iron. ....................... Sulphur trioxide ..................... Phosphorus pentoxide ................ Silica .............................. Chloi*ine ............................ Manganese .......................... Magnesia ........................... - Deduct oxygen equivalent to chlorine ...43 -28 4 *18 18 -57 10.05 1'12 4.61 14 *05 1-11 3 '89 trace 100 -88 0.88 --- Fern. -- 38 '53 3 -31 11 -69 6 -93 0 9 1 7.93 4.60 1'7.51 11 *09 - -- 102 * 50 2 -50 100 *oo 31 *7'4 6.98 19 *78 13 *28 3 -06 8'14 2.73 13 '47 2 -35 trace 100 *53 0 *53 loo*oo I loo'oo Fern and broom thus contain six times, and heather twice as much nitrogen as rye-straw, and their ashes are rich in phosphoric acid and potash. J. M. H. M. Beet Cultivation. By CRAH~ and others (Bied. Centr., 1883, 333).-CrahB found on large plots that a mixture of Chili saltpetre and Baker guano was a more productive manure than ammoninni sul- phate and guano, both as regards yield of root and of sugar. Marcker found that in 1880 Simon le Grand Rose was the best cropper but lowest yielder of sugar, but in 1881 Klein Wanzlebene was the highest cropper and Vilmorin Blanche gave the best yield of sugar.Potatoes and Sweet Potatoes. By SACC ( B i d Centr., 1883, 337).-Potatoes which are planted at all seasons of the year, as in Monte Video, are watery and tasteless, and have the composition- albumin 0*71-0*81, dextrin 0.02-0.05, sugar 1.3, starch 10.2- 12.81, bitter extract 2-25, fibre 13.18-11.59, calcium bimalate 0.05, water 73.59-72.91, but if they are planted in October then the com- position is normal. Sweet potatoes (ConvoZvuZus batatas) require more heat, and contain-albumin 0.56-OG4, glucose 4.0-0.3, muci- lage 1.15, pectic acid 1.27, starch 15*0-1341, fibre 10*02--17*83, ash 1, water 67.0-68.19. They require an open soil and but little manuring. The sweet potato is finer than the potato, and is quite as useful, being largely used in the manufacture of spirits.Assimilation of the Organic Matter of Arable Soil. Part I. E. W. P. E. W. P. Historical RksurnB. By P. P. DOHBRAIN (Ann. Agrononziques, 9, 258-265) .-The idea that plants directly assimilate the organic matter of the soil was supported by de Saussure, Malaguti, and Soubeyran, and opposed by Liebig and Boussingault. The iast-named chemist contended that the utility of humus to vegetation consists inVEGETABLE PHYSIOLOGY AND AGRICULTURE. 209 the continuous disengagement of large quantities of carbonic anhy- dride in the soil, and subsequent writers have supposed that this carbonic anhydride is absorbed by the roots, conveyed to the leaves, and there decomposed in presence of chlorophyll and sunlight. No evidence in favour of the absorption of carbonic anhydride by roots could be obtained by Corenwinder from direct experiments on the point ; on the contrary, he has shown that roots take part in respira- tion, absorbing oxygen and emitting a little carbonic anhydride.Grandeau has attributed another function t o humus. He found that the ammonium carbonate extract of soil contains, besides the brown humus bodies, considerable quantities of phosphoric acid, oxide of iron, magnesia, lime, and soluble silica. When this solution is dialysed, only the mineral constituents pass through the septum, forming a colourless solution, the brown matter left on the septum containing only 8 per cent. of ash, whereas before dialysis i t contains 53 per cent.From these experiments Grandeau concludes-(1) that the minerals combined with humus are directly assimilable by the roots of plants ; (2) that the organic matter itself does not enter the roots, but is the vehicle of the mineral aliment ; ( 3 ) that the combination of minerals with hunius is similar to that found in the liquor of a dung-heap ; and (4) that the fertility of a soil is proportional to the quantity of minerals associated with humus and soluble in ammonium carbonate. Petermann has recently demonstrated (and his experiments have been repeated by Grandeau) that soil not treated with ammonium carbonate does contain dialysable organic matter, and the question remains, does this organic matter serve directly as plant food ? The author’s obser- vations on the experimental maize plots at Grignon render an affirma- tive reply probable.The plots dressed each year with 40,000 kilos. farmyard manure have given an average annual yield of 90,000 kilos. green maize, whilst the highest yield obtained by the use of chemical manures is 68,000 kilos. When maize is grown with the aid of farm- yard manure, the soil is found t o be much more impoverished of carbon than in the case of potatoes or wheat, which do not benefit so much from the same manure. The author finally quotes the opinion of Sachs, who, after noting the direct assimilation of organic niatter by fungi, germinating seeds, and certain parasites, considers it probable that green plants also may share in this function. The direct experiments of the author will be given in a future number.Ammonia, Chlorine, and Sulphuric Acid in Rain collected at Rothamsted. By Sir J. B. LAWES, J. H. GILBERT, and R. WARING- TON (Jour. Roy. Agri. Soc., 1883, 313).-The results of earlier deter- minations have been given in a previous paper (Abstr., 1882, 889). 1. Ammonia in Rain.-The new determinations were made both in daily rainfalls and in monthly mixtures. The rain was distilled, and the distillate Nesslerised. I n 152 daily collections of rain, dew, &c., in the large rain-gauge (0.001 acre), extending from June ‘22, 1881, to January 5, 1882, the nitrogen as ammonia varied from 0.043 per mil- lion (in a rainfall of 0.713 inch on Nov. 27) to 5-49 per million (in a deposit of dew of 0.007 inch on September 17).The rainfall during the whole period amounted fo 219645 inches, and contained an average J. M. H. MI.210 ABSTRACTS OF CHEMlCAL PAPERS. of 0.254 of nitrogen as ammonia per million. The proportion of ammonia is much greater in small deposits than in large; it is affected to a still greater extent by the amount of previous washing which the atmosphere has undergone. Ammonia was also determined in 50 monthly mixtures of rain-water. I n 24 recent months the analysis of the water was made a t the end of each month ; the earlier monthly samples were in most cases of considerable age when analysed. In the 24 recent samples the nitrogen RS ammonia averaged 0.316 per mil- lion; in the whole series of 50 months the average was 0.361. Evidence is given showing that the ammonia in the rain-water generally tended to increase by keeping.Nitrification was possibly prevented by the lead present in the water. The rainfall of summer was generally richer in ammonia than that of winter. The nitrogen as ammonia contributed annually by rain to an acre of land amounts to 2.37 lbs. if calculated from the da.ily determinations during six months, to 2.47 lbs. calculated from two years’ determinations in fresh monthly mixtures, and to 2.66 lbs. if calculated from determina- tions in 50 monthlymixtures, many of them old. From the last series of determinations it appears that to double the quantity of ammonia per acre the rainfall must be increased about six-fold. From Frank- land and Way’s results, the nitrogen as nitric acid appears to be about 1 lb.per acre, and the nitrogen as organic matter a similar amount. The total combined nitrogen in the annual rainfall a t Rothamsted is thus about 4.5 lbs. per acre. %. Chlorine in Rniiz.-The determinations of chlorine in monthly mixtures of rain extend over six years, 1877-83. The mean propor- tion found was 1.99 per million of water, or 14.92 lbs. per acre, equd to 24.59 lbs. of sodium chloride. Two-thirds of the chlorides fall in the six winter months, October to March. The minimum quantity falls in July, the matximuin in October and November. The supply of chlorides in summer seems to be very limited, as a large increase in the rainfall produces but little increase in the quantity of chlorides per acre. In winter the increase in the quantity of chlorides with a rise in the rainfall is much greater.3. Xulphuric Acid in Rair~.--The sulphuric acid was determined gravimetrically in mixtures representing the rainfall of summer (April-Sep tember) and winter (October-March) ; the determina- tions extended over two yeam. When the rain was collected in glass vessels only, the average amount of sulphuric anhydride was 2.41 per million of rain or 18.5 lbs. per acre. When the rain was collected in the large rain-gauge the amount of sulphuric anhydride was 3.95 per million, or 30.3 lbs. per acre. There seems little doubt that in this latter case a part of the sulphuric acid was derived from the vulca- nised caoutchouc used for the connections. The rain appears to be slightly richer in sulphuric acid in summer than in winter.Influence of Artificial Manures on the Physical Properties of Soil. By E. WOLLNY (Ann. Agronomiques, 9, 129-131 ; from Zeits. des Vereins fiir die Rubenzuck~!1.industrie, November, 1682) .-The addition of small quantities of ammonia or fixed alkalis, or of alkalirie phosphates or carbonates to water holding clay in suspension, causes R. W.VEGETABLE PHYSJOLOGY AND AGRICULTURE. 211 the immediate precipitation of the clay in a dense form. Mineral acids and their salts, such as sodium nitrate, act in the opposite manner, precipitating the clay in a light and spongy form, which occupies much space. Hence the author argues that the addition of substances of the former class to soils is injurious to their por0sit.y and lightness, and consequently to fertility, and cites as examples the alkali plains of Nevada and California, the soil of which is hard, dense, non-porous, and sterile.On the other hand, salts such as sodium nitrate, sal tpetre, and potassium sulphate exercise an imme- diate beneficial effect on the porosity of arable soil, but as they are quickly washed out the effect is not lasting, and the fertility is then found to be impaired. Of all artificial manures, lime exercises the most favourable influence on the properties of soil, causiiig it to aggregate into flocculent particles which persist for years, and render it light and fertile. Weeds in Soils. By H. PUTENSEN (Bied. Centr., 1883, 295- 297).- In this paper it is shown that repeated ploughings and harrow- ings diminish the number of weeds in the soil.Manuring Experiments at Kiel. By A. EMMERLING (Bied. Centr., 1883, 297406) .-This is a report of the experiments made in 1881, which are a continuation of tJhose conducted in 1880; the season was bad, yet conclusions niay be drawn which are not without interest, as showing the action of artificial manures under unfavour- able circumstances. There were 24 sets of plots on various soils, the crops being generally oats, but buckwheat, barley, and beans were also grown. The manures were superphosphate, precipitated phos- phate, dissolved and raw Peruvian guano, steamed and dissolved bone-meal, blood, ammonium salts, and Chili saltpetre (86.9 per cent.). The results are given in full detail in a series of tables. A short summary of these is given here. Ammonia acted but feebly on clay loam, and not at all on sand, hut well on black humus earth.Salt- petre was satisfactory in all classes. Phosphates with ammonia pro- duced a low yield in that district where the weather was unpropitious. Phosphates and saltpetre gave contradictory results owing to bad weather. Steamed bones raised the yield of grain, and especially at the drier stations ; whilst steamed bones are best, on dry lands, the dissolved meal best acted at those stations where rain had fallen in June. Blood failed at all the dry places. In spite of the unfavourable conditions, the guano (raw and dissolved) greatly increased the crop ; the latter had, however, increased the grain and straw more than the former. E. W. P. Manurial Value of Nitrogenous Refuse.IT. Dried Blood. By A. PETERMANN (Ann. Agronomipes, 9, 241-251) .-Thirty-two samples of dried blood examined in 1880-81 gave an average of 11-23 per cent. nitrogen ; the physical condition also was satisfactory, being dry, friable, pulverulent, and almost without odour. The manurial value was determined by experiments on plants grown in pots, in two soils of very different physical characters, and the results were compared on the one hand with those obtaiued without manure, J. M. H. M. E. W. P.212 ABSTRACTS OF CHEMICAL PAPERS. and on the other hand with those obtained by using a quantity of sodium nitrate equivalent in nitrogen to the dried blood. The effect of adding phosphoric acid and potash to the dried blood was also studied. The results given in this abstract are in all cases the mean of two or three concordant experiments.The first series consisted of 15 flower-pots filled with loamy soil from Gembloux mixed with a quarter of its bulk of quartz sand ; the second, 15 pots filled with sand from Campine. Ten grains of spring wheat were sown in each pot on March 17th, 1882 ; on August 20th, 1882, the plants were removed from the pots, and the straw and grain weighed separately ; the results are given in the table. ~~ ~ Loam. Mean weight of Manure. Straw. No manure.. ........................... Dried blood = 0.25 gram N .............. Sodium nitrate = 0'25 gram N.. .......... Dried blood (= 0.25 gram N) + precipitated Sodium nitrate (= 0*;5 gram N) + precipi- tated phosphate (= 0.30 gram P,05). .... Dried blood ( = 025 grain N) + precipitated phosphate (= 0.30 gram P205) + potas- sium chloride (= 020 gram K,O) .......Sodium nitrate (= 0.25 gram N) + precipi- tated phosphate (= 0.30 gram P,05) + potassium chloride (= 0.20 gram K20). .. phosphate (= 0.30 warn P2OS), ......... 18 -19 42 '51 44 *,25 42 -90 44 -96 43.73 45 -01 Grain. 7 '94 19 -56 20 -14 19 *51 19 -62 19 -44 19.80 - Sand. Mean weight of Straw. -- 5.35 10 -70 19 -51 20 -46 21 *36 22 -59 23 -99 Grain. 2 -08 5 -05 7 -51 8.94 9 *76 12 -19 12 -98 The highest yields are obtained in the loam, but the effect of the manures is greatest in the sand. In the loam, dried blood produces an increase in the crop practically identical with that given by a quantity of sodium nitrate containing the same amount of nitrogen ; the addition of phosphoric acid, or potash, or both, has little effect.In the sand, on the contrary, dried blood is decidedly inferior to its equivalent of sodium nitrate, and both phosphoric acid and potash produce considerable effect ; the effect of the phosphatic manure, in all the pots in which it was used, was to hasten the period of ripening. As the result of these and previous experiments, the author arranges the nitrogenous manures which he has tried in the following order of efficiency (such quantities being employed as contain equal weights of nitrogen) :- Sodium nitrate, dried blood, dissolved wool, wool refuse, leather refuse. The efficiency is plainly related to the solubility and readiness to decompose in each case. Preparation of Manure from Furnace Slag. J.M. H. M. By WINKEL- HOFER (Bied. Cent?.., 1883, 354).-The excess of lime in the slag obtained in the '' basic process " is to be removed by tlreatment withANALYTICAL CHEMISTRY. 213 molasses and water, which leaves the phosphates undissolved ; the lime is then separated from the saccharate by passing the products of combustion from tlie furnaces through the solution. E. W. P. Insoluble Phosphates. By F. J. LLOYD (Chem. News, 48, 164- 165) .-The “ insoluble phosphates ’’ from superphosphates are divided into two classes, the “ white” and the “ red.” The white are obtained only from manures made from bones, and represent approximately the amount of phosphate not dissolved. The author has analysed the “ red” phosphate with the following result :- CaO. Fe203.P205. 32.53 31.80 35-77 per cent. These numbers correspond with 60.01 per cent. calcium phosphate, 17.63 per cent. ferric phosphate, 22.46 per cent. ferric oxide. D. A. L.200 ABSTRACTS OF CHEMICAL PAPERS.:::::)--.-Normal . . . 1.76Bprouted.. 1.17Chemistry of Vegetable Physiology and Agriculture.Other NitrogenDextrin. Dextrose. Maltose. soluble 2::;. in drymatter. matter.------ ----1.1 0 0 3.12 5.64 64.10 1.900.0 492 7-32 5-23 53-98 2.045Valuation of Seeds. By A. MAYER and others (Bied. Centr.,1883, 324--325).-Mayer employs as a germinator a glass fla& 15 cm.high and 6 cm. broad, having an opening close to the bottom, whichallows of the free circulation of air, and removal of excess water.The seeds are laid on blotting paper o r cotton stuff placed iaside t<lieflask.When compared with Nobbe’s germinator, it was found thatMayer’s was best for clover, whilst Nobhe’s was best for most grassseeds. The reports of germinative power of a sample are made thus :, (2) percentage of foreign (1) Value =seeds, which are divided into harmful and harmless. As regards theinfluence of light, the author finds that the germination of Poa pra-tensis and Dactylis glomerqta is accelerated, whilst the admission of airhas no effect on Pinus silvestris, Loliwrn perenne, Festzcca oZiina, andF. dwriuscula. Nobbe considers that germination should be tried in hisgerminator, on paper, in sand and in mould, before a satisfactory reportcan be made. A previous soaking for 6-12 hours is recommendedf o r hard seeds, as also to remove the mucilage from the seeds of Limm,Camelina, C‘ydonia, &c., so its to admit oxygen more readily to theembrj-o.E. W. P.purity x germinative power.100--.Normal. . . . .Sprouted.. . .Nitrogen ‘ Nitrogen Nitrogen Nitrogen xitrogennitrates. amide. ammonia. albumin. albumin.as. t t S as as soluble asinsoluble--- --- -- --trace 0’028 0.045 0.087 1.740trace 0’454 0044 0.036 1.5111 I I I VEGETABLE PHYSIOLOGY AND AGRICULTURE. 201Robus found that in wheat, under similar circumstances, the nitro-genous matter was most affected, the gluten being reduced by 20-25per cent. E. W. P.Function of Silica in the Vegetation of maize. By V. JODIN(Cow@ rend., 97, 344--346).-A grain of maize cultivated in asuitable solution of inorganic salts will develop and form a plant ofnormal appearance without assimilating any notable proportion ofsilica.This deprivation of silica produces no physiological degene-ration in the plant, which can be cultivated in a similar mannerthrough several generations. Under somewhat similar conditions amaize plant will develop and attain full maturity, although retainingin its tissues only one-quarter the normal amount of phosphoric acidand one-half the normal amount of potassium. By cultivating inwell moistened vegetable soil, a grain from a plant of the fourthgeneration cultivated in water free from silica, a strong and vigorousplant is obtained which contains only one-sixth the normal amount ofpotassium.These facts confirm DBh&ain’s srqyosition that the ash of a plantcontains an amount of inorganic salts greatly in excess of thatactually required for the proper development of the plant.Theaccumulation of this excesa in the tissues of the plant is due to thepurely physical forces, diff nsion and evaporation. C. H. B.Constant Production of Oxygen by the Action of Sunlighton u Protococcus pluvialis.” By T. L. PHIPSON (Chem. News, 48,205-206) .-In the summer Zygnema and Conferca may frequently beseen borne to the surface of pools of stagnant water by innumerableminute bubbles of oxygen-gas. Some of the simplest of the unicel-lular algce, e.g., Protococcus yhcvialis and P . palustris, exhibit thispeculiarity to a remarkable degree.The author has cultivated someof the last-mentioned plmts by exposing pump-water t o air andlight for some weeks, and, as soon as good growth was obtained,small dead branches of poplar were put in the water ; the protococ-cus developed rapidly upon them. The branches can then be put inflasks full of water and the production of oxygen observed; thistakes place immediately the flasks are exposed to the sun’s rays ; theoxygen comes off in the minutest bubbles, but in such great numbersas t o form a froth on the surface ; in some higher plants, e.g., Achilleamillifolium, the gas collects at the ends of the leaves and comes tothe surface in large bubbles. If the flask is inverted the evolution ofgas continues €or about three days; the introduction of a minutequantity of caustic soda stops it on the first day by depriving theplant of carbonic anhydride.On renewing the water, after threedays, the evolution recommences, and so by keeping up a constantsupply of pump-water, the production of oxygen may be kept up toall appearance indefinitely. The author has devised a simple appa-ratus for this purpose-a wide-mouthed bottle with tubulure near thebottom is fitted with a gas delivery tube and a tube with tap connectedwith a water supply ; the water must neither be boiled nor distilled,nor must, it be in the slightest degree alkaline. A tap is put in theVOL. XIAVI. 202 ABSTRACTS OF CHEMICAL PAPERS.tubulure and is used to empty the bottle. Some of the workingpoplar branches are placed in the bottle, water is run in, and thebottle exposed to sunlight ; the oxygen can be collected in a gas-holder.After three days the old water is run out of the bottle andfresh waterrun in. The author suggests that by employing graduatedvessels, &c., the apparatus might be used as an actinometer. The gasproduced contains about 98 per cent. oxygen. The author remarksincidentally that carbonic anhydride in presence of sunlight is notdecomposed by plants, but simply absorbed, water and hydrogendioxide being equally essential for the product'ion of oxygen, and thegas being evolved from the tissue as a consequence of the absorption.Aldehydic Nature of Protoplasm. By A. B. GRIFFITHS (Chem.News, 48, 179--18O)=--After reference to the work of Loew andBokorny (Abstr,, 1883, 546, 447, and 882), of Reinke (ibid., 243 and13121, of Mori (Chem.Centr. [3], 13, 565), of Beyer, of Kretzschmar( B i d Centr., 1882,830), and to his own comninnication to this Journal(Trans., 1883, 195), the author proceeds to describe his new experi-ments. He has examined the protoplasm of living and dead cells ofSpirogyra, and finds that it reduces alkaline solutions of cupric salts ;that crystals are formed in it by treatment with weak sodium chloride,and that the addition of ahsolute alcohol to the cells of the Spirogyracauses the deposition of crystals of anhydrous dextrose. It is there-fore probable that the reducing properties of protoplasm are due t othis glucose, and that the crystals formed with sodium chloride areC,H,@,,NaC1 + HzO.This view is supported by the following ex-periments:-Albumin (white of fresh egg) mixed with a smallquantity of a very dilute solution of dextrose, when treated as abovedescribed, behaves in a manner precisely similar to the spirogyracells. Moreover, if the living plant is kept in the dark for a coupleof days and is then examined, none of these reactions are observed.This is evidently,due to the dextrose being used up in the dark tonourish the cell-walls and tissues, for after a short exposure to sun-light the dextrose reappears and the usual phenomena are to be observedin the plant cells. The author concludes with some remarks on thealdehydic nature of dextrose, on the assimilation of carbon by plants,and on the importance of researches on albumin.By P.MALERBA(Gaxzetta; 13, 173).--l)ry chestnuts contain at least 3 per cent. offatty matters, for the most part liquid and of oily aspect, while thesmaller portion is solid, the proportion of fatty matter increasing withage, and fatty acids being formed a t the same time.Cocoa and Chocolate. By BOTJSSINGAULT (Ann. Chim. PAYS. [ 5 ] ,28, 433-456) .-The cacao plant rarely flowers before it is 30 monthsold, but the first flowers are generally destroyed, as the planters donot permit the plants t o bear fruit before they are four years old ;100 kilos. of fresh fruit yield from 45 to 30 kilos. of dry cocoa. InVenezuela, after a plant is seven years old, it yields 0.75 kilo. annually.In Magdalena a tree yields 2 kilos.of dry cocoa per annum. TheD. A. L.D. A. L.Fatty Constituents of Common Chestnuts.H. WVEGETABLE PHYSIOLOGY AND AGRICULTURE. 203kernel of the species 1M0,itaraz contains : Butter, 53.3 ; albumin, 12.9 ;theobromine, 2.4 ; gum and tartaric acid, 6.7 ; cellulose, lignose,starch, 9.1 ; ash, 4.0 ; water, 11% per cent. The ash consists chieflyof phosphate of calcium, magnesium, and potassium ; it also containssilica, carbonic and sulphuric acids. The husk has the followingpercentage composition :-Butter, 3.9 ; nitrogenous matter, 14.25,containing 2.8 N ; gum, 12.12 ; tartaric acid and tannin, 5-05 ; ash,6.89 ; water, 12.18 ; lignose, cellulose, and other compounds not esti-mated, 45.61. The process of decortication is generally accomplishedby means of gentle heat.The following table shows the compositionof Trinidad cocoa, decorticated A by heat, B without heating :-A.13 utter ............ 54.0Starch and glucose . . 2.5Theobromine ........ 3.6Asparagine ........ traceAlbumin .......... 11.8Gum .............. 2.5Tartaric acid.. ...... 3.7Tannin ............ 0.2Soluble cellulose .... 11.5Ash .............. 4-4Water -Not estimated ...... 5.8............B.49.92.43-3trace10.92.43.40.210.64-07.65.3Cocoa butter is a white solid which melts at 30" and solidifies at23". The gum resembles gum arabic in appearance, and also yieldsmucic acid when treated with nitric acid. It is powerfully dextrogy-rate. Chocolate, prepared by grinding together sugar and gentlyroasted cocoa, contains varying amounts of sugar.Spanish chocolatecontains from 40.6 to 54 per cent. of sugar, and French chocolatecont,ains from 56 to 59 per cent.The relative value of chocolate and milk as food is seen from thefollowing analysis of equal weights of milk and an emulsion contain-ing 20 per cent. of chocolate :-Chocolat,eemulsion. Milk.Albumin ........ 3.0 13%Fats ............ 14.0 15.0Sugar.. .......... 32.0 15.0Salts ............ 1.0 2.7The large proportion of sugar in chocolate diminishes its nutritiveAnalysis of some Cider Apples. By R. LEZB (Ann. Agronomipues,9, 105).-The fruits were exhibited a t the Apple Congress of St. LB,November, 1882, and analysed by the author a t the end of Decem-ber :-power. w.c. w204 ABSTRACTS OF CHEMICAL PAPERS.Variety.Haut griset. ...........Avoine. ...............Doux lozon. ..........Aufriche tardive .......Cartigny gros ..........A iru ..................Petit rouget ...........Frkquin. ..............Water.80 *9683 -3880 -6482 '0281 *0884 *0283 -9084 *90 -Sugar.7 -649 -199 -228 -5910 -416 -088 -507 .a --Ash.0-520 '370 -360 -460 -340 -280 *360 -32-Tannin.--0 *500 -210 -190 -350 -570 -720 -230 -27Cellulose,albuminolds, &c.10 -386 -859 -598 -587 *608 *907.017 -11The variety Frequin is well known as yielding good cider, whichwill keep well. J. M. H. M.Poisonous Properties of Edible Fungi.By G. DUPETIT (BieJ.Centr., 1883, 356).-The physiological action of the juices of manyfungi on animals is detailed in this paper. The poisonous principle issoluble in water, but insoluble in ether, chloroform, carbon bisulphide,and alcohol ; it is precipitated from its solutions by alcohol, tannin,lead acetate, and hydroxide ; it therefore less resembles the alkaloidsthan the soluble ferments, and its action is destroyed at 100". I nBoEetus two non-poisonous alkaloids have been found, the one resem-bling neurine, the other the ptoma'ines. E. w. P.Report on Experimental Plots at Grignon in 1882. ByP. P. D ~ H ~ R A L N (Ann. Agronomiques, 9,106-124).-The crops grownin 1882 were wheat, oats, green maize, sugar-beet, and sainfoin.Theyield of oats was under average, and that of wheat very poor, 35 hec-tolitres per hectare against 50 harvested in 1880. The authorattributes the difference, not to the rainfall, which was less and moreequally distributed in 1882 than in 1880, but to the difference in tem-perature, the monthly mean from March to September being from1.3" to 5%" (July) less in 1882 than in 1880. For the same reasonthe vintage of 1882 was a bad one, as the grapes never ripenedperfectly .Wheat.-All the plots carried potatoes from 1875-1879, and wheat1880-1882 ; since 1879 no nitrogenous manure has been used. Thebest yield (27-30 hectolitres) was on those plots which had receiveddressings of farmyard manure from 1875-1879 ; plots dressed withsodium nitrate during the same period gave no more grain than theplot unmanured since 1875, although the straw was slightly heavier ;and plots which received ammonium snlphate, 1875-1877, yielded lessof both grain and straw than the plot unmanured since 1875.Theentire wheat crop of the neighbourhood suffered much from rust inJune; 10 grams of wheat from one of the plots contained 128 welldeveloped grains weighing 6.12 grams, and 132 stunted badly filledgrains weighing 3.88 grams. The two lots were analysed and foundto be almost identical in composition.Outs.-The harvest from the experimental plots was worse than thVEGETABLE PHYSIOLOGY AND AGRICULTURE. 205:werage of the four years 1878-1881, but better than 1881; thedeficiency was most marked in the grain, and the author attributesthe falling off to the difficulty of cleaning land carrying the samecereal crop so many years in succession. Oats have been grown onall the plots for the last eight years, and in 1882 the yield from mostof the manured plots wad3 actually less than that on the two plotsreceiving no manure, owing to the encouragement afforded by themanures to &he growth of weeds.Green $Iuize.-The seventh consecutive year of this crop has yieldedresults similar to those of the preceding years. The yield, favouredby a, wet season, has shown no falling off: and farmyard manure in quan-tities up to 29,000 kilos.per hectare, has proved by far the most efficaci-ous and remunerative dressing; with 40,000 kilos. instead of 20,000, theincreased yield is nof sufficient t o cover the extra cost of the manure.A moderate dressing of farmyard manure each year has given betteraggregate results than the same total quantity distributed over thethree years 1875-1877.Partial or complete substitution of sodiumnitrate for farmyard manure has resulted in diminished crops.Sugur-beet.-l'his crop has been grown in 1881 aad 1882 on sixplots which carried green maize for the six previous years ; the previousdressings on half the plots having been farmyard manure, and on theothers ammonium snlphate. The results of 1881 were so decidedlyworse on the ammonium sulphate plots, that in 1882 an atcempt wasmade to restore their fertility by new dressings of farmyard manurealone or with artificials : '20,000 kilos.farmyard manure, together with200 kilos. each of sodium nitrate, superphosphate, and potassiumchloride, was the only application which raised the produce of theammonium sulphate plots t o a level with the plots which received nomanure in 1881 or 1882, but had been dressed with farmyard manurein 1878, ' i 9 , '80. The sugar in average samples of roots from eachplot was determined by the polariscope, the percentage varying from12-04! to 13.73 (the variety grown was Vilmorin's betterave CLU colletrose). The results confirm the author's previoiis conclusions that therichness in sugar is lowered by nitrogenous manures, and is notsensibly raised eitber by potassium salts or superphosphate. Themost remarkable fact in this series of experiments is the decreasedcrops on the plots which formerly received ammonium sulphate, aresult which the author attributes to the injurious action of this salton the physical properties of the soil.Sainfoirz.--The sainfoin grown in 1879 had become replaced bygrasses at the end of 1881 ; a new sowing was therefore made in 1882,and a satisfactory crop obtained, the best plots being those whichwere heavily dressed with farmyard manure from 1875-1878.Analyses of the soil and subsoil, made in the four years preceding1879, during which the plots carried sugar-beet and green maize,showed a slight progressive diminution in the percentage of nitrogen,even in those plots which received large dressings of farmyardmanure ; since the occupation of the ground by sainfoin, however, thepercentage of nitrogen has remained stationary or has slightlyincreased.No ilgures are given on this point. J. M. H. M206 ABSTRACTS OF CHEMICAL PAPERS.Influence of Rainfall on the Wheat Crop. (Bid. Cen,tr.,1883, 291-294.)-A table of the rainfall and temperature in Englandduring July and August, in the years 1846-1876, is given, and thisis divided into four groups; comparing this table with the wheatcrops, it appears that when the average temperature of July andAugust is above the mean, the crop is above average: rain duringwarm seasons does not lower the quantity although the quality maybe deteriorated ; however good a season may be in June, no good cropis obtained-that is one above the average-if the average tempera-ture in July and August is below the mean ; even if the weather inthose months be fine, the quality only is good.If during July andAugust there is both wet and cold, the yield is always low and thequality poor. E. W. P.Comparative Feeding Value of Barley, Malt, and Peas.By A. VOELCHER (Jour. Roy. Agri. Soc., 1883, 422).-These experi-ments were conducted at Woburn. The barley an2 malt were usedin the proportion shown in the malt'ing operation, 140 lbs. of barleyyielding 11'7 lbs. of malt and malt-dust. Three pens, each of tensheep (10 months old), received throughout the same quantity ofswedes, with hay and straw chaff. During the first period of eightweeks, each sheep had in addition 4 lh. of linseed cake per day;pen 1, 4 lb.of barley meal ; pen 2, the equivalent in malt-meal andmalt-dust; pen 3, 4 lb. of pea-meal. In the second period of twoweeks the additional foods were increased to .$ lb. per head per day.In the third period of two weeks they were raised to 2 lb. In thefourth period of two weeks they were raised to 1 lb. The gain inlive-weight of the sheep of each pen was as follows :-Pen I. Barley. I Pen 11. Malt. I Pen 111. Peas.lbs. lbs. lbs.First eight weeks.. . .. . .Following six weeks . . . .Total fourteen weeks.. . . 1 293k I 301P 1 3413The feeding values of the barley, and of its equivalent in malt,were thus practically equal, whilst that of the peas was distinctlygreater.The maximum rations were continued for two weeks longer;during this time the sheep of pen 1 refused a part of their barley, theresults therefore ceased to be comparative.Composition and Digestibility of Serradella at variousAges.By H. WEISKE, G. KENNEPOEL, and B. SCHULZE (Bied. Cewtr.,1883, 307--309).-The seed was sown in the middle of April on twoplots, from the first of which a crop was taken on July 22, and fromthe latter on October 2, also an aftermath was taken from the firstplot on October 2.R. W.The composition of the crops was as follows :VEGETABLE PHYSIOLOGY AND AGRICULTURE. 207I Plot 1.1 July 22.Yield -Fresh. ..........Dry.. ...........A lb \ imin ........Fat, &c. ........Fibre. ..........Cellulose, &c. . , . .Ash ............Containing-110 *O kilos.13.83 ,)22 -62 p.c.5.2 ,329.65 ,,30.89 ,,11.64 ,,October 2.--4 ~345 kilos.0.577 ),24.75 p.c.5-12 ,,27 -11 ),34.33 ,)8.69 ,,Plot 2.October 2.85 -00 kilos.17-15 ),19-13 p .~ ;3.95 ,,35-71 *,32-39 ,,8-82 ,,Feeding experiments showed that the younger plant was moreeasily digested than the older.Analyses of Heather (Erica vulgaris), Braken (Pteris aqui-lina), and Broom (Genista pilosa). By A. PETERMANN (Am.Agronomiques, 9,251-255).-Vast tracts of poor soil in the Ardennes(derived from schists and quartzose schists) ars covered with a thickvegetation of heather, broom, and fern, which is useful to the inhabi-tants in many ways. The dense mass of vegetation assists in the dis-integration of the rock, and acts as a sponge in storing up andgradually giving out the rainfall.Sheep and horses readily eat theyoung shoots of broom and heather, and the ashes of these plants,burnt on the spot, are found to be a good manure for oats. Cutwith the scythe, air-dried, and stacked, these plants furnish fuel inthe winter aud litter for cattle.* Sometimes they are, ploughed inas green manure, and frequently broom in flower is made into a com-post with soil and refuse. The analyses in the subjoined tableswere made on the air-dried plants, including stems, leaves,. andflowers :--E. W. P.Water ..................+Organic matter .........Mineral matter ..........+Containing nitrogen .....Fern. 1 Htather. 1 Broom.12 -70 12 -3085 *06 84.792.24 1 , 2.91* Fern litter is also extensively used in the New Borest.-J. M.H. M208 ABSTRACTS OF CHEMICAL PAPERS.Heather.Composition of the Ash after Deducting Carbon, Sand, andCarbonic Anhydride.Brcom.-.- ---Potash.. .............................Soda ...............................Lime.. .............................Oxide of iron. .......................Sulphur trioxide .....................Phosphorus pentoxide ................Silica ..............................Chloi*ine ............................Manganese ..........................Magnesia ...........................-Deduct oxygen equivalent to chlorine ...43 -284 *1818 -5710.051'124.6114 *051-113 '89trace100 -880.88---Fern.--38 '533 -3111 -696 -930 9 17.934.601'7.5111 *09 ---102 * 502 -50100 *oo31 *7'46.9819 *7813 *283 -068'142.7313 '472 -35trace100 *530 *53loo*oo I loo'ooFern and broom thus contain six times, and heather twice as muchnitrogen as rye-straw, and their ashes are rich in phosphoric acid andpotash.J. M. H. M.Beet Cultivation. By CRAH~ and others (Bied. Centr., 1883,333).-CrahB found on large plots that a mixture of Chili saltpetreand Baker guano was a more productive manure than ammoninni sul-phate and guano, both as regards yield of root and of sugar. Marckerfound that in 1880 Simon le Grand Rose was the best cropper butlowest yielder of sugar, but in 1881 Klein Wanzlebene was the highestcropper and Vilmorin Blanche gave the best yield of sugar.Potatoes and Sweet Potatoes.By SACC ( B i d Centr., 1883,337).-Potatoes which are planted at all seasons of the year, as inMonte Video, are watery and tasteless, and have the composition-albumin 0*71-0*81, dextrin 0.02-0.05, sugar 1.3, starch 10.2-12.81, bitter extract 2-25, fibre 13.18-11.59, calcium bimalate 0.05,water 73.59-72.91, but if they are planted in October then the com-position is normal. Sweet potatoes (ConvoZvuZus batatas) requiremore heat, and contain-albumin 0.56-OG4, glucose 4.0-0.3, muci-lage 1.15, pectic acid 1.27, starch 15*0-1341, fibre 10*02--17*83,ash 1, water 67.0-68.19. They require an open soil and but littlemanuring. The sweet potato is finer than the potato, and is quite asuseful, being largely used in the manufacture of spirits.Assimilation of the Organic Matter of Arable Soil.Part I.E. W. P.E. W. P.Historical RksurnB. By P. P. DOHBRAIN (Ann. Agrononziques, 9,258-265) .-The idea that plants directly assimilate the organicmatter of the soil was supported by de Saussure, Malaguti, andSoubeyran, and opposed by Liebig and Boussingault. The iast-namedchemist contended that the utility of humus to vegetation consists iVEGETABLE PHYSIOLOGY AND AGRICULTURE. 209the continuous disengagement of large quantities of carbonic anhy-dride in the soil, and subsequent writers have supposed that thiscarbonic anhydride is absorbed by the roots, conveyed to the leaves,and there decomposed in presence of chlorophyll and sunlight. Noevidence in favour of the absorption of carbonic anhydride by rootscould be obtained by Corenwinder from direct experiments on thepoint ; on the contrary, he has shown that roots take part in respira-tion, absorbing oxygen and emitting a little carbonic anhydride.Grandeau has attributed another function t o humus. He found thatthe ammonium carbonate extract of soil contains, besides the brownhumus bodies, considerable quantities of phosphoric acid, oxide ofiron, magnesia, lime, and soluble silica.When this solution is dialysed,only the mineral constituents pass through the septum, forming acolourless solution, the brown matter left on the septum containingonly 8 per cent. of ash, whereas before dialysis i t contains 53 per cent.From these experiments Grandeau concludes-(1) that the mineralscombined with humus are directly assimilable by the roots of plants ;(2) that the organic matter itself does not enter the roots, but is thevehicle of the mineral aliment ; ( 3 ) that the combination of mineralswith hunius is similar to that found in the liquor of a dung-heap ; and(4) that the fertility of a soil is proportional to the quantity ofminerals associated with humus and soluble in ammonium carbonate.Petermann has recently demonstrated (and his experiments have beenrepeated by Grandeau) that soil not treated with ammonium carbonatedoes contain dialysable organic matter, and the question remains, doesthis organic matter serve directly as plant food ? The author’s obser-vations on the experimental maize plots at Grignon render an affirma-tive reply probable.The plots dressed each year with 40,000 kilos.farmyard manure have given an average annual yield of 90,000 kilos.green maize, whilst the highest yield obtained by the use of chemicalmanures is 68,000 kilos. When maize is grown with the aid of farm-yard manure, the soil is found t o be much more impoverished ofcarbon than in the case of potatoes or wheat, which do not benefitso much from the same manure. The author finally quotes theopinion of Sachs, who, after noting the direct assimilation of organicniatter by fungi, germinating seeds, and certain parasites, considers itprobable that green plants also may share in this function. Thedirect experiments of the author will be given in a future number.Ammonia, Chlorine, and Sulphuric Acid in Rain collectedat Rothamsted.By Sir J. B. LAWES, J. H. GILBERT, and R. WARING-TON (Jour. Roy. Agri. Soc., 1883, 313).-The results of earlier deter-minations have been given in a previous paper (Abstr., 1882, 889).1. Ammonia in Rain.-The new determinations were made both indaily rainfalls and in monthly mixtures. The rain was distilled, andthe distillate Nesslerised. I n 152 daily collections of rain, dew, &c.,in the large rain-gauge (0.001 acre), extending from June ‘22, 1881, toJanuary 5, 1882, the nitrogen as ammonia varied from 0.043 per mil-lion (in a rainfall of 0.713 inch on Nov. 27) to 5-49 per million (in adeposit of dew of 0.007 inch on September 17). The rainfall duringthe whole period amounted fo 219645 inches, and contained an averageJ.M. H. MI210 ABSTRACTS OF CHEMlCAL PAPERS.of 0.254 of nitrogen as ammonia per million. The proportion ofammonia is much greater in small deposits than in large; it is affectedto a still greater extent by the amount of previous washing which theatmosphere has undergone. Ammonia was also determined in 50monthly mixtures of rain-water. I n 24 recent months the analysis ofthe water was made a t the end of each month ; the earlier monthlysamples were in most cases of considerable age when analysed. In the24 recent samples the nitrogen RS ammonia averaged 0.316 per mil-lion; in the whole series of 50 months the average was 0.361.Evidence is given showing that the ammonia in the rain-watergenerally tended to increase by keeping.Nitrification was possiblyprevented by the lead present in the water. The rainfall of summerwas generally richer in ammonia than that of winter. The nitrogenas ammonia contributed annually by rain to an acre of land amountsto 2.37 lbs. if calculated from the da.ily determinations during sixmonths, to 2.47 lbs. calculated from two years’ determinations infresh monthly mixtures, and to 2.66 lbs. if calculated from determina-tions in 50 monthlymixtures, many of them old. From the last seriesof determinations it appears that to double the quantity of ammoniaper acre the rainfall must be increased about six-fold. From Frank-land and Way’s results, the nitrogen as nitric acid appears to be about1 lb.per acre, and the nitrogen as organic matter a similar amount.The total combined nitrogen in the annual rainfall a t Rothamstedis thus about 4.5 lbs. per acre.%. Chlorine in Rniiz.-The determinations of chlorine in monthlymixtures of rain extend over six years, 1877-83. The mean propor-tion found was 1.99 per million of water, or 14.92 lbs. per acre, equdto 24.59 lbs. of sodium chloride. Two-thirds of the chlorides fall inthe six winter months, October to March. The minimum quantityfalls in July, the matximuin in October and November. The supplyof chlorides in summer seems to be very limited, as a large increasein the rainfall produces but little increase in the quantity of chloridesper acre. In winter the increase in the quantity of chlorides with arise in the rainfall is much greater.3.Xulphuric Acid in Rair~.--The sulphuric acid was determinedgravimetrically in mixtures representing the rainfall of summer(April-Sep tember) and winter (October-March) ; the determina-tions extended over two yeam. When the rain was collected in glassvessels only, the average amount of sulphuric anhydride was 2.41 permillion of rain or 18.5 lbs. per acre. When the rain was collected inthe large rain-gauge the amount of sulphuric anhydride was 3.95 permillion, or 30.3 lbs. per acre. There seems little doubt that in thislatter case a part of the sulphuric acid was derived from the vulca-nised caoutchouc used for the connections. The rain appears to beslightly richer in sulphuric acid in summer than in winter.Influence of Artificial Manures on the Physical Propertiesof Soil.By E. WOLLNY (Ann. Agronomiques, 9, 129-131 ; from Zeits.des Vereins fiir die Rubenzuck~!1.industrie, November, 1682) .-Theaddition of small quantities of ammonia or fixed alkalis, or of alkaliriephosphates or carbonates to water holding clay in suspension, causesR. WVEGETABLE PHYSJOLOGY AND AGRICULTURE. 211the immediate precipitation of the clay in a dense form. Mineralacids and their salts, such as sodium nitrate, act in the oppositemanner, precipitating the clay in a light and spongy form, whichoccupies much space. Hence the author argues that the addition ofsubstances of the former class to soils is injurious to their por0sit.yand lightness, and consequently to fertility, and cites as examples thealkali plains of Nevada and California, the soil of which is hard,dense, non-porous, and sterile.On the other hand, salts such assodium nitrate, sal tpetre, and potassium sulphate exercise an imme-diate beneficial effect on the porosity of arable soil, but as they arequickly washed out the effect is not lasting, and the fertility is thenfound to be impaired. Of all artificial manures, lime exercises themost favourable influence on the properties of soil, causiiig it toaggregate into flocculent particles which persist for years, and renderit light and fertile.Weeds in Soils. By H. PUTENSEN (Bied. Centr., 1883, 295-297).- In this paper it is shown that repeated ploughings and harrow-ings diminish the number of weeds in the soil.Manuring Experiments at Kiel.By A. EMMERLING (Bied.Centr., 1883, 297406) .-This is a report of the experiments madein 1881, which are a continuation of tJhose conducted in 1880; theseason was bad, yet conclusions niay be drawn which are not withoutinterest, as showing the action of artificial manures under unfavour-able circumstances. There were 24 sets of plots on various soils, thecrops being generally oats, but buckwheat, barley, and beans werealso grown. The manures were superphosphate, precipitated phos-phate, dissolved and raw Peruvian guano, steamed and dissolvedbone-meal, blood, ammonium salts, and Chili saltpetre (86.9 per cent.).The results are given in full detail in a series of tables. A shortsummary of these is given here.Ammonia acted but feebly on clayloam, and not at all on sand, hut well on black humus earth. Salt-petre was satisfactory in all classes. Phosphates with ammonia pro-duced a low yield in that district where the weather was unpropitious.Phosphates and saltpetre gave contradictory results owing to badweather. Steamed bones raised the yield of grain, and especially atthe drier stations ; whilst steamed bones are best, on dry lands, thedissolved meal best acted at those stations where rain had fallen inJune. Blood failed at all the dry places. In spite of the unfavourableconditions, the guano (raw and dissolved) greatly increased the crop ;the latter had, however, increased the grain and straw more than theformer. E.W. P.Manurial Value of Nitrogenous Refuse. IT. Dried Blood.By A. PETERMANN (Ann. Agronomipes, 9, 241-251) .-Thirty-twosamples of dried blood examined in 1880-81 gave an average of11-23 per cent. nitrogen ; the physical condition also was satisfactory,being dry, friable, pulverulent, and almost without odour. Themanurial value was determined by experiments on plants grown inpots, in two soils of very different physical characters, and the resultswere compared on the one hand with those obtaiued without manure,J. M. H. M.E. W. P212 ABSTRACTS OF CHEMICAL PAPERS.and on the other hand with those obtained by using a quantity ofsodium nitrate equivalent in nitrogen to the dried blood. The effectof adding phosphoric acid and potash to the dried blood was alsostudied. The results given in this abstract are in all cases the meanof two or three concordant experiments.The first series consisted of 15 flower-pots filled with loamy soil fromGembloux mixed with a quarter of its bulk of quartz sand ; the second,15 pots filled with sand from Campine. Ten grains of spring wheatwere sown in each pot on March 17th, 1882 ; on August 20th, 1882,the plants were removed from the pots, and the straw and grainweighed separately ; the results are given in the table.~~ ~Loam.Mean weight ofManure.Straw.No manure.. ...........................Dried blood = 0.25 gram N ..............Sodium nitrate = 0'25 gram N.. ..........Dried blood (= 0.25 gram N) + precipitatedSodium nitrate (= 0*;5 gram N) + precipi-tated phosphate (= 0.30 gram P,05). ....Dried blood ( = 025 grain N) + precipitatedphosphate (= 0.30 gram P205) + potas-sium chloride (= 020 gram K,O) .......Sodium nitrate (= 0.25 gram N) + precipi-tated phosphate (= 0.30 gram P,05) +potassium chloride (= 0.20 gram K20). ..phosphate (= 0.30 warn P2OS), .........18 -1942 '5144 *,2542 -9044 -9643.7345 -01Grain.7 '9419 -5620 -1419 *5119 -6219 -4419.80 -Sand.Mean weight ofStraw.--5.3510 -7019 -5120 -4621 *3622 -5923 -99Grain.2 -085 -057 -518.949 *7612 -1912 -98The highest yields are obtained in the loam, but the effect of themanures is greatest in the sand. In the loam, dried blood producesan increase in the crop practically identical with that given by aquantity of sodium nitrate containing the same amount of nitrogen ;the addition of phosphoric acid, or potash, or both, has little effect.In the sand, on the contrary, dried blood is decidedly inferior to itsequivalent of sodium nitrate, and both phosphoric acid and potashproduce considerable effect ; the effect of the phosphatic manure, in allthe pots in which it was used, was to hasten the period of ripening.As the result of these and previous experiments, the authorarranges the nitrogenous manures which he has tried in the followingorder of efficiency (such quantities being employed as contain equalweights of nitrogen) :- Sodium nitrate, dried blood, dissolved wool,wool refuse, leather refuse. The efficiency is plainly related to thesolubility and readiness to decompose in each case.Preparation of Manure from Furnace Slag.J. M. H. M.By WINKEL-HOFER (Bied. Cent?.., 1883, 354).-The excess of lime in the slagobtained in the '' basic process " is to be removed by tlreatment witANALYTICAL CHEMISTRY. 213molasses and water, which leaves the phosphates undissolved ; thelime is then separated from the saccharate by passing the productsof combustion from tlie furnaces through the solution.E. W. P.Insoluble Phosphates. By F. J. LLOYD (Chem. News, 48, 164-165) .-The “ insoluble phosphates ’’ from superphosphates are dividedinto two classes, the “ white” and the “ red.” The white are obtainedonly from manures made from bones, and represent approximately theamount of phosphate not dissolved.The author has analysed the “ red” phosphate with the followingresult :-CaO. Fe203. P205.32.53 31.80 35-77 per cent.These numbers correspond with 60.01 per cent. calcium phosphate,17.63 per cent. ferric phosphate, 22.46 per cent. ferric oxide.D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600200

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 213 An a 1 y t i c a I C h e m i s t r y. Volumetric Analysis. By E. REICHARDT (Arch. Pharm. [3], 21, 106--115).-This paper contains instructions for the performance of the ordinary operations in volumetric analysis, including the pre- cautions to be observed in the preparation of standard solutions, &c. W. R. D. Determination of the Density of Solids and Liquids by means of the Specific Gravity Bottle. By S. PAGLIANI (Gazxettn, 13, 172).-The author points out, as a source of error in these deter- minations, the fact that flat-bottomed glass bottles when filled with liquid exhibit very sensible alterations of level, even when only a slight pressure is exerted on the bottom ; and in endeavouring to determine the capacity at 0" of one of these vessels, he observed that the level of the liquid contained in it at 0" was higher than a t the ordinary temperature.He therefore recommends for liquids the use of the bottles described by Regnnult (Ann. Chim. Phys. [3], 9, 438) ; and in cases when it is necessary to use the ordinary bottles, as in determin- ing the densities of solid bodies, he suggests a previous examination, with the view of ascertaining whether they exhibit the defect above mentioned. H. W. Apparatus for the Rapid Analysis of Gases. By A. A. BRENEMAN (Chew. News, 48, 156).-The apparatus consists of a eudio- meter fitted with a soft india-rubber stopper bored with two holes, through which pass two tubes closed by valves; one is connected with an exhausted receiver, whilst the other has simply a pointed gIass214 ABSTRACTS OF CHEMICAL PAPERS.tube attached to it. When in use the gas is introduced into the eudiometer over a pneumatic trough, a8nd the volume read off in a convenient cylinder sufficiently full of water. The eudiometer is re- transferred t o the trough of water, the stopper inserted, and most of the water drawn from the interior of the eudiometer by opening the valve in connection with the exhaust chamber ; the absorbent is intro- duced by applying the point of the pipette to the pointed tube and opening the valve connected with it, when the liquid rushes in to replace the water which has been withdrawn. The absorption being complete, the liquid is removed by opening the exhaust valve (by which means all subsequent absorbents and washings are removed), the eudiometer well rinsed with water, and the volume again read off in the cylinder of water.The mouth of the burette is kept below the surface of water as much as possible. A special form of cup, with a long bent-up handle, is used for transferring the eudiometer from the trough to the cylinder, and vice vers$, Apparatus for the Rapid Analysis of Gas. By A. H. ELLIOT (Chem. News, 48, 189-191) .-This apparatus consists of two glass tubes of the same length; one graduated from the top to within a short distance from the bottom, in tenths C.C. to 100 C.C. ; the other plain. Both are connected at the lower end with two distiuct reservoirs of water by means of flexible tubing ; there is a three-way cock at the bottom of the plain tube, with one delivery through the stem. The top of the graduated tube terminates in a capillary tube, bent at a right angle, and fitted with a stopcock.At the top of the plain tube there is a straight capillary tube fitted with a stopcock, below which a lateral capillary tube is fused, which is joined to the capillaryof the graduated tube by a rubber connection. Above the stopcock the operator can attach either a movable cylindrical funnel which is ground to fit over the tube, or the tube for the admission of the gas to be analysed. I n use, the tubes are filled with water by opening the stopcocks in a suitable manner, and the plain tube is charged with gas, lowering or raising the water reservoirs ; the gas is then transferred to and adjusted in the graduated tube, the volume is read off, and the absorbent having been run in to the plain tube through the funnel, the gas is retransferred to the last-mentioned tube, &c.In washing out the plain tube, use is made of the three-way cock; by bringing it into connection with the inside of the tube, and allowing the washings to run out. Absorbents are used in the following order-potash, bromine, potassium pyrogallate, and cuprous chloride. A special arrangement is employed for explosions : a stout glass tube is graduated in tenths C.C. and of 100 C.C. capacity to within a few inches from the bottom; the lower end is connected with a water reservoir, and has a lateral tube fused in the side and fitted with a stopcock ; the upper end is closed by a capillary tube and stopcock (to which either a funnel or a piece of bent capillary tubing can be attached), and has platinum wires fused in through the glass. To use this, the tube is filled with water, and by means of the bent tube and india-rubber connections and the water reservoirs and stopcocks, a sufficient amount of gas is admitted from the absorption-tube, the D.A. L.ANALP TICAL CHEMISTRY. 215 level adjusted, the volume read, and the oxygen allowed to enter by the lateral tube a t the bottom, the explosion is proceeded with as soon as t,he gases have been mixed by slight agitation : the analysis is then finished in the usual manner, absorbents being run in through the funnel. After some practice, a complete gas analysis, using both absorption and explosion tubes, can be made in less than an hour, and results are obtained within a few tenths of a per cent.of the truth. D. A. L. Estimation of Bromine in Presence of Large Quantities of Chlorides, By A. CAVAZZI (Gazzetta, l3,174).-The author's method consists in the use of oxygenated water (Ba02 and dilute sulphuric acid), which a t 100" liberates all the bromine without decomposing the chlorides. The bromine-vapour is passed into a solution of arsenious acid in hydrochloric acid (0.10 g. AS& in 20 C.C. of liquid) which absorbs it rapidly. To determine the quantity of bromine thus absorbed, a solution of potassium permanganate is prepared contain- ing 3.55 g. KMnO, in a litre of distilled water. Now the author finds that 18.30 C.C. of such a solution is just sufficient to impart a perma- nent red or yellow tint to 20 C.C.of the arsenical solution ; and hence by a simple calculation, it is found that 1 C.C. of the same perman- ganate solution is equivalent to 0.00888 gram of bromine. If iodides are also present, the iodine must first be separated by means of an acetic solution of barium dioxide and carbon bisulphide (as described by the author in another place), after which the solution containing the bromides and chlorides is mixed with pure lime to alkaline reaction, then evaporated to dryness, and the residue is calcined to convert the acetates of barium and calcium into carbonates. Lastly, the residue is treated with boiling water, and the bromine is determined by the method above described. Purification of Hydrogen Sulphide. By W. LENZ (Chem. News, 48, 147).-It is very important that all arsenic should be removed from the hydrogen sulphide employed in chemico-judicial investiga- tions, and the author suggests the following process with this object.Four consecutive wash-bottles kept a t a temperature of 60-7'0" are used to purify the gas. The first bottle contains a mixture of 1 part strong hydrochloric acid with 2 of water ; the second, a solution of 1 part of this mixture to 4 of water; the third a similar solution containing 1 to 8; in the fourth, pure water. Neither caoutchouc stoppers nor vulcanised india-rubber connections are permissible. This washing system is very efficient. Testing for Free Sulphuric Acid in Wines and Vinegar. By E. POLLACCI (Gazzetta, 13, 315--316).-The author states that neither Nessler's method nor Lessaigne's gives satisfactor7 results, and pro- poses the following :-Strips of filtering-paper, purified by treatment with hydrochloric acid and washing, are immersed in a beaker con- taining the wine, so that they adhere to the sides, one end touching the bottom and the other projecting about a centimeter above the top, a sufficient number of strips being used to line the interior of the H.W. D. A. L.216 ABSTRACTS OF CHEMICAL PAPERS. vessel. After 24 to 36 hours, bythe spontaneous evaporation of the liquid, a, sufficient quantity of the acid will have accumulated in the upper extremities of the strips of paper; these are now cut off and repeatedly triturated with ether in a glass mortar. The ether is evaporated, the residue taken up by water and tested for sulphuric acid in the usual way.This method has the advantage that the free acid alone is separated and detected. Direct Estimation of Carbonic Anhydride in Presence of Sulphides, Sulphites, and Thiosulphates of the Alkali-metals. By M. KONW and E. ZATZEK (Monatsh. Chem., 4, 733-737).--Por the simultaneous estimation of carbonic anhydride and hydrogen sul- phide, Fresenius has given a method depending on the retention of hydrogen sulphide by copper sulphate (this Journal, 1871, p. 582) ; but for the direct estimation of carbonic anhydride under conditions which involve the simultaneous formation of SO, and SH,, as in the examination of crude soda, soda-lyes, &c., no accurate method has hitherto been published. This object may however be attained by the following method, depending on the principle that potassium perman- ganate, under conditions already described (p.151 of this volume), converts the sulphides, sulphites, and thiosulphates of the alkali- metals almost entirely into sulphates, so that when a mixture of these salts with carbonates has been thus treated, its subsequent decomposi- tion by an acid gives rise to the evolution of nothing but carbonic anhydride. The method is applied as follows :-The substance is introduced into a 300 C.C. flask closed by a perforated caoutchouc stopper, through one of the holes of which is inserted a stoppered funnel-tube reaching nearly to the bottom of the flask, and through the other a tube con- necting the flask (1) with a Liebig’s bulb-apparatus containing an acidulated solution of permnnganate ; (2) with a CaCl,-tube ; ( 3 ) with a bulb-apparatus containing caustic potash ; (4) with a CaCl,-tube.The apparatus having been made air-tight, a concentrated solution of permanganate is poured in slight excess into the flask, and the carbo- nate is then decomposed with dilute nitric, sulphuric, or acetic acid (not by hydrochloric acid) ; the stopcock of the funnel-tube is then closed, and the decomposition of the carbonate is completed by heating the liquid gently at first, and ultimately to the boiling point. The heating is then discontinued ; the cock of the funnel-tube is opened ; this tube is connected either with a U-tube filled with lumps of solid potash, or with a wash-bot’tle containing potash-lye ; and a slow stream of airis drawn through the apparatus for half to three-quarters of an hour, after which the apparatus may be disconnected.The insertion of the bulb-tube cont,aining the permanganate solution is for the purpose of retaining any portion of SOz or SH, that, may have escaped oxidation in the flask. The accuracy of the method may be judged of by the following examples, in the first and second of which pure sodium carbonate, Na2C03, was mixed with sulphite ; in the second with thiosulphate ; in the third with s~lphide,~sulphite, and thiosulphate together ; in the fourth with potassium sulphide, sodium sulphite, and sodium C. E. G.ANALYTICAL CHERlISTRY. 217 thiosulphate ; and in the fifth a mixture of Iceland spar, barium sul- phite, and barium thiosulphate was decomposed by dilute nitric acid.c 0, CO, found. calculated. 1.. ........ 41.54 per cent.] ........ ........ 44.00 ,, 3.. 41-35 ,, 4.. 41-33 ,, 5.. ........ 43.75 ,, In one case in which the absorption-apparatus containing perman- ganate was not introduced, a mixture of sodium carbonate and sulphite gave 4‘7.01 per cent. COz, whereas the amount according to calcnlation should have been only 41.51. This method also gives the means of determining the amount of sulphur contained in the sulphur-compounds mixed with the carbonate. For this purpose, after the carbonic anhydride has been determined as above, the contents of the reaction flask and of the absorption-tube containing permanganate are poured into a beaker, the excess of per- manganate and the precipitate of manganite formed in the reaction are decomposed by heating with hydrochloric acid, and after the chlorine has been expelled by boiling, the sulphuric acid is precipitated by barium chloride, &c.H. W. Estimation of Phosphoric Acid in Manures. By GASSEND and CAMPREDON (Ann. Agronomipues, 9, 266-270) .-After having obtained the precipitate of ammonio-magnesian phosphate, there are two ways of dealing with it in common use : it is either calcined and weighed as magnesium pyrophosphate, or it is dissolved in acetic acid and titrated with standard uranium acetate. The authors state that, when applied to commercial fertilisers, the first method invariably gives results which are too high, unless solution of the precipitate in hydrochloric acid and reprecipitation are resorted to, necessitating a further delay of over twelve hours.Titration with uranium acetate they believe to be quite accurate and more expeditious than the gravimetric method, even when only one precipitation is employed. A sample of mixed bone superphosphate and precipitated phosphate gave the following per- centages of P206 :- Uranium Gravimetric method. method. P,Os solnble in water.. .......... 14.08 15.35 7 , ?, ammonium citrate 14.99 16.18 ,, total ...................... 16.11 17.14 The excess by the gravimetric method was proved to be due to impurities retained by the magnesium precipitate, consisting of iroo and alumina (traces), lime, sulphuric acid, and silica. The mean quantity of silica in the three precipitates wag 0.008 gram, and the authors find t8hat the ammonio-magnesium phosphate retains silica, even after a day’s washing with dilute ammonia. J.M. H. M, VOL. XLPI. ¶218 ABSTRACTS OF CHEMICAL PAPERS. Testing of Potassium Bromate. By G. VULPIUS (Arch. Phmrm. [3], 21, 186-190, and UingZ. polyt. J., 249, 47).-For the determi- nation of phenol, according to the equation- CJ&O + 5KBr + K&03 + 3H2s04 = C6H3Bra0 + 3K2s04 + 3H20 + 3HBr, the new German Pharmacopeia stipulates the use of normal solutions of potassium bromide and bromate. The latter, according to Vulpius, often contains a large proportion of potassium bromide, which may be estimated in the following manner :-O*J gram of the bromate is mixed in a tared beaker with 2 grams of potassium iodide, and the mixture dissolved in *5 C.C.of hot water; 10 C.C. of cold water, and 15 grams of a 25 per cent. solution of hydrochloric acid are then added, and the solution is titrated with decinormal sodium thiosulphate. 1 C.C. c f this solution corresponds with 2.785 mgrms. of potassium bromate, taking the equivalent for potassium bromate a t 167.1. D. B. Action of Ammonium Sulphide on Metallic Pyrophosphates. By G. BUCHNER (Arch. Pharm. [3J 21, 115--120).-The author has investigated the action of ammonium sulphide on the solution ob- tained by adding excess of sodium pyrophosphate to solutions of the salts of those metals which, in the ordinary course of analysis, are precipitated by ammonium sulphide. 'If sodium pyrophosphate ( 5 per cent. solution) is added to solutions of the salts of these metals, a pre- cipitate is obtained which is soluble in excess of the reagent.The addition of ammonium sulphide to this solution precipitates the metals as sulphides in the case of zinc, cobalt, nickel, and iron (ferrous and ferric), but produces no precipitate with manganese (manganons and manganic), uranium, chromium, or aluminium. When these last- mentioned solutions are heated, or allowed to stand for some time, the manganese is precipitated as pyrophosphate of manganese, ammonium, and sodium (MnNH,NaP,O,). The solutions containing aluminium and chromium become turbid, if boiled and subsequently cooled ; but in the case of uranium the solution remains clear even after boiling. I f a solution of an iron salt is precipitated by ammonium sulphide, and a solution of sodium pyrophosphate subsequently added, the ferrous sul- phicle dissolves when the liquid is boiled, forming a colourless solution, which becomes dark green on cooling, and finally deposits nearly all the iron as sulphide.When a solution of manganese salt is treated in a similar way, the liquid deposits crystals of manganese sodium ammonium pyrophosphate. W. R. D. Specific Gravity of Commercial Copper. By D. WATSON (Dingl. polyt. J., 249, 48).--The author found that copper, when pre- cipitated electrolytically from a solution of the sulphate, has a sp. gr. of 8-95,',. The sp. gr. of copper is materially affected by different impurities contained in the metal, cuprous oxide having the greatest effect: the following table illustrates this circumstance :-ANALYTICAL CHEMISTRY.219 With + p.c. With $ p.c. With ' P.'' I 'p' gr' 1 Pb. 1 As. 1 p p.c. As. Pb and Copper free from Cu,O.. . . . . . . . . 8 *955 8.961 8.939 8 *945 Copper containing 1 p.c. Cu,O . . . 8 *925 8 -909 8 *915 Copper containing 2.5 p.c. Cu,O, , 1 8 *88L 1 :'::; 1 8.865 1 8.871 The author is of opinion that the sp. gr., in conjunctiorr with the estimation of lead and arsenic, suffices to approximately determine the amount of cuprous oxide in a sample of commercial copper. D. B. Estimation of Carbon in Cast Iron. By A. A. BRENEMAN (Chem. News, 48, 168).-In the process recommended, the carbonace- ous residue obtained when cast iron is dissolved, is filtered in a small platinum tube, which is subsequently put, with its contents, into the combustion tube and burnt in oxygen.The platinum tube is made of stout foil, and is fitted with a small disc of perforated platinum to support the asbestos for filtering ; the air-tight connection, with the necessary glass tube, is made by means of soft india-rubber tubing, one end of which is inserted in the platinum. The ends of the glass tube are conical, so that the connection may be made without injury to the platinum. Combnutions should be conducted in porcelain tubes, as these last longer and can be heated more strongly than glass tubes, and the platinum tube should be made to fit well, so that the oxygen may pass mainly through the filter and its contents. D. A. L. Apparatus for Estimating Carbon in Steel. By A. B. CLEMENCE (Chem. News, 48, 206).-The author has introduced an apparatus to avoid the errors attached to the old process of filtering in a glass funnel, &c., and to do away with the expense and incon- venience of the platinum funnel, porcelain tube, combustion fuimace method (preceding Abstr.j. The apparatus consists of a platinum tube llQinches long, with a diameter of $-inch for 7 inches, the remaining 44 inches being & inch diameter. In use, an asbestos plug is placed at the point in the tube where the contraction commences, the carbon is filtered on this, washed well with hot water, any adhering carbon being swept down by moist asbestos, the tube is then dried at 150-170" for an hour. A hard rubber stopper with glass tube passing through is now put into the wide end, through which the current of oxygen enters, a single thickness of filter-paper, 2 inches wide, being wound round the tube by the stopper, and kept wet by a stream of water; the tube, at the part where the filter is placed, is heated with a Bunsen burner for an hour, at the end of which time the potash bulbs can be weighed.The author takes from 3 to 5 grams of borings, which he dissolves in cuprammonium chloride, 36 grams to 120 C.C. water for 3 grams of steel ; when the deposited copper is com- pletely dissolved, he proceeds as above described. Good results have been obtained. D. A. L. q 2220 ABSTRACTS OF CHEMICAL PAPERS. Volumetric Estimation of Manganese. By J. B. MACKINTOSH (Chem. News, 48, 176--177).-1t has been suggested that the precipitate obtained by treating the boiling nitric acid solution of a manganese salt with potassium chlorate is not pure Mn02, but a mixture of 10Mn02 + MnO.This being of importancein the titration of manganese, the author has studied the subject, and publishes his observations in the present paper. The experiments are based on the facts that potassium permau- ganate has an oxidising power equal to five of oxygen for every two of manganese, and that the same quantity of manganese, in the state of dioxide, has an oxidising power equal to 2 atoms of oxygen ; so that, if a solution of permanganate is reduced to dioxide, the oxidising power of the dioxide thus formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. The analyses were conducted in the following manner :-The permanganate was decomposed with hydrochloric acid and concentrated.The hydro- chloric acid was removed by boiling with excess of nitric acid, and the manganese precipitated by successive alternate additions of potas- sium chlorate and nitric acid, until no more yellow fumes were observed. When cool the precipitate was filtered through asbestos, washed with nitric acid and with water, and then treated with a volume of oxalic acid, with a known permanganate equivalent, and a little sulphuric acid. The excess of oxalic acid was determined by permnnganate, and t,he oxidising power of the precipitate found by subtracting the excess from the whole quantity. The results obtained are as follows :- Perman- ganate used. Oxidising power of precipitate in terms of permanga- nate.45 C.C. 17-80 C.C. 35 13.93 25 9.90 15 3.96 Per cent. of Theoretical theoretical cor- Average for rected for burette true MnOz. error. per cent. 18 C.C. 99.37 - 14 100.07 99.99 10 99.86 - 6 100.6 7 - Great importance is attached to the method of precipitating the manganese ; for by adding the potassium chlorate a t once, and boiling until the action ceases, an error of from 1 to 2 per cent. is almost certain. The author points out that not too much value must be set on the above results, as of course there are many experimental errors involved in the process. It is, however, safe to conclude that the precipitate obtained in this process, when the necessary precau- tions are taken, is not 10MnOz + MnO (which would have an oxidis- ing power = 90.91 per cent.) but MnOz.Arsenic in Glass. By W. FRESENIUS (Chem. News, 48, 147).- Jn connection with the removal of arsenic from apparatus, &c., used in cases of judicia,l investigation, the author has observed that the glass of the vessels employed contained arsenic. A sample of Bohemian glass contained 0.20 per cent., of hard glass 0.08, and anothei- sample of hard glass a trace. The author attributes the D. A. L.ANALYTICAL CHEMlSTRY. 221 browning of glass when heated to arsenic and not to lead. Further experiments show that alkaline solutions take up arsenic from glass ; acids do not. D. A. L. Microscopic Examination of Water for Organic Impurities. By J . BRAUTLECHT (Chew. News, 48, 180).-100 C.C. of the water are treated with five drops of a solution containing 1 part of aluminium sulphate, 1 part hydrochloric acid, and 8 parts of water, and one to three drops of ammonia ; the precipitate is filtered off and redissolved in 10 to 15 drops of dilute acetic acid ; and the clear solution thus obtained is examined under the microscope both before and after the addition of saffranine.By the addition of + per cent. gelatin, per- manent preparations on Koch’s principle may be obtained. Detection and Estimation of Trinitrophenol (Picric Acid). By G. CHRISTEL (Arch. Pharm. [3], 21, lYO--200).-This paper contains an examination of the principal reactions of trinitrophenol made with a view to its qualitative detection and quantitative estimation. The aqueous solution of picric acid is not precipitated by neutral solutions of lead or copper salts; neither is ammo- nium picrate, unless the solution is alkaline, when lead acetate gives a reddish-yellow precipitate, and copper sulphate a yellowish- green precipitate in dilute solutions, and a bright green in con- centrated solutions.A solution containing half a milligram of picric acid in 5 C.C. of water is not at once precipitated by a solution of cupramnionium snlphate, but on standing for 24 hours a distinct precipitate is obtained, which is insoluble in ammonia, but is decom- posed by water. Solution of basic lead acetate is a very delicate test for picric acid, yielding a bright yellow precipitate. A solution containing the tenth of a milligram of picric acid in 5 C.C. of water, gives after 12 hours a distinct precipitate, and a solution con- taining the twentieth of a milligram in 5 C.C.of water a strong opalescence, which snbsequently forms a distinct sediment. When this sediment is decomposed by the addition of 1 drop of sulphuric acid, and the solution is rendered alkaline with ammonium hydrate and evaporated to dryness, a residue is left which, when dissolved in a little water and warmed with a drop of potassium cyanide solution, gives a distinct red colour. The yellow colouring matters of the bark of Quercus tinctoria (quercitron), and the root of Broussonefia tinctoria also give precipitates with basic and neutral lead acetate, but the pre- cipitates do not give the reaction witch potassium cyanide when treated as above described. An aqueous solution of methyl green pre- cipitates solutions of picric acid.The green precipitate dissolves in ammonia, forming a deep yellow solution, which is precipitated by basic lead acetate, and tbis precipitate gives the reaction with potas- sium cyanide. This test cannot be applied for the detection of picric acid in beer, for 1 litre of beer which contained 5 mgrms. of picric acid was not precipitated by a solution of methyl green. Solutions of picric acid are precipitated by stannous chloride, and if a small quantity of ammonia is added, the solution becomes red. The same reaction is obtained when a solution, prepared by adding potassium D. A. L.222 ABSTRACTS OF CHEMICAL PAPERS. hydroxide to a solution of stannous chloride until the precipitate at first formed is redissolved, is added to a, solution of picric acid.The red colour is due to the formation of dinitroamidophenol (picramic acid) : hydrogen and ammonium sulphides give a similar reaction. If a solution of picric acid or a picrate is acted on with zinc and dilute sdphuric acid, a yellowish-red turbid solution is obtained, which, when poured off and mixed with alcohol, develops a green colour, changing through blue to a violet-green. For the detection of picric acid in sweetmeats or other coloured substances containing sugar, the potassium cyanide reaction can be applied directly ; or the colour- ing matter may be extracted with alcohol, the residue from this solu- tion, aft,er dissolving in water, precipitated by lead acetate ; and the potassium cyanide reaction obtained after decomposing the precipitate in the manner above described.For the detection of picric acid in wool or cellulose, the hydrochloric acid solution may be reduced by zinc, and the reaction with alcohol obtained. The substance may also be digested with ammonia, and the potassium cyanide reaction tried with this solution. The detection of picric acid in beer cannot be accomplished by means of lead acetate, on account of the other snb- stances in the liquid, which are precipitated by this reagent ; neither can the colouring matter be removed by animal charcoal, for this also retains the picric acid. For the detection of picric acid in beer, the author recommends the following method:-200 C.C. of the beer are evaporated to a syrupy consistence on the water-bath, and then digested in a flask with 50 C.C.of alcohol (90 per cent.), the mixture being allowed to stand for 24 hours, when it is filtered, and the residue washed with 31 C.C. more alcohol. The mixed filtrates are evaporated to the consistence of a syrup and acidified with two or three drops of dilute sulphuric acid. The mixture is then extracted with five or six times its volume of ether, the latter removed, the solution again acidu- lated and extracted with ether. The ethereal solutions are spontaneously evaporated, and the residue dissolved in 5 or 10 C.C. of water, the solution filtered, neutralised with ammonia, and tested by one of the methods above described. For the estimation of picric acid, the author proposes a colorimetric method, based on the potassium cyanide reac- tion.The ethereal residue is diluted to 10 C.C. with a little ammonia, 5 or 10 drops of a 10 per cent. potassium cyanide solution added, and the liquid, after heating it to 80°, is diluted to 100 C.C. with dilute ammonia. The colour produced is compared with that given by a certain quantity of a standard solution of picric acid, 100 C.C. of which contain 0.1 gram of pure picric acid, the operation being con- ducted in the same way. W. R. D. Detection of Hydrocyanic Acid in Chemico- Judicial Investi- gations. By H. BECKURTS (Chem. News, 48, 199).-After poiiiting out that the presence or absence of hydrocyanic acid or poisonous metallic cyanides in the presence of a harmless cyanide, is not effi- ciently demonstrated by treatment with tartaric acid and distillation, &c.; the author recommends as efficient, Jacqnemin's process, namely, distilling the sample t o be tested with concentrated solution of sodium hydrogen carbonate, and testing the distillate for hydrocjanic acid ;TECHNICAL CHEMISTRY. 223 or Barfoed's process, in which the mass is acidified with sulphuiic or tartaric acid and agitated with ether, which takes up hydmcyanic but not hydroferrocyauic acid. Soap Analysis. By A. R. LEEDS (Chem. News, 48,166-168) .- The soap, cut in thin shavings, is dried at 100" ; the loss is water. It is then exhausted with light petroleum, and the extract containing the free f a t s is dried and weighed. The residue is exhausted with 95 per cent. alcohol, and the extract of it containing any free soda is titrated with sulphuric acid, using ghenolphthaleh m indicator.The neutralised liquid is largely diluted with water, the alcohol boiled off, and a large excess of normal sulphuric acid added. The whole mass is boiled, cooled and filtered, and the precipitate of f a t t y acids and resin is well washed with hot water, then dried, and weighed. The resin is determined by Gladding's method (Anzer. Chem. J., 3, 416), and the amount subtracted from the last total, the diffmence being the amount of fatty acids. The filtrate from the sulphuric acid is neutralised with normal soda, the combined soda calculated, evaporated to dryness, aud the yZyce?.ol extracted with absolute alcohol, dried and weighed ; any residue is added to the fatty acid and resin precipitate. The residue from the first alcoholic exhaustion is washed with cold water; the washings are divided into four equal parts ; and the sodium carbonate, clilorde, sulpliate, arid silicate determined in the separate portions. The residue containing the starch and insoluble inorganic matter is dried and weighed, the starch being subsequently converted into glucose, and titxated with Fehling's solution.D. A. L. D. A. L.ANALYTICAL CHEMISTRY. 213An a 1 y t i c a I C h e m i s t r y.Volumetric Analysis. By E. REICHARDT (Arch. Pharm. [3], 21,106--115).-This paper contains instructions for the performanceof the ordinary operations in volumetric analysis, including the pre-cautions to be observed in the preparation of standard solutions, &c.W. R. D.Determination of the Density of Solids and Liquids bymeans of the Specific Gravity Bottle.By S. PAGLIANI (Gazxettn,13, 172).-The author points out, as a source of error in these deter-minations, the fact that flat-bottomed glass bottles when filled withliquid exhibit very sensible alterations of level, even when only a slightpressure is exerted on the bottom ; and in endeavouring to determinethe capacity at 0" of one of these vessels, he observed that the levelof the liquid contained in it at 0" was higher than a t the ordinarytemperature. He therefore recommends for liquids the use of thebottles described by Regnnult (Ann. Chim. Phys. [3], 9, 438) ; and incases when it is necessary to use the ordinary bottles, as in determin-ing the densities of solid bodies, he suggests a previous examination,with the view of ascertaining whether they exhibit the defect abovementioned.H. W.Apparatus for the Rapid Analysis of Gases. By A. A.BRENEMAN (Chew. News, 48, 156).-The apparatus consists of a eudio-meter fitted with a soft india-rubber stopper bored with two holes,through which pass two tubes closed by valves; one is connected withan exhausted receiver, whilst the other has simply a pointed gIas214 ABSTRACTS OF CHEMICAL PAPERS.tube attached to it. When in use the gas is introduced into theeudiometer over a pneumatic trough, a8nd the volume read off in aconvenient cylinder sufficiently full of water. The eudiometer is re-transferred t o the trough of water, the stopper inserted, and most ofthe water drawn from the interior of the eudiometer by opening thevalve in connection with the exhaust chamber ; the absorbent is intro-duced by applying the point of the pipette to the pointed tube andopening the valve connected with it, when the liquid rushes in toreplace the water which has been withdrawn.The absorption beingcomplete, the liquid is removed by opening the exhaust valve (bywhich means all subsequent absorbents and washings are removed),the eudiometer well rinsed with water, and the volume again read offin the cylinder of water. The mouth of the burette is kept belowthe surface of water as much as possible. A special form of cup,with a long bent-up handle, is used for transferring the eudiometerfrom the trough to the cylinder, and vice vers$,Apparatus for the Rapid Analysis of Gas.By A. H. ELLIOT(Chem. News, 48, 189-191) .-This apparatus consists of two glasstubes of the same length; one graduated from the top to within ashort distance from the bottom, in tenths C.C. to 100 C.C. ; the otherplain. Both are connected at the lower end with two distiuct reservoirsof water by means of flexible tubing ; there is a three-way cock at thebottom of the plain tube, with one delivery through the stem. Thetop of the graduated tube terminates in a capillary tube, bent at aright angle, and fitted with a stopcock. At the top of the plain tubethere is a straight capillary tube fitted with a stopcock, below whicha lateral capillary tube is fused, which is joined to the capillaryof thegraduated tube by a rubber connection.Above the stopcock theoperator can attach either a movable cylindrical funnel which isground to fit over the tube, or the tube for the admission of the gasto be analysed. I n use, the tubes are filled with water by openingthe stopcocks in a suitable manner, and the plain tube is chargedwith gas, lowering or raising the water reservoirs ; the gas is thentransferred to and adjusted in the graduated tube, the volume is readoff, and the absorbent having been run in to the plain tube throughthe funnel, the gas is retransferred to the last-mentioned tube, &c.In washing out the plain tube, use is made of the three-way cock;by bringing it into connection with the inside of the tube, andallowing the washings to run out.Absorbents are used in thefollowing order-potash, bromine, potassium pyrogallate, and cuprouschloride. A special arrangement is employed for explosions : a stoutglass tube is graduated in tenths C.C. and of 100 C.C. capacity to withina few inches from the bottom; the lower end is connected with awater reservoir, and has a lateral tube fused in the side and fitted witha stopcock ; the upper end is closed by a capillary tube and stopcock (towhich either a funnel or a piece of bent capillary tubing can beattached), and has platinum wires fused in through the glass. Touse this, the tube is filled with water, and by means of the bent tubeand india-rubber connections and the water reservoirs and stopcocks, asufficient amount of gas is admitted from the absorption-tube, theD.A. LANALP TICAL CHEMISTRY. 215level adjusted, the volume read, and the oxygen allowed to enter bythe lateral tube a t the bottom, the explosion is proceeded with assoon as t,he gases have been mixed by slight agitation : the analysis isthen finished in the usual manner, absorbents being run in throughthe funnel. After some practice, a complete gas analysis, using bothabsorption and explosion tubes, can be made in less than an hour, andresults are obtained within a few tenths of a per cent. of the truth.D. A. L.Estimation of Bromine in Presence of Large Quantities ofChlorides, By A. CAVAZZI (Gazzetta, l3,174).-The author's methodconsists in the use of oxygenated water (Ba02 and dilute sulphuricacid), which a t 100" liberates all the bromine without decomposingthe chlorides.The bromine-vapour is passed into a solution ofarsenious acid in hydrochloric acid (0.10 g. AS& in 20 C.C. of liquid)which absorbs it rapidly. To determine the quantity of bromine thusabsorbed, a solution of potassium permanganate is prepared contain-ing 3.55 g. KMnO, in a litre of distilled water. Now the author findsthat 18.30 C.C. of such a solution is just sufficient to impart a perma-nent red or yellow tint to 20 C.C. of the arsenical solution ; and henceby a simple calculation, it is found that 1 C.C. of the same perman-ganate solution is equivalent to 0.00888 gram of bromine.If iodides are also present, the iodine must first be separated bymeans of an acetic solution of barium dioxide and carbon bisulphide(as described by the author in another place), after which the solutioncontaining the bromides and chlorides is mixed with pure lime toalkaline reaction, then evaporated to dryness, and the residue iscalcined to convert the acetates of barium and calcium into carbonates.Lastly, the residue is treated with boiling water, and the bromine isdetermined by the method above described.Purification of Hydrogen Sulphide.By W. LENZ (Chem. News,48, 147).-It is very important that all arsenic should be removedfrom the hydrogen sulphide employed in chemico-judicial investiga-tions, and the author suggests the following process with this object.Four consecutive wash-bottles kept a t a temperature of 60-7'0" areused to purify the gas.The first bottle contains a mixture of 1 partstrong hydrochloric acid with 2 of water ; the second, a solution of1 part of this mixture to 4 of water; the third a similar solutioncontaining 1 to 8; in the fourth, pure water. Neither caoutchoucstoppers nor vulcanised india-rubber connections are permissible.This washing system is very efficient.Testing for Free Sulphuric Acid in Wines and Vinegar. ByE. POLLACCI (Gazzetta, 13, 315--316).-The author states that neitherNessler's method nor Lessaigne's gives satisfactor7 results, and pro-poses the following :-Strips of filtering-paper, purified by treatmentwith hydrochloric acid and washing, are immersed in a beaker con-taining the wine, so that they adhere to the sides, one end touchingthe bottom and the other projecting about a centimeter above the top,a sufficient number of strips being used to line the interior of theH.W.D. A. L216 ABSTRACTS OF CHEMICAL PAPERS.vessel. After 24 to 36 hours, bythe spontaneous evaporation of theliquid, a, sufficient quantity of the acid will have accumulated in theupper extremities of the strips of paper; these are now cut off andrepeatedly triturated with ether in a glass mortar. The ether isevaporated, the residue taken up by water and tested for sulphuricacid in the usual way. This method has the advantage that the freeacid alone is separated and detected.Direct Estimation of Carbonic Anhydride in Presence ofSulphides, Sulphites, and Thiosulphates of the Alkali-metals.By M.KONW and E. ZATZEK (Monatsh. Chem., 4, 733-737).--Porthe simultaneous estimation of carbonic anhydride and hydrogen sul-phide, Fresenius has given a method depending on the retention ofhydrogen sulphide by copper sulphate (this Journal, 1871, p. 582) ;but for the direct estimation of carbonic anhydride under conditionswhich involve the simultaneous formation of SO, and SH,, as in theexamination of crude soda, soda-lyes, &c., no accurate method hashitherto been published. This object may however be attained by thefollowing method, depending on the principle that potassium perman-ganate, under conditions already described (p. 151 of this volume),converts the sulphides, sulphites, and thiosulphates of the alkali-metals almost entirely into sulphates, so that when a mixture of thesesalts with carbonates has been thus treated, its subsequent decomposi-tion by an acid gives rise to the evolution of nothing but carbonicanhydride.The method is applied as follows :-The substance is introducedinto a 300 C.C.flask closed by a perforated caoutchouc stopper, throughone of the holes of which is inserted a stoppered funnel-tube reachingnearly to the bottom of the flask, and through the other a tube con-necting the flask (1) with a Liebig’s bulb-apparatus containing anacidulated solution of permnnganate ; (2) with a CaCl,-tube ; ( 3 ) witha bulb-apparatus containing caustic potash ; (4) with a CaCl,-tube.The apparatus having been made air-tight, a concentrated solution ofpermanganate is poured in slight excess into the flask, and the carbo-nate is then decomposed with dilute nitric, sulphuric, or acetic acid(not by hydrochloric acid) ; the stopcock of the funnel-tube is thenclosed, and the decomposition of the carbonate is completed by heatingthe liquid gently at first, and ultimately to the boiling point.Theheating is then discontinued ; the cock of the funnel-tube is opened ;this tube is connected either with a U-tube filled with lumps of solidpotash, or with a wash-bot’tle containing potash-lye ; and a slow streamof airis drawn through the apparatus for half to three-quarters of anhour, after which the apparatus may be disconnected. The insertionof the bulb-tube cont,aining the permanganate solution is for thepurpose of retaining any portion of SOz or SH, that, may haveescaped oxidation in the flask.The accuracy of the method may be judged of by the followingexamples, in the first and second of which pure sodium carbonate,Na2C03, was mixed with sulphite ; in the second with thiosulphate ;in the third with s~lphide,~sulphite, and thiosulphate together ; inthe fourth with potassium sulphide, sodium sulphite, and sodiumC.E. GANALYTICAL CHERlISTRY. 217thiosulphate ; and in the fifth a mixture of Iceland spar, barium sul-phite, and barium thiosulphate was decomposed by dilute nitric acid.c 0,CO, found. calculated.1.. ........ 41.54 per cent.]................44.00 ,,3.. 41-35 ,,4.. 41-33 ,,5.. ........ 43.75 ,,In one case in which the absorption-apparatus containing perman-ganate was not introduced, a mixture of sodium carbonate and sulphitegave 4‘7.01 per cent. COz, whereas the amount according to calcnlationshould have been only 41.51.This method also gives the means of determining the amount ofsulphur contained in the sulphur-compounds mixed with the carbonate.For this purpose, after the carbonic anhydride has been determined asabove, the contents of the reaction flask and of the absorption-tubecontaining permanganate are poured into a beaker, the excess of per-manganate and the precipitate of manganite formed in the reactionare decomposed by heating with hydrochloric acid, and after thechlorine has been expelled by boiling, the sulphuric acid is precipitatedby barium chloride, &c.H. W.Estimation of Phosphoric Acid in Manures. By GASSEND andCAMPREDON (Ann. Agronomipues, 9, 266-270) .-After having obtainedthe precipitate of ammonio-magnesian phosphate, there are two waysof dealing with it in common use : it is either calcined and weighed asmagnesium pyrophosphate, or it is dissolved in acetic acid and titratedwith standard uranium acetate. The authors state that, when appliedto commercial fertilisers, the first method invariably gives resultswhich are too high, unless solution of the precipitate in hydrochloricacid and reprecipitation are resorted to, necessitating a further delayof over twelve hours. Titration with uranium acetate they believe tobe quite accurate and more expeditious than the gravimetric method,even when only one precipitation is employed.A sample of mixed bonesuperphosphate and precipitated phosphate gave the following per-centages of P206 :-Uranium Gravimetricmethod. method.P,Os solnble in water.. .......... 14.08 15.357 , ?, ammonium citrate 14.99 16.18,, total ...................... 16.11 17.14The excess by the gravimetric method was proved to be due toimpurities retained by the magnesium precipitate, consisting of irooand alumina (traces), lime, sulphuric acid, and silica. The meanquantity of silica in the three precipitates wag 0.008 gram, and theauthors find t8hat the ammonio-magnesium phosphate retains silica,even after a day’s washing with dilute ammonia. J. M. H. M,VOL. XLPI. 218 ABSTRACTS OF CHEMICAL PAPERS.Testing of Potassium Bromate.By G. VULPIUS (Arch. Phmrm.[3], 21, 186-190, and UingZ. polyt. J., 249, 47).-For the determi-nation of phenol, according to the equation-CJ&O + 5KBr + K&03 + 3H2s04 = C6H3Bra0 + 3K2s04 +3H20 + 3HBr,the new German Pharmacopeia stipulates the use of normal solutionsof potassium bromide and bromate. The latter, according to Vulpius,often contains a large proportion of potassium bromide, which may beestimated in the following manner :-O*J gram of the bromate is mixedin a tared beaker with 2 grams of potassium iodide, and the mixturedissolved in *5 C.C. of hot water; 10 C.C. of cold water, and 15 gramsof a 25 per cent. solution of hydrochloric acid are then added, andthe solution is titrated with decinormal sodium thiosulphate.1 C.C.c f this solution corresponds with 2.785 mgrms. of potassium bromate,taking the equivalent for potassium bromate a t 167.1. D. B.Action of Ammonium Sulphide on Metallic Pyrophosphates.By G. BUCHNER (Arch. Pharm. [3J 21, 115--120).-The author hasinvestigated the action of ammonium sulphide on the solution ob-tained by adding excess of sodium pyrophosphate to solutions of thesalts of those metals which, in the ordinary course of analysis, areprecipitated by ammonium sulphide. 'If sodium pyrophosphate ( 5 percent. solution) is added to solutions of the salts of these metals, a pre-cipitate is obtained which is soluble in excess of the reagent. Theaddition of ammonium sulphide to this solution precipitates themetals as sulphides in the case of zinc, cobalt, nickel, and iron (ferrousand ferric), but produces no precipitate with manganese (manganonsand manganic), uranium, chromium, or aluminium.When these last-mentioned solutions are heated, or allowed to stand for some time, themanganese is precipitated as pyrophosphate of manganese, ammonium,and sodium (MnNH,NaP,O,). The solutions containing aluminiumand chromium become turbid, if boiled and subsequently cooled ; butin the case of uranium the solution remains clear even after boiling.I f a solution of an iron salt is precipitated by ammonium sulphide, and asolution of sodium pyrophosphate subsequently added, the ferrous sul-phicle dissolves when the liquid is boiled, forming a colourless solution,which becomes dark green on cooling, and finally deposits nearly allthe iron as sulphide. When a solution of manganese salt is treated ina similar way, the liquid deposits crystals of manganese sodiumammonium pyrophosphate.W. R. D.Specific Gravity of Commercial Copper. By D. WATSON(Dingl. polyt. J., 249, 48).--The author found that copper, when pre-cipitated electrolytically from a solution of the sulphate, has a sp. gr.of 8-95,',. The sp. gr. of copper is materially affected by differentimpurities contained in the metal, cuprous oxide having the greatesteffect: the following table illustrates this circumstance :ANALYTICAL CHEMISTRY. 219With + p.c. With $ p.c. With ' P.'' I 'p' gr' 1 Pb. 1 As. 1 p p.c. As.Pb andCopper free from Cu,O... . . . . . . . 8 *955 8.961 8.939 8 *945Copper containing 1 p.c. Cu,O . . . 8 *925 8 -909 8 *915Copper containing 2.5 p.c. Cu,O, , 1 8 *88L 1 :'::; 1 8.865 1 8.871The author is of opinion that the sp. gr., in conjunctiorr with theestimation of lead and arsenic, suffices to approximately determine theamount of cuprous oxide in a sample of commercial copper.D. B.Estimation of Carbon in Cast Iron. By A. A. BRENEMAN(Chem. News, 48, 168).-In the process recommended, the carbonace-ous residue obtained when cast iron is dissolved, is filtered in a smallplatinum tube, which is subsequently put, with its contents, into thecombustion tube and burnt in oxygen. The platinum tube is madeof stout foil, and is fitted with a small disc of perforated platinum tosupport the asbestos for filtering ; the air-tight connection, with thenecessary glass tube, is made by means of soft india-rubber tubing,one end of which is inserted in the platinum.The ends of the glasstube are conical, so that the connection may be made without injuryto the platinum. Combnutions should be conducted in porcelaintubes, as these last longer and can be heated more strongly than glasstubes, and the platinum tube should be made to fit well, so that theoxygen may pass mainly through the filter and its contents.D. A. L.Apparatus for Estimating Carbon in Steel. By A. B.CLEMENCE (Chem. News, 48, 206).-The author has introduced anapparatus to avoid the errors attached to the old process of filteringin a glass funnel, &c., and to do away with the expense and incon-venience of the platinum funnel, porcelain tube, combustion fuimacemethod (preceding Abstr.j. The apparatus consists of a platinum tubellQinches long, with a diameter of $-inch for 7 inches, the remaining44 inches being & inch diameter. In use, an asbestos plug is placed atthe point in the tube where the contraction commences, the carbon isfiltered on this, washed well with hot water, any adhering carbonbeing swept down by moist asbestos, the tube is then dried at150-170" for an hour. A hard rubber stopper with glass tube passingthrough is now put into the wide end, through which the current ofoxygen enters, a single thickness of filter-paper, 2 inches wide, beingwound round the tube by the stopper, and kept wet by a stream ofwater; the tube, at the part where the filter is placed, is heatedwith a Bunsen burner for an hour, at the end of which time the potashbulbs can be weighed. The author takes from 3 to 5 grams ofborings, which he dissolves in cuprammonium chloride, 36 grams to120 C.C.water for 3 grams of steel ; when the deposited copper is com-pletely dissolved, he proceeds as above described. Good results havebeen obtained. D. A. L.q 220 ABSTRACTS OF CHEMICAL PAPERS.Volumetric Estimation of Manganese. By J. B. MACKINTOSH(Chem. News, 48, 176--177).-1t has been suggested that theprecipitate obtained by treating the boiling nitric acid solution of amanganese salt with potassium chlorate is not pure Mn02, but amixture of 10Mn02 + MnO.This being of importancein the titrationof manganese, the author has studied the subject, and publishes hisobservations in the present paper.The experiments are based on the facts that potassium permau-ganate has an oxidising power equal to five of oxygen for every two ofmanganese, and that the same quantity of manganese, in the state ofdioxide, has an oxidising power equal to 2 atoms of oxygen ; so that,if a solution of permanganate is reduced to dioxide, the oxidisingpower of the dioxide thus formed will be equal to that of two-fifths thequantity of the permanganate solution originally taken. The analyseswere conducted in the following manner :-The permanganate wasdecomposed with hydrochloric acid and concentrated.The hydro-chloric acid was removed by boiling with excess of nitric acid, andthe manganese precipitated by successive alternate additions of potas-sium chlorate and nitric acid, until no more yellow fumes wereobserved. When cool the precipitate was filtered through asbestos,washed with nitric acid and with water, and then treated with avolume of oxalic acid, with a known permanganate equivalent, and alittle sulphuric acid. The excess of oxalic acid was determined bypermnnganate, and t,he oxidising power of the precipitate found bysubtracting the excess from the whole quantity. The results obtainedare as follows :-Perman-ganateused.Oxidising power ofprecipitate interms of permanga-nate.45 C.C. 17-80 C.C.35 13.9325 9.9015 3.96Per cent.ofTheoretical theoretical cor- Averagefor rected for burette trueMnOz. error. per cent.18 C.C. 99.37 -14 100.07 99.9910 99.86 -6 100.6 7 -Great importance is attached to the method of precipitating themanganese ; for by adding the potassium chlorate a t once, and boilinguntil the action ceases, an error of from 1 to 2 per cent. is almostcertain. The author points out that not too much value must beset on the above results, as of course there are many experimentalerrors involved in the process. It is, however, safe to conclude thatthe precipitate obtained in this process, when the necessary precau-tions are taken, is not 10MnOz + MnO (which would have an oxidis-ing power = 90.91 per cent.) but MnOz.Arsenic in Glass.By W. FRESENIUS (Chem. News, 48, 147).-Jn connection with the removal of arsenic from apparatus, &c., usedin cases of judicia,l investigation, the author has observed that theglass of the vessels employed contained arsenic. A sample ofBohemian glass contained 0.20 per cent., of hard glass 0.08, andanothei- sample of hard glass a trace. The author attributes theD. A. LANALYTICAL CHEMlSTRY. 221browning of glass when heated to arsenic and not to lead. Furtherexperiments show that alkaline solutions take up arsenic from glass ;acids do not. D. A. L.Microscopic Examination of Water for Organic Impurities.By J . BRAUTLECHT (Chew. News, 48, 180).-100 C.C. of the water aretreated with five drops of a solution containing 1 part of aluminiumsulphate, 1 part hydrochloric acid, and 8 parts of water, and one tothree drops of ammonia ; the precipitate is filtered off and redissolvedin 10 to 15 drops of dilute acetic acid ; and the clear solution thusobtained is examined under the microscope both before and after theaddition of saffranine.By the addition of + per cent. gelatin, per-manent preparations on Koch’s principle may be obtained.Detection and Estimation of Trinitrophenol (Picric Acid).By G. CHRISTEL (Arch. Pharm. [3], 21, lYO--200).-This papercontains an examination of the principal reactions of trinitrophenolmade with a view to its qualitative detection and quantitativeestimation. The aqueous solution of picric acid is not precipitatedby neutral solutions of lead or copper salts; neither is ammo-nium picrate, unless the solution is alkaline, when lead acetategives a reddish-yellow precipitate, and copper sulphate a yellowish-green precipitate in dilute solutions, and a bright green in con-centrated solutions.A solution containing half a milligram of picricacid in 5 C.C. of water is not at once precipitated by a solution ofcupramnionium snlphate, but on standing for 24 hours a distinctprecipitate is obtained, which is insoluble in ammonia, but is decom-posed by water. Solution of basic lead acetate is a very delicatetest for picric acid, yielding a bright yellow precipitate. A solutioncontaining the tenth of a milligram of picric acid in 5 C.C. ofwater, gives after 12 hours a distinct precipitate, and a solution con-taining the twentieth of a milligram in 5 C.C.of water a strongopalescence, which snbsequently forms a distinct sediment. Whenthis sediment is decomposed by the addition of 1 drop of sulphuricacid, and the solution is rendered alkaline with ammonium hydrate andevaporated to dryness, a residue is left which, when dissolved in alittle water and warmed with a drop of potassium cyanide solution,gives a distinct red colour. The yellow colouring matters of the barkof Quercus tinctoria (quercitron), and the root of Broussonefia tinctoriaalso give precipitates with basic and neutral lead acetate, but the pre-cipitates do not give the reaction witch potassium cyanide whentreated as above described. An aqueous solution of methyl green pre-cipitates solutions of picric acid.The green precipitate dissolves inammonia, forming a deep yellow solution, which is precipitated bybasic lead acetate, and tbis precipitate gives the reaction with potas-sium cyanide. This test cannot be applied for the detection of picricacid in beer, for 1 litre of beer which contained 5 mgrms. of picricacid was not precipitated by a solution of methyl green. Solutions ofpicric acid are precipitated by stannous chloride, and if a smallquantity of ammonia is added, the solution becomes red. The samereaction is obtained when a solution, prepared by adding potassiumD. A. L222 ABSTRACTS OF CHEMICAL PAPERS.hydroxide to a solution of stannous chloride until the precipitate atfirst formed is redissolved, is added to a, solution of picric acid.Thered colour is due to the formation of dinitroamidophenol (picramicacid) : hydrogen and ammonium sulphides give a similar reaction.If a solution of picric acid or a picrate is acted on with zinc and dilutesdphuric acid, a yellowish-red turbid solution is obtained, which,when poured off and mixed with alcohol, develops a green colour,changing through blue to a violet-green. For the detection of picricacid in sweetmeats or other coloured substances containing sugar,the potassium cyanide reaction can be applied directly ; or the colour-ing matter may be extracted with alcohol, the residue from this solu-tion, aft,er dissolving in water, precipitated by lead acetate ; and thepotassium cyanide reaction obtained after decomposing the precipitatein the manner above described.For the detection of picric acid inwool or cellulose, the hydrochloric acid solution may be reduced byzinc, and the reaction with alcohol obtained. The substance may alsobe digested with ammonia, and the potassium cyanide reaction triedwith this solution. The detection of picric acid in beer cannot beaccomplished by means of lead acetate, on account of the other snb-stances in the liquid, which are precipitated by this reagent ; neithercan the colouring matter be removed by animal charcoal, for this alsoretains the picric acid. For the detection of picric acid in beer, theauthor recommends the following method:-200 C.C. of the beer areevaporated to a syrupy consistence on the water-bath, and thendigested in a flask with 50 C.C.of alcohol (90 per cent.), the mixturebeing allowed to stand for 24 hours, when it is filtered, and the residuewashed with 31 C.C. more alcohol. The mixed filtrates are evaporatedto the consistence of a syrup and acidified with two or three drops ofdilute sulphuric acid. The mixture is then extracted with five or sixtimes its volume of ether, the latter removed, the solution again acidu-lated and extracted with ether. The ethereal solutions are spontaneouslyevaporated, and the residue dissolved in 5 or 10 C.C. of water, thesolution filtered, neutralised with ammonia, and tested by one of themethods above described. For the estimation of picric acid, the authorproposes a colorimetric method, based on the potassium cyanide reac-tion. The ethereal residue is diluted to 10 C.C. with a little ammonia,5 or 10 drops of a 10 per cent. potassium cyanide solution added, andthe liquid, after heating it to 80°, is diluted to 100 C.C. with diluteammonia. The colour produced is compared with that given by acertain quantity of a standard solution of picric acid, 100 C.C. ofwhich contain 0.1 gram of pure picric acid, the operation being con-ducted in the same way. W. R. D.Detection of Hydrocyanic Acid in Chemico- Judicial Investi-gations. By H. BECKURTS (Chem. News, 48, 199).-After poiiitingout that the presence or absence of hydrocyanic acid or poisonousmetallic cyanides in the presence of a harmless cyanide, is not effi-ciently demonstrated by treatment with tartaric acid and distillation,&c. ; the author recommends as efficient, Jacqnemin's process, namely,distilling the sample t o be tested with concentrated solution of sodiumhydrogen carbonate, and testing the distillate for hydrocjanic acid TECHNICAL CHEMISTRY. 223or Barfoed's process, in which the mass is acidified with sulphuiic ortartaric acid and agitated with ether, which takes up hydmcyanic butnot hydroferrocyauic acid.Soap Analysis. By A. R. LEEDS (Chem. News, 48,166-168) .-The soap, cut in thin shavings, is dried at 100" ; the loss is water. Itis then exhausted with light petroleum, and the extract containingthe free f a t s is dried and weighed. The residue is exhausted with95 per cent. alcohol, and the extract of it containing any free soda istitrated with sulphuric acid, using ghenolphthaleh m indicator. Theneutralised liquid is largely diluted with water, the alcohol boiled off,and a large excess of normal sulphuric acid added. The whole mass isboiled, cooled and filtered, and the precipitate of f a t t y acids and resinis well washed with hot water, then dried, and weighed. The resin isdetermined by Gladding's method (Anzer. Chem. J., 3, 416), and theamount subtracted from the last total, the diffmence being the amountof fatty acids.The filtrate from the sulphuric acid is neutralised with normalsoda, the combined soda calculated, evaporated to dryness, aud theyZyce?.ol extracted with absolute alcohol, dried and weighed ; anyresidue is added to the fatty acid and resin precipitate. The residuefrom the first alcoholic exhaustion is washed with cold water; thewashings are divided into four equal parts ; and the sodium carbonate,clilorde, sulpliate, arid silicate determined in the separate portions.The residue containing the starch and insoluble inorganic matter isdried and weighed, the starch being subsequently converted intoglucose, and titxated with Fehling's solution.D. A. L.D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8844600213

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

TECHNICAL CHEMISTRY. 223T e c h n i c a1 C h em i s t ry,Employment of Limed Coal in Gas Making. By J. A.WANKLYN (Chem. News, 48, 174--176).-The coal is mixed with24 per cent. of lime previous to being put in the retort. The lime isslaked before mixing. The author claims many advantages for thisintroduction, viz., increase in the yield of ammonia to the extent of20-36 per cent. ; of liquor to the extent of about 35 per cent. ; of tar6 per cent. ; and of gas, which is also improved in quality, being fra-grant instead of unpleasant to the smell, and not deteriorated inilluminating power. These advantages are supplemented by a con-siderable decrease in the quantity of hydrogen sulphide and carbonbisulphide, and in fact the author anticipates the abolition of lime-purifiers if this liming (Cooper’s) process is introduced.The coke,too, is much improved bay this addition of lime ; it is more readily com-bustible, and does not give off sulphurous anhytlride when burnt. Inthe author’s opinion ga,s works will cease to be the nuisance they noware when the process is introduced. D. A. L224 ABSTRACTS OF CHEMICAL PAPERS.Methods for Coking Coal. By W. SMITH (Chem. News, 48,185-187).-In the present paper the author reviews the various methodsnow employed for the production of coke from coal. The simplest,the Meiler or mound method, is that in which the coal is burnt inmounds, similar to those employed for the production of wood char-coal ; the coke produced is good, and freer from sulphur than oven-coke, but it is not so hard.The beehive oven produces a cokealmost unsurpassable for metallurgical purposes, but wastes all bye-products. The AppoEt oven and t,he Coppe'e oven are constructed so asto use the gases and vapours produced during the cokiug for heatingthe ovens. The coke is excellent. The Janzeson oven is a modificationof the beehive oven, and is constructed with a floor of perforatedquarles instead of the solid floor of the latter ; these perforations areconnected with a short vertical flue below the floor, and from this apipe passes a t right angles to the hydraulic main, and to exhaustappliances, the exhaustion being carried on as is usual in gas works.The gas produced is not employed in the operation, and can thereforebe conveyed to a distance and used for heating purposes.The cokeis good. The amrnoniacal liquor contains a large quantity of ammo-nium sulphate, and according t o Jameson, the yield of liquor is equalto a production of 5-15 lbs. ammonium sulphate for a ton of coke.The yield of tar or " oils " is from 6-15 gallons per ton of coke ; itcontains neither benzene, nor naphthalene, nor anthracene, only asmall quantity of toluene, but large quantities of xylene mixed withparaffins. The chief bulk of the Jameson tar consists of oils (sp. gr.0.960, and boiling a t 250-350"), which are of little value for burning,and of only secondary value as lubricants. They have no fluorescence.A considerable proportion of the oils distils above 350", and depositsparaffins, melting at 58". The oils boiling between 200" and 300"contain a fairly large proportion of phenols, some of which resemblethe constituents of wood-tar creasote.They contain a mere trace ofphenol, but more cresols, and the largest quantity boils from 250-300". The 300" fraction is resinous, and perfectly soluble in causticsoda, with a red colour. Some other of these phenols yield reds andblues with alkalis, but of no stability or value. In Sinton-Carrdso w n the coking process is one of destructive distillation, and is simi-lar to that of a gas works. The temperature employed is very great,2200" or even 3000" being reached. The gas is burnt in the ovens.The ammoniacal liquors are of good strength, 6--7"T. The tar,black and thick (sp.gr. 1*20), is exceedingly rich in naphthaleneand anthracene, contains as much benzene, toluene, xylene, andphenol as any London tar, aiid is moreover free from paraffins. Thecoke is very good; it has not the silvery glance of the beehive andJameson oven coke, but is quite as solid, hard, and compact. Theseproperties are obtained by using large charges of coal ( 4 4 tons), piledup in masses of great height (6 feet or so), and considerable thickness(19 inches), but not too thick for the heat of the oven to penetratesufficiently well. Mellor has introduced a process f o r separating thebenzene from gas, which consists in washing the latter with strongnitric acid in earthenware towers filled with broken glass, and as ben-zene is soluble in nitrobenzene, the same acid strengthened with sulTECHNICAL CHEMISTRY.225phuric acid is repeatedly passed down the tower. The benzene canbe removed from this solution by steam-distilling. Another processwith the same object in view is due to G. E. Davis : refrigerated coal-gas is washed with refrigerated heavy coal-tar oils, which remove thebenzene. The author is of opinion that the Simon-Car% method,especially if combined with one of these benzene removing processes,is the coking process of the future. D. A. L.Atmospheric Dust. By A. SCHUSTER (Bied. Centr., 1883, 354).-Sand taken from the neighbourhood of the Great Pyramid, and Nilemud contain a considerabIe quantity of magnetic particles, somemeasuring 0.1-0.2 mm. These particles may b.e derived fromexploded meteorites, which by reason of' insufficiency of oxygen inthe upper atmosphere have not yet been oxidised.Existence of Germs in the Air at Great Heights.By P.GIACOSA (Gazzetta, 13, 176)-The author's experiments were made onthe summit of Monte Marzo (2756 m. abovesea-level), and at the footof the same mountain (2300 m.), with the following results :-Schizo-mycetes exist in quantities diminishing as t,he altitnde increases.Throughout the experiment (first three days of August) the air on thetop of the mountain contaiued germs of leaven, and the air at thefoot of the mountain was sometimes found t o contain cells of tlhesame fungus. Germs of the common moulds are likewise abundanta t both altitudes. I n no instance were any forms observed whichcould be referred to animal organisms.E.W. P.H. W.Properties of Antiseptics and of the Volatile Products ofDecay. By G. LE BON (Bied. Ceutr., 1883, 350--352).-The actionof antiseptics is weaker the further the decomposition has pro-ceeded. The best antiseptics are as follows, commencing with thestrongest :-Potassium permanganate, chloride of lime, ferrous sul-phate acidified with acetic acid, phenol, and sodium and potassiumglycoborates. The action of these compounds as antiseptics isdifferent from their action as microbes ; they cannot alerest decay, butmay prevent its commencement. As a rule antiseptics have but littleaction on bacteria; in phenol these organisms live for a long time.A t present it is uncertain whether the volatile alkalo'ids from decom-posing animal matter are poisonous, but in a few cases death hasoccurred after inhaling the volatile products given off by decomposingmatter.I t is dangerous to exhume a corpse, and the air of church-yards is poisonons.The Future of the Chlorine Industry. By F. HURTER (Dilzql.yolgt. J., 249, 126--133j.-The only hope that the Leblanc processwill not be completely wrecked by the ammonia-soda process is thatthe world requires chloriue as well as soda. Weldon, Solvap, andMond are doing their best to combine the manufacture of chlorinewith the ammonia-soda process. The author attempts to show inwhat way the ammonia-soda process niay endanger the manufactureof chlorine, and how the same may be prevented.E.W. P226 ABSTRACTS OF CHEMICAL PAPERS.1. Replacing Chlorine by other Bleaching Agents.-Perceiving thedifficulty of utilising the chlorine from the calcium chloride liquorsobtained in the ammonia-soda process, Mond has recently pat'ented avery ingenious method f o r obtaining calcium peroxide, and for itsapplication as a bleaching and disinfecting agent, but as calciumperoxide is insoluble, it will probably be necessary to convert it intohydrogen peroxide by treatment, with a dilute acid, before it can beused for blenching, &c. The process consists in introducing into acupola dried blocks of a mixture of h r i u m carbonate, pitch, andsawdust, and heating to about 1200". The barium carbonate is con-verted into barium oxide, and the carbonaceous products are burntout.The mass as it descends meets a current of air, which cools theoxide to about 500", when i t absorbs oxygen and is changed intobarium peroxide. This when cold is decomposed by means of car-bonic anhydride and water, under pressure, into barium carbonate andhydrogen peroxide. The former is used afresh, whilst caiciumperoxide is prepared from the hydrogen peroxide by adding milk oflime to it. Calcium peroxide is a hydrate of the formula Ca02,8H20,containing 7.4 per cent. of available oxygen, equivalent to 32% peroent. of available chlorine. According to Lunge, the manufacture ofbarium hydroxide is carried out on a large scale in France, and con-sequently the production of the peroxide should present no diffi-The peroxides are all very powerlul oxidisers.According toThomsen, the amount of heat produced by oxidation with hydrogenperoxide is 23,064 units larger per molecule than by the directoxidation with free oxygen. In spite of its energetic oxidisingaction, hydrogen peroxide is SO slow a bleaching agent that it appearsas though it is not available oxygen but chlorine that is required forthe bleaching of vegetable fibres. Gerhardt attributes the bleachingaction of chlorine to the facility with which it is substituted incrgariic substances in the place of hydrogen. The author has foundthat by igniting bleached cotton with soda the presence of chloridescan be detected in the melt, whilst unbleached cotton when similarlytreated does not exhibit this reaction.Hydrogen peroxide is theonly compound which could be prepared cheaply enough to com-Pete with bleaching powder, but on account of its slow action com-petition will be impossible. Other bleaching agents have from timet o time been recommended, all of which are in reality oxidisingagents. If, therefore, available chlorine and not oxygen effects thebleaching of vegetable tissues, it is highly improbable that thesesubstances will ever supersede chloride of lime.2. Production of Hydrochloric Acid.-It has not yet been possible t oprepare chlorine directly from sodium chloride. I n the Leblanc processthe sodium in common salt is replaced by hydrogen derived from sul-phuric acid, which costs nearly 2000 marks per ton, whilst in theammonia-soda process it is calcium, which costs only about 15 marksper ton.Besides calcium and hydrogen, there are no elements suit-able for the purpose which could be obtained at a smaller cost.Solvay and Weldon have been endeavouring to utilise the calciumchloride liquors for the preparation of chlorine. Their process con-cultyTECHNICAL CHEMISTRY., 227sists in replacing the calcium in calcium chloride by hydrogen. Thecalcium chloride is mixed with clay, formed into lumps, and subjectedto the action of superheated steam at a high temperature. A verydilute hydrochloric acid is produced, from which the excess of steamis removed by the addition of coucentrated calcium chloride liquorsbefore the hydrochloric acid is condensed. The process is not onlyvery costly, but requires :I very large plant.It is therefore notlikely to endanger the Leblanc process, which promises to remain thechief source of chlorine.Vorster and Gruneberg recommended some years ago to heatsodium chloride and clay, and obtain sodium silicate and hydrochloricacid. Their process, however, was abandoned, as the reaction wasfound to require an extremely high temperature, and the cost forrepairs was too excessive.Other ChZorine Processes.-By decomposing sodium chloride withsulphuric acid, the resulting gaseous or liquid hydrochloric acid canbe used for the preparation of chlorine, according ae the Deacon orWeldon process is employed. With Hargreaves’ process liquidhydrochloric acid only can be used, as the gas contains too muchnitrogen and too little oxygen.The conversion of hydrochloric acidinto chlorine necessitates the presence of another element with whichto combine the hydrogen, the only element which has a, greateraffinity for hydrogen than chlorine being oxygen. The affinitiesbetween hydrogen and chlorine and hydrogen and oxygen approacheach other so closely that the mere change from the liquid state tothat of a gas alters the proportions. In consequence of thesevariations a direct decomposition of liquid hydrochloric acid byoxygen is impossible, whilst in the gaseous form hydrochloric acidcan be decomposed directly by oxygen, To prepare chlorine fromliquid hydrochloric acid a certain amount of chemical energy mustbe supplied in addition to oxygen, &e., nascent oxygen, which isliberated from an oxide wibh evolution of heat, is required. Sincethe oxide must contain more oxygen than is equivalerit to the chlo-rine, which afterwards forms chloride, a peroxide is required.Thereis no better material than manganese for the purpose. Althoughbarium and lead form two oxides and only one chloride, the transfor-mation of the chloride into peroxide in the case of barium willalways be difficult on account of the large differences in the heatof formation G f the two compounds, whilst in the case of lead, itsprice and high equivalent weight render it useless. Weldon’s pro-cess can be superseded only by a peroxide which is cheaper thanthe expense of recovering the manganese dioxide, or which itself canbe regenerated at a less cost.The disadvantage in connection withthe Weldon process is that it only yields theoretically one-third of thehydrochloric acid as chlorine. This difficulty is said t o be removedby Weldon’s new process (No. 2). Magnesium manganite obtainedby process No. 1 is decomposed with hydrochloric acid in the chlorinestills. One-fourth the chlorine contained in the hydrochloric acid isgenerated, and a solution of manganese and magnesium chloridesformed. The latter is evaporated to a syrupy consistency, mixedwith a certain amount of solid manganite, eormed into balls, intro228 ABSTRACTS OF CHEMICAL PAPERS.duced into an apparatus similar t.0 the Hargreaves, and exposed toa current of heated air, when 90 per cent.of the chlorine con-tained in the mixture is liberated, magnesium manganite beingformed.The author is of opinion t,hat where still-work has to be done, thechloride of lime cannot be obtained at a lower cost, as the onlysaving in Weldon’s new process is the lime required for oxidation,abont, 500 kilos. of bleaching powder; the labour in this process,however, forms a much greater item, so that bleaching powder madeby the new process will cost fully as much, if not more than thatobtained by the old process.By comparing the Deacon process with Weldon’s No. 2, we findthat it is the only process in use in which gaseous hydrochloric acidcan be decomposed into chlorine by a simple reaction, 2HC1 + 0 =H,O + C12, accompanied by evolution of heat, The decompositionis accelerated by catalytes. On account of its capability of beingdissociated at a high temperature, cupric chloride is the cheapestand most efficient catalyte; moreover, copper is the only metalwhich forms two oxides and two chlorides, in all of which the com-bination is of a very loose character.It appears, therefore, highlyprobable that the Deacon process will continue to be the only oneavailable for the conversion of gaseous hydrochloric acid intochlorine.The author concludes this paper with the following remarks:-No other chloride is better adapted for the manufacture of chlorinethan hydrogen chloride. If the latter is to be decomposed in the liquidstate, the decomposition can be effected only by means of manganesedioxide, as there is no other peroxide so readily regenerated from thechloride.If hydrogen chloride is to be decomposed in tlie gaseousstate catalytes are required, and should it be possible to obtain acheaper catalyte than copper the apparatus now in existence wouldbe equally applicable. Neither the Weldon process nor the Deaconprocess is perfect ; both are capable of improvement, especially theWeldon process, inasmuch as the quantity of chlorine which it yieldsis considerably less than that which should be obtained from thehydrochloric acid consumed. D. B.Schaffner and Helbig’s Process for the Recovery of Sulphur.By A. M. CHANCE (Dingl. yoZyt. J., 249, 33-35).-Chance (Jour.SOC. Chein. Ind., 2, 202) gives an interesting account of his results andexperiences in working with the Schaffner and Helbig sulphur recoveryprocess.The residue is worked up in the decomposers in the follow-ing manner :-The solution of magnesium chloride-whose tempera-ture must not exceed 60°, otherwise sulphuretted hydrogen will beevolved-is introduced into the decomposer, and the residue isthrown in, after which the mixture is heated by means of wetsteam, in order to expel the air above the charge, and prevent itsadmission into the decomposer ; thus the formation of an explosivemixture is rendered impossible. The heating by means of dry steamis then proceeded with, the mixture being well agitated ali the time.The best results are obtained with jacketted decomposers, althougTECHNICAL CHEMISTRY. 229cast-iron steam coils are attacked less readily than wrought-ironjackets. For carbonating the liquors containing magnesium hy-droxide and calcium chloride, vertical vessels without agitators arethe most useful.The deeper the column of liquid and the greaterthe percentage of carbonic anhydride, the quicker and better arethe results obtained. The average strength of the carbonic acidgases was 26 per cent, To work off 8 tons of residue from five tosix hours are required. The lime mud is sifted, filter-pressed, andwashed. The first washings are concentrated in steam boilers,together with the stronger liquors, whilst the last washings arethrown away. No mention is made of the action 0% the magnesiumchloride liquors on the plates of the steam boilers.The sulphurettedhydrogen gas is collected in gas-holders, the inlet and outlet beingconnected with a water-seal to prevent explosions. The burning ofthe sulphuretted hydrogen gas for the manufacture of sulphuric acidhas been a great success, but a satisfactory process of recoveringsulphur direct from the gas has not yet been introduced. The loss ofmagnesium chloride corresponds with 4 to 4.5 tons per 100 tons ofsulphate, or 20 tons per 100 tons sulphur, more than one-half the lossbeing attributable to mechanical defects, which should be graduallyreduced.In discussing the value of the lime mud and its adaptability forthe manufacture of soda, Chance shows that, as the mud leaves thepresses it contains about 50 per cent. of moisture, which must be re-moved, an operation which in itself is a great disadvantage ; moreover,the resulting crude soda contains large quantities of chlorides as wellas calcium carbonate.Referring to the probable cost of working theprocess, a detailed estimate is given, from which it is concluded thatit would no longer pay should the price of pyrites be reduced by one-half, especially if it were found that the resulting lime mud was ofno value for black ash making. The future of this process dependson a good method of extracting pure sulphur from the generatedsnlphuretted hydrogen.Weldon mentioils that England and America alone consume150,000 tons of Silician sulphur per annnm, or 50 per cent. morethan the total quantity capable of being yielded by the whole Englishsoda industry.Schaffner’s sulphur, which is absolutely pure, shouldeasily displace Sicilian sulphur. As to the market price of sulphur,Muspratt and Mactear show that, although recovered sulphur has beenoffered a t considerably less than Sicilian sulphur, great difficulty hasbeen experienced in selling ii.Hurter gives analyses of soda waste and soda liquors obtained fromcrude soda made exclusively from recovered lime mud by Chance.The waste obtained from four samples of black ash contained in thedry state-Soluble Calciumsoda. Total soda. sulphide.I.. .......... 0.550 1 - 7 7 30.0011.. .......... 0.440 0.97 33.40111.. .......... 0.360 1.52 29.1IV ............ 0-175 0.73 23.230 ABSTRACTS OH CHEMICAL PAPERS.Ordinarily the waste contains 40 per cent.calcium sulphide. 1 litreNa,O. NaHO. Naps. Na2S04. NaCl. Na,Fe(CN),.165.2 44.27 5.08 6-77 42.57 0.01 gram.of the vat liquors obtained from the crude soda contained-D. B.Manufacture of Sulphuric Acid in America. (Dingl. pol?~i. J.,249, 48.)-Until quite lately sulphuric acid has been manufacturedin America almost exclusively from sulphur. On account of therapid rise in the price of sulphur, the manufacture of pyrites acid hasrecently been commenced by various manufacturers, but by far thelargest proportion of acid is still made from sulphur. The price ofAmerican sulphur acid compared with English pyrites acid, is said tobe so high that English superphosphate, prepared from Americanphosphate, can be sold in America at prices against which theAmerican manure manufacturers have a difficulty to compete. Thesulphur for 10 tons (= 9071.8 kilos.) sulphuric acid 66” costs 63dollars; the cost of Spanish pyrites, however, amounts to only49 dollars.Besides Rio Tinto pyrites, a variety of native iron sulphide of greatpurity has recent,ly been brought into the American market.It isobtained from the Davis mine in Massachusetts, and contains 47 percent. of available sulphur. Zinc, lead, and lime are present only inminute traces, whilstt arsenic is quite absent. The following is thecomposition compared with the Spanish ore :-5. Fe. Cu.Spanish pyrites.. ............ 47.87 40.93 3.82Pyrites from the Davis mine , . 50.30 42-63 3.07CaO andPb.Zn. MgO. As. SiO,.u-.”-,-Spanish pyrites. ........... 0.62 0.10 0.19 0.26 5.42Pyrites from the Davis mine 0.61 3-19D. B.Manufacture of Aluminium. (DingZ. poZyt. J., 249, 86-88.)-It is stated that Salinders is the only place in the world where alumi-nium is manufactured, about 2400 kilos. of metal being producedannually. The sodium used in the manufacture is obtained byigniting sodium carbonate with carbon in presence of a smallquantity of lime, which is said to facilitate the distillation. Thedouble chloride of aluminium and sodium is prepared by stronglyheating a mixture of alumina, carbon, and sodium chloride in acurrent of chlorine. The resulting double chloride is then fused withthe sodium in sma,ll reverberatory furnaces, cryolite being added asflux.Much has recently been said in the newspapers with respect t o aninvention by which it is supposed that Webster of the AluminiumCrown Metal Works, Hollywood, has greatly cheapened alumininm.The preparation of 1 ton of aluminium is said to cost only 2,00TECHNICAL CHEMISTRY.231marks. The method consists in strongly heating bauxite with sodiumcarbonate, decomposing the sodium aluminate with carbonic anhy-dride, heating the deposited alumina with carbon in a current ofchlorine, and fusing the resulting double chloride of aluminium andsodium with sodium and cryolite. This process is neither new nor isit possible to produce aluminium at a lower cost than at Salinders.Webster has also patented a method for preparing alumina for themanufacture of aluminium, which relates t o the obtainment of anhy-drous alumina from potash alum.The method is impracticable andMorris obtains aluminium by treating a mixture of alumina andcarbon with carbonic anhydride. A solution of aluminium chlorideis mixed with pulverised charcoal or lampblack, evaporated to a thickpaste, cooled, and made into balls, which after drying are placed iniron tubes and heated. The last traces of chlorine are removed bypassing steam through the tubes. The heat is then increased to dullredness and carbonic anhydride introduced. The carbon reduces thecarbonic anhydride to oxide, and this is said to reduce the alumina toaluminium. D. B.costly.Electroplating Zinc with Nickel. By MEIDINGER (DingZ. polyt.J., 249, 90).-Meidinger states that in electroplating with nickel,copper, brass, and iron can be well coated, whilst zinc is coated withdifficulty.It is therefore recommended to slightly amalgamate thezinc before it is electroplated with nickel by placing it in a solution ofmercuric chloride or nitrate acidified with sulphnric or hydrochloricacid. The nickel then deposits well, adheres firmly, and takes a goodpolish. It is thought that the zinc plates brought into commerce aretreated in this manner, as they are more brittle than pure zinc shouldbe. It is therefore necessary not to let the amalgamation go too far,I t has been difficult to electroplate derman silver with nickel, and theauthor is of opinion that in this case also amalgamation would givegood results.D. B.Asphalt or Bitumen of Judea. By B. DELACHANAL (Compt. rend.,97, 491494).-A specimen of bitumen of Judea, obtained fromPalestine through M. de Lesseps, was in the form of large, somewhatfriable lumps, very deep brown in colour, but not black, and break-ing with a conchoxdal fracture. When heated, it gave off hydrogensulphide, and was found to cont,ain 3.02 per cent. of sulphur. Acommercial sample of bitumen of Judea contained 3.14 per cent. ofsulphur. The bitumen does not leave more than 0.273 per cent. ofash, hence the greater part of the sulphur does not exist in the formof metallic sulphides. When bitumen of Judea is heated, it softens,melts, and at a sufficiently high temperatme gives off hydrogensulphide and gaseous hydrocarbons, together with a dark-coloured oil,whilst a bulky carbonaceous residue is left in the retort.This oilcan be separated into several fractions which closely resemble theproducts obtained by the distillation of crude petroleum. The oils arepartly soluble in fuming nitric acid, leaving a residue of paraffinwhich solidifies at 13'. C. H. B232 ABSTRACTS OF CHEMICAL PAPERS.Manufacture of Cellulose. (DiqZ. pohyt. J., 249, 23-29 and124--126.)-The use of sulphurous anhydride in the manufacture ofcellulose is becoming of more importance every day. In 1876 Mits-cherlich recommended treating finely-divided wood under pressurewith a solution of calcium bisulphite obtained by placing calciumcarbonate in a tower and introducing water into the top and sulphu-rous anhydride into the bottom.Paper made from the resultingcellulose was found to be exceedingly tough, and has been sold as asecond quality parchment-paper, although it does not possess thequalities which characterise this paper. The details of Mitscherlich'sprocess have since been kept secret. Francke works with solutions ofcalcium, magnesium, or sodium sulphite of 4" to 5" B., at a pressureof 4 to 5 atmospheres, the operation being completed in 12 to 15 hours.He uses rotary horizontal cylindrical boilers lined with lead, thelining being independent of the outer casing, thus forming a separateboiler. The essential theoretical difference between the lime and themagnesia process is that the resulting calcium sulphate, being almostinsoluble, remains in the lignose, whilst the magnesium sulphate isremoved during the washing operation.At present it is uncertainwhether other differences exist between the two processes.The cost of pulp by Eckmann's method, depending on the use ofmagnesium sulyhite, is 26 marks per 100 kilos., the selling price beingabout 40 marks. During last summer this method was tested by anumber of French paper manufacturers with the following results :-The quantity of wood employed was 4395 kilos. in the form of firplanks. The loss by removal of knots in chopping, grinding, &c.,amounted to 825 kilos. The remaining 3570 kilos. yielded 1437kilos. dry cellulose corresponding witlh 32.68 per cent. of the originalwood. The latter contained 21 per cent.of moisture, so that the yieldon the dry substance is equal to 40 per cent. This is considerablyless than the yield obtained by the Francke-Mitscherlich process ;t>he quality of the pulp, however, is far superior. According to recenttrials made by Eckmann, it is shown that it is possible to obtain a twill either isolated cells or fibrous bundles by using either hydrogenmagnesium sulphite, or maTnesium sulphite. I n the former case, thecolonring and glutinous substances are completely dissolved, whilst inthe latter case a portion of the gluten remains in the fibres.Archbold macerates the woody tissue with dilute milk of lime,saturates with sulphurous anhydride at a pressure of 4 to 5 atmo-spheres, and washes the mass with water.Tilghnian's method consists in boiling i n closed vessels wood, espartoor flax, with sulphurous anhydride or calcium bisulphite, or both.Pictet recommends the use of liquid sulphurous anhydride.Finely-divided wood is first immersed in water, and for every litre 120 gramsof liquid sulphurous anhydride is added. At a temperature of 85" apressure of 7 atmospheres is produced, SO that the incrustating sub-stances of the wood are strongly attacked. The pulp has the greycolour of the original wood, but may be easily bleached.I n discussing the sulphite treatment, Bourdilliat contradicts thestatement that sulphuric acid is formed when wood is boiled withsulphites ; moreover, he believes that the sulphurous anhydride disTECHNICAL CHEMISTRY.233solves the incrustating substances of the wood, bleaches the colouringmatters, and deposits finely-divided sulphur in the fibres, whilst theresins, which are attacked by sulphurous anhydride, form soaps withthe base of the bisulphite. These, together with the sulphur, remainin the fibre and add considerably to its weight ; the loss during thewashing operations is therefore not of fibre but of the mass-compoundof sulphur, resin, and lime.Cross is under the impression that the action of the magnesiumsulphite is to prevent the oxidation of wood and lignified cellulosewhen heated with water under pressure. For comparing the successof tbe different sulphite processes, the test for lignose with anilinesulphate is said to give unsatisfactory results : it is preferable to treatthe cellulose first with chlorine and then with sodium sulpliite ; iflignose is present, a magenta colour is produced.Alcohd from Melon-juice. By LEVAT (Compt.rend., 97, 615-GlG).-Melon-juice does not undergo fermentation directly, but onboiling it with very dilute sulphuric acid, the sugar in the juice isinverted, and fermentation then takes place readily, 5 litres of alcoholbeing obtained from 30 kilos. of melons.D. B.C. H, B.Clouding and Fining of Wines. By J. NESSLER (Bid. Ct?ntr.,3 883, 342-344).-Seven vasieties of Greek wines, when exposed tolow temperatures, become cloudy, but a young wine clouded as thetemperature rose ; the substance rendered insoluble by the loweringof the temperature redissolved as the temperature rose, but whensome wine had been withdrawn from the cask, while it was cloudy,the wine refused to clear, Fining with albumin, &c., prevents cloudi-ness, and the browning and thickening which 80 frequently occur aredue to decomposed husks introduced during manufacture.To finewines which have refused to clear by means of albumin, “ Spanishearth ” (100-200 grams per hectolitre) is recommended ; this is alsothe best material to use in the preparation of sparkling wines.E. W. P.Plastered Wine. By M. NENCKI (Bied. Centr., 1883, 345-347).-This paper is an answer to questions laid before the author by themunicipal authorities of Berne. Plastered wines are not of necessityprejudicial to health, although in a few cases they may be so, and thenonly when a strongly “plastered” wine has bcen regularly used.Probably Marsala, &c., which is more strongly “ plastered,” may beharmful, but the author has no proof as to whether it is o r is not so.Natural wines may contain as much as 0.503 gram K2S04 per litre.Plastering should introduce into the wine only a quantity of sulphatesequivalent to 2 grams K2S04, and no more.Free sulphuric acid hasoccasionally been detected in wine ; this arises from the formation ofethyl sulphate, which has been mistaken for the other acid.(Dingl. pohyt. J., 249, 133--139.)--Rungenerand Fries have found that boiling water containing 1 per cent.salicylic acid, readily dissolves starch, forming a tllick syrupy nJfiss,which, on cooling, deposits tabular crystals of starch.On boilingE. W. P.Barley and Malt.VOL. XLVI. 234 ABSTRACTS OF CHEMICAL PAPERS.63-9662.3265.2563.0264.1764.494 to 5 grams of finely ground barley with 150 C.C. water and 1.5 gramsalicylic acid for three-quarters of an hour, all the starch is dissolved.The hot opalescent colourless liquid is filtered, and the residue washedwith hot water until the filtrate ceases to react with iodine. Hydro-chloric acid is then added to the starch in the filtrate, and the result-ing glucose determined by means of copper solution. The results are1 to 2 per cent. higher than those obtained when the starch is dis-solved in water at 135". In the latter case, a dark-coloured solutionis formed, probably due to decomposition.According to Aubrey, five Ramples of Alsatian Chevalier barley(1882 crop) contained the following ingredients, calculated.on the drysubstance :-0.560.600.530.580-550.55I. 11. 111. IV. v.Starch . . . , .. .. 62.73 58.20 60.39 65.49 66.34Nitrogen . . . . . . 1.9008 1.9456 1.6208 1.6400 1.7456Prote'ids corre-sponding withnitrogen . . . . 11.88 19.16 10.13 10.25 10.91Phosphoric acid. 1.053 1.082 1.064 1.030 1.062Similar samples, from the year 1880, made into malt and dried at81", gave the following results :-The barley containedStarch. Nitrogen. I62 '5765.3565 -1461-2064 -2065 -781 -6591 -4431.6461 -6461 -6251 -819Phosphoricacid.1 -0150 -9101.1151 *0230 -9651 -098Yield ofextractfrom drysubstanceper cent.81 -6284 *3684 '0983-2680 '6779 90Maltose in I 7extractSchwarz has invwtigated different kinds of American barley.Heshows that the weight of the grain is no criterion as to the amount ofsolid matter, starch, prote'ids (nitrogen x 6-25], and ash contained inthe barley. The subjoined table illustrates the results of hisinvestigation :TECHNICAL CHEMISTRY. 235Quality.Minnesota barley. . . . . . .Scotch, quality I1 . . . . . .Scotch, quality I . .. .. ..Choice Scotch . . . . . . . . .Wisconsin barley. . . . . . .Scotch Wisconsin barleyCanada, quality 11.. . . . .Canada, quality I . . . . . .West Canada.. . . . . . . . .Chevalier California . . . .State barley . . .. . . . . . . .Canada barley . . . . . . . . .Weightgrain. of.30 *935 -439.531 -232 -635 -229 -032 -830 *743.735 -028.6Per-centageOfwater.14.1314 -3511.9014 -3316 -1414 '3415 -3116.9613 -2913 -3111 -2410.46The dry substance containsStarchPercent.67 '3163 '7764.8565 -2065 -4766 -1265 '3368 '5367 *5468 -3366 -3566-48--Prote'idsPercent.---13 *5813 -3411-9311 -6710 -809 -2510 -2712 -7311 -0110 -4211 a4510 -47AshPercent.--2 -772 -822 -863 -282'832 -743 *163 -743 -022-862-722 -92Phosphoricacid percent. --1'0500 -9851 -0310 -9340 -9970 *9290 -9690 *9960 -9540 *9800 '9350 -856With regard to the changes in weight and volume which barley andmalt undergo, Chodounsky found that kiln-dried malt, immediatelyafter being dried, shows a diminution in volume, whilst malt, whenkept, increases both in weight and volume, 100 hectolitres of barleyyield 97 to 99 hectolitres of kiln-dried malt, and 99 to 101 hectolitresof stored malt.Lintner states that the defects in the present malting processes aredue mainly to the want of uniformity of temperature in the germinat-ing heaps, and the difference in the amount of moisture which existsin the various layers.The gradual discharge of carbonic anhydride,and the defective admission of oxygen, has a marked effect on themalt. These imperfections are said to be removed by the pneumaticmalting process, in which the barley, after germination, is thrown ona plate having fine perforations; the air underneath the plate isthen exhausted.Thus the heat is withdrawn and the carbonicanhydride removed in a regular stream, so that the germinating grainis situated in a bath of pure air, having always the same temperatureand containing the same amqunt of moisture. To effect this the air ispreviously purified and heated to the necessary temperature.D. B.The System on which Rice may be Used in Brewing. ByA. MARKL (Bied. Celztr., 1883,348) .-The analyses of rice published byBraconnot show that it is better adapted for brewing than barley, butowing to its higher sp. gr., precautions must be taken to prevent itssettling to the bottom of the mash-tub ; to obtain the best results, therice must be previously boiled and steamed before mashing; thewort may be strongly hopped, and then kept cool to ensure normalf ementation.E. W. P.Fermentation of Bread. By G. CHICANDARD (Compt. rend., 97,616-617).--8 reply to Mmcano, Mousette, and Boutroux236 ABSTRAWS OF CHEMICAL PAPERS.Alteration of Flour by Age. By BALLAND (Compt. rend., 97,346--347).-The proportion of water is slightly variable, and alterswith the hygrometric condition of the atmosphere. Fatty mattersexperience no sensible alteration in weight, but become rancid. Thesaccharine substances decrease in amount, but the diminution bearsno relation to the degree of acidity. Tlie degree of acidity dependson the nature of the grain, flour from soft grain becoming acid morerapidly than flour from hard grain.This acidity is apparently con-nected directly with the alteration of the albumino?ds, which at firstexist in the form of insoluble gluten, but gradually decompose with-out 106s of weight. The amylaceous constituents would seem toremain unchanged. Flour which has not been finely sifted keepsbadly, and is always more acid ; it contains a higher propoption ofwoody9 fatty, and saccharine substances, and more glutes. Flour keptin bags alters. more rapidly than flour preserved in closed vessels.For the same degree of sifting, flour obtained by millstones keeps aswell as that obtained by cylinders ; the acidity is independent of thegrinding. The farinaceous portion of the grain in contact with theexternal envelope is more acid thm the internal portion ; it containsthe same amount of gluten, but alters more rapidly.C. H. B.Notes on Milk and Bqtter. By M. SCHMOGER and others (BidCeiLtr,, 1883, 418-419) .-Experiments were made to discover whetherit is better to cool milk before skimming or not. The instmment usedwas a tubular cooler, similar to that of Rossler, but with oval tubesinstead of circular. It worked well, bringing the milk in a shorttime to within 2” of the temperature of the water employed. Thecooled milk was compared with some from the same milking not arti-ficially cooled ; the results were decidedly in favour of the former,Experiments in butter-making were made with the Holstein, Lefeldt,and a rocking churn of American invention, using sweet and sourcream.Fat left, in buttermilk.(--”---’--Sweet cream. Sour cream.0.71 per cent,7Holstein system .. . . . .Lefeldt ,, . . . . . . 1.51 ,, 0-84 ,8Rocking churn.. . . . . . . 1.20 ,, 0.50 ,,Q.85 per cent,Average duration of process was less by the Holstein process thanby the two others.Artifiieial Butter Colourings. By E. SCHMITT (Ann. Agronomipues,9, 255-257) .-Amongst the substances employed for this purpose,the author enumerates marigold and carthamus flowers, saffron, carrotjuice, and turmeric ; more recently coal-tar colours have been intro-duced, such as coralline-yellow and Victoria-yellow, and also leadchromate. The two most widely sold colourings are Krick’s “ Orantia”and Trannoy’s ’‘ Carottine”; the author shows that annntto is thehasis of both.“ Omntia” can be exactly imitated by digesting30 grams annatto with 100 grams crystallised sodium carbonate, dis-J. FTECHNICAL CHEMISTRY. 237solved in a litre of water, and evaporating down to half a litre." Carottine" is a much better preparation, and may be imitated bydigesting 125 grams annatto in half a litre of oil ; a mixture of equalparts of annatto and turmeric root will give a lighter yellow. It isused in the proportion of a teaspoonful t o 25 litres of cream, and thecolour diff uies Gery rapidly and&uniformly throughout the butter.J. M. H. M.New Dyestuffs. (Dingl. poZyt. J., 248, 340--343.)-Whereasthe monosulphonic acids of phenylamidoazobenzene produce reddish-yellow to orange dyes, the corresponding tri.and tetra-sulphonicacids yield pure yellow shades. For the preparation of the polysul-phonic acids of phenylamidoaaobenzene, NHPh.C&N2.C6H5, 20 kilos.of the latter are treated in the cold with 100 kilos, fuming s-7-lphuricacid ctontaining 20 per cent. anhydride. The mixture is warmed to60-70", and the temperature reduced after three or four hours. Thema98 is then thrown into water, treated with milk oE lime, and thecalcigm compound with the sulphonic acids converted into sodiumsalts. This polysulphonic acid is obtained also by heating to 70-80"20 kilos. of the monosulphonic acid with 80 kilos. fuming sulphuricacid, and completing the process as before. These dyes are broughtinto eommerce as potassium or sodium salts in the dry state.FOP the production of artificial indigo from the orthamido-deriva-tires of acetophenone and phenylacetylene, the Badische Anilin nndSoda Fabri k treats a concentrated solution of acetylortharuidoaceto-phenone, or of aaetylorthamidophenylacetylene in carbon bisulphidein the cold with an equal weight of dry bromine.A crystallinebromine amppound is formed, which is dissolved in 10-20 times itsweight of concentrated sulphuric acid. Dilution of this with watercauses the precipitation of colourless flakes ; these dissolve in warmsoda solution to a, clear deep yellow liquid, from which indigoseparates out on contact with the air .Aocording to the Farbwerke, late Meister, Lucius, and Briining,tolylaldehyde from metaxylene is converted by nitration into meta-mekhylorthonitrobenzaldehyde.This on treatment with twice itsweight of acetone, and 25 times its weight of a 2 per cent. solution ofsoda, is readily transformed into methyl-indigo, a, substsbnoe closelyresembling natural indigo, but from which it may be distinguishedby its ready solubility in water. From the same source, processes forthe preparation of azo-dyes from the trisulphonic acids of pnaphtholare given. The trisulphonic acid is obtained by treating @-naphtholwith fuming sulphuric acid containing 20 per cent. anhydride at 140-160", until the mass gives a pure green fluorescent solution withammonia. Combined with various diazo-compounds this acid yieldsyellow, orange-red, and bluish-red dyes, of which the three followingare specially adapted for dyeing cotton :-(1.) A red dye, obtained bythe aetion of the diazo-compound of a-naphthylaminesulphonic acidon sodium P-naphtholtrisulphonate in presence of ammonia.(a,.) Abluish-red dye, resulting from the action of the diazo-compound ofamidoazobenzene on sodium 6-naphtholtrisulphonitte in presence ofammonia. (3.) A bluish-red colouring matter, obtained from thediamcompound of amidoazobenzenesulphonic acid. In the abov238 ABSTRACTS OF CHEMICAL PAPERS.three cases the dye is thrown down as a bulky precipitate on mixinga solution of sodium P-naphtholtrisulphonate with that of any of thediazo-compounds. The precipitate is purified by dissolving it inwater and reprecipitating with salt.New Coal-tar Dyes.(Dingl. pol& J., 248, 252-256.)-Ac-cording to C. Reichl, a new phenyl colouring matter is obtained bythe cohobation in molecular proportions of an alkaline xanthateand resorcinol dissolved in a small quantity of water or alcohol, solong as carbon bisulphide is returned. Water is added to the darkyellow liquid obtained, which is then filtered, and the colouringmatter precipitated with hydrochloric acid from its previous combi-nation with the alkali. It may be obtained by recrystallisation fromhot water in slender yellow needles, insoluble in cold, but readilysoluble in hot water; alcohol, acetic acid, and alkalis dissolve it withease. Wool and silk are dyed a brilliant yellow in a weak acid solu-tion. Orcinol, quinol, pyrogallol, naphthol, and quinone similarlytreated also yield yellow dyes.For the preparation of a monosulphonic acid of P-naphthylamineand /%naphthol, the Baden Anilin und Soda Fabrik allow sulphuricacid (96 t o 97 per cent.) to act on P-naphthylamine at a temperatureof 100" to 105", the sparingly soluble modification of the monosul-phonic acid being exclusively formed.By converting this into thediazo-compound and decomposing the latter with water, &naphthol-monosulphonic acid is obtained, the acid sodium salt of which issparingly soluble in hot alcohol. By evaporating the aqueous solu-tion of the free acid, it is split up into p-naphthol and sulphuric acid.When the alkaline solution of the acid is brought in contact with thediazomonosulphonic acid of azobenzene, orange-coloured flakes arethrown down.A process for preparing red and brown azo-dyes from anthrol,anthrolsulphonic acids, and dioxyanthracene has been patented bythe Actien.Ges. f. Anil. Fab. Berlin. The claims are the pairing ofanthrol, anthrolsulphonic acid, anthroldihydride and its sulphonicacid, as well as a- and P-oxyanthrol with diazobenzene and its homo-lopes, diazonaphthalene, diazoanisoil, the sulphonic acids of thesediazo- bodies, with diazoant hraminesulphonic acid, diazoamidoazoben-zene and its homologues, and mono- and di-sulphonio acids of thesediazo-compounds. The products containing the sulphuryl-group aresoluble in water, the remainder dissolve in alcohol.D. B.This azo-colouring matter dyes ponceau-red shades.D.B.Composition of Turkey-red Oil. By L. LIECHTI and W. SUIDA(Ber., 16, 2453-2458).-Glycerol trioleate and triricinoleate weretreated with sulphuric acid, and the products separated in a similarmanner to that employed in the manufacture of Turkey-red oil. Theproducts of the reaction in each case consist essentially of two sub-stances, of which the one is more soluble in ether, the other in water.The compound soluble in water derived from glycerol trioleate isglyceryl sdphate hydroxyozeate, CazH;~OlzS = SO4[ C3H5(OH) .C&L,O,],,an oily substance of acid nature, very soluble in water and alcohol,more sparingly in ether, carbon bisulphide, and benzene. WheTECHNICAL CHEMISTRY. 239heated with water, it yields glycerol, hydroxyolexc acid, and sulphuricacid.When mixed in aqueoussolution with metallic acetates, it yields salts, of which the followinghave been analysed :-Copper salt, Ci2H74012SC~2 ; barium salt,,C42H76012SBa ; silver salt, C12H,6012SAg ; aluminium salt,( C4,H7401zS)3A14 ; zinc salt,, Ca2H7,OI2SZnz.It unites with bromine in the co!d.Glyceryl sulplhate trihydroxyoleate,Ca~H78OisS = SO,[ C,&( 0 H) - CieH330,]2,the corresponding derivative from glyceryl triricinoleate, closely re-sembles the preceding compound in all its properties. The followingsalts have been analysed :-Copper salt, C4,H&6SCU ; barium salt,( C42H77016S)2Ba + C42H76016SBa ; silver salt, c42H76u16sfig2 +C4,H,,Ol6SAg ; aluminium salt, (CQ2H74016S)3A14.The subRtances soluble in ether proved to be identical with thehydroxyolek acids contained in the foregoing conjugated compounds.They are both crystalline, insoluble in water, readily soluble in ether,alcohol, carbon bisulphide, and benzene.Hydroxy olezc acid, C1,H,O,,melts at 56-58' ; the following salts have been analysed :--Normalcopper salt, (C,,H,0JzCu ; acid copper salt, (ClsH3303)2C~ +2CleH3403 ; acid barium salt, (C18H3,03),Ba + 2C1RH3103 ; acid calciumsalt, (C1RH3033)2Ca + 2C1&&403 ; aluminium salt, ( c,pH3303)6Alz.Trihydroxtjolezc acid, C18H340,, melts at 64" ; the following salts wereobtained :-Copper salt, (C18H3705)2C~ ; barium salt, (CleH3305)2~a + 2C18H3405 ; aluminium salt, (C18H&s)6Al, ; silver salt, CI8H3,O5Ag.The reaction occurring in the manufacture of Turkey-red oil istherefore expressed by the equations-2C3H,(C1J3&0,)3 + 7H2SO4 = C*ZH7,0&3 + 6S0, + 4H2O + 4Cl8H3403.2C,H6(CJXsO3)3 + 13HzSOa = Ca2H;,O16S + 12SOz + 10H2O + 4Cl*H3406.I n confirmation of this view, it was found that on heating sulphuricacid with ole'ic acid, hydroxyolek acid was obtained, and that a mix-ture of glycerol, olejic acid, and sulphnric acid, when heated, yieldedglycerol sulphate hydroxyoleate.Compounds similar to the lastnamed were prepared by heating ole'ic and sulphuric acids withmannite, grape-sugar, starch, cellulose, or dextrin. They are allsoluble in water, give metallic derivatives, and are decomposedwhen boiled with alkalis, with separation of hydroxyolei'c acid.A. J. G.Explosives and their Application. (Dingl. pohlt. J., 248,509--513).-Dollink at'tributes the presence of metal-dust in gun-powder to the wear and tear of the machines used for finely dividingand intimately mixing the powder.Straw nitrocellulose is more unstable and therefore less secure thangun-cotton. This is due to the fact that although before nitratingthe straw it is digested in a solution of potash, the cellulose of thestraw fibre is not separated entirely in the pure state, but is contami240 ABSTRACTS OF CHEMICAL PAPERS.-~ ~Gunpowder. . . . . . . . . . . .Dynamite, No. 11 .. .. . .nated with fat, wax, resin, or pectins, which form unstable nitro-compounds.For the preparation of a new gun- and blasting-powder, Himly andFriitzockler-Falkenstein grind and mix together the followirlg sub-stances in proportions so that when the mixture is ignited completecombustion occurs : nitre, potassium chlorate, and a solid hydrocarbon.The mixture is treated with a light hydrocarbon, and the plastic massmade into flat cakes, from which the liquid hydrocarbon is expelledby evaporation. The solid residue is then broken up into grains ofthe required size.Reid recommends to moisten the explosive compound cmtainingnitrocellulose with alcohol and dry it, --hereby a hard and uniformmass is obtained,It is stated that a determination of the heat produced and an esti-mation of the gaseous products formed by the combustion of amexplosive, is not sufficient to show its value. The lead test in thiscase is said to give more accurate results. The active force of avariety of explosives was determined according to this test with thefollowing results :-Proportion ofhollowlead test. St. Gothardt. Ramsbeck. Zankeroda,Acthe force according to trials madea t the following places :-spaces in the T----A----- 7NitPoglycerol, , . . . . . 1000 - - -Blasting gelatine . . . . 1000 1000 1000 1000Gelatine dynamite . . 770 -Mercury fulminate , , 300 - - -- 730Kieselguhr dymmite 700 698 683 68839,40031,600The followiag comparison by Steiner illustrates the working of Rlignite coal mine wit'h gunpowder and dynamite No. 11, the total out-put being 50,000 tons:-With the uae ofTons at2.60 fl.Produce.Tons at1 '60 fl.'71009200TonswithoutFalue.35009200--Cnflent Workingfl. 50,000 1 tons fl.These results confirm the fact that dynamite is less suitable thangunpowder for blasting coa!, as it's shattering effect is more powerfulthan that of gunpowder. D, R

ISSN:0368-1769    

DOI:10.1039/CA8844600223

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

241General and Physical Chemistry.Separation of Rays of High and Low Refrangibility. By F.v. ASSCHE (Compt. rend., 97, 838--840).-A thin layer of selenium,obtained by compressing a drop of the fused substance between platesof glass at 250°, and allowing it to cool slowly under pressure,only transmits the rays between Fraunhofer's lines A-C. Theamount of absorption increases with the thickness of the layer.When a beam of white light is passed first through a sollition ofalum and then through a film of selenium, all the luminous rays arearrested. A thin film of selenium, if heated to 250", is apparentlyopaque to all luminous radiation. C. H. 33.Atmospheric Absorption by Aqueous Vapour. By W. W.ABNEY and R. FESTING (Proc. Roy. Soc., 35, 328-341).-1n thecourse of some investigations on the atmospheric absorption in theinfra-red of the solar spectrum, the authors established the coinci-dence of the absorption-bands of the spectrum with those due towater.They have further confirmed Langley's researches as regardsCauchy's formula for refraction.I n this paper, the spectrum is examined, which is obtained by usingthe crater of the positive pole of the electric light as a source ofradiation by means of a thermopile, and the variations produced byplacing layers of water of different thickness in front of the slit.The diagrams show that the thermograms of the water spectra areabsolutely coincident with the absorption in the photographs, butthe former method is probably the more delicate.By means of the thermograms, the solar temperature may beapproximately estimated ; for Dewar has shown that the temperatureof the source of heat is nearly proportional to the square root of thetotal variation represented by the area of the thermogram curve.The temperature of the crater is calculated at about 6000, and in theprismatic solar spectrum the scale is 4.5 times that of the scale of thecrater thermogram ; the highest solar temperature, therefore, would bed$.5 x 6000 = 12,700, a value far higher than that put forward bySiemens.Among other results, the existence of a large quantity of solarradiation, due to low temperature, is shown to be more than pro-bable.V. H. V.Radiant Matter Spectroscopy. By W. CROOKES (PTOC. R o y .SOC., 35, 262-271) .-Whilst studying the phenomena presented byvarious substances when struck by the molecular discharge from thenegative pole in a highly exhausted tube-the so-called radiant matter-the author observed a bright citron line or band : this appearedmore markedly when the substance under examination was convertedVOL. XLVI.242 ABSTRACTS OF CHEMICAL PAPERS.into the sulphate by evaporation with strong sulphuric acid. Pre-liminary evidence tended to show that this band was due to calcium,for most native compounds of this element produced it, and it becamebetter defined when solutions of these substances were precipitated byammoniu& oxalate. But if the calcium compound gave no bandoriginally, it could not be brought out by any process, chemical 01'physical. Tentative experiments established that this line was due t osome member of the yttrium and its allied families present in samars-kite, and by the method of differences these were ultimately restrictedto the four following : mosandrum, lithium, ytterbium, and yttrium.By a long series of separations, this citron band was shown finally tobe due to yttrinm, whose sulphate in a " radiant matter " tube con-sists essentially of a broad red band, an intensely brilliant citronband, and two equally brilliant green bands.The above investigations show that yttrium is more widely dis-tributed than has been suspected hitherto.From the results ofquantitative spectrixm analysis it is seen that amongst other sub-stances a specimen of coral contains 1 part of yttrium in 200 parts ;strontianite, 1 part in 500 ; chondrodite from Mount Somma, 1 partin 4,000; calcite, 1 partl in 10,000 ; ox-bone, 1 part in 10,000; ameteorite (Alfianello), 1 part in 100,000 ; and tobacco-ash, 1 part in1,000,000. V.H. V.Line Spectra of Boron and Silicon. By W. N. H a T L E y(Proc. Roy. Xoc., 35, 301--304).-Among other spark spectra ofsaline solutions, those of boron and silicon present a particular interest.In the spectrum of sodium diborate, three sharp lines X 3450.3, k 2497,and X2496.3 appear, and if the solution of the salt be sufficientlystrong, the sodium lines are not visible. A detailed description andthe wave-lengths of the spark spectrum of silicon compounds aregiven, and it is noted that a certain group of these lines is attributedby Liveing and Dewar to the element carbon, although the author didnot observe them in his spectrum of graphite.Probably the specimenof graphite used by Liveing and Dewar, although purified with t,hegreatest care, contained traces of silicon, for not only graphite, butother elements, as aluminium and iron, are invariably contaminatedwith traces of silicon. V. H. IT.Ultra-violet Absorption Spectra of Albuminoids. By J. L.SORET (Compt. rend., 97, 642--644).-Diluted white of egg allmmiiiprecipitated by hydrochloric acid and redissolved in excess, &albumindissolved in hydrochloric acid, purified albumin, protalbin, artificialpro talbin, pepsino-pseudopeptone, pancro- pseudopep tone, casein frommilk, serum from the blood of the pig, mucin from Helix pomatia,globulin, myosin, and syntonin all give practically the same spectrum,which is characterised by an absorption-band coincident with thecadmium line at 17, and a band of no absorption at 18.This factindicates that all these albumino'ids contain a, common principle towhich the absorption-band is due. Gelatin, which differs from albu-min in other respects, is much more transparent to ultra-violet rays,and does not give the absorption-bandGENERAL AND PHYSICAL CHEMISTRY. 243Hydrochloric acid has no sensible effect on the character of thespectrum, but slightly diminishes the general absorption. Sodiumhydroxide or ammonia, on the other hand, produces considerablealteration ; 'the band of no absorption, coincident with the cadmiumline at 18, disappears entirely; whilst the band at 17 remains un-altered or diminishes in intensity, and the curve from this pointdecreases regularly to the end of the spectrum.In many cases afaint, absorption-band appeass between 14 and 16 ; in others the bandis reduced to a simple irdection. That is to say, the general absorp-tion between 17 and 22 increases considerably, and the absorption-band becomes almost invisible and is displaced towards the morerefrangible end. On neutralising the soda with hydrochloric acid, theoriginal spectrum reappears without any sensible alteration. Sodiumhydroxide alone is very transparent to this region of the spectrum.These results show that alkalis produce an alteration in the molecularconstitution of albumino'ids, and afford further proof that the lattercontain a common principle.Other organic bodies, such as sarcine and tyrosine, which combinewith acids and bases, behave in a similar manner.Their spectra arenot affected by hydrochloric acid, but are altered by alkalis, thechange consisting in an alteration in the position of the bands or intheir intensities, some of them disappearing altogether.Production of Electricity by Evaporation, and ElectricalNeutrality of Vapour arising from Electrified Surfaces ofLiquids. By L. J . BLAKE (PhiZ. Nag. [ 5 ] , 16, 211--224).-0f thehypotheses proposed to explain the origin of atmospheric electricity,twg have received considerable support among physicists, namely,the productiori of electricity by simple evaporation, and the convec-tion of electricity upon the surface of any evaporating liquid.In this paper the hypotheses are investigated experimentally bymeans of Kohlrausch's condenser with moveable plate, and aa electro-meter, which is described at length.As regards the former hypothesis, the tabulated results indicate noproduction of electricity by simple evaporation.Similarly as regardsthe latter hypothesis, experiments on the evaporation of distilledwater, sodium chloride solution, absolute alcohol, concentrated sul-phuric acid, and sea water, showed that there is no convection ofelectricity from the electrified surface of a liquid when evaporating.In some experiments with sea water, the kind of electricity upon thesurface of the condenser was of opposite sign to that of the water,whereas, had convection occurred, the reverse would have been thecase.In order to put the hypothesis to a favourable test, experimentswere made with evaporating mercury, but with negative results, andthus it must be concluded that the vapour arising from electrifiedstill surfaces of liquids is electrically neutral.C.H. B.V. H. V.Effect of Temperature on the Electromotive Force andResistance of Batteries. By W. H. PREECE (PTOC. Roy. SOC., 35,250--257).-As a continuation of former researches (cf. Abstracts,$ 844 ABSTRACTS OF CHEMICAL PAPERS.Percentageof acid.1883, p. 840), the effect of an increase of temperature on the electro-motive force and resistance of secondary batteries containing plates oflead and lead peroxide in sulphuric acid of various degrees of con-centration. From an inspection of the tables and diagrams in theoriginal paper, it is seen that the effect produced by heating thesecondary batteries is the same in kind, but different in degree, fromthat on the Daniel1 cell.The E.M.F. practically remains constant,but the internal resistance diminishes with rise of temperature,increasing again as the temperature is lowered. Variations ofstrength of acid do not produce any very marked effect. The follow-i n g short table illustrates the above remarks :-Resistance in ohms.Decreaseper cent.oo. 1 100".10 .............20 .............30 .............Mean. ..........0.0'752 0.046 61 -00.08 0 *457 57 -00.062 0.0338 58-00.0724 0.425 59 *6------V.H. V.Benzene as an Insulator. By H. HERTZ (Wied. Ann., 20, 279-284) .-Ro wland and Nichols have established that in certain insu-lating crystals dielectric polarisation is not accompanied with theformation of any residual charge. They consider this latter pheno-menon to be a necessary consequence of non-homogeneity of theinsulating material. This view led the writer to examine a series ofliquids, of which benzene is the most advantageous, as of a sufficientresistance and not giving any residual charge.The apparatus used was practically a modificat'ion of a Leyden jar,in which the zinc plates, in circuit with a battey and electrometer,were the inner and outer coatings, and a layer of benzene the dielec-tric.The following phenomena were observed. A t first the resist-ance was too small for measurement, and the residual nearly one-tenthof the original charge. After a short time these properties diminishedpari passu until at the end of 24 hours the benzene became a perfectinsulator, without any residual charge. The conductivity displayedat first by the benzene doubtless arises from impurities, and it isshown that the transference of the benzene from one vessel to another,or the introduction of the trace of any powder, will increase the con-ductivity of the benzene. On the other hand, the decrease of con-ductivity is due in part to the action of the carrent.Electrically pure benzene seems to be the best approximation toan ideal insulating liquid, both as regards resistance and residualcharge ; its sole disadvantage is its volatility.The residual charge, which makes its appearance in impure benGENERAL AND PHYSICAL CHEMISTRY.245zene, arises from a subsequent polarisation, of whatever nature it maybe, and not from an interpenetration of free electricity.V. H. V.Electrical Resistance of Insulators. By G. FOUSSEREAU(Conzpt. rend., 97, 996-998) .-The resistances were determined inthe manner previously described, by measuring the time required t ocharge a condenser at a given difference of potential across the pw-ticular substance. The resistance of porcelain varies with the tem-perature in the same rnaiiner as that of the more highly insulatingvarieties of glass: it is 751 at 60", and 0.052 at lSO".*The resistance of sulphur, previously fused and then allowed tocool slowly in the prismatic condition, is 7.39 at 112*1", and 3930 at69" ; below the latter temperature, the conductivity is inappreciable.When the same sulphur is allowed to remain at the ordinary tem-perature for some time, so that it devitrifies, its conductivity gradu-ally increases: in one case the resistance after one day was 1170 at17" ; after two days, 705 at 17".Octahedral sulphur shows no traceof conductivity at the ordinary temperature, and the conductivityonly becomes appreciable at about 80". T t would appear from thesefacts that sulphur has a higher resistance when crystalline.When sulphur melts, its resistance diminishes to one-fortieth itsoriginal amount.If the temperature is gradually raised from 114"to 150°, the resistance gradually diminishes as the temperature rises,and it varies between these limits in the ratio of 9 to 1. When thetemperature rises to 160°, the sulphur becomes darker coloured andpasty, and its resistance increases. If the liquid is again cooled tothe melting point, it retains a resistance higher than the originalresistance, and the difference is greater the higher the temperaturet o which the sulphur has been heated, the longer it has been kept atthis temperature, and the more quickly it has passed 155" in the pro-cess of cooling, this being about the temperature at which the inversechange takes place.By repeatedly heating the sulphur in this wayto a high temperature, its original resistance at the melting point caiibe increased twelvefold.When sulphur is allowed to cool in the prismatic form and is thenremelted, it shows a diminished resistance at the same temperatures.Similarly, when octahedral sulphur is repeatedly crystallised in theprismatic for=, its resistance at 115" is gradually reduced to one half.These results agree with Gernez' supposition that one variety ofsulphur fully acquires the properties of another variety, only afterrepeated crystallisations.The resistance of carefully dried ordinary phosphorus is 84,000megohms at 15", and 15,600 megohms at 42" ; it is of the same orderof magnihde as that of liquid sulphur.The resistance of liquidphosphorus is 2.32 megohms at 25",f and 0.34 megohm at 100".C. H. B.* All the resistances except those of phosphorus are given in millions oft This is the temperature given in the original paper. Apparently it shouldmegohms per cubic centimeter.be 45'246 ABSTRACTS OF CHEMICAL PAPERS.A High Pressure Electric Accumulator. BJP F. J. SMITH (Phil.Mag. [ 5 ] , 15, 203--204).--Grove's gas battery cannot be convenientlyused as an accumulator, or secondary brtttery, owing to t'he smallquantities of gases contained in it. Its use may however be extendedby storing the electrolytic gases under high pressure in a suitably con-structed apparatus, such as the following. I n a strong lead vessel,partly filled with 10 per cent.sulphuric acid, are enclosed platinisedplatinum cylinders in inverted tubes, the terminals being broughtthrough insulating stoppers : with this arrangement a pressure ofseven atmospheres can be easily used. It appears from preliminaryexperiments that the E.M.F. of this accumulator varies consideraldywith the pressure. V. H. V.Measurement of Electromotive Force. By E. REYNIER (Conzpt.rend., 9'7, 1056-1059).- The author measures the maximum electro-motive force of a couple with a single electrolyte by means of a cellin which the active surface of the positive plate is 300 times thatof the negative plate, and he measures the minimum electromotiveforce by means of a cell in which the surface of the negative plate isvery much greater than that of the positive plate, the measurement inthis latter case being made immediately after the battery has beenworking on short circuit, for several hours.The maximum andminimum electromotive forces of several couples are given in a table.The author concludes that the electromotive force of a couple witha single electrolyte must be regarded as the true electromotive forceof the system, and its increase up to the maximum results from theaddition of products formed by the action of the air. The effect ofthese products must not be confounded with the chemical energies dueto the couple itself. C. H. B.Chemical Affinities in Terms of Electromotive Force, ByC. R. A. WRIGHT and C. THOMPSON (Phil. Mag. [ 5 ] , 16, 25-48>.On the E.M.F.of C'lrxrk's Cell.-In this paper are described a series ofexperiments on the E.M.F. of Clark's cells (HgJ HgLSOaj ZnS0,i Zn),compared with one another and with other cells, by means of thequadrant electrometer, so that they never generated any current,other than the minute leakage current. With cells constructedstrictly in accordance with Clark's directions, a slight rise in E.M.F.was observed during the first few days, then the values became andremained constant. Increase of dilution of the zinc sulphate solutionincreased the E.M.F., whilst dissolved air produced no alteration ;the presence of mercuric sulphate, in the form of turpeth mineral,caused a progressive decrease of the E.M.F., amounting to about4 per cent. after 6-20 months. It was found that an increase of onedegree in temperature produced a diminution 0.04 per cent.in theE.M.F. ; and from the experiments with five cells described in thispaper, it follows that between 2" and 27" the E.M.F. of the cell forany temperature t may be determined by the formulaassuming Clark's original valuation to be correct.1*457(1 -(t - 15.5) x 0*000041) voltGENERAL AND PHYSICAL CHEMISTRY. 247On the Wo& done during Electrolysis.-Previous researches by theauthors have established that, when a current is passed through anelectrolytic cell, the amount of energy expended in performing a givenamount of electro-chemical work (apart from that transformed intoheat) is not constant, but increases algebraically w i t h the current density.In this connection, experiments by Favre appear to show that cer-tain forms of electromotor cells can generate currents capable of doingmore work externally t o the cell than corresponds with the netchemical action, this extra work being gained at the expense of thesensible heat of the cell, which becomes cooled by the currents.Although Favre's results have been refuted by Weber, yet experi-ments described at length in the present paper point to the followingresults :-(1.) When an electrolytic cell is of such a nature that the counterE.M.P.is negative, the E.M.F. developed is less the greater thedensity of the current generated. With small current densities, theE.M.F. has a, maximum value, identical in somecases with the E.M.F.representing the algebraical sum of the chemical affinities involved ;in other cases the maximum E.M.F.is below that due to chemicalaction.(2.) Some kinds of combinations, more especially those in whichlead is the metal dissolved, develop a greater E.M.F. than that due tochemical action. Recent experiments of Braun ( A n n . Phys. C'hem.[2], 16, 561) confirm these general results, in proving that some com-binations give an E.M.F. sensibly identical with that calculated fromthermo-chemical data, whilst others fall short of and some exceedthese values.(3.) When the electrolytic cell is not an electromotor, the counterE.3f.F. increases in amount with the current density. When the +electrode is of such a nature as to combine with the products ofelectrolysis, the rate of increase is slower the greater the chemicalaffinity between t,he so-called nascent products of electrolysis.(4.) Whether the cell be an electromotor or not, there is always agreater or less degree of nonadjuvancy owing to the development ofheat in place of electricity ; the particular extent to which this non-adjuvancy extends appears to be a complex function, not only of thechemical nature and physical condition of its surface, but also of thedegree of concentration of the electrolyte.When a gas is one of the permanent products of electrolysis, theyreirter the surfuce condensing power of the material of the electrode, theLess is the degree of non-adjuvuncy.V. H. V.Conditions Affecting Area of Electrification. By A.TRIBE( P h i l . Nag. [ S ] , 16, 90--95).-The areas of electrifications on ananalysing silver plate in a solution of copper sulphate, can be deter-mined by measuring the copper and silver peroxide respectivelydeposited on the plate ; the former gives the area of -, the latter thatof the + electrification. The influence of strength of current, tem-perature, and strength of electrolyte is examined; in all cases aninequality in the magnitude of the electrifications of opposite strengthwas observed ; generally the area of + elect'rification is the greater248 ABSTRACTS OF CHEMICAL PAPERS.but with rise of temperature the relation is reversed. These experi-ments, taken in connection with others by the author on dissymmetryin the electrolytic discharge, in which it was inferred that the electro-motive force on the + side of the trough is the greater, seem to berelated to Faraday’s observation that negative electricity dischargesinto the air at a somewhat lower tension than positive electricity;for if this be true of molecules of air, it is probably also true of mole-cules of ot,her fluid media, as copper sulphate.A difference in theE.M.F. of the molecules in corresponding positions is therefore afeature of dissymmetry of certain electrolytic fields. This effect isobserved i n the phenomena mentioned above, viz., the differences inthe area of like electrifications in analysing plates placed in cor-responding positions. V. H. V.Distribution of Electricity on Hollow Conductors in Elec-trolytes.By A. TRIBE (Phil. Mag. [5], 16, 384--386).-It wouldd priori be concluded that the closest analogy exists between the dis-tribution of electricity on hollow conductors in electrolytic anddielectric fields. In this paper this conclusion is confirmed experi-mentally.Hollow silver tubes were placed in an electrolytic cell containingcopper sul phate, midway between the electrolytes and perpendiculart o them; through the cell a current of one ampere flowed for sixminutes. It was €ouad that the intermediate space of no electrifica-tion was far greater within than without the tube. Similarly thesilver tube exerted a sort of protective action on a plate of silver en-closed within, but not in metallic connection with it. But in theseexperiments the area of + was always greater than that of - electri-fication (see preceding Abstract).Other experiments were also made,substituting tubes of wire gauze of various diameters for those ofmetallic silver, and a similar result arrived at. As foreseen, increaseof diameter of tube decreases the power of protection from electri-fi cat iou. V. H. V.Electrolysis of Sodium Chloride and its Industrial Applica-tions. By E. ROTONDI (Cazzetta, 13, 279-280) .-The author’s firstexperiments were made with a glass cylinder closed at bottom withparchment-paper and placed within a glass jar, both vessels contain-ing a saturated solution of sodium chloride. On passing a currelitthrough the liquid, the positive pole of the battery being placed inthe inner vessel, chlorine was there evolved, and hydrogen in theouter vessel, where also sodium hydroxide was formed, which was sub-sequently converted into carbonate by a stream of carbonic anhydride.In other experiments the inner vessel was made of porous earthen-ware-in others again of poplar wood.By these means solutions ofsodium carbonate were formed, equal in strength to those obtainedby Leblanc’e process. I n all the experiments, however, free chlorinewas detected after a certain time in the inner vessel, its presencethere being due to an alteration in the diaphragm. To avoid this in-convenience, the inner vessel was filled with distilled water, andthe outer with a solution of sodium chloride, which was kept conGENERAL AND PHYSICAL CHEMISTKY.249stantly saturated. With this arrangement, the chlorine separated a tthe anode, being insoluble in the saturated solution, was evolved inthe free state, and thus the alteration of the diaphragm and theformation of chlorinated compounds were avoided.The electrolysis of sodium chloride in this manner may be utilisedin several branches of industry, as in the bleaching of vegetablefibres, in calico-printing, &c., since by the expenditure of a moderateamount of mechanical power to generate the electric current, a power-ful bleaching and oxidising agent may be obtained, together withcaustic or carbonated alkali. H. W.Relation between Radiation, Energy, and Temperature. ByW. W. ABNEY and R. FESTING (Phil. Mug. [ 5 ] , 16, 234--229).-1nthis paper a series of determinations is quoted of the radiation andof the energy of incandescent, lamps, when currents of varying strengthwere passed through the filaments.A Grove’s battery was used asthe source of energy, the intensity of which was measured by atangent galvanometer, and the radiation of the lamp by a thermo-pile, whose surface was coated with lampblack. The lamps wereheated in ovens heated to 300°, and the change of resistance measureddirectly by resistance coils.The results obtained may be summed up thus : the current can beexpressed as a function of the potential ; the radiation, after a certaintemperature has been reached, bears a simple proportion to the energyexpended; the resistance can be formulated as a function of theenergy, and therefore of the radiation ; and the temperature appearsto be a simple function of the resistance.The curves expressing therelation between the first two quantities, current and potential, can berepresented by the equation c = up + Lpe; from this equation canbe deduced another for the value of the energy in water,w = pz(u + b p i ) ; the resistance in ohms would be ~- whilsta + bp+’the form of the equation between energy and resistance is expressedthus: 20 = (yy x -. 1Appended are the results of typical experiments with four differentpatterns of lamps, in which the dimensions of the carbon filamentsdiffer considerably. V. H. V.Heats of Combustion and Formation of Carbon Bisulphideand Carbonyl Sulphide. By J. THOMSEN (Bw., 16, 2616-2619).-The heat of combustion of liquid carbon bisulphide, according toFavre and Silbermann, is 258,400 c., or calculated for the gaseouscondition, 264,800 c.; according to Berthelot’s experiments, it is253,300 c. The author’s results both with carbon bisulphide andcarbonyl sulphide, COS, are the following :250 ABSTRACTS OF CHEMICAL PAPERS.Heat of com-bustion. Reaction. Heat of forma-tion. Reaction.(CS, + 0,) ......... 365,130 c. (C,S,) ............. I - 26,010 c.(COS + 0,) ........ i 131,010 ,, 1 (C,O,S) ........... , + 37,030 .. (C0,S) ............ + 8,030 ..Reaction.--(CO,Cl,) .(PCl,,O).(dO,,Cl,).The heat of combustion of carbon bisulphide in the liquid conditionis 6400 c. less, and the heat of formation 6400 c.greater than in thegaseous state. A. I(. M.Heat of Formation of the Oxychlorides of Carbon, Phos-phorus, and Sulphur. By J. THOMBEN (Ber., 16, 2619-2621).-The results are contained in the following table :-Heat.-_I-26,140 c .70,660 ,,18,700 ,,Reaction.(C,O,Cl,). .(P,O,CI,). .---(S,O&l%) .Heat.-55,140 c.145,960 ,,89,780 ,,Reaction. ------(COCl,,Aq) * a(l?OCl,,Aq) . .(SO,Cl,,Aq) . .A. I(. M.Heat.57,970 C.72,190 ,,62,900 ,,Heat of Formation of Pyrosulphuric Chloride. By D.KONOWALOPF (Ber., 16, 2629 -2631).--This was determined from itsheat of decomposition by potash solution (896.2 cnl.). Ca.lculatedfrom this, its heat of formation is 1882 cal., or calculated for thegaseous condition, 180.6 cal.A. I(. M.Heats of Solution and Hydration of the Alkaline Earthsand the Alkalis. By J. THOMSEN (Ber., 16, 2613-2615).-Theresults are shown in the following tables, Berthelot's figures beinggiven for comparison :-Heat of Solution of the Otcides and Hydrates.Reaction.(Ba0,Aq) ....................(Sr0,Aq) .....................(Ca0,Aq) .....................(CaO,H,,Aq) .................(KOH,Aq) ...................aO,H,,Aq) .................. ..................(NaOH,Aq) ..................(Ba02H2.8f120,Aq) ............(Sr02Kp8H20,Sq) ............Thornsen.34,520 c.29,340 ),18,330 )y12,260 ,,11,640 ,,3,790 ,,13,290 ,)9,940 ,,-14,640 ,, -115,210 ,,Berthelot.27,880 c.26,800 ,,10,260 ,, 18,100 ,,9,600 Y )3,000 3,9,780 ,)12,460 ,,GENERAL AND PHYSICAL CHEMISTRY.Heat of H?jdratioia.251Reaction.(BaO,H,O) ....................(CaO,H,O) ....................(BaO2H2,8H,O). ...............(SrO,H,O) ....................(SVO?H~,~H~O) ................Thornsen.---I-22,260 c.17,700 ,,15,540 ,,27,470 ,,26,280 ,,Berthelot.17,620 c.17,200 ,,15,100 ,) - -A.K. M.Densities of Solutions of Salts. By C. BENDER (Ber., 16, 2556-2559).--From an examination of solutions of salts containing a numberof gram-molecules to a litre, the author has arrived a t a general law,according to which the density can be calculated from the numbel.of gram-molecules of the anhydrous salt contained in a litre of thesolution a t a given temperature, namely, 15" and 18".This dependson the supposition that an atom of an element (also certain groups ofatoms) has R definite solubility value independent of the second atomor group of atoms with which it is united in a salt, as was shown byValson ( C o q A . ?*end., 77, 806) in the case of moderately concentratedsolutions. The author gives the following equation, d p = dp(u) +p(m, + m,), f o r determining the density of a solution, p being thenumber of gram-molecules of the salt, dp(u) the density of a solutionof ammonium chloride containing the same nurnber of gram-molecul~sto the litre, mb the solubility d u e of the metal, aud mu that of theacid radicle. The following is anexample i n which the density of a solution of' copper nitrate a t 1.5" isto be calculated : p = 3, nzb = 0.043'7 (obtained from following table),m, = 0.01Ci3, and = 1.0451. The calculated density is accordiiigly1.2251, that found being 1.2250.The following values of m, and9 1 , for different metals and acid radicles are in some cases onlyapproximate :-Water at 4" is'taken as unity.NH,. ..........K.... ........R'a ............Li. ............+Bs ...........tSr. ...........4 Ca ...........~ ~~c1 .............Br ............I ..............At 15'.00 -02890 -02380 -00780 -07350 -0500 -00 -0373 -At lao.--00 *02960 -023.30 *00770 -07390 *05220 -028200 * 03700 '0733--I At 15".iMg.. ........+Mn. .........i z n ..........+Cd ..........1,Pb ..........+cu ..........Ag ...........NO,. .........C2h302....... +(SPA) ........0 -02100 -03560 *04100 -10870 *0437-- --0.01630.0206 - 0 -0015At 18".--0 -02210 -04100 -06060 '04130 -10690 '01600 *0200----252 ABSTRACTS OF CHEMICAL PAPERS.Critical Temperatures. 11. By B. PAWLEWSKI (Bey., 16, 2633-2636) .-For first communication, see Abstr., 1883, 2'76.Substance.Phosphorus trichloride ........Te trachlor me t haneEthylene chloride. ....... (about)Ethglidene chloride ............A1 1 yl chloride .......... (a bout)Ethyl bromide ................Met hylal ......................E thylal ......................Triethylarriine ................Isopentane ....................Amylene ......................Hexane ......................Dially 1........................D iisobu tyl ....................Octylene.. ...................Toluene ......................Trimethylcarbindl ..............Ethyl crotonate ..............Ethylpropyl ether.. . . . . . . . . . . .Allylethyl ether. ...............Acetic acid.. ..................Propionic acid ............................Butyl a,lcohol. .................Isopentylalcobol ..............(T.1285.5"285.3283.0254.5240.7236.0236%254.4267.1194.8201.0250.3234.4270.8298%320.8287.1234.9306.6326.0233.4245.0321.5339.9(t.)75.5"75.485.057.845.539.043.0104-390.131.038-068.059.1107.5123%111.0117.283.0132-1138.863.967.2118.5138.5(T-t).210.0"209.9198.0196-7195.2197.0180.6150.1177.0163.8163.0182.3175.3163.3175.0169.9151.9174.5187.2169.517 7.8203-0201.4209.8The author disputes some points in connection with Nadejdine'slaw (BeibZutter, x .Ann. Phys. Chern., 1883, 678). A. K. M.Influence of Pressure on the Temperature of Volatilisationof Solids. By W. RAMSAY and S. YOUNG (Proc. Roy. Soc., 35, 305-310).-Experiments were undertaken in order to ascertain whethersolids have definite volatilising points under different pressures, andwhether these pressures are identical with their vapour-tensions. Asolid has a limited surface, which cannot on heating be increased byformation of bubbles ; i t would d yriori be expected that increasingthe supply of heat, the temperature of the solid would rise until atemperature is reached at which the rate of evaporation is equivalentto the rate at which heat is communicated to it. By such reasoning.the existence of hot ice was maintained by Cnrnelley and others.If, then, the rate of evaporation at the surface of a solid is inde-pendent of the extent of that surface, but influenced only by the rateat which heat is communicated to it, and as in the case of liquids, bythe pressure to which i t is exposed, it follows that solids have definitetemperatures of evaporation, corresponding to definite pressures, asliquids have definite boiling points.Experiments with ice and cam-phor show that these pressures are sensibly the same as the maximumtensions of the vapours of these solids at corresponding temperaturesQENERAL AND PHYSICAL CHEMISTRY.253In the case of ice, the maximum temperature attainable under auygiven pressure is indicated by Thomsen’s ice-steam line.By W. W. J. NICOL (Phil. Mag. [ 5 ] , 15,91--lOl).--The phenomenon of solution is usually explained by theformation of a hydrate, more or less stable, of the substance to bedissolved, this hydrate diffusing throughout the mass of the liquid withproduction of a homogeneous solution. But this hypothesis fails toexplain the alteration in the solubility of salts when simultaneouslydissolved, the greater or lesser solubility of various salts, and thegreater or lesser increase of solubility of salts with rise of temperature.Further, the experiments of Wiedemann and of the author on sodiumsulphate tend to prove that the crystalline salt parts with its water ofcrystallisation at 34”, whether in solution or not.Thus the dilemmasarise of an explanation of solution by hydration, and increased solu-bility by diminished hydration, whilst an example of a salt is offered,which dissolves in the anhydrous state, and is then less soluble thanwhen hydrated.In this paper the following hypothesis is brought forward: thesolution of a salt in water is a consequence of the at,traction of themolecule of water for a molecule of salt, exceeding that of the mole-cules of the salt for one anot.her. At the saturation point, the attractionof dissimilar molecules is counterbalanced by that of similar mole-cules.This hypothesis receives experimental support, not only fromKremer’s researches on the influence of the temperature at whichcrystallisation takes place, on the sp.gr. of the salt, but also byBerthelot’s determinations on the heats of solution of various saltsbefore and after fusion. The latter has established that the solutionof that form of salt which crystallises at ordinary temperatures, isattended by absorption of heat, due to the heat absorbed by the lique-faction of the salt exceeding that of its combination with water; or inother words, the work to be done in separating the molecules of saltrequires a greater expenditure of energy in the form of heat thanthat given out by the union of the water with the salt.Again, in most cases the volume of the solution is usually less thanthe sum of the volumes taken together of the salt and water beforesolution. In this connection the experiments of Gerlach show thatthe amount of contraction does not increase regularly as t’he amountof salt dissolved increases.This is in accordance with the theoryenunciated above, that the greater the amount of salt already in solu-tion, the less is the result of the attraction of dissimilar, but the greaterthat of similar molecules.Again determinations by GerIach and Rremer on the coefficient ofexpansion of salt-solutions have proved that for weak solutions ofsalts the coefficient of expansion is in most cases greater than that ofwater; and the same obtains with strong solutions up to a certaintemperature.In a solution, the effect of heat on the attraction ofwater for water, and of water for salt, will be to produce expansion,but on the attraction of salt for salt, to produce contraction. In dilutesolution this last need not be considered, so that the net result is anV. H V.Nature of Solution254 ABSTRACTS OF CHEMICAL PAPERS.,expansion due not only t o that of water, but also to the attraction ofthe water for the salt. If this theory be correct, it will be possible toconnect together the molecular volume of solids and their soh bility.V. H. V.Solubility of Salts in Water at High Temperatures. By W.A. TILDPX and W. A. SHENSTONE (Proc. Roy. Xoc., 35, 345-346).-This paper contains a brief description of experiments made with aview of determining the solubility of salts in water at temperaturesabove its boiling point.As a general result it may be stated that solubility and fusibilityare phenomena intimately connected : for increase of solubility con-sequent on a rise of temperature above 100" is the greatest in themost fusible, and least in the least fusible.If the results are repre-sented graphically, taking for abscissae degrees of temperature, andfor ordinates the quantities of salt dissolved in 100 parts of water,then the higher the melting point, the more nearly the curves approxi-mate to a straight line.These relations can be illustrated by potassium chlorate and potas-sium halo'id salts. As regards sodium sulphate, the solubility increasesfrom 6-34', the melting point of the decahydrated salt, N%SO,,lOH,O ;then the solubility diminishes until a temperature of 120" is reached.From 120" to 140" there is no appreciable change, but at 160" there isa notable increase of solubility, which is still further increased at180" and again at 230".Parts by Weight of Arzlzydrous NasS04, dissolved by 100 parts ofOo. 34".100". 120". 14.0". 160". 180". 230".Water at5 78.8 42.7 41.95 42 42.9 44.25 46.4I n view of these facts the act of solut,ion can no longer be explainedby the formation of hydrates of the dissolving salt. V. H. V.General Law of the Freezing of Solvents. (Compt. rend., 97,825-831 .)-A report by Cahours, Berthelot, and Debray on Raoult'smemoir.By I?.M. RAOULT(Cofi2pt. rend., 97, 941--943).-The following results were obtaiued :(See Abstr., 1882, p. 1260; 1883, p. 223.) C. H. B.Freezing Point of Alkaline SolutionsGENERAL AND PHYSICAL CHEMISTRY. 255Base.Barium hydroxide ............Strontium ,, ............Calcium ,, ............Lithium ,, ............Sodium ............Potassium ., . . . . . . . . . . . .Thallium ,, ............Cesium . . . . . . . . . . . .Rubidium ,, . . . . . . . . . . . .Tetramethylammonium hydroxideTrimethyiethylammoninm , ,7 77 9Reduction in freezingpoint caused by 1 grain Mol.Mol. of the base in reduc-weight. 100 grams of water. tion.171.0 0.290 49.7121.5 0.396 48.274.0 0.648 48.024.0 1.558 37.440.0 0.905 36.256.0 0 630 35.3221.0 0.150 33.1149.6 0.237 35.5102.4 0.360 36-991.0 0.404 36.8105.0 0 353 37.1Ammonia .................... 17.0 1.117 16.9Methylamine .. . . . . . . . . . . . . . . . SI.0 0.638 19.8Ethylamine .................. 45.0 0.411 18.5Aniline ...................... 93.0 0.164 1S.3Nicotine ...................... 162.0 0.124 20.2Trimethylamine ................ 59.0 0.342 2,0.2Propylamine . . . . . . . . . . . . . . . . . . 59.0 0.312 18.4It is evident that in accordance with the general law, soluble basesmay be divided into two classes, one of which gives a molecularreduction between 33 and 48 (mean = 39), whilst the other gives amolecular reduction between 16 and 20 (mean = 19), or practicallyone-half. The differences between the molecular reductions of indi-vidual members of each group are considerably greater than in thecase of acids.The first group may in fact be divided into twosub-groups : one containing the hydroxides of dyad metals with amolecular reduction of about 48, and the other the hydroxides ofmonad metals with a molecular reduction of about 35.Berthelot, Menschutkin, and the author have previously shown thatpotash and soda displace ammonia, methylamine, ethylamine, triethyl-amine, trimethylamine, and aniline almost completely from their saltsin dilute alcoholic solution. The author also finds that bariumhydroxide and rubidium hydroxide displace ammonia completely fromammonium chloride, and that triruethylet.hylammonium hydroxide dis-places ammonia almost completely from ammonium iodide.Hence itmay be said that any member of the first group can almost completelydisplace any member of the second group from its salts in dilutesolution. A similar relation has been found to hold in the case of thetwo groups of acids, and it may be stated as a general law that strongacids and strong bases in solution in water produce the normd mole-cular reduction of the freezing point (about 40), whilst feeble acidsand feeble bases produce the abnormal molecula,r reduction (about20). It is worthy of note that all the organic acids aiid bases, withthe exception of the hydroxides of organic ammonias, are found inthe second group. The relation which exists between the chemicalenergies of acids and bases and the molecular reduction in the freez256 ABSTRACTS OF CHEMICAL PAPERS.ing point of water, does not however hold good in the case of allsolvents. In the case of certain solvents, acetic acid for example,strong acids, such as sulphuric and hydrochloric acids, produce onlyhalf the reduction in freezing point which is produced by weak acids,such as benzoic acid and phenol.The relation observed in the case ofwater is probably due to the fact that the strong acids and bases havea greater attraction for water, and therefore their molecules are morecompletely separated by solution, whilst the weak acids and baseshave very little attraction for water, and their molecules consequentlyremain united together after solution. most probably in pairs.ThisIwtter supposition would explain the fact that they produce only halfthe normal molecular reduction. C. H. B.Perfect Elasticity of Solid Bodies : a New Relation betweenSolids and Liquids and Gases. By W. SPRING (Ber., 16, 2723-2728).-The author has subjected a large number of metals andmetallic salts to a pressure of 20,000 atmospheres, and determinedtheir density before and after the operation. As a rule no alterattionin density and, consequently, no permanent change in volume, is pro-duced by the pressure, excepting that due to cavities in the solids. Ifthe solid is capable of existing in a denser allotropic modification,ihen a permanent compression ensues.When a bar of metal is bent, the concave portion experiences pres-sure and the convex undergoes expansion.If the bar remains curvedafter the force which altered its shape is removed, the result is due toa passage of matter from the concave to the convex side. The limitof elasticity of a solid is the critical moment at which the particlesbegin to " flow " under the influence of the forces exerted on them.A body is brittle when its particles no longer have the power of w. c. w.Determination of Atomic Weights by Means of MetallicSulphates. Atomic Weights of Copper, Zinc, and Nickel. ByH. BAUBIGNY (Cornpt. reyd., 97, 854-856, 906-908, 951-954).-The principal source of error in previous determinations of the atomicweights of metals by means of their sulphates has been the difficultyof expelling the last traces of free acid and moisture without at thesame t4ime partially decomposing the sulphate.The author finds thatall sulphates, with the exception of those of gold and tho platinummetals, may be heated for several days at 4M0, the temperature ofIioiling sulphur, without undergoing any decomposition, and that,even at this high temperature some sulphates lose the last tracesof free acid very slowly. By this method the preparation of sul-phates in a definite form is easier than the preparation of chlorides.Ferric sulphate, for example, can readily be obtained quite purea s a white salt with a pinkish tinge. The normal anhydrous sul-phates thus obtained can be completely converted into oxides byheating them at a high temperature in a platinum boat placed insidea platinurn tube heated by a muffle, one end of the tube being open tothe air.The use of the platinum tube renders it easy to ascertainwhether any spirting has taken place, and also protects the oxide" flowiug " under pressureGENERAL AND PHYSICAL CHEMISTRY. 257from the reducing gases of the furnace. Tn an actual determinat'ion,the purified sulphate is placed in a weighed platinum boat, and thelatter is placed inside a glass tube which is heated in sulphur vapouruntil the sulphate ceases to lose weight. The boat with its contentsis then put inside the platinum tube in the muffle and heated untilall the acid is expelled. After the residual oxide has been weighed,it is dissolved in hydrochloric acid and the solution tested withbarium chloride.This method is of course inapplicable to sulphateswhich volatilise without decomposition, or to sulphates which yieldoxides which are volatile a t high temperatures, like those of bariumand strontium. In such cases the synthetical method must beadopted, the last traces of water and free acid being expelled byheating at 440".The atomic weights given below have been calculated on theassumption that the atomic weight of oxygen is 16.Copper.-Pure metallic copper or pure artificial atacamite was dis-solved in dilute sulphuric acid, and the solution carefully evaporated.Determinations were made with the first crop of crystals, and alsowith the residue obtained by evaporating the mother-liquor left afterthe separation of a second crop of crystals.The mean of the deter-minations is Cu = 63.468 if S = 32.074, or Cu = 63.396, ifS = 32.Zinc.-Distilled zinc was treated with a quantity of sulphuric acidinsufficient to dissolvc it, and the filtered solution was evaporated todryness. The residue was heated a t 440", dissolved in water, aportion of the zinc precipitated by hydrogen sulphide, and the liquiddigested with the precipitate for eome tinie in order to remove cad-mium, lead, &c. The liquid was then tiltered, the zinc precipitatedas sulphide, the precipitate washed with very dilute sulpburic acid,a,nd then dissolved in sulphuric acid, and the solution evaporated.The mean of the determinations is Zn = 65.403 if S = 32.074, orZn = 65*334* if S 32.NickeZ.--The commercial nitrate was very carefully purified, andwas eventually convert,ed into the anhydrous sulphide by saturatinga solution of t'he sulphate with hydrogen sulphide, and beating itin closed vessels a t 100".The nickel sulphide thus obtained wasdissolved i n aqua regia and the solution evaporated with excess ofsulphuric acid. Nickel sulphate obstinately retains traces of freeacid even at 440°, and prolonged heating is necessary in order toobtain i t perfectly pure. The monoxide left on ignition of the sul-phate has no tension of dissociation at the melting point of gold,even in a vacuum. The mean of the determinations is Ni = 58.748if S = 32.074, or Ni = 58.678 i f S = 32. C. H. B.Molecular Weight of the Amiiies : Trimethylamine. ByJ. DEWAR and A.SCOTT (Proc. Roy. Xoc., 35, 347--349).-The sub-stituted ammonias are peculiarly fitted to reveal the small differencesfrom whole numbers in the conjoint values of atomic weights ofcarbon and hydrogen. By selecting arnines of sufficiently high* Note 7y Abstractor.-This number is identical with that recently obtained byMarignac (Zeitsch. Anal. Chem., 1884, 133).VOL. XLJ.1. 258 ABSTRACTS OF CHEMICAL PAPERS.molecular weights, butylamine for example, it is possible t o integratethese m a l l positive and negative increments : and, theoreticallv, itshould be possible to ascertain whether the atomic weight ofhydrogen differs from unity, when 0 = 16 is taken as the standard,provided the atomic weight of carbon be accepted as sufficiently welldefined by independent investigations.The crude base mas trans-formed into tetrethylammoniun~ bromide, decornposed by dry dis-tillation, separated from the chloride with potassium hydroxide, andfi-actionally distilled. The portion boiling between 90-91" was treatedwith nitrous acid to eliminate traces of the primary and secondaryamines, and finally converted into the bromide. The relation betweenthis salt, Et3NHHr, and silver was then determined, and the averageresult of fairly coricordant experiments gave as the molecular weightof the bromide 182.012. The value for triethylammonium is 102.061 ;and if fi-om this be subtracted Stas' value for amrnonium, 18.074, theresultant, 83.987, is the molrcular weight of the hydrocarbon C,H,,.These results are sufficient to prove that if the atomic weight ofhydrogen be taken as unity, the atomic weight of carbon is 12, andthus the addition of 6 atoms of carbon to 12 of hydrogen results in acompuund, whose molecular weight is the integer 84. But this valnemay be due to the summation of positive and negative variationsfrom the respective values 12 or 1 respectively.This investigation will be continued, and Schutzenberger's hypo-thesis on the variability of the atomic weight of carbon will be niadethe subject of a future discussion. V. H. V.Demonstration of the Increase of Weight of Bodies onCombustion. By M. ROSENFELD (Ber., 16, 27s-2758) .-In ordert o show the increase in weight which potassium, sodium, magnesium,tinfoil, sulphur, carbon, and a taper undergo on combustion, theauthor employs a Nicholson's areometer instead of a balance.In the experiment with tinfoil, it is necessary to affix a thin iron o rbrass wire (25 cm. long) across the pan of the areometer. The tinfoilhangs on each end of this wire.For sulphur and charcoal, a small tube containing soda-solution isused. The tube is closed by a cork through which two narrow tubespass ; the longer tube dips into the soda. The sulphur or charcoaland the absorption tube are placed on the scale of the areometer.The sulj'hur is then brought into a hard glass tube, through whichoxygen is passed. The tube is heated, and the products of combus-tion are passed into the absorption tube, which is again placed ou theareometer after the experiment. A somewhat similar arrangementis used in the case of the taper. w. c. w.Lecture Experiments. By M. ROSENFELD (Bet-., 16, 2750-2752).-I. The preparation of mercuric oxide niny be shown by heat-ing potassium amdgam a t 225" in a long-necked flilsk. The flask isclosed by a cork through which two tubes are inserted. One tubedipping down to the surface of the mercury is connected with a gaso-meter filled with oxygen. Through the second tube, the excess oINORGANIC CHEMISTRY. 259oxygen escapes into a cylinder filled with water, standing in apneumatic trough.11. Zinc oxide is prepared by melting about 40 grams of ziiic in aflat evaporating basin. A small piece of sodium is added, and acurrent of air is forced on the surface of the metal.111. To obtain nitrogen from the air, the author recommends thatthe oxygen should be removed by means of a sheet of buriiiiig tin-foil. w. C.W

ISSN:0368-1769    

DOI:10.1039/CA8844600241

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. I n o r g a n i c Chemistry. 259 Purification of Hydrochloric Acid. By E. BENSEMANN (Arch. Phnrrn. [3], 21, 291).-Hydrochloric acid can be entirely freed from arsenic by diluting it with water, adding potassium chlorate in small quantity, and warming the liquid. On distilling this mixture, hydro- chloric: acid free from arsenic is obtained, but of course it contains free chlorine. W. R. D. Some Reactions of Ozone. By A. WAGNER (Zeds. Anal C'hen?., 22, 316-318).-0n placing a piece of filter-paper, soaked in a boiling ethereal solution of anthracene, in a, bottle containing phos- phorus partially covered with water, anthraquinone is formed. Similar treatment causes aniline hydrochloride to turn brown, whilst exposure to air through which strong electric sparks are passing, produces a reddish-brown colour.In like manner diphenylamine gives a deep brown when the ozone is produced by phosphorus, and a lemon-yellow when the electrical discharge is used. Diphenylaniine- sulphoiiic acid similarly treated becomes blue, passing into green in the former case, and deep blue in the latter. By W. SPRING ( B e d . Centr., 1883, 289-291). --E'resh distilled water in tubes S metres x 4 CM. appears of il sky-blue colour, which however changes after a few hours to a pale green ; but if 0.~001 of mercuric chloride is added to the original water, no change occurs; if it he added to the green water, a blue-green tint is obtained, but never the original colour; it is therefore concluded that, the change from blue to g-een is effected by minute organisms.A beam of light sent through the column of water is invisible (later- ally ?), consequent~ly the colour is natural to the water and not to reflection from minute particles. Amy1 and ethyl alcohol, and acetic acid are colourless. Pure blue water trcated with lime and theri with carbonic anhydride appeared a t first black, changing to brown, jellow, and green ; similar results were obtained with baryta-water contain- ing free silicic acid alid sodium silicate. The final conclusions drawn are :-light does not pass through a thick layer of water containing solids in suspension ; the yellow colour is due to suspended matter, or to that matter forming a saturated solution; as carbonates are P. F. F. CoIour of Water. t 22 60 ABSTRACTS OF CHEMICAL PAPERS. deposited, the colour approaches more nearly to blue.In natural blue waters, calcium and magnesium carbonates, silica and alumina are in solution ; whilst in the green they are partly undissolved through a deficiency in the carbonic anhydride. I n t'he blue Rhine we have 786 CaC03 and 79.5 CO,, whilst in the green Rhine 1056 CaCOJ and 76 CO,. E. W. P. Hydrated Carbon Bisulphide. By F. P. VENARLE (Amer. Chem. J., 5, 15-19) .-The author confirms Ballo's statement that the white substance obtained by the rapid evaporation of carbon bisulphide is a hydrate, as it cannot be formed in dry air under conditions similar t o those in which it is readily formed in moist air. The tem- perature of -12", given by Wartha as that of its formatmion or decomposition, does not appear to be correct.(For previous experi- ments on this subject see Watts's Dictionary, Suppl. 2, 264.) Modification of Noack's Method of Preparing Carbonic Oxide. By L. P. KINNICUTT (Amer. Chem. J., 5, 43--44).-Noack has recently shown that carbonic oxide can be prepared by passing carbonic anhydride over heated zinc-dust (Ber., 16, 7ii). It may however be prepared mpre convenieutlg by heating a mixture of mag- uesite with twice its wdght of zinc-dust. After the first five minut'es, the gas is nearly pure carbonic oxide. Manufacture of Phosphoric Acid. By E. W. RUNYON (Pharm,. Jourrz. [3], 14, 48).-The preparation of phosphoric acid free from arsenic has hitherto been a matter of difficulty, as commercial phos- phorus is always contaminated with arsenic, which is not removed in the ordinary process of oxidation by nitric acid.It. has been pro- posed to remove the arsenic from the acid thus prepared by hydrogen sulphide, b u t the author finds that owing to the long time occupied in removing every trace of arsenic, this method is not a practicable one. He recommends the process proposed by Wenzell, which depends on the aerial oxidation of the phosphoras by exposure in trays in presence of water : full details of the apparatus used are given in the paper. The solntion of phosphorous acid obtained is heated, where- upon the arsenic separates in the meiallic condition, and after being kept a t a temperature of about 190" for 30 minutes, the separation is complete, This liquid (sp. gr. 1.75) is diluted with an equal bulk of water, filtered through paper, and oxidised by nitric acid in the ordinary way.W. R. D. A. J. G. A. J. G. Borax in California. By AYRES (Arch. Pharm. [3], 21, 297).- The borax imported from California is principally obtained from two lakes, Borax Lake and Clear Lake, which are about 80 miles north of San Francisco. Borax Lake is about three-quaaters of a mile long, and has an average depth of four feet. Crystals which were taken from the mud a t the bottom were found to be pure sodium pyro- borate ; 1.077 gram of total solid residue were yielded by 30 grams of the water. This residue contained 0.618 gram of sodium carbonate. v 0.204 gram of sodium chloride, and 0.175 gram of borax. W. R. D.INORGANIC CHEMISTRY. 2 61 Silver Nitrate and Ammonia.By A. REYCHLER (Bey., 16, 242 I.-2424) .--M-onammonia silver nitrate, AgNO,NH,, was described by the author (Abstr., 1883, 902) as a nitrate of argentammonium, a view which is found to be incompatible with the behaviour of this compound when treated with ethyl iodide. Ethyl iodide reacts with it at the ordinary temperature, heat being evolved, and silver iodide, ethyl nitrate, and diammonia silver nitrate formed, thus :- 2AgNO3,NH, + nEtI = AgI + Et.NO3 + AgNO,,(NH,), + (n--1)Etl. The diammonia silver nitrate is also acted on by ethyl iodide, with AgN03,(NH3)2 + nEtI = AgI + EtN03 + 2NH3 + (n-1)EtI. Some ethylamine is also produced by the action of the ammonia on the ethyl nitrate and ethyl iodide. I f monammonia silver nitrate were a derivative of argentammonium, then ethyl iodide would react with it, so as to form ethylnmine nitrate, a s follows:- AgNH,.N03 + EtJ = AgI + NEtH3.N03. Butl in light of the above reactions, the author is inclined to regard monammonia silver nitrate either as a molecular compound of ammo- nia with silver nitrate, or as a compound having the following con- stitution : OH.NO(NH2).0Ag. formation of silver iodide, ethyl nitrate, and ammonia, thus :- P.P. B. Atomic Weight of Beryllium. By J. E. REYNOLDS (Proc. Roy. Soc., 35,248-2SO).-Although specimens of beryllium used for deter- minations of the specific heat of the metal were impure, yet the results are all in one direction, that is, indicating apparent gain in specific heat with increased purity of material. “he spectroscopic evidence of Hartley (Trans., 1883, 316) shows that beryllium is the first member of a dyad series of elements, of which calcium, barium, and strontium are probably homologues.Thus two independent .methods of research tend to prove that the atomic weight of 9.2 is the more correct, and that berylliiim is the first member of Mendelejeff’s second series of elements. V. H. V. Reply to the Above Paper. By T. S . HUMPJDGE (PTOC. Roy. Xoc., 35, 358--359).-1n this paper, exception is taken to the state- ment of Reynolds that the results of determinations of the specific heats of beryllium are higher, the less the proportion of impurities. But even admitting this, it is hardly probable that the specific heat of the fused metal could be 50 per cent. greater than that of the crys- talline metal.The author has prepared purer samples, analyses of which are promised. As regards the observations of Hartley, the slight spectroscopic resemblance between beryllium and the alkaline earth-metals can hardly outbalance all the weighty chemical and physical differences between them ; and even if beryllium is a dyad, its nearest homologues are decidedly magnesium and zinc, not calcium, strontium, and barium. V. H. V.262 ABSTRACTS OF CHEMICAL PAPERS. Diffusion of Didymium. By A. COSSA (Gaxzetta, 13, 280).- Thid metal, besides being found in apatites, scheelite, and various kinds of limestone, occurs in large quantity in the sphene of the syenite of the Biellese and of the Collegno limestone. The frequent association of didyminm-compounds with those of calcium in homo- geneous and perfectly crystallised minerals is regarded by Cossa as a confirmation of his opinion, that didymium, a t least in compounds in which it is associated with calcium, may be regarded as a bivalent metallic radicle.H. W. Magnesium Bromide and Iodide. By 0. LERCH (,T.pr. Chent. [ 21, 28, 338-356).-Although magnesium bromide has been pre- pared by the action of bromine vapour on a strongly heated mixture of carbon and magnesium oxide, it could never, owing to its non- volatility, be purified and analysed. The author has observed that bromine vapour combines directly with magnesium with the greatest readiness at a very high temperature, namely, a t the melting point of the metal. By heating small pieces of magnesium in a vertical hard glass tube before the blowpipe, SO that only the lower end of the tube is heated, and admitting bromine vapour by a smaller tube passing through the magnesium almost to the bottom of the larger tube, mag- nesium bromide may be obtained in quantity.The greatest caution is required in this dangerous operation. Magnesiunz bromide is a white crystalline mass, having the appearance of magnesium chloride. It is easily oxidised on exposure to air, is not volatile, and is more hygro- scopic than the chloride. Analysis agrees with the formula MgBr, ; hut owing to the action of this metal on glass at a high temperature, the estimated quantity of bromine is slightly lower than that calcu- lat'ed. The salt was also obtained by evaporating a solution of hydrated magnesium bromide and ammonium bromide to dryness, and driving off the latter by heat; also by melting anhydrous mag- nesium chloride with ammonium bromide.Magnesiunz Iodide.-This salt was also obtained by heating pieces of magnesium in a vertical tube to the melting point, and adding slowly small quantities of iodine ; the reaction takes place with great violence. The iodide sinks below the molten metal, and also some- what attacks the glass. It has the same appearance as the bromide, but melts at a higher temperature, and is more readily oxidised on exposare to the air. The salt was also obtained from hydrated magnesium iodide and ammo- nium iodide, and by melting magnesium chloride with ammonium iodide. Hydrated magnesium bromide is obtained by the action of bromine on magnesium dust and water.Crystallised over sulphuric acid, it is obtained in hygroscopic crystals, and analysis agrees with the formula MgBr, + 6H20. Hydrated magnesium iodide, obtained in a similar way to the above, has the formula MgT, + 8H20. Nagnesizrm potassizcm bromide was formed by adding to a known quantity of hydrated magnesium bromide sufficient potassium bromide to form the double salt 2(KBr),MgBr2 + 6H20, as mentioned by Analysis agrees with the formula MgI,,INORGANIC CHEMISTRY. 2 63 Lowig (Xepert., 29,261). On evaporating the solution over sulphuric acid, potassium bromide containing only 2 per cent. magnesium lwomide crystallised out a t first, and for some time after crystals con- taining no definite quantity of magnesium bromide were obtained ; finally, however, a salt was obtained of a composition similar to that of carnallit>e, KCl,MgCl, + 6H,O.Analysis agreed with the formula KBr,MgBr2 + 6H,O. A deficiency of over 2 per cent. of bromine was observed ; but on analysis of carnallite prepared by crystallisation from its mother-liquor, there was a similar deficiency of chlorine, probably owing in both cases to the difficulty of purifying the very deliquescent crystals. Magnesium ammonium bromide . . MgBr2,NH4Br + 6H,O MagrLesium potassium i o d i d e . . . . . . Magnesium ammonium iodide . . . . BlgIa,NHiI + 6&0. Mgl,,KI + 6H20 The halogen compounds of magnesium are similar in their behaviour towards water, in melting only a t a high temperature, and in soli- difying to crystalline masses; they differ in their behaviour to the air, for whilst the chloride is but slowly decomposed at the melting point, the bromide is more easily decomposed and the iodide with great rapidity at ordinary temperatures.The hydrated and double halts show the same characteristics respectively as do the halogen compounds. The author purposes continuing his investigation. A. B. Cadmium Oxide. By J. TEOXSEN (Bey., 16, 2616).-The author has shown that hydrochloric, hydrobromic, and hydriodic acids ex- hibit the same heat of neutralisation with sodium hydroxide in ayneous solution, and that practically the same result is obtained when the ahove acids are neutralised with baryta, magnesia, zinc oxide? and copper oxide. Cadmium oxide is distinguished from the magnesium group by many of its chemical properties, and by its heat of neutralisation, which is greater for hydrohromic than f o r hydrochloric acid, and greater for hydriodic than for hydrobromtc acid: in this respect it bears more resemblance to the heavy metals :- Cd0,H2,2HC1Aq = 20,290 c.CdO2H,,2HBrAq = 21,560 ,, Cd0,H2,2111Aq = 24,210 ,, A. I(. M. Spontaneous Oxidation of Mercury. By D. MACALUSO (Gazzettu, 13, 48548Y).--The author has shown, by a series of careful expe- riments, that mercury is not oxidised by exposure to pure dry air or to pure aqueous vapour, but that in a mixture of the two, oxidation takes place, with production of the well-known grey pellicle of sub- oxide. This action is analogous to the formatlion of mercurous chloride when mercury is left in contact with gaseous hydrogen chloride or its aqueous solution in presence of air, whereas in pure hydrogen chloride, or its pure aqueous solution perfectly deprived of air, no such formation takes place. H.W.264 ABSTRACTS OF CHEMICAL PAPERS. Double Fluorides and Oxyfluorides of Titanium. By A. PICCINI (Compt. rend., 97, 1064-1067) .-When an aqueous solution of titanium trichloride is added gradually to a concentrated solution of ammonium fluoride, or, better, when a solution of the normal fluotitanate in a solution of ammonium fluoride is reduced by electro- lysis, the compound TiF,,3NH4F is obtained as a crystalline violet precipitate, slightly soluble in water, but insoluble in a solution of ammonium fluoride. If this precipitate is washed successively with water, a concentrated solution of ammonium fluoride, and strong alcohol, and exposed to the air, its violet cnlour changes t o dirty yellow, and when perfectly dry, it has a deep yellow colour.This yellow substance dissolves completely in water, but the solution de- composes even a t the ordinary temperature with evolution of bubbles of gas. When the aqueous solution is evaporated in a vacuum or by exposure to air, small brilliant transparent yellow regular octohedrons are obtained, often mixed with very slender yellow needles. If, however, the aqueous solution is mixed with ammonium fluoride, a, Frecipitate is obtained which consists of the regular octohedrons alone, These crystals are insoluble in a solution of ammonium fluoride, but dissolve readily in water, forming a golden-yellow solution, which, when acidified with dilute sulphuric acid, bleaches, and is bleached by a solution of potassium permangasate, with evolution of oxygen.Ammonia produces a yellow flocculent precipit,ate, soluble in cold dilute sulphuric acid with formation of a reddish-yellow solutiou, which behaves in a similar manner with a solution of potassium per- manganate. If the reddish-yellow solution is mixed with potassium hydrofluoride, a, portion of the titanium is precipitated as TiF4,2KF + HzO, and the liquid is decolorised and gives Barreswil’s reaction. The octohedral crystals have the composition Ti02Fz,SNH4F, and it would appear that the oxygen is irr a condition similar to that in which it exists in hydrogen peroxide. This compound is the first example of a substance passing from a lower form to the highest form, in pre- sence of the most stable or normal compound.As prepared by expo- sure to air, the yellow substance contains a considerable proportion of normal fluotitnnale, and it is probably Formed in accordance with the equation 2(TiF,.SNH4F) + 0 2 = TiP4,3NHJ + TiOzF,:3NH4F, the violet compound absorbing oxygen and splitting up into the normal salt and the oxysalt. When hydrogen peroxide is added to a sulphuric acid solution of titanic acid in the proportion TiOz : Hz02, a reddish-yellow liquid is obtained, which gives Barreswil’s reaction on adding a further sn~all quantity of hydrogen peroxide. I f the liquid is now neutralised with ammonia, a yellow solution is obtained, from which neutral ammonium fluoride precipitates yellow octohedra identical with those obtained by the other method.If sufficient ammonium fluoride is not presenq the liquid remains slightly coloufed, and when evapo- rated in presence of air, it deposits very slender yellow needles similar to those obtained by the first method. These needles consist of a hydrated oxyfluoride containing less fluorine than the octohedral compound. This series of oxyfluorides throws light on the nature of the reac-MINERALOGICAL CHEMISTRY. 265 tion between titanic acid and hydrogen peroxide. They are evidently derived from the radicle of the acid formed by TiO,, in which an atom of oxygen has been replaced by two atoms of fluorine, as i n the case of the oxyflnomolybdates and the oxyfluotungstates. They differ in constitution from the latter, however, in that they correspond with a higher state of oxidation.The octohedral salt is decolorised by hydrofluoric acid, the oxygen being replaced by fluorine atom for atom, that is to S H Y , the couple 0, is equivalent to two atoms of fluorine: TiO,F, + 'LHF = TiF4 + H,Oz. I n crystalline form, the compound TiOzFz,3NH4F is analogous to NbOP3,3NH,F, which cou- titins the same number of atoms. C. H. B.INORGANIC CHEMISTRY.I n o r g a n i c Chemistry.259Purification of Hydrochloric Acid. By E. BENSEMANN (Arch.Phnrrn. [3], 21, 291).-Hydrochloric acid can be entirely freed fromarsenic by diluting it with water, adding potassium chlorate in smallquantity, and warming the liquid. On distilling this mixture, hydro-chloric: acid free from arsenic is obtained, but of course it containsfree chlorine.W. R. D.Some Reactions of Ozone. By A. WAGNER (Zeds. Anal C'hen?.,22, 316-318).-0n placing a piece of filter-paper, soaked in aboiling ethereal solution of anthracene, in a, bottle containing phos-phorus partially covered with water, anthraquinone is formed.Similar treatment causes aniline hydrochloride to turn brown, whilstexposure to air through which strong electric sparks are passing,produces a reddish-brown colour. In like manner diphenylaminegives a deep brown when the ozone is produced by phosphorus, and alemon-yellow when the electrical discharge is used. Diphenylaniine-sulphoiiic acid similarly treated becomes blue, passing into green inthe former case, and deep blue in the latter.By W.SPRING ( B e d . Centr., 1883, 289-291).--E'resh distilled water in tubes S metres x 4 CM. appears of il sky-bluecolour, which however changes after a few hours to a pale green ; butif 0.~001 of mercuric chloride is added to the original water, nochange occurs; if it he added to the green water, a blue-green tint isobtained, but never the original colour; it is therefore concludedthat, the change from blue to g-een is effected by minute organisms.A beam of light sent through the column of water is invisible (later-ally ?), consequent~ly the colour is natural to the water and not toreflection from minute particles. Amy1 and ethyl alcohol, and aceticacid are colourless. Pure blue water trcated with lime and theri withcarbonic anhydride appeared a t first black, changing to brown, jellow,and green ; similar results were obtained with baryta-water contain-ing free silicic acid alid sodium silicate.The final conclusions drawnare :-light does not pass through a thick layer of water containingsolids in suspension ; the yellow colour is due to suspended matter,or to that matter forming a saturated solution; as carbonates areP. F. F.CoIour of Water.t 2 60 ABSTRACTS OF CHEMICAL PAPERS.deposited, the colour approaches more nearly to blue. In natural bluewaters, calcium and magnesium carbonates, silica and alumina are insolution ; whilst in the green they are partly undissolved through adeficiency in the carbonic anhydride. I n t'he blue Rhine we have786 CaC03 and 79.5 CO,, whilst in the green Rhine 1056 CaCOJ and76 CO,. E.W. P.Hydrated Carbon Bisulphide. By F. P. VENARLE (Amer. Chem.J., 5, 15-19) .-The author confirms Ballo's statement that the whitesubstance obtained by the rapid evaporation of carbon bisulphideis a hydrate, as it cannot be formed in dry air under conditionssimilar t o those in which it is readily formed in moist air. The tem-perature of -12", given by Wartha as that of its formatmion ordecomposition, does not appear to be correct. (For previous experi-ments on this subject see Watts's Dictionary, Suppl. 2, 264.)Modification of Noack's Method of Preparing CarbonicOxide. By L. P. KINNICUTT (Amer. Chem. J., 5, 43--44).-Noackhas recently shown that carbonic oxide can be prepared by passingcarbonic anhydride over heated zinc-dust (Ber., 16, 7ii). It mayhowever be prepared mpre convenieutlg by heating a mixture of mag-uesite with twice its wdght of zinc-dust.After the first five minut'es,the gas is nearly pure carbonic oxide.Manufacture of Phosphoric Acid. By E. W. RUNYON (Pharm,.Jourrz. [3], 14, 48).-The preparation of phosphoric acid free fromarsenic has hitherto been a matter of difficulty, as commercial phos-phorus is always contaminated with arsenic, which is not removed inthe ordinary process of oxidation by nitric acid. It. has been pro-posed to remove the arsenic from the acid thus prepared by hydrogensulphide, b u t the author finds that owing to the long time occupiedin removing every trace of arsenic, this method is not a practicableone.He recommends the process proposed by Wenzell, which dependson the aerial oxidation of the phosphoras by exposure in trays inpresence of water : full details of the apparatus used are given in thepaper. The solntion of phosphorous acid obtained is heated, where-upon the arsenic separates in the meiallic condition, and after beingkept a t a temperature of about 190" for 30 minutes, the separation iscomplete, This liquid (sp. gr. 1.75) is diluted with an equal bulkof water, filtered through paper, and oxidised by nitric acid in theordinary way. W. R. D.A. J. G.A. J. G.Borax in California. By AYRES (Arch. Pharm. [3], 21, 297).-The borax imported from California is principally obtained from twolakes, Borax Lake and Clear Lake, which are about 80 miles northof San Francisco.Borax Lake is about three-quaaters of a mile long,and has an average depth of four feet. Crystals which were takenfrom the mud a t the bottom were found to be pure sodium pyro-borate ; 1.077 gram of total solid residue were yielded by 30 grams ofthe water. This residue contained 0.618 gram of sodium carbonate. v 0.204 gram of sodium chloride, and 0.175 gram of borax.W. R. DINORGANIC CHEMISTRY. 2 61Silver Nitrate and Ammonia. By A. REYCHLER (Bey., 16,242 I.-2424) .--M-onammonia silver nitrate, AgNO,NH,, was describedby the author (Abstr., 1883, 902) as a nitrate of argentammonium, aview which is found to be incompatible with the behaviour of thiscompound when treated with ethyl iodide. Ethyl iodide reacts withit at the ordinary temperature, heat being evolved, and silver iodide,ethyl nitrate, and diammonia silver nitrate formed, thus :-2AgNO3,NH, + nEtI = AgI + Et.NO3 + AgNO,,(NH,), +(n--1)Etl.The diammonia silver nitrate is also acted on by ethyl iodide, withAgN03,(NH3)2 + nEtI = AgI + EtN03 + 2NH3 + (n-1)EtI.Some ethylamine is also produced by the action of the ammonia onthe ethyl nitrate and ethyl iodide.I f monammonia silver nitrate werea derivative of argentammonium, then ethyl iodide would react with it,so as to form ethylnmine nitrate, a s follows:-AgNH,.N03 + EtJ = AgI + NEtH3.N03.Butl in light of the above reactions, the author is inclined to regardmonammonia silver nitrate either as a molecular compound of ammo-nia with silver nitrate, or as a compound having the following con-stitution : OH.NO(NH2).0Ag.formation of silver iodide, ethyl nitrate, and ammonia, thus :-P.P. B.Atomic Weight of Beryllium. By J. E. REYNOLDS (Proc. Roy.Soc., 35,248-2SO).-Although specimens of beryllium used for deter-minations of the specific heat of the metal were impure, yet the resultsare all in one direction, that is, indicating apparent gain in specificheat with increased purity of material. “he spectroscopic evidenceof Hartley (Trans., 1883, 316) shows that beryllium is the firstmember of a dyad series of elements, of which calcium, barium, andstrontium are probably homologues. Thus two independent .methodsof research tend to prove that the atomic weight of 9.2 is the morecorrect, and that berylliiim is the first member of Mendelejeff’s secondseries of elements.V. H. V.Reply to the Above Paper. By T. S . HUMPJDGE (PTOC. Roy.Xoc., 35, 358--359).-1n this paper, exception is taken to the state-ment of Reynolds that the results of determinations of the specificheats of beryllium are higher, the less the proportion of impurities.But even admitting this, it is hardly probable that the specific heat ofthe fused metal could be 50 per cent. greater than that of the crys-talline metal. The author has prepared purer samples, analyses ofwhich are promised. As regards the observations of Hartley, theslight spectroscopic resemblance between beryllium and the alkalineearth-metals can hardly outbalance all the weighty chemical andphysical differences between them ; and even if beryllium is a dyad,its nearest homologues are decidedly magnesium and zinc, not calcium,strontium, and barium.V. H. V262 ABSTRACTS OF CHEMICAL PAPERS.Diffusion of Didymium. By A. COSSA (Gaxzetta, 13, 280).-Thid metal, besides being found in apatites, scheelite, and variouskinds of limestone, occurs in large quantity in the sphene of thesyenite of the Biellese and of the Collegno limestone. The frequentassociation of didyminm-compounds with those of calcium in homo-geneous and perfectly crystallised minerals is regarded by Cossaas a confirmation of his opinion, that didymium, a t least in compoundsin which it is associated with calcium, may be regarded as a bivalentmetallic radicle.H. W.Magnesium Bromide and Iodide. By 0. LERCH (,T.pr. Chent.[ 21, 28, 338-356).-Although magnesium bromide has been pre-pared by the action of bromine vapour on a strongly heated mixtureof carbon and magnesium oxide, it could never, owing to its non-volatility, be purified and analysed. The author has observed thatbromine vapour combines directly with magnesium with the greatestreadiness at a very high temperature, namely, a t the melting point ofthe metal. By heating small pieces of magnesium in a vertical hardglass tube before the blowpipe, SO that only the lower end of the tubeis heated, and admitting bromine vapour by a smaller tube passingthrough the magnesium almost to the bottom of the larger tube, mag-nesium bromide may be obtained in quantity. The greatest caution isrequired in this dangerous operation.Magnesiunz bromide is a whitecrystalline mass, having the appearance of magnesium chloride. Itis easily oxidised on exposure to air, is not volatile, and is more hygro-scopic than the chloride. Analysis agrees with the formula MgBr, ;hut owing to the action of this metal on glass at a high temperature,the estimated quantity of bromine is slightly lower than that calcu-lat'ed. The salt was also obtained by evaporating a solution ofhydrated magnesium bromide and ammonium bromide to dryness,and driving off the latter by heat; also by melting anhydrous mag-nesium chloride with ammonium bromide.Magnesiunz Iodide.-This salt was also obtained by heating piecesof magnesium in a vertical tube to the melting point, and addingslowly small quantities of iodine ; the reaction takes place with greatviolence.The iodide sinks below the molten metal, and also some-what attacks the glass. It has the same appearance as the bromide,but melts at a higher temperature, and is more readily oxidised onexposare to the air. Thesalt was also obtained from hydrated magnesium iodide and ammo-nium iodide, and by melting magnesium chloride with ammoniumiodide.Hydrated magnesium bromide is obtained by the action of bromineon magnesium dust and water. Crystallised over sulphuric acid, itis obtained in hygroscopic crystals, and analysis agrees with theformula MgBr, + 6H20.Hydrated magnesium iodide, obtained in a similar way to theabove, has the formula MgT, + 8H20.Nagnesizrm potassizcm bromide was formed by adding to a knownquantity of hydrated magnesium bromide sufficient potassium bromideto form the double salt 2(KBr),MgBr2 + 6H20, as mentioned byAnalysis agrees with the formula MgI,INORGANIC CHEMISTRY.2 63Lowig (Xepert., 29,261). On evaporating the solution over sulphuricacid, potassium bromide containing only 2 per cent. magnesiumlwomide crystallised out a t first, and for some time after crystals con-taining no definite quantity of magnesium bromide were obtained ;finally, however, a salt was obtained of a composition similar to thatof carnallit>e, KCl,MgCl, + 6H,O. Analysis agreed with the formulaKBr,MgBr2 + 6H,O. A deficiency of over 2 per cent.of brominewas observed ; but on analysis of carnallite prepared by crystallisationfrom its mother-liquor, there was a similar deficiency of chlorine,probably owing in both cases to the difficulty of purifying the verydeliquescent crystals.Magnesium ammonium bromide . . MgBr2,NH4Br + 6H,OMagrLesium potassium i o d i d e . . . . . .Magnesium ammonium iodide . . . . BlgIa,NHiI + 6&0.Mgl,,KI + 6H20The halogen compounds of magnesium are similar in their behaviourtowards water, in melting only a t a high temperature, and in soli-difying to crystalline masses; they differ in their behaviour to theair, for whilst the chloride is but slowly decomposed at the meltingpoint, the bromide is more easily decomposed and the iodide withgreat rapidity at ordinary temperatures.The hydrated and doublehalts show the same characteristics respectively as do the halogencompounds. The author purposes continuing his investigation.A. B.Cadmium Oxide. By J. TEOXSEN (Bey., 16, 2616).-The authorhas shown that hydrochloric, hydrobromic, and hydriodic acids ex-hibit the same heat of neutralisation with sodium hydroxide inayneous solution, and that practically the same result is obtainedwhen the ahove acids are neutralised with baryta, magnesia, zincoxide? and copper oxide. Cadmium oxide is distinguished from themagnesium group by many of its chemical properties, and by itsheat of neutralisation, which is greater for hydrohromic than f o rhydrochloric acid, and greater for hydriodic than for hydrobromtcacid: in this respect it bears more resemblance to the heavymetals :-Cd0,H2,2HC1Aq = 20,290 c.CdO2H,,2HBrAq = 21,560 ,,Cd0,H2,2111Aq = 24,210 ,, A.I(. M.Spontaneous Oxidation of Mercury. By D. MACALUSO (Gazzettu,13, 48548Y).--The author has shown, by a series of careful expe-riments, that mercury is not oxidised by exposure to pure dry air orto pure aqueous vapour, but that in a mixture of the two, oxidationtakes place, with production of the well-known grey pellicle of sub-oxide. This action is analogous to the formatlion of mercurouschloride when mercury is left in contact with gaseous hydrogenchloride or its aqueous solution in presence of air, whereas in purehydrogen chloride, or its pure aqueous solution perfectly deprived ofair, no such formation takes place.H. W264 ABSTRACTS OF CHEMICAL PAPERS.Double Fluorides and Oxyfluorides of Titanium. By A.PICCINI (Compt. rend., 97, 1064-1067) .-When an aqueous solutionof titanium trichloride is added gradually to a concentrated solutionof ammonium fluoride, or, better, when a solution of the normalfluotitanate in a solution of ammonium fluoride is reduced by electro-lysis, the compound TiF,,3NH4F is obtained as a crystalline violetprecipitate, slightly soluble in water, but insoluble in a solution ofammonium fluoride. If this precipitate is washed successively withwater, a concentrated solution of ammonium fluoride, and strongalcohol, and exposed to the air, its violet cnlour changes t o dirtyyellow, and when perfectly dry, it has a deep yellow colour.Thisyellow substance dissolves completely in water, but the solution de-composes even a t the ordinary temperature with evolution of bubblesof gas. When the aqueous solution is evaporated in a vacuum or byexposure to air, small brilliant transparent yellow regular octohedronsare obtained, often mixed with very slender yellow needles. If,however, the aqueous solution is mixed with ammonium fluoride, a,Frecipitate is obtained which consists of the regular octohedrons alone,These crystals are insoluble in a solution of ammonium fluoride, butdissolve readily in water, forming a golden-yellow solution, which,when acidified with dilute sulphuric acid, bleaches, and is bleachedby a solution of potassium permangasate, with evolution of oxygen.Ammonia produces a yellow flocculent precipit,ate, soluble in colddilute sulphuric acid with formation of a reddish-yellow solutiou,which behaves in a similar manner with a solution of potassium per-manganate.If the reddish-yellow solution is mixed with potassiumhydrofluoride, a, portion of the titanium is precipitated as TiF4,2KF + HzO, and the liquid is decolorised and gives Barreswil’s reaction.The octohedral crystals have the composition Ti02Fz,SNH4F, and itwould appear that the oxygen is irr a condition similar to that in whichit exists in hydrogen peroxide. This compound is the first exampleof a substance passing from a lower form to the highest form, in pre-sence of the most stable or normal compound. As prepared by expo-sure to air, the yellow substance contains a considerable proportionof normal fluotitnnale, and it is probably Formed in accordance withthe equation 2(TiF,.SNH4F) + 0 2 = TiP4,3NHJ + TiOzF,:3NH4F,the violet compound absorbing oxygen and splitting up into thenormal salt and the oxysalt.When hydrogen peroxide is added to a sulphuric acid solution oftitanic acid in the proportion TiOz : Hz02, a reddish-yellow liquid isobtained, which gives Barreswil’s reaction on adding a further sn~allquantity of hydrogen peroxide. I f the liquid is now neutralisedwith ammonia, a yellow solution is obtained, from which neutralammonium fluoride precipitates yellow octohedra identical with thoseobtained by the other method. If sufficient ammonium fluoride isnot presenq the liquid remains slightly coloufed, and when evapo-rated in presence of air, it deposits very slender yellow needlessimilar to those obtained by the first method. These needles consistof a hydrated oxyfluoride containing less fluorine than the octohedralcompound.This series of oxyfluorides throws light on the nature of the reacMINERALOGICAL CHEMISTRY. 265tion between titanic acid and hydrogen peroxide. They are evidentlyderived from the radicle of the acid formed by TiO,, in which an atomof oxygen has been replaced by two atoms of fluorine, as i n the caseof the oxyflnomolybdates and the oxyfluotungstates. They differ inconstitution from the latter, however, in that they correspond with ahigher state of oxidation. The octohedral salt is decolorised byhydrofluoric acid, the oxygen being replaced by fluorine atom foratom, that is to S H Y , the couple 0, is equivalent to two atoms offluorine: TiO,F, + 'LHF = TiF4 + H,Oz. I n crystalline form, thecompound TiOzFz,3NH4F is analogous to NbOP3,3NH,F, which cou-titins the same number of atoms. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8844600259

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. 265 M i n e r a 1 o g i c a 1 C h e m i s t r y. Dopplerite. By A. MAYER (Lardw. Versu,chs.-Xtat., 29, 313- 315).-'l'he sample of dopplerite was obtained from peat beds in Holland : it contained $4.6 per cent. water, and in the dried substance was found 4.2 per cent. ash. The relation of carbon, hydrogen, and oxjgen in the remainder led to the empirical formula C1,HleOs. The ash constituents were chiefly calcium carbonate and ferric oxide. Dopplerite is perfectly soluble in caustic potash or soda, but oiily partially in ammonia. Acids precipitate it from solution, and salts of alkaline earths throw it down in combination with base. A calcium salt was thus obtained having 8.1 per cent. of lime. J. K. C. Natural Fluorine Compounds. By P. GROTH (Jahb. f.&fin,., 1883, 2, Ref., 324---327).-This paper gives a detailed description of the fluorine minerals, analyses of which have already been published by Brand1 (Abstr., 1882, 1176). = 89" 40'. The planes occurring most frequently are mP, OP, + Ex, Pco. The chemical formula calculated from Brandl's analyses is 3NaF,ALF3. Pachnolite is motloclinic : a : b : c = 1.1626 : 1 : 1.5320, 8 = 89- 40'. wP, -€', OP are the planes occurring most frequently. The rhombic section is very characteristic of pachnolite, that of t homsenolite being rectangular. The chemical formula is NaF,CaF,,AlF,. Tliomsenoliteis monoclinic: a : b : c = 0-9$!5!) : 1 : 1.0887, p = 87" 374'. The most iuiportant forms are mP, +- P, OP. The chemical formula is NaF,CaF,,AIF,,H,O. 1. Crlyolite is monoclinic : a : b : c = 0.9662 : 1 : 1.5882, Ralstonite crystallises in octohedrons. 3 ( NaaMgCa)F,, 8A1F,,6H20.Chiolite has the formula FiNaF,SAlF. Arlcszctite is probably a partially altered cryolite, that is a mixture Hagemaimite is probably thomsenolite Gcarksrdite appears to be the The formula is of cryolite and pachnolite. mixed with siliceous brown ironstone.266 ABSTRACTS OF CHEMICAL PAPERS. final product of the alteration of cryolite, whereby Na is replaced by Ca and water taken up. 2. Fluellite is rhombic : Q : b : c = 0.77 : 1 : 1.874. Forms observed are P and OP. 3. Prosopite is monoclinic : a : b : c = 1.318 : 1 : 0.5912, /3 = 86" 2'. Forms observed are mP, mPm, +P, 2P2, gem, -39g, mP2. Tbe formula is CaAl,(FHO),. Sp. gr. = 2-17'. The formula is A1F3 + H20.B. H. B. Zinc Bleade and Prehnite from Cornwall, Lebanon Co., Pa. By F. A. GEBTH (Juhrb. f. -&fin., 1883,2, Ref.,322--323j.-Tncavities of the magnetite from Cornwall Ore Bank, fine crystals of zinc blende occur associated with prehnite, magnetite, iron pyrites, and chlorite. They have a sp. gr. of 4.033, and gave on analysis :- S. Zn. co. Pe. Total. 32.69 66-47 0.34 0.38 913.88 Prehnite forms crystalline incrustations upon magnetite. It has a sp, gr. of 3.042, and gave on analysis :- SiO,. A1103. Pe,03. CaO. H20. Total. 42-40 20.88 5.54 27.02 4.G1 99.85 B. 33. B. Artificial Alisonite. By F. A. GExw (Jahrb. f. Min., 1883, 2, Ref., 324) .-At the smelting works at Argo, Colorado, octohedral crystals have been observed in the furnace bottoms. They have an iron-black colour, metallic lustre, sp.gr. = 5.545, and gave on aualysis the following results :- S. Age CU. Pb. Fe Total. 15-23 2.16 51.33 31-15 trace 9987 E. H. B. Reebanyite, a New Mineral Species. By A. FRENZEL (Juhrb. f. Mi%., 18t'S, 2, Ref., 314).-This mineral occurs at Rezbanya, asso- ciated with cosalite. It has a metallic lustre, a lead-grey colour and black streak. H. = 2.5 to 3. Sp. gr. = 6.09 to6.38. It forms com- pact masses with copper pyrites and calcite, or is disseminated through quartz. From the analyses, the formula, of rezbanyite is calculated to be 4PbS,5Bi,Sj. B. H. R. Alloclasite. By A. FRENZEL (Jahrb. f. Jfin., 1883, 2, Ref., 314- 315).-1n order to determine the composition of' this mineral, which still remains doubtful, the author made six analyses of compact material, and although the results obtained were rather variable, he is of opinion that Groth's formula (CoFe)(AsBi)S, is the correct one for this mineral. B.H. B. Kupfernickel from Colorado. By F. A. GENTH (Jahrb. f. Min., 1883, 2, Ref., 324).-In silver Cliff, Colorado, rounded masses of kupfernickel occur in granular limestone. Sp. gr. = 7.314. The analysis gave :-MINERALOGICAL CHEMISTRY. 267 As. Sb. S. Cu. Ni. Co. Fe. Total. 46.81 2.24 2.52 1.59 44.76 1.70 0.60 100.22 B. H. B. Corundum. By F. A. GENTH (Jahrb. .f. Min., 1883, 2, Ref., 316 -319) .-This paper is a description of a few remarkable occurrences, as a continuation of the paper formerly published by the author (this Joiir., 18 74, 549). 1. Comndwn altered into spinel is found at the Carter Mine, Madi- son Co., N.C.The spinel finally passes into chlorite. The analysis, aRer deducting silica and corundum, gave the follow- It has a sp. gr. of 3.751. ing results :- A1203. Fe,O,. CuO. NiO. ZnO. FeO. MgO. Total. 66.74 1-34 0-09 0.33 0.22 11.94 19.34 100.00 Corundum altered to a slight extent into spinel has also been found After deducting at Shimersviile in Lehigh Go. 1.47 per cent. Si02, the analysis gave :- Sp. gr. = 4.056. A1203. Fep03. FeO. MgO. TiOP Total. 56.42 13.17 22-95 4.94 2.62 100.10 2. Corundum altered into zoisite is of rare occurrence. 3. Corundum altered into felspar and dmrnwurite occurs at Unions- ville. The analysis gave :- SiO,. Al,O,. Fe,O,. MgO. CaO. Ka20. K20. Ignition. Total. 62.62 22.59 0.22 0.18 1.94 7.41 2.52 2.45 99.1.13 Another interesting occurrence is that at the Black Horse Tavern, Sp.gr. = 2.611. The analysis gave :- near Media in Delaware CCL SO2. Al,O,. Be203. MgO. CaO. BaO. Na20. KgO. Ignition. Total. 58-42 23-14 0.18 O*S5 3.13 2.56 3-68 7.06 1.54 100.06 The Presley Mine in Hajwood Co., N.C., has furnished some remarkable specimens of corundum altered into albite and muscovite. Aiialybes of the albite (I) and of the muscovite (11) are given :- SiO,. A120,. Fez03. MgO. CaO. Nit,O. KyO. Ignition. Total. I. 65.52 22-25 trace - 1-96 9-54 0.53 022 100.02 11. 45.26 36.33 1.96 0.14 0.35 0.48 11-OH 4.50 100.11 Corundum altered chiefly into damourite has been found at Belt's Bridge, Iredell Go., N.C. After deducting 3.51 per cent. of corundum, the analysis of the mica gave :- SiO,.Al,O,. Fe203. CaO. Li20. Na@. K@. Ignition. Total. 45-96 38.22 0.61 0.37 trace 0.74 9.21 4.89 100-00 From the same locality a fragment of a hexagonal prism was found. It consisted of a core of grey corundum surrounded by mica enclosing268 ABSTRACTS OF CHEMICAL PAPERS. tourmaline, and disseminated through the unaltered tourmaline are rounded masses of garnet. SiOz. A1203. Fe203. CaO. Li20. Na20. K20. Ignition. Total. 44.03 40.16 trace 3-14 trace 1.42 6.66 5-04 100.45 4. Gorundzcmn altered into D//nrgarite.-This change is far less com- Remarkable specimens occur a t The analysis of the purest margarite The analysis of the mica gave :- mon than that into potassium mica. Hendrick’s Farm, Iredell Co. obtainable gave :- SiO,. Al,03. Pe203.MgO. CaO. LiOP N%O. KSO. Ignition. Total. 32.55 48.87 0.60 0.23 10.48 trace 2.38 0.43 4.34 99.88 5. Corundum altered into Jibrolite is found at Norwich, Conn., and at Shoup’s Ford, Burke Co., N.C. 6. Corurdum altered info cyanite is found a t Statesville, Iredell Co., and in Wilkes Go., N.C. The author comes finally to the conclusion that since the p e a t gravel deposits in the S. States of N. America were formed, no alteration of the corundum in these deposits has taken place. B. H. B. Gahnite. By F. A. GENTH (Jahrb. f. Min., 18E3, 2, Ref., 321- 322).-In the Deake Mica Mine, Mitchell Co., N.C., a mineral occurs which the author recognised as gahnite. It is apparently without form, has a splintery to concho‘idal fracture and a dark green colour. H. = 7.5. Sp.gr. = 4.576. It gave on analysis the following results :- AI,O,. Fe,O,. FeO. MnO. CuO. ZnO. MgO. Total. 54.86 4.50 1-14 0.29 0.30 38.05 0.79 99.93 Gahnite has also been found a t the Cotopaxi Mine, Chaffee Co., Carefully selected material gave on analysis the following Colorado. Iaesults :- Al,O,. Fe20,. FeO. ZnO. MgO. Total. 60.76 0.58 4.56 23.77 10.33 100*00 The gahnite from Cotopaxi is frequently coated with a white earthy It gave on mineral, soluble in strong boiling hydrochloric acid. analysis the following results :- Ignition. SiO,. A1,0,. Fe203. CuO. PbO. ZnO. MgO. Total. 13-82 28-08 18.20 4-32 0.82 1.80 1-75 29.85 98-64 Lead and zinc are probably present as carbonates, the Fe203 as such, and if these impurities be deducted, the composition places the mineral near ripidolite.Another alteration of the gahnite is that into a micaceous chloritic mineral, which gave on analysis :- SiO2. A1,0,. FeO. CuO. ZnO. MgO. Ignition. Total. 31.15 13.12 10.74 0.77 0.39 2923 11.78 97.18 B. H. B.MINERALOGICAL CHEMISTRY. 269 Apatite from Horrsjoberg, Sweden. By IGELSTROM (Jahrb. f. Min., 1883, 2, Ref., 312-313).-Apatite occurs at Horrsjoberg, together with disthene, lazulite, rutile, mennccanite, damourite, talc, triplite, and quartz, in beds conformable to the surrounding gneiss. The analysis gave :- PzO5. Ca. FeO. MnO. B. H. B. 41.14 50.56 trace Turquoise Found at Alexandria. By A. PRENZEL (Ja7~7-7,. f. -Min., 1883, 2, Ref., 315).-The analysis of a turquoise found a t Alexandria gave the following results :- Organic P,O,. SO3.A1,0,. Fe203. CuO. H,O. matter. Total. 28.14 0.68 41.09 1-08 4.54 20.96 4-49 100.98 It had a dark-green colour. It probably B. H. B. Roemerite, Botryogen, and Native Magnesium Iron Sul- phate. By J. BLAAS (Monatsh. Chem., 4, 833-849) .-Berzelius, in 1815, described as " red iron vitriol " a mineral which was afterwards more exactly investigated by Haidinger, from whose analysis it ap- peared to be a hydrated sulphate of iron and magnesium. The crystals were found to be monoclinic, and from their tendency to aggregate in spherical groups, attached like bunches of grapes, the mineral received the name of botryogen. Grailich, in 1858, described a new mineral, roemerite, which, from an analysis by Tschermak, appeared to be a hydrated sulphate of iron and zinc, and from a crystallographic exaniination by Grailich him- self was inferred to be monoclinic, and closely related to botryogen.More recently a mineral having the characters of roemerite, but in better defined crystals, has been obtained from Persia, and examined by the author, who has shown that it has the chemical composition of roemerite, and that the crystals belong, not to the monoclinic, but to the triclinic system, exhibiting the axial ratio a : b : c = 0.8791 : 1 : 0.8475, and the axial angles bc = 89" 44'; ac = 102" 17'; ab = 85" 18'. The paper gives elaborate details of the crystallo- graphic and optical characters of the mineral. The differences between roemerite and botryogen may be tabulated as follows :- Crystalline form ........ Triclinic Monoclinic Habit.................. Tabular Short prismatic Colour ................ Light to dark-brown Hyacinth-red to H. = 5 ; sp. gr. = 2.39. was brought to Alexandria from Sinai. Roemerite. Botryogen. violet yellow Dichroikm,. ............ Weak Very decided The author has also examined another mineral from Fablun in Sweden, hitherto regarded as botryogen. It forms stalactites or crusts, orange-coloured on the surface, white beneath, the orange270 ABSTRACTS OF CHEMICAL PAPERS. colour disappearing when the mineral is moistened and kept for some time in a closed vessel. On closer exarrlination, the mineral is seen to be formed of several portions, partly supwposed, partly intergrown, the lowest layer consisting of a green crystalline mass resembling ferrous sulphate, but much lighter in colour, and having here and there a radiate structure.Above this is a layer composed chiefly of small splinters of magnesium sulphate imbedded in a yellowish-white fibrous mass. Chemical examination showed the pyesence of magnesia in the substratum consisting chiefly of ferrons sulphate, and, on the other hand, the crystals of magnesium sulphate were found to contain ferrous oxide. An analysis of these crystals separated from the whitish-green substratum gave 31.57 per cent. SOj, 7-25 FeO, 9.05 MgO, 1.d4Al20,, and (by difference) 50.49 water. The compound Fe,S04 + 7H2O is known to be dimorphous, crgs- tallising in the monoclinic system as rnelanterite, and in the rhombic as tuuriscite, while MgSOa + 7HZO is likewise dimorphous, separating in monoclinic crystals, like those of melanterite, a t temperatures between 25" and 30".It is therefore not surprising that these two members of the isomorphous group R"S04 + 7H20 should occur together in nature, as well as when artificially crystallised. H. W. Rutile and Zircon from the Itacolumite of Edge Hill. By F. A. GENTH (Jahrb. f. Min., 1883, 2, Ref., 322) -The itacolumite rocks of the Potsdam sandstone of Edge Hill, Bucks Co. Pa, contain exceedingly minute yellow grains consisting of rutile. Associated with the yellow grains are small crystals of tourmaline, menaccanite, and colourless o r brownish-white zircons, showing the planes mP, I?, mPm, 3P3. B. H. B. Chemico-mineralogical Studies on Italian Minerals. By A. FUNARO and L. BUSATTI (Gazzetta, 13, 433-436) .--1.Wollastoibite from Sardinia.--This mineral is found a t S. Vito, a mineralogical district of Sarrahus in Sardinia, implanted on certain schists in small needles grouped in stars or rosettes. Colour light-grey. Transparent or translucent. Tinstre strong and nacreous, especially along the cleavage-planes. Powder white. Hardness, 4.5. Density, 2.7 to 2.8. Heated before the blowpipe in small splinters, it melts with great difficulty, and only along the edges, to a tumefied transparent glass. Gently heated with strong hydrochloric acid it dissolves and gel&- tinises. 'Its analysis gives: 49.78 SiO.?, 45.12 CaO, 1.20 MgO, 2-20 Pe203, 0-6 H,O = 98.90, whence, regarding the greater part of the water as combined with the ferric oxide, and the excess as an im- purity, varying in specimens of the mineral from different €ocslities, we find, reducing the numbers to 100 parts : 51.80 SiOz, 46.95 CaO, and 1.25 MgO ; and hence, calculating the magnesia together with the lime, we deduce the formula SiCaO,.The rock on which this wollastonite is implanted is dark-coloured, almost black, compact, tenacious, and possesses considerable hardness. It is composed of silica, alumina, and graphite, wikh mere traces of earthy-alkaline metals, perhaps due to wollastonite penetrating itsMINERALOGICAL CHEMISTRY. 271 mass, and not separable by inechanica1 means. When examined with $he microscope in very thin sections, it appears to be composed of g~annlo-crystalline silica diffused through a pct'ro-siliceous ground- ~ R S S or magma, exhibiting scattered reddish spots referable to limo- nite, and numerous black, opaque, irregularly disseminated masses, apparently consisting of graphite, and so abundant in certain sections as to render the specimen perfectly opaque.I n this rock, the wollas- tonite appeal's in small crystalline masses recognisnhle by its fibrous structure, absence of colour, and the tints which it exhibits in polariscd light. 2. Chlorite front the Bottino (Serravezxa).-The chlorite of this niineralogical district in the Apuan Alps occurs massive and in radiate groupings, amongst the beautiful crystallisations of metallic sulphides in the quartzoso-metalliferous vein of the said district. Lustrous and minutely crystal- line. The powder appears under the microscope to consist of minute greenish scales or ci*ystalline lamina: joined together in a spiral column.The crystalline lamina?:, usually of rounded outline, often exhibit the form of regular hexagons. When rery thin, they are perfectly transparent, slightly dichroic, and exhibit faint interference colours. Hardness about 1.5. Density 2.8 to 2.9. Wit,h borax the mineral forms a bead, reddish-yellow while hot, changing as it cools to light green, and finally to yellow. Heated in a closed tube, it gives off water, turns brown, and retains that colour if heated t o redness on platinum foil. Strong hydrochloric acid attacks it, eliminating a t first a small quantity of carbonic anhydride, and on prolonged ebulli- tion decomposes it completely:, with deposition of gelatinous silica.Quantitative analysis of several specimens showed the absence of alkaline bases and the presence of traces of lime in a few eperimens only. The chief constituents are iron in the ferrous state, alumina, ;ilica, and magnesia. By quantitative analysis of A specimen free from lime, Funaro obtained the results given on the first line of the following table, those on the second and third lines having been obtained respectively by Erlenmeyer and Nies (Rammelberg's Hand- bzcch der Xineyalogie, i, 495). Aspect scaly ; colour apple-green. Si02. A1,03. FeO. Fe.0,. MgO. CnO. H.0. COs. 23.69 21.63 34.33 4.27 4.82 - 7.00 4.12 = 100.06 25.72 20.69 27.79 4.01 11.70 - 10.05 - = 99.96 23.67 24.26 29.41 8.17 1.75 1-28 8.83 1.01 = 98.38 Achiardi in his Mineralogia della Toscana (ii, 231) mentions this chlorit,e, which, with reference to its external characters, he regards as a ripidolite, and especially as belonging to the variety called aphro- siderite.This conclusion is in accordance with the analyses above given. The constant presence of carbonic acid in this aphrcisiderite leads to the idea that its normal composition has undergone some alteration, inasmuch as the carbonic acid must be regarded as com- bined with the ferrous oxide or the magnesia, and not as entering into the chloritic molecule. H. W.272 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Notices. By G. FREDA (Qnzzettrc, 13, 498-499). -1. Gyeen, H?LWV&S fyom, Ilfonfe Bomn?a.-Large crystalline grains having a light green colour and vitzeoiis lustre. Sp. gr. 3-21. Infusible before the blowpine; loses 1.08 per cent.when strnngly heated. 11. Cupriferoirs Variety qf PYrorP??e.--Irre,anlar kidney-shaped lumps o f various sizes, having a fine sky-blue colour, and very fine granular texture. H. 5.5. Sp. gr. 3.19. Melts before the blowpipe to a glass having the colour of turquoise ; its powder, which has an ashv colour, assumes a fine roseate tint when heated in the air. 111. With some specimens of the last-descrihed subptance. there occurs a colourlesr, highlv translucent mineral, having a dull glassy lustre: hardness a little less than that of fluorspar, and sp. gr. = 3.05; it melts before the blowpipe to a limpid glass. IT. Nevi Case of Metaworphism of Leircita.-In certain crystalline masses from Pomma there occur, in the midst of a mixture of melilite, rrianesia-mica, and pleonast, large scattered nodules of leucite, pre- senting the singular character of being formed of a white opaque zone enclosing a yellow glassy nucleus of undecomposed leucitc.The following are analyses of these minerals :-IV a is the white zone; b the same deprived of calcium carbonate; c the leucite nucleus. H. 6.5. IV. SiO, ........ F .......... co, ........ A1203 ...... FeJI, ...... CaO ........ MgO. ....... FeO ........ CUO ........ KzO ........ I. 35.17 3.41 L - 1-69 54.83 3.76 TT. 52.73 - 1.06 24.1 8 17-80 4.22 0.94 - I 1 IT. a. 46.70 38.40 - 4.27 1.09 20.18 - trnce 39.62 26.83 13.38 396 - - 7 -h-- 6 . c. 4-2-61 55.78 - - 20.96 22.12 trace 0.59 24.47 - 428 - - - - - 6.49 19.81 98.86 100.93 100.79 99.24 98.81 98.30 H.W. Alteration of Talc into Anthophyllite. By F. A. GENTR (Jnh,~b. f. Min., 1883, 2, Ref., 320-321).-1n Pennsylvania unaltered olivine rock has never yet been found. An enstatitc rock has, how- ever, been found containing small grains of olivine. It is best developed a t Castle Rock, Delaware Co., and near Wood’s chrome mine, Lancaster Co. Grains of chromite are disseminated through- out all the olivine rock, and tliroiighout the serpentine which has resulted from the alteration of this rock. This is also the case with a talc which occurs near Castle Rock. This talc has a sp. gr. of 2-789 and H. = 2. The analysis gave:- SiO,. Chromite. Cr203. AI,O,. NiO. FeO. MgO. H20. Total. 62.48 0.20 0.13 0.59 0.16 4.95 27.60 4.81 100.92MINERALOGICAL CHEMISTRY.273 It i A now converted into anthophyllite, for it is enveloped hy a radiated fibrous mineral, which encloses, like the original talc, grains of chromite. Its sp. gr. is 2,983. The analysis gave- Si02. A l 2 0 , . Cr,Ol. FeO. MnO. NiO. MgO. NapO. K20. H20. Total. 56.W 2-43 trace 9.20 0.28 0.17 28.50 0.18 0.03 2.28 99.97 This analysis corresponds with that of the anthophyllite from Her- mannschlag. B. H. B. Talc, Paeudornorphous after Magnetite. By F. A. GENTH (Jahrb. f. Min., 1883, 2, Ref., 321).--Near Dnblin, in Harford Co., Md., a coarse scaly chlorite, in immediate contact with talc slate, has disseminated through it numerous small octohedrons of talc pseudo- morphous after magnetite, an alteration which has never been observed before. I n these crystals, the talc scales are arranged parallel to the octohedral platies, whilst in the centre there is occasionally a small nucleus of magnetite, sometimes associated with pulverulent limo- nite.B. H. B. Pyrophyllite in Anthracite. By F. A. GENTH (JahrB. f. Bin., 1883, 2, Ref., 323).-Pyrophyllitme has recently been found near Drifton, Luzerne Co., Pa. It is found in the stratification planes and fissures, and also in the most compact anthracite. The analysis of a specimen from Cross Creek Colliery, near Drifton, gave :- Sp. gr. = 2.81. SiO,. A1203. Fe,O,. H,O. Total. 65.77 29.36 0.12 4.85 100.10 B. H. 13. Occurrence of Kaolin in North Sweden. By A. LINDSTROH (Jahrb. f. Bin., 188:3, 2, Ref., 365-;366).--From the sketch map given Iby the author it may be seen that all the localities a t which kaolin is found are situated in a, zone 11-16 km.broad, and 48-54 km. long, where iron gneiss forms the adjacent rock. Alteration of Orthoclase into Albite. By F. A. GENTH (rJ~~7~rb. f. Mi%., 1883, 2, Ref., 320).-In the gneiss of Upper Avondale, Dela- ware Go., Pa., druses have been found lined with crystals of albite, muscovite, and sometimes with beryl, tourmaline, and calcite. The colourless albite crystals form a coating either directly above flesh- coloured orthoclase or, sometimes, with the intermediate development of greyish-white plagioclase. Analyses of the albite (.I) and the flesh- coloured orthoclase (11) are given. I n some instances there is, between the orthoclase and albite, a greyish felspar, which proves on analysis (111) to be a mixture of albite and oligoclase, the oxygen ratio being 1 : 3.1 : 10.6.At the same locality orthoclase has also been found in B. H. B. colourless crystals (Analysis 1V)'snd in a white cleavage mass (Ans- I ys is. V) . VOL. XLVJ. tb274 ABSTRACTS OF CHEMICAL PAPERS. SiOz .......... A1,03. ......... Fe203 ........ MnO .......... M go ......... CaO .......... BaO .......... Na20 ........ K20 .......... PzOa .......... Ignition ...... I. 11. 68.52 64.53 1 9 . a 19.64 - tlrace -- 0.25 - 0.1 6 11-42 1.77 0.65 13-62 - 0 71 - - - - - - 111. 65.22 21-44 0.20 traco 2-07 9.36 1.16 0.58 - - - IT. 65.84 19.50 trace 0.08 3-93 10.69 0.22 - V. 65-03 19.22 trace 0-32 1-il 14.18 0.08 0.13 - - Total. ......... 100.03 100.68 100.03 100.26 100.67 Sp. gr. ........ 2.604 2.555 2.620 2.595 2.572 B.H. B. Beryl and Allanite from Alexander Co-, N.C. By P. A. GENTH (Jahrb. J. Min., 1883, 2, Ref., 322).-The analysis of a beryl, with a sp. gr. of 2.703, gave the following results :- SiOs. A1202. Beso,. FeO. H,O. Total. 66.82 18-60 13.61 0.22 0.83 100.08 An analysis of allanite, with sp. gr. = 3.005, from the same locality, gave :- SiOz. A1203. Fe203. MnO. (CeDiLa),O,. Y20,. MgO. CaO. 32.05 22.93 11-04 1-99 14.81 0.85 1-28 9.43 0.54 0.20 3.64 98-76 Na,O. K20. Ignition. Total. B. H. B. Occurrence of Gedrite as Essential Constituent of certain Rocks. By H. SJOGREN (Juhrb. f. E n . , 1883, 2, Ref., 366-367).- Gedrite, a rhombic anthophyllite rich in alumina, occurs as essential constituent of several Scandinavian rocks. An analysis of this mineral from Hilsen gave the following results :- Si02.Al2O,. FeO. MnO. CaO. MgO. Ignition. Total. 43.92 11.34 16.81 1.47 3.02 19.14 1.68 97.38 The alkalis were not determined. An amphibolite schist from Hilsen, near Snarum, was found on examination to be composed half of gedrite and half of black horn- blende ; biotite, apatite, rutile, and magnetic pyrites occurring as accessory constituents. B. H. B. The Phyllites of the Tyrolean Alps. By A. PICHLER (Jahrb. f. &tin., 1883, 2, Ref., 366). This paper gives the results of the micro- scopic investigation of the numerow varieties of phyllite (clay-slate) which are found in the Tyrolean Central Alps. Microscopic tourmn-MINERALOGICAL CHEMISTRY. 275 line occurs to a p e a t extent, and is very characteristic.ance similar t o the fluxion structure may frequently be detected. An appear- B. H. B. Hornblende-diabase from Graveneck. By A. STBESG (J~hrb. f. -iWh., 1883, 2, Ref., 367--369).-This diabase, inteisesting 011 account of the large amount of basaltic hornblende it contains, occurs at Graveneck near Weilburg on the Lahn. The analysis of the diabase disseminated through it gave the following results :- 44.13 2.66 7.45 7.73 7-02 20.46 10.64 0.90 1-00 101.99 The rock is of a blue to greenish-grey colouir. SiO,. TiO,. AI,O, Fe20,. FeO. Cax). MgO.. Na20. &O. Total. Crystals of basaltic hornblende occur more rarely. The amlgsis of pure material, with sp. gr. = 3.25, gave :- SiO,. TiO,. AL.0,. Pe,03. FeO. CaO. MgO. K20. 41.35 497 13-48 5.14 10.33 10.93 11-44 0.62 KalO.H,O. Total. 2.10 0-48 100.84 Among the other minerals disseminated through the mass, plagioc-lase, iyon-ore, pyrites and apatite may be mentioned. The iron ore is strongly magnetic, and contains 17.81 per cent. of TiO,. In conclusion, Senfter's complete analysis of this rock is given (this Journal, 1873, 738). B. H. B. By A. STRENG (Juhrb. f. Jfii7~., 1883, 2, Ref., 369-370).-This diabase occurs a t Graveneck. It contains an unusual amount of apatite columns with the forms mP, P, OP, wP2. The composition of the rock is in other i~espects quite normal. Diabase rich in Apatite from G.raveneck The analyses gave the following results :- Ti02. SiO,. AL,03. Fe,03. FeO. NnOt CeO. MgO. K,O. 2-08 46.53 18-07 6.13 7-27 0.30 7-87 3.78 0.55 3.51 2.1 7 0.51 1.33 100.60 Na,O.HZ0 . GO,. P2O5 Total. B. H. B. Nepheline Rocks from the Vogelsberg. By H. SOMMERLAD (,Juhrb. f. Bin., 1883, 2, Ref., 372).-With the nephelinite of Meiches, a basalt occurs in which Ludwig foiind the nephelinite in the form of veins 1.5 mm. thick. This proved to be a nepheline- basalt (Analysis I) with sp. gr. = 3.103. The nepheline-dolerite of Gunzenau occurs in blocks. The microscopic examination of the rock showed it t o have the normal composition of a nepheline-tephrite, with dark mica and some olivine as accessory constituents. Sp. .gr. = 2-745. The analjsis gave the results given under 11. The phonolites shown on the geological map of the Grand Duchy of Hesse, near Salzhausen and Herchenhnin, appear to be trachytoid phonolites poor in nepheline, whilst those near Wohnfeld and Weniiigs are basalts 21 2276 ABSTRACTS OF CHEMICAL PAPERS.with a very coarsely granular structure and light colour. An analysis of'the rock from Ziegenbals, near Wohnfeld, is given (111). SB,. Bd203. Fe203. FeO. CaO. MgO. K,O. I. ........ 42.3'7 8.88 11-26 7.80 10.93 13.01 1.21 IT. ........ 49.35 11.50 6.54 9.93 5-92 3.61 2-43 111. ........ 55-70 14.55 B.68 10.71 6.91 5-81 0.51 Na,O. H,O, Ti02. P,Ob. Total. L ...... 6.51 0.34 1.55 0.21 102.07 XI. .. a-... 7-01 0.91 - 1.41 98.41 111. ...... 4.12 0.59 0.20 0.88 101.66 B. H. B. Phonolites of Elfdalen. By A. E. TORNEBOHM (Jahrb. f. Min., 1883, 2, Ref., 370-371).-The author has discovered three veins of the so-called ghonolite of Elfdalen traversing porpyhyry and, perhaps, also sandstone at Heden, in Dalarne.The new material allowed a more exact petrographical examination than has been the case hitherto. The grouud-mass is finely granular and crystalline, and is composed of felspar, cancri nite, nepheline, aegirine, titanite, and apatite ; whilst felspar and cancrinite occur in porphyritic crystals. The felspar is orthoclase, mierscline, and plagioclase. The cancrinite is, when fresh, coburless and perfectly clear, but alters into a brick- red and almost opaque mass, which was formerly thought to be felspar converted into zeolite. For the rock, the author proposes the name Cancrinite-aegirine-syenite. This is not only the first time that cancrinite has been found in Smeden, but also the first time that cancrinite has been proved to be an essential constituent of a rock.B. H. l3. Analysis of a Meteorite which fell at Alfianello on the 13th of February, 1883. By G. CAVAEZI (Gnzzetta, 13, 492).-The anlsysis of this meteorite gave 45.1 per cent. Si02, 3.7 S, 26.38 MgO, 19.8 Fe (as sulphide, .phosphide, silicate, and metallic), perceptible traces of phosphorus, nickel, and sodium, scarcely perceptible traces of potassium, aluminium, calcium, manganese, and copper. By W. FLIGHT (Proe. Xoy. SOC., 35, 258--260).-1n this paper an analysis is given of a mGteorite which fell on February 16th, 1883, a t Alfianello, in the district of Vero- lannova, in the provinoe of Brescia, I t d y . The fall was accompanied by a loud detonation beard ia the neighbouring provinces. In struchure, the meteorike belongs to the gmup sporadosideres oligosideses, and resembles aumalite, being nearly identical with the meteorite of New Concord, Ohio.It was finely granular, containing disseminated metallic grains ; its sp. gr, was 347 3.5.. On aiialysis, the following numbers were obtained :- H. W. Meteorite of Alfianello. Troilite.. ................ 6.919 Nickel iron .............. 2.108 Sohble silicate .......... 50.857 Insoluble silicate. ......... 40.1 16ORGANIC CHEMlSTRY . 2'77 The soIuble silicate contained the following constituents ... Silica .................... 35.12 Ferrous oxide ............ 51.45 Alumina ................ 1.518 Lime .................... 4644 Magnmia ............... 7.269 And the insoluble silicate had the composition- Silica. ................... 56.121 Ferrous oxide ............13.397 Chromic oxide ............ 8.281 Lime.. .................. 6.712 Magnesia ................ 17.263 From the results, it appears not improbable that this latter portioii contains some tridymite . v . €i . v .MINERALOGICAL CHEMISTRY. 265M i n e r a 1 o g i c a 1 C h e m i s t r y.Dopplerite. By A. MAYER (Lardw. Versu,chs.-Xtat., 29, 313-315).-'l'he sample of dopplerite was obtained from peat beds inHolland : it contained $4.6 per cent. water, and in the dried substancewas found 4.2 per cent. ash. The relation of carbon, hydrogen, andoxjgen in the remainder led to the empirical formula C1,HleOs. Theash constituents were chiefly calcium carbonate and ferric oxide.Dopplerite is perfectly soluble in caustic potash or soda, but oiilypartially in ammonia. Acids precipitate it from solution, and salts ofalkaline earths throw it down in combination with base.A calciumsalt was thus obtained having 8.1 per cent. of lime. J. K. C.Natural Fluorine Compounds. By P. GROTH (Jahb. f. &fin,.,1883, 2, Ref., 324---327).-This paper gives a detailed description ofthe fluorine minerals, analyses of which have already been publishedby Brand1 (Abstr., 1882, 1176).= 89" 40'.The planes occurring most frequently are mP, OP, + Ex, Pco. Thechemical formula calculated from Brandl's analyses is 3NaF,ALF3.Pachnolite is motloclinic : a : b : c = 1.1626 : 1 : 1.5320, 8 = 89- 40'.wP, -€', OP are the planes occurring most frequently. The rhombicsection is very characteristic of pachnolite, that of t homsenolite beingrectangular. The chemical formula is NaF,CaF,,AlF,.Tliomsenoliteis monoclinic: a : b : c = 0-9$!5!) : 1 : 1.0887, p = 87" 374'.The most iuiportant forms are mP, +- P, OP.The chemical formulais NaF,CaF,,AIF,,H,O.1. Crlyolite is monoclinic : a : b : c = 0.9662 : 1 : 1.5882,Ralstonite crystallises in octohedrons.3 ( NaaMgCa)F,, 8A1F,,6H20.Chiolite has the formula FiNaF,SAlF.Arlcszctite is probably a partially altered cryolite, that is a mixtureHagemaimite is probably thomsenoliteGcarksrdite appears to be theThe formula isof cryolite and pachnolite.mixed with siliceous brown ironstone266 ABSTRACTS OF CHEMICAL PAPERS.final product of the alteration of cryolite, whereby Na is replaced byCa and water taken up.2.Fluellite is rhombic : Q : b : c = 0.77 : 1 : 1.874. Forms observedare P and OP.3. Prosopite is monoclinic : a : b : c = 1.318 : 1 : 0.5912, /3 = 86" 2'.Forms observed are mP, mPm, +P, 2P2, gem, -39g, mP2. Tbeformula is CaAl,(FHO),.Sp. gr. = 2-17'. The formula is A1F3 + H20.B. H. B.Zinc Bleade and Prehnite from Cornwall, Lebanon Co., Pa.By F. A. GEBTH (Juhrb. f. -&fin., 1883,2, Ref.,322--323j.-Tncavitiesof the magnetite from Cornwall Ore Bank, fine crystals of zinc blendeoccur associated with prehnite, magnetite, iron pyrites, and chlorite.They have a sp. gr. of 4.033, and gave on analysis :-S. Zn. co. Pe. Total.32.69 66-47 0.34 0.38 913.88Prehnite forms crystalline incrustations upon magnetite. It has asp, gr.of 3.042, and gave on analysis :-SiO,. A1103. Pe,03. CaO. H20. Total.42-40 20.88 5.54 27.02 4.G1 99.85B. 33. B.Artificial Alisonite. By F. A. GExw (Jahrb. f. Min., 1883, 2,Ref., 324) .-At the smelting works at Argo, Colorado, octohedralcrystals have been observed in the furnace bottoms. They have aniron-black colour, metallic lustre, sp. gr. = 5.545, and gave onaualysis the following results :-S. Age CU. Pb. Fe Total.15-23 2.16 51.33 31-15 trace 9987E. H. B.Reebanyite, a New Mineral Species. By A. FRENZEL (Juhrb.f. Mi%., 18t'S, 2, Ref., 314).-This mineral occurs at Rezbanya, asso-ciated with cosalite. It has a metallic lustre, a lead-grey colour andblack streak. H. = 2.5 to 3. Sp. gr. = 6.09 to6.38. It forms com-pact masses with copper pyrites and calcite, or is disseminated throughquartz. From the analyses, the formula, of rezbanyite is calculated tobe 4PbS,5Bi,Sj. B.H. R.Alloclasite. By A. FRENZEL (Jahrb. f. Jfin., 1883, 2, Ref., 314-315).-1n order to determine the composition of' this mineral, whichstill remains doubtful, the author made six analyses of compactmaterial, and although the results obtained were rather variable, heis of opinion that Groth's formula (CoFe)(AsBi)S, is the correct onefor this mineral. B. H. B.Kupfernickel from Colorado. By F. A. GENTH (Jahrb. f. Min.,1883, 2, Ref., 324).-In silver Cliff, Colorado, rounded masses ofkupfernickel occur in granular limestone. Sp. gr. = 7.314. Theanalysis gave :MINERALOGICAL CHEMISTRY. 267As. Sb. S. Cu.Ni. Co. Fe. Total.46.81 2.24 2.52 1.59 44.76 1.70 0.60 100.22B. H. B.Corundum. By F. A. GENTH (Jahrb. .f. Min., 1883, 2, Ref., 316-319) .-This paper is a description of a few remarkable occurrences,as a continuation of the paper formerly published by the author(this Joiir., 18 74, 549).1. Comndwn altered into spinel is found at the Carter Mine, Madi-son Co., N.C. The spinel finally passesinto chlorite.The analysis, aRer deducting silica and corundum, gave the follow-It has a sp. gr. of 3.751.ing results :-A1203. Fe,O,. CuO. NiO. ZnO. FeO. MgO. Total.66.74 1-34 0-09 0.33 0.22 11.94 19.34 100.00Corundum altered to a slight extent into spinel has also been foundAfter deducting at Shimersviile in Lehigh Go.1.47 per cent. Si02, the analysis gave :-Sp.gr. = 4.056.A1203. Fep03. FeO. MgO. TiOP Total.56.42 13.17 22-95 4.94 2.62 100.102. Corundum altered into zoisite is of rare occurrence.3. Corundum altered into felspar and dmrnwurite occurs at Unions-ville. The analysis gave :-SiO,. Al,O,. Fe,O,. MgO. CaO. Ka20. K20. Ignition. Total.62.62 22.59 0.22 0.18 1.94 7.41 2.52 2.45 99.1.13Another interesting occurrence is that at the Black Horse Tavern,Sp. gr. = 2.611. The analysis gave :- near Media in Delaware CCLSO2. Al,O,. Be203. MgO. CaO. BaO. Na20. KgO. Ignition. Total.58-42 23-14 0.18 O*S5 3.13 2.56 3-68 7.06 1.54 100.06The Presley Mine in Hajwood Co., N.C., has furnished someremarkable specimens of corundum altered into albite and muscovite.Aiialybes of the albite (I) and of the muscovite (11) are given :-SiO,.A120,. Fez03. MgO. CaO. Nit,O. KyO. Ignition. Total.I. 65.52 22-25 trace - 1-96 9-54 0.53 022 100.0211. 45.26 36.33 1.96 0.14 0.35 0.48 11-OH 4.50 100.11Corundum altered chiefly into damourite has been found at Belt'sBridge, Iredell Go., N.C. After deducting 3.51 per cent. of corundum,the analysis of the mica gave :-SiO,. Al,O,. Fe203. CaO. Li20. Na@. K@. Ignition. Total.45-96 38.22 0.61 0.37 trace 0.74 9.21 4.89 100-00From the same locality a fragment of a hexagonal prism was found.It consisted of a core of grey corundum surrounded by mica enclosin268 ABSTRACTS OF CHEMICAL PAPERS.tourmaline, and disseminated through the unaltered tourmaline arerounded masses of garnet.SiOz. A1203. Fe203.CaO. Li20. Na20. K20. Ignition. Total.44.03 40.16 trace 3-14 trace 1.42 6.66 5-04 100.454. Gorundzcmn altered into D//nrgarite.-This change is far less com-Remarkable specimens occur a tThe analysis of the purest margariteThe analysis of the mica gave :-mon than that into potassium mica.Hendrick’s Farm, Iredell Co.obtainable gave :-SiO,. Al,03. Pe203. MgO. CaO. LiOP N%O. KSO. Ignition. Total.32.55 48.87 0.60 0.23 10.48 trace 2.38 0.43 4.34 99.885. Corundum altered into Jibrolite is found at Norwich, Conn., andat Shoup’s Ford, Burke Co., N.C.6. Corurdum altered info cyanite is found a t Statesville, Iredell Co.,and in Wilkes Go., N.C.The author comes finally to the conclusion that since the p e a tgravel deposits in the S. States of N.America were formed, noalteration of the corundum in these deposits has taken place.B. H. B.Gahnite. By F. A. GENTH (Jahrb. f. Min., 18E3, 2, Ref., 321-322).-In the Deake Mica Mine, Mitchell Co., N.C., a mineral occurswhich the author recognised as gahnite. It is apparently withoutform, has a splintery to concho‘idal fracture and a dark green colour.H. = 7.5. Sp. gr. = 4.576. It gave on analysis the followingresults :-AI,O,. Fe,O,. FeO. MnO. CuO. ZnO. MgO. Total.54.86 4.50 1-14 0.29 0.30 38.05 0.79 99.93Gahnite has also been found a t the Cotopaxi Mine, Chaffee Co.,Carefully selected material gave on analysis the following Colorado.Iaesults :-Al,O,. Fe20,. FeO. ZnO. MgO. Total.60.76 0.58 4.56 23.77 10.33 100*00The gahnite from Cotopaxi is frequently coated with a white earthyIt gave on mineral, soluble in strong boiling hydrochloric acid.analysis the following results :-Ignition.SiO,. A1,0,. Fe203. CuO. PbO. ZnO. MgO. Total.13-82 28-08 18.20 4-32 0.82 1.80 1-75 29.85 98-64Lead and zinc are probably present as carbonates, the Fe203 as such,and if these impurities be deducted, the composition places themineral near ripidolite.Another alteration of the gahnite is that into a micaceous chloriticmineral, which gave on analysis :-SiO2. A1,0,. FeO. CuO. ZnO. MgO. Ignition. Total.31.15 13.12 10.74 0.77 0.39 2923 11.78 97.18B. H. BMINERALOGICAL CHEMISTRY. 269Apatite from Horrsjoberg, Sweden. By IGELSTROM (Jahrb. f.Min., 1883, 2, Ref., 312-313).-Apatite occurs at Horrsjoberg,together with disthene, lazulite, rutile, mennccanite, damourite, talc,triplite, and quartz, in beds conformable to the surrounding gneiss.The analysis gave :-PzO5.Ca. FeO. MnO.B. H. B. 41.14 50.56 traceTurquoise Found at Alexandria. By A. PRENZEL (Ja7~7-7,. f.-Min., 1883, 2, Ref., 315).-The analysis of a turquoise found a tAlexandria gave the following results :-OrganicP,O,. SO3. A1,0,. Fe203. CuO. H,O. matter. Total.28.14 0.68 41.09 1-08 4.54 20.96 4-49 100.98It had a dark-green colour. It probablyB. H. B.Roemerite, Botryogen, and Native Magnesium Iron Sul-phate. By J. BLAAS (Monatsh. Chem., 4, 833-849) .-Berzelius, in1815, described as " red iron vitriol " a mineral which was afterwardsmore exactly investigated by Haidinger, from whose analysis it ap-peared to be a hydrated sulphate of iron and magnesium.Thecrystals were found to be monoclinic, and from their tendency toaggregate in spherical groups, attached like bunches of grapes, themineral received the name of botryogen.Grailich, in 1858, described a new mineral, roemerite, which, froman analysis by Tschermak, appeared to be a hydrated sulphate of ironand zinc, and from a crystallographic exaniination by Grailich him-self was inferred to be monoclinic, and closely related to botryogen.More recently a mineral having the characters of roemerite, but inbetter defined crystals, has been obtained from Persia, and examinedby the author, who has shown that it has the chemical compositionof roemerite, and that the crystals belong, not to the monoclinic,but to the triclinic system, exhibiting the axial ratio a : b : c =0.8791 : 1 : 0.8475, and the axial angles bc = 89" 44'; ac = 102" 17';ab = 85" 18'.The paper gives elaborate details of the crystallo-graphic and optical characters of the mineral.The differences between roemerite and botryogen may be tabulatedas follows :-Crystalline form ........ Triclinic MonoclinicHabit.. ................ Tabular Short prismaticColour ................ Light to dark-brown Hyacinth-red toH. = 5 ; sp. gr. = 2.39.was brought to Alexandria from Sinai.Roemerite. Botryogen.violet yellowDichroikm,. ............ Weak Very decidedThe author has also examined another mineral from Fablun inSweden, hitherto regarded as botryogen.It forms stalactites orcrusts, orange-coloured on the surface, white beneath, the orang270 ABSTRACTS OF CHEMICAL PAPERS.colour disappearing when the mineral is moistened and kept forsome time in a closed vessel. On closer exarrlination, the mineralis seen to be formed of several portions, partly supwposed, partlyintergrown, the lowest layer consisting of a green crystalline massresembling ferrous sulphate, but much lighter in colour, and havinghere and there a radiate structure. Above this is a layer composedchiefly of small splinters of magnesium sulphate imbedded in ayellowish-white fibrous mass. Chemical examination showed thepyesence of magnesia in the substratum consisting chiefly of ferronssulphate, and, on the other hand, the crystals of magnesium sulphatewere found to contain ferrous oxide.An analysis of these crystals separated from the whitish-greensubstratum gave 31.57 per cent.SOj, 7-25 FeO, 9.05 MgO, 1.d4Al20,,and (by difference) 50.49 water.The compound Fe,S04 + 7H2O is known to be dimorphous, crgs-tallising in the monoclinic system as rnelanterite, and in the rhombicas tuuriscite, while MgSOa + 7HZO is likewise dimorphous, separatingin monoclinic crystals, like those of melanterite, a t temperaturesbetween 25" and 30". It is therefore not surprising that these twomembers of the isomorphous group R"S04 + 7H20 should occurtogether in nature, as well as when artificially crystallised.H. W.Rutile and Zircon from the Itacolumite of Edge Hill.By F. A. GENTH (Jahrb. f. Min., 1883, 2, Ref., 322) -The itacolumiterocks of the Potsdam sandstone of Edge Hill, Bucks Co. Pa, containexceedingly minute yellow grains consisting of rutile. Associatedwith the yellow grains are small crystals of tourmaline, menaccanite,and colourless o r brownish-white zircons, showing the planes mP, I?,mPm, 3P3. B. H. B.Chemico-mineralogical Studies on Italian Minerals. By A.FUNARO and L. BUSATTI (Gazzetta, 13, 433-436) .--1. Wollastoibitefrom Sardinia.--This mineral is found a t S. Vito, a mineralogicaldistrict of Sarrahus in Sardinia, implanted on certain schists in smallneedles grouped in stars or rosettes. Colour light-grey. Transparentor translucent. Tinstre strong and nacreous, especially along thecleavage-planes.Powder white. Hardness, 4.5. Density, 2.7 to 2.8.Heated before the blowpipe in small splinters, it melts with greatdifficulty, and only along the edges, to a tumefied transparent glass.Gently heated with strong hydrochloric acid it dissolves and gel&-tinises. 'Its analysis gives: 49.78 SiO.?, 45.12 CaO, 1.20 MgO, 2-20Pe203, 0-6 H,O = 98.90, whence, regarding the greater part of thewater as combined with the ferric oxide, and the excess as an im-purity, varying in specimens of the mineral from different €ocslities,we find, reducing the numbers to 100 parts : 51.80 SiOz, 46.95 CaO,and 1.25 MgO ; and hence, calculating the magnesia together with thelime, we deduce the formula SiCaO,.The rock on which this wollastonite is implanted is dark-coloured,almost black, compact, tenacious, and possesses considerable hardness.It is composed of silica, alumina, and graphite, wikh mere traces ofearthy-alkaline metals, perhaps due to wollastonite penetrating itMINERALOGICAL CHEMISTRY.271mass, and not separable by inechanica1 means. When examined with$he microscope in very thin sections, it appears to be composed ofg~annlo-crystalline silica diffused through a pct'ro-siliceous ground-~ R S S or magma, exhibiting scattered reddish spots referable to limo-nite, and numerous black, opaque, irregularly disseminated masses,apparently consisting of graphite, and so abundant in certain sectionsas to render the specimen perfectly opaque. I n this rock, the wollas-tonite appeal's in small crystalline masses recognisnhle by its fibrousstructure, absence of colour, and the tints which it exhibits inpolariscd light.2.Chlorite front the Bottino (Serravezxa).-The chlorite of thisniineralogical district in the Apuan Alps occurs massive and inradiate groupings, amongst the beautiful crystallisations of metallicsulphides in the quartzoso-metalliferous vein of the said district.Lustrous and minutely crystal-line. The powder appears under the microscope to consist of minutegreenish scales or ci*ystalline lamina: joined together in a spiralcolumn. The crystalline lamina?:, usually of rounded outline, oftenexhibit the form of regular hexagons. When rery thin, they areperfectly transparent, slightly dichroic, and exhibit faint interferencecolours. Hardness about 1.5.Density 2.8 to 2.9. Wit,h borax themineral forms a bead, reddish-yellow while hot, changing as it coolsto light green, and finally to yellow. Heated in a closed tube, it givesoff water, turns brown, and retains that colour if heated t o rednesson platinum foil. Strong hydrochloric acid attacks it, eliminating a tfirst a small quantity of carbonic anhydride, and on prolonged ebulli-tion decomposes it completely:, with deposition of gelatinous silica.Quantitative analysis of several specimens showed the absence ofalkaline bases and the presence of traces of lime in a few eperimensonly. The chief constituents are iron in the ferrous state, alumina,;ilica, and magnesia. By quantitative analysis of A specimen freefrom lime, Funaro obtained the results given on the first line of thefollowing table, those on the second and third lines having beenobtained respectively by Erlenmeyer and Nies (Rammelberg's Hand-bzcch der Xineyalogie, i, 495).Aspect scaly ; colour apple-green.Si02.A1,03. FeO. Fe.0,. MgO. CnO. H.0. COs.23.69 21.63 34.33 4.27 4.82 - 7.00 4.12 = 100.0625.72 20.69 27.79 4.01 11.70 - 10.05 - = 99.9623.67 24.26 29.41 8.17 1.75 1-28 8.83 1.01 = 98.38Achiardi in his Mineralogia della Toscana (ii, 231) mentions thischlorit,e, which, with reference to its external characters, he regardsas a ripidolite, and especially as belonging to the variety called aphro-siderite. This conclusion is in accordance with the analyses abovegiven. The constant presence of carbonic acid in this aphrcisideriteleads to the idea that its normal composition has undergone somealteration, inasmuch as the carbonic acid must be regarded as com-bined with the ferrous oxide or the magnesia, and not as entering intothe chloritic molecule.H. W272 ABSTRACTS OF CHEMICAL PAPERS.Mineralogical Notices. By G. FREDA (Qnzzettrc, 13, 498-499).-1. Gyeen, H?LWV&S fyom, Ilfonfe Bomn?a.-Large crystalline grainshaving a light green colour and vitzeoiis lustre. Sp. gr.3-21. Infusible before the blowpine; loses 1.08 per cent. whenstrnngly heated. 11. Cupriferoirs Variety qf PYrorP??e.--Irre,anlarkidney-shaped lumps o f various sizes, having a fine sky-blue colour,and very fine granular texture. H. 5.5. Sp.gr. 3.19. Melts beforethe blowpipe to a glass having the colour of turquoise ; its powder,which has an ashv colour, assumes a fine roseate tint when heated inthe air. 111. With some specimens of the last-descrihed subptance.there occurs a colourlesr, highlv translucent mineral, having a dullglassy lustre: hardness a little less than that of fluorspar, andsp. gr. = 3.05; it melts before the blowpipe to a limpid glass.IT. Nevi Case of Metaworphism of Leircita.-In certain crystallinemasses from Pomma there occur, in the midst of a mixture of melilite,rrianesia-mica, and pleonast, large scattered nodules of leucite, pre-senting the singular character of being formed of a white opaquezone enclosing a yellow glassy nucleus of undecomposed leucitc.The following are analyses of these minerals :-IV a is the whitezone; b the same deprived of calcium carbonate; c the leucitenucleus.H.6.5.IV.SiO, ........F ..........co, ........A1203 ......FeJI, ......CaO ........MgO. .......FeO ........CUO ........KzO ........I.35.173.41L-1-6954.833.76TT.52.73-1.0624.1 817-804.220.94-I1 IT. a.46.70 38.40- 4.271.09 20.18- trnce39.62 26.8313.38 396- -7 -h--6 . c.4-2-61 55.78- -20.96 22.12trace 0.5924.47 -428 -- - - -6.49 19.8198.86 100.93 100.79 99.24 98.81 98.30H. W.Alteration of Talc into Anthophyllite. By F. A. GENTR(Jnh,~b. f. Min., 1883, 2, Ref., 320-321).-1n Pennsylvania unalteredolivine rock has never yet been found.An enstatitc rock has, how-ever, been found containing small grains of olivine. It is bestdeveloped a t Castle Rock, Delaware Co., and near Wood’s chromemine, Lancaster Co. Grains of chromite are disseminated through-out all the olivine rock, and tliroiighout the serpentine which hasresulted from the alteration of this rock. This is also the case witha talc which occurs near Castle Rock. This talc has a sp. gr. of 2-789and H. = 2. The analysis gave:-SiO,. Chromite. Cr203. AI,O,. NiO. FeO. MgO. H20. Total.62.48 0.20 0.13 0.59 0.16 4.95 27.60 4.81 100.9MINERALOGICAL CHEMISTRY. 273It i A now converted into anthophyllite, for it is enveloped hy aradiated fibrous mineral, which encloses, like the original talc, grainsof chromite. Its sp.gr. is 2,983. The analysis gave-Si02. A l 2 0 , . Cr,Ol. FeO. MnO. NiO. MgO. NapO. K20. H20. Total.56.W 2-43 trace 9.20 0.28 0.17 28.50 0.18 0.03 2.28 99.97This analysis corresponds with that of the anthophyllite from Her-mannschlag. B. H. B.Talc, Paeudornorphous after Magnetite. By F. A. GENTH(Jahrb. f. Min., 1883, 2, Ref., 321).--Near Dnblin, in Harford Co.,Md., a coarse scaly chlorite, in immediate contact with talc slate, hasdisseminated through it numerous small octohedrons of talc pseudo-morphous after magnetite, an alteration which has never been observedbefore. I n these crystals, the talc scales are arranged parallel to theoctohedral platies, whilst in the centre there is occasionally a smallnucleus of magnetite, sometimes associated with pulverulent limo-nite.B. H. B.Pyrophyllite in Anthracite. By F. A. GENTH (JahrB. f. Bin.,1883, 2, Ref., 323).-Pyrophyllitme has recently been found nearDrifton, Luzerne Co., Pa. It is found in the stratification planes andfissures, and also in the most compact anthracite.The analysis of a specimen from Cross Creek Colliery, near Drifton,gave :-Sp. gr. = 2.81.SiO,. A1203. Fe,O,. H,O. Total.65.77 29.36 0.12 4.85 100.10B. H. 13.Occurrence of Kaolin in North Sweden. By A. LINDSTROH(Jahrb. f. Bin., 188:3, 2, Ref., 365-;366).--From the sketch map givenIby the author it may be seen that all the localities a t which kaolin isfound are situated in a, zone 11-16 km. broad, and 48-54 km. long,where iron gneiss forms the adjacent rock.Alteration of Orthoclase into Albite.By F. A. GENTH (rJ~~7~rb.f. Mi%., 1883, 2, Ref., 320).-In the gneiss of Upper Avondale, Dela-ware Go., Pa., druses have been found lined with crystals of albite,muscovite, and sometimes with beryl, tourmaline, and calcite. Thecolourless albite crystals form a coating either directly above flesh-coloured orthoclase or, sometimes, with the intermediate developmentof greyish-white plagioclase. Analyses of the albite (.I) and the flesh-coloured orthoclase (11) are given. I n some instances there is, betweenthe orthoclase and albite, a greyish felspar, which proves on analysis(111) to be a mixture of albite and oligoclase, the oxygen ratio being1 : 3.1 : 10.6. At the same locality orthoclase has also been found inB.H. B.colourless crystals (Analysis 1V)'snd in a white cleavage mass (Ans-I ys is. V) .VOL. XLVJ. t274 ABSTRACTS OF CHEMICAL PAPERS.SiOz ..........A1,03. .........Fe203 ........MnO ..........M go .........CaO ..........BaO ..........Na20 ........K20 ..........PzOa ..........Ignition ......I. 11.68.52 64.531 9 . a 19.64 - tlrace-- 0.25- 0.1 611-42 1.770.65 13-62- 0 71- -- -- -111.65.2221-440.20traco2-079.361.160.58---IT.65.8419.50trace0.083-9310.690.22-V.65-0319.22trace0-321-il14.180.080.13--Total. ......... 100.03 100.68 100.03 100.26 100.67Sp. gr. ........ 2.604 2.555 2.620 2.595 2.572B. H. B.Beryl and Allanite from Alexander Co-, N.C.By P. A. GENTH(Jahrb. J. Min., 1883, 2, Ref., 322).-The analysis of a beryl, with asp. gr. of 2.703, gave the following results :-SiOs. A1202. Beso,. FeO. H,O. Total.66.82 18-60 13.61 0.22 0.83 100.08An analysis of allanite, with sp. gr. = 3.005, from the samelocality, gave :-SiOz. A1203. Fe203. MnO. (CeDiLa),O,. Y20,. MgO. CaO.32.05 22.93 11-04 1-99 14.81 0.85 1-28 9.430.54 0.20 3.64 98-76Na,O. K20. Ignition. Total.B. H. B.Occurrence of Gedrite as Essential Constituent of certainRocks. By H. SJOGREN (Juhrb. f. E n . , 1883, 2, Ref., 366-367).-Gedrite, a rhombic anthophyllite rich in alumina, occurs as essentialconstituent of several Scandinavian rocks. An analysis of this mineralfrom Hilsen gave the following results :-Si02.Al2O,. FeO. MnO. CaO. MgO. Ignition. Total.43.92 11.34 16.81 1.47 3.02 19.14 1.68 97.38The alkalis were not determined.An amphibolite schist from Hilsen, near Snarum, was found onexamination to be composed half of gedrite and half of black horn-blende ; biotite, apatite, rutile, and magnetic pyrites occurring asaccessory constituents. B. H. B.The Phyllites of the Tyrolean Alps. By A. PICHLER (Jahrb. f.&tin., 1883, 2, Ref., 366). This paper gives the results of the micro-scopic investigation of the numerow varieties of phyllite (clay-slate)which are found in the Tyrolean Central Alps. Microscopic tourmnMINERALOGICAL CHEMISTRY. 275line occurs to a p e a t extent, and is very characteristic.ance similar t o the fluxion structure may frequently be detected.An appear-B.H. B.Hornblende-diabase from Graveneck. By A. STBESG (J~hrb.f. -iWh., 1883, 2, Ref., 367--369).-This diabase, inteisesting 011account of the large amount of basaltic hornblende it contains, occursat Graveneck near Weilburg on the Lahn.The analysis of thediabase disseminated through it gave the following results :-44.13 2.66 7.45 7.73 7-02 20.46 10.64 0.90 1-00 101.99The rock is of a blue to greenish-grey colouir.SiO,. TiO,. AI,O, Fe20,. FeO. Cax). MgO.. Na20. &O. Total.Crystals of basaltic hornblende occur more rarely. The amlgsis ofpure material, with sp. gr. = 3.25, gave :-SiO,. TiO,. AL.0,. Pe,03. FeO. CaO. MgO. K20.41.35 497 13-48 5.14 10.33 10.93 11-44 0.62KalO. H,O. Total.2.10 0-48 100.84Among the other minerals disseminated through the mass, plagioc-lase,iyon-ore, pyrites and apatite may be mentioned.The iron ore isstrongly magnetic, and contains 17.81 per cent. of TiO,. In conclusion,Senfter's complete analysis of this rock is given (this Journal, 1873,738). B. H. B.By A. STRENG(Juhrb. f. Jfii7~., 1883, 2, Ref., 369-370).-This diabase occurs a tGraveneck. It contains an unusual amount of apatite columns withthe forms mP, P, OP, wP2. The composition of the rock is in otheri~espects quite normal.Diabase rich in Apatite from G.raveneckThe analyses gave the following results :-Ti02. SiO,. AL,03. Fe,03. FeO. NnOt CeO. MgO. K,O.2-08 46.53 18-07 6.13 7-27 0.30 7-87 3.78 0.553.51 2.1 7 0.51 1.33 100.60Na,O. HZ0 .GO,. P2O5 Total.B. H. B.Nepheline Rocks from the Vogelsberg. By H. SOMMERLAD(,Juhrb. f. Bin., 1883, 2, Ref., 372).-With the nephelinite ofMeiches, a basalt occurs in which Ludwig foiind the nephelinite inthe form of veins 1.5 mm. thick. This proved to be a nepheline-basalt (Analysis I) with sp. gr. = 3.103. The nepheline-dolerite ofGunzenau occurs in blocks. The microscopic examination of therock showed it t o have the normal composition of a nepheline-tephrite,with dark mica and some olivine as accessory constituents. Sp. .gr.= 2-745. The analjsis gave the results given under 11. The phonolitesshown on the geological map of the Grand Duchy of Hesse, nearSalzhausen and Herchenhnin, appear to be trachytoid phonolites poorin nepheline, whilst those near Wohnfeld and Weniiigs are basalts21 276 ABSTRACTS OF CHEMICAL PAPERS.with a very coarsely granular structure and light colour.An analysisof'the rock from Ziegenbals, near Wohnfeld, is given (111).SB,. Bd203. Fe203. FeO. CaO. MgO. K,O.I. ........ 42.3'7 8.88 11-26 7.80 10.93 13.01 1.21IT. ........ 49.35 11.50 6.54 9.93 5-92 3.61 2-43111. ........ 55-70 14.55 B.68 10.71 6.91 5-81 0.51Na,O. H,O, Ti02. P,Ob. Total.L ...... 6.51 0.34 1.55 0.21 102.07XI. .. a-... 7-01 0.91 - 1.41 98.41111. ...... 4.12 0.59 0.20 0.88 101.66B. H. B.Phonolites of Elfdalen. By A. E. TORNEBOHM (Jahrb. f. Min.,1883, 2, Ref., 370-371).-The author has discovered three veins ofthe so-called ghonolite of Elfdalen traversing porpyhyry and, perhaps,also sandstone at Heden, in Dalarne. The new material allowed amore exact petrographical examination than has been the casehitherto. The grouud-mass is finely granular and crystalline, and iscomposed of felspar, cancri nite, nepheline, aegirine, titanite, andapatite ; whilst felspar and cancrinite occur in porphyritic crystals.The felspar is orthoclase, mierscline, and plagioclase. The cancriniteis, when fresh, coburless and perfectly clear, but alters into a brick-red and almost opaque mass, which was formerly thought to befelspar converted into zeolite. For the rock, the author proposes thename Cancrinite-aegirine-syenite. This is not only the first timethat cancrinite has been found in Smeden, but also the first time thatcancrinite has been proved to be an essential constituent of a rock.B. H. l3.Analysis of a Meteorite which fell at Alfianello on the13th of February, 1883. By G. CAVAEZI (Gnzzetta, 13, 492).-Theanlsysis of this meteorite gave 45.1 per cent. Si02, 3.7 S, 26.38 MgO,19.8 Fe (as sulphide, .phosphide, silicate, and metallic), perceptibletraces of phosphorus, nickel, and sodium, scarcely perceptible traces ofpotassium, aluminium, calcium, manganese, and copper.By W. FLIGHT (Proe. Xoy. SOC., 35,258--260).-1n this paper an analysis is given of a mGteorite whichfell on February 16th, 1883, a t Alfianello, in the district of Vero-lannova, in the provinoe of Brescia, I t d y . The fall was accompaniedby a loud detonation beard ia the neighbouring provinces.In struchure, the meteorike belongs to the gmup sporadosideresoligosideses, and resembles aumalite, being nearly identical with themeteorite of New Concord, Ohio.It was finely granular, containing disseminated metallic grains ; itssp. gr, was 347 3.5..On aiialysis, the following numbers were obtained :-H. W.Meteorite of Alfianello.Troilite.. ................ 6.919Nickel iron .............. 2.108Sohble silicate .......... 50.857Insoluble silicate. ......... 40.1 1ORGANIC CHEMlSTRY . 2'77The soIuble silicate contained the following constituents ...Silica .................... 35.12Ferrous oxide ............ 51.45Alumina ................ 1.518Lime .................... 4644Magnmia ............... 7.269And the insoluble silicate had the composition-Silica. ................... 56.121Ferrous oxide ............ 13.397Chromic oxide ............ 8.281Lime.. .................. 6.712Magnesia ................ 17.263From the results, it appears not improbable that this latter portioiicontains some tridymite . v . €i . v

ISSN:0368-1769    

DOI:10.1039/CA8844600265

出版商:RSC    

年代:1884

数据来源: RSC

摘要:

ORGANIC CHEMlSTRY. 2'770 r g an i c C h e m i 8 try.Physical Properties of Petrolmms. By S, PAGLIANI (Gazreiftr,13, 455).--Mendelejeff found, for the petroleum of Baku, a verysimple relation between the densities and boiling points of the severalfractions, represented by the equation d = u + bt, in which a and bare constant,s, the values of which have to be determined by experi-ment for different intervals of temperature and for different kinds ofpetroleum in the same intervals. For the fractions of Baku petro-leum boiling at 100-180", Mendelejeff found d = 669.5 + 0*80t, andfbr the interval 180 -240", d = 71 2.9 + 0*56t, the density of water at15" being taken as 1000. E'or the petroleum of Montechino nearNontanaro (Piacenza), the author finda the following relations :-t ..60-69" 90-100" 1.30-200" 2Q0-250"d . . 504.8 + 2,425 593.1 + 1*68t 704.7 + 0.61t 668.2 + O%ltThese densities me somewhat greater than those found by MendelejelYfor the Russian petroleum.By S. 31. LOBANITSCH (Bey., 16, 2730-2731).-The author gives analytical data showing that the coin-pound which he described as dibromodinitromethane is not a mixtureof nionobromodini tromethane and carbon tetrabromide, as KachlerH. W.Dibromodinitromethane.and Spitzer (Ber., 16, 471 ; 16, 61) assume. w. c. w.Conversion of Fulminates into Hydroxylamine. By A.STEINER (Bey., 16, %l9-2420) .-In a former communication (Abstr.,1883, 1074j the author has shown that mercury fulminate yield2 78 ABSTRACTS OF CHEMICAL PAPERS.hydroxylamine when treated with hydrochloric acid ; a quantitativeexamination of this reaction shows thatl both the nitrogen-atoms ofthe fulminate are converted into hydroxylamine, lending additionalsupport to the hypothesis that fulminic acid is an isonitroso-com-pound, having the formula HO.NC CN.OH.Moreover, in mercuryfulminate, the mercury can be replaced by acid radicles, by actingupon it with acetic or benzoic chlorides, and the author hopes toohtain a further clue to the constitution of fulminic acid from a studyof the compounds formed.Absorption of Ammonia-gas by Alcohols. By S. PAGLIANI andEwo (Gazzetta, 13, 2'78).-It has been shown by one of the authors,in conjunction with Nacari, that ammonia-gas, unlike the majority ofgaseous bodies, is more soluble in water than in ethyl alcohol.Tbcpresent paper contains the details of similar experiments withnormal propyl and isopropyl alcohols, leading to the following con-clusions :-1. Ammonia-gas is much more soluble in water than in the alcoholsmentioned.2. Ammonia-gas, within the limits of pressure observed (417 t o734 mm.), does not conform, in its absorption by these alcohols, toHenry's law, the valuesfof oc ~ not being constant, but tending atany given temperature to diminish with increase of pressure,behaving indeed in this respect as with water.3. At equal pressure, as f o r a11 other gases, the coefficient of solu-bility of ammonia-gas increases with diminution of temperature.4. At equal temperatures and pressures, the coefficient of solubility(at least for these three alcohols) diminishes as the molecular weightof the alcohol increases.H. W.P. P. B.'760PAction of Polyhydric Alcohols on Borax. By W. R. DUNSTAN(Phamrr. Journ. [3], 14, 41-44).-Thc author has previously shown(Pharm. Journ. [ 3 1, 1325) that when certain polyhydric alcohols,mannitol, erythrol, glycerol, saligenol, pyrogallol and guaiacol as wellas dextrose, levulose, lactose, and mycose? are added in aqueous solu-tion to a moderately strong solution of sodium pyroborate, they producean acid reaction in this alkaline liquid; this acid solution becomesalkaline when largely diluted with water or when heated, in whichease t h e liquid becomes acid again on cooling. I f much more of thesubstance is added than is necessary to produce a distinctly acid reac-tion, no change is effected by heat or by dilution.These effects areriot well defined when litmus is employed as an indicator, but are verydistinct with phenolphthalein, Glycocine, which has many reactionsin common with &he above compounds, does not react in thisway. I n the present paper, the general reaction which gives rise totbe above results is investigated. The action of glycerol on sodiump-j-roborate has been examined by Senier and Lowe (Pharnz. Joum.[ 3 ] , 8, S19), who concluded that boric acid, and a more basic sodiumborate were formed, but were unable either directly or indirectly toisolate the free boric acid. The author shows that when anhydrouORGANlC CHEMISTRY.279glycerol and anhydrous sodium pyroborate are heated together a t12G", water is given off, and on extracting the mass with ether anuncrystallisable, extremely deliquescent body is obtained, whichimparts a green tinge to the Bunsen flame. It was not appreciablyacid in reaction, bat became so on adding a small quantity of water,when a crystalline mass was formed and recognised as boric acid.This aqueous solution also contained glycerol. The original mass,after being extracted with ether, contained sodium metaborate.Thus the action of anhydrous glycerol on anhydrous sodium pyro-borate yields gZyceroZ-borin, ( C3H,B0,), and sodium metaborate ; theformer compound is decomposed by water yielding boric acid andregenerating glycerol, hence the acidity which is produced whenaqueous solutions of sodium pyroborate and glycerol are mixed.Theabove reactions are represented thus :2C,H5(OH), + 2NaB02,B20d = 2C3H,B0, + 2NaB0, + 3H,O.As water itself is a product of this decomposition, the reaction isnever complete, except at high temperatures, owing to the pariialconversion of the glycerol-borin into boric acid, thus: C3H5B03 +3H,O = C,H,(OH), + H3B03. I n aqueous solution, the reaction is2C3H5(OH), + (2NaB0,,B20,) + 3H20 = 2NaB02 + 2H3BU3 +2C,H5(OH),. The action of mannitol on sodium pjroborate has beenstudied by Klein (Bull. Xoc. Chim., 29, 3591, who, by precipitatingriqueous solutions of these compounds with alcohol, obtained a substance which was not fully examined, but was supposed to Ee :Lconjugate acid.I n a similar manner Klein obtained a bariumbiboromannitate. The author points out that Klein's investigationdeals only with a secondary reaction, owing to the influence of thewater employed in his experiments. By the action of anhydrousmannitol on anhydrous sodium pyroborate at 140°, a mass wasobtained which yielded to ether a substance crystallising with difficultyin feathery tufts and giving a vivid green flame reaction. This bodywas easily soluble in absolute alcohol, the solution being but faintly acid,although the aqueous solution was strongly so, and gave the reactionfor boric acid and for mannitol. The mass which had been extractedby ether contained sodium metaborate. These experiments indicatethat mannitol deconiposes sodium pyroborate in a manner similar toglycerol. The action of dextrose and levulose, when heated withimhgdroas sodium pyroborate, was also examined, and in each case asubstance was extracted by ether giving a green flame reaction, whilstthe residue contained sodium metaborate.The nature of the primary reaction between sodium pyroborate andglycerol, mannitol, dextrose, and levulose having been thus deter-mined, it was found by further experiments that the change fromacidity to alkalinity, occasioned by heat in aqueous solutions, was dueto the dissociation of the undecomposed sodium pyroborate and meta-borate.When boric acid or other acid is added to an aqueous andtherefore partially decomposed solution of sodium meta- or pyro-borate, until the liquid is faintly acid, alkalinity is reproduced by theaddition of more water as this further decomposes these salts, iiber-ating alkali in quantity more than sufficient to neutralise the acid280 ABSTRACTS OF CHEMICAL PAPERS.The same result is obtained when the faintly acid liquid is heated, batthe acidity is reproduced as the solution cools. W.R. D.Synthesis of Lecithin. By F. HUNDESHAGEN (J.py. Chem. [a],28, 219--255).-As Diaconow has stated that lecithin splits up intoneurine and dis terylglycerolphosphoric acid on treatment withdilute sulpburic acid, the first step towards the synthesis of lecithinwas to prepare this acid, which can exist, in two isomeric forms:(CH,.OSt),CH.O.PO(OH), or CH,(OSt).CH(OSt).CH2.0.PO(OH),,where St = C0.C17H,.Two general methods seemed t,o be adaptedfor this purpose, namely, substitution of the hydroxylic hydrogen inglycerolphosphoric acid by stearyl, or the union of phosphoric acidwith a glyceryl stearate. From the readiness with which glycerol-phosphoric acid decomposes, experiments based on the first metho{ldid not yield the desired result, although they gave rise to some ncwcompounds which are described further on.Arnoiigst the reactions founded on the second rnet'hod, the action ofphosphoric acid,, tribasic potassium phosphate, and phosphorus oxy-chloride on tristearin all failed to form the distearyl acid, but betterresults were obtained with distearin.Monosteurin was prepared by heating stearic acid with anhydrousglycerol (2.5 parts) in sealed tubes a t 200-220" for about 40 hours ;and the upper layer consisting of the crude monost8Parin was purified byrepeated crydallisation from alcohol and ether.It melts at 60--62",and is very soluble in warm alcohol and ether. The distearin wasprepared by heating molecular weights of stearic acid and crudernonostearin in a retort a t 150-HO", until the water which distilledover was that which should have been eliminated theoretically ; it isadvisable to somewhat increase the temperature (to 200") towards theend of the reaction. To purify the crude product, it is first heated withabsolute alcohol (50- 60 parts), when the greater part of the distenrinremains undissolved, and nearly all the rest is deposited as the liquitlcools; the monoste:trin and stearic acid remain in solution.Thedistearin is then dissolved in hot light petroleum, agitated withcalcium hydroxide t o remove the last traces of stearic acid, and thedistearin which separates on cooling is repeatedly recrystallised fromlight petroleum until its melting point is constant a t 76.5". It cry,-tallises from hot alcohol, in which it is but sparingly soluble (1 : 150)in tufts of glistening needles. From ether,. petroleum, benzene, $c.,in which it is far more soluble, it separates in compact nodules builtup of slender needles.Although there appeared to be another isomeric distearin in themother-liquors, as well as other easily soluble compounds, the authorwas unable to isolate them, and therefore confined his investigationsto the derivatives of the disteariu just described, which he callsa-distearin.Anzmoni?~/iz distearyZ gZyceroZ, CsH,( OSt)2.0NH4, is obtained as avoluminous precipitate consisting of thin prismatic crystals on passingdry ammonia into a warm ethereal solution of distearin.I t is some-what unstable, losing part of its ammonia on exposure to the air, andthe whole at 100-120". The corresponding sodium conipound seemORGANIC CHEMISTRY. 281to be formed on treating a Benzene solution of distearin with sodium ;the metal dissolves, with evoliltion of hydrogen, and the liquidgradually becomes changed into an opalescent gelatinous mass.Acetyl distearyl glyceyol is formed when distearin is heated withacetic anhydride, acetic acid, and metaphosphoric acid at 120'; nodoubt acetic anhydride alone with distearin would give the sameresult.After being purified by crystallisation from alcohol, it melts at28-30'. It does not crystalhe well, and decomposes when stronglyheated.n-Distear?/lglycero~pho,sphoric Acid. - This acid is formed whendistearin is heated with ethylphosphoric acid, metaphosphoric acid,or phosphoric anhydride. The best method is to heat the distearilnwith about its own weight of phosphoric anhydride for some hours a t100-110" : the product is macerated under alcoho!, digested forsome time with warm alcohol to remove adhering phosphoric acid,and finally collected and washed with cold alcohol. The residue con-taining distearin and the glycerol acid is now extracted with hotalcohol, and excess of finely powdered sodium hydroxide is added tothe hot solution, when carbonic anhydride is evolved, and the sodiumsalt of the acid separates ; this is collected a t once and washed withhot alcohol.In the washings there is, besides sodium stearate andethyl stearate, a readily soluble sodium salt of an acid containingphosphorus, probably an isomeric distearylglycerolphosphoric acid ;t>his crystallises in scales melting a t about 60". The crude sodiumsalt above mentioned is purified by repeated recrptallisation fromlight petroleum. The free acid may be obtained from this b j dis-solving it in a little warm acetic acid, decomposing it with dilutesulpliuric acid, collecting the acid which is deposited in a floccnlcntRtate, and purifying it by solution in ether and evaporation.Theacid is, however, more conveniently prepared from the ammoniumsalt obtained by passing ammonia into a warm petroleum solution ofthe crude acid, collecting the crystalline precipitate, and washing i twith hot alcohol; when this is heated a t 130-140" for some time,ammonia is given ~ f f , and the free acid is left. It crystallises fromits solutions as a fatty mass consisting of minute needles, which softena t 55" and melt a t 62.5". It is easily decomposed when heated withdilute acids. The author has prepared and described the potassium,sodium, ammonium, calcium, ferrons, ferric, copper, lead, silver, andmercury salts of the a-distearylgl~cerolphospl~oric acid.Both theacid and its salts burn with a green-edged flame when strongly heated.a-Distear!llglycerolyhos~horia chloride is formed when distearin(4 parts) is heated with phosphorus oxychloride (1 part); hydro-chloric acid is evolved, and a very dark-brown liquid is left ; this isfirst freed, as far as possible, from hydrochloric acid and excess of oxy-chloride by a current of warm air, then taken up with ether, and theethereal solution mixed with about twice its volume of absolute alco-hol, when dark-brown impurities are thrown down and are remoredby filtration. The ethereal solution is evaporated in a vacuum, a,ndthe crystalline crusts which form again dissolved in a little ether andevaporated. The colourless crystals of the chloride obtained in thisway are very soluble in most menstrua, melt a t 24", and are sQmewl.irt282 ABSTRACTS OF CHEMICAL PAPERS.hygroscopic. It is very readily decomposed ; with water at theordinary temperature, it yields stearic acid, glycerolphosphoric acid,and hydrochloric acid, but 110 distearglglycerolphosphoric acid.When distearylglycerolphosphoric acid is warmed with a slightexcess of neurine carbonate in alcoholic solution, and then evaporated,an indistinctly crystalline hygroscopic mass is left, which is easilysoluble in water, alcohol, and ether.The neutral neurine distearyl-glycerolphosphate crystallises from the last-mentioned solvents inminute needles. The acid distearylglycerolphosphate,CJH,( 0s t).-. 0.PO (OH). ONMe2.C,H4.0H,is obtained by mixing neurine and the acid in proper proportions inalcoholic solution and evaporating.Its properties differ entirely fromthose of lecithin, so that these are isomeric compounds.The author then gives an account of some neurine compounds, Thehydroch Zoride is dimorphous, crystallising in long needles and in thinrhombic plates. The iodide of the hydrochloride, C1NMe,.C2H41,obtained by the action of strong Iiydriodic acid on the hydrochloride,separates from hot solutions in prisms, and from cold in rhombicplates. The iodide of the hydriodide forms thin iridescent plates.The platinochloride is trimorphous, cry stallising in large orange-coloured prisms, in red-brown rhombic plates, and in regular octo-hedrons ; both the other forms gradually change into the rhombicplates.This change can be easily seen under the microscope, and Rdetailed description of the best methods of observing it is given.The platinochlorides of other two bases formed during the prepma-tion of ueurine are also described ; one of these the author believes tobe an amine, the other a higher homologue of neurine.I n an appendix, some substances which have been prepared in thecourse of this research are described.By the action of metaphosphorio acid at 120-150" on distearinthat was not quite pnre, the sodium salt, of an acid containing atearyland phosphoric acid was obtained ; it is easily soluble in water, andcrystallises in needles which melt at about 35". The sodium salt isinsoluble in alcohol, but soluble in ether, and very soluble in water.I t is possibly a monostearylgl~cerolphosphoric acid derived frommonostearin existing as an impurity in the distearin.Another sodium salt, insoluble in water, was obtained by treatingethyl phosphate with distesrin in alcoholic solution, distilling off theresidue, and converting the acids into sodium salts.The sodium saltis almost. insoluble in water and ether, but easily sohble in aqueousalcohol, and cryst'allises in microscopic scales.Monostea.1.?!ZdiyZyceroZ, C,H,(OH) (OStl).0.C,H5(OH)2, was preparedby heating stearic acid and glycerol a t 230-250". It is very solublein ether and in hot alcohol, crystallising from the latter in microscopicplates which melt a t about 30".NormaZ glyceryl phosphate, C3H5iPOP, seems to be formed whenglyceryl tribrornide, C3H5Br3, is treated with normal silver phosphate.A syrupy substance is obtained which, when heated with water,yields glycerol phosphoric acid.The normal phosphate seems to bedecomposed in a somewhat similar manner by t.rcatment with alcoholORGANIC CHEMlSTRY. 253for Then glyceryl tribromide is heated a t 200" with silver phos-phate and absolute alcohol, two isomeric dieth~lg7ycero~~hosphoAc acidsare formed, apparently CH,( OE t) . CH ( OEt ) .C Hz. 0 .PO (OH) '1 and( CH,.0Et),.CH.0.PO(OH)2. The contents of the tubes are filteredfrom silver bromide, the alcohol removed by distillation, and thesyrupy residue dissolved in water and saturated with barium carbon-ate. On concentrating the clear solution and adding alcohol, thebarium salts are precipitated ; these may, to a certain extent, be sepa-rated by carefully evaporating the aqueous solution of this precipi-tate; the barium salt of one of the acids thus separates as a whitegranular precipitate, whilst the amorphous barium salt of the otheracid remains in solution.C. E. G.Behaviour of Dextrose with Ammoniacal Alkaline SilverSolution. By B. TOLLENS (Landw. Verszichs.-Stat., 29, 392-3951.-With silrer solution containing 0.034 gram Ag to the cubic centi-meter, and prepared with equal quantities of silver nitrate and causticsoda dissolved in excess of ammonia, dextrose reduces 12 atoms ofsilver: the reaction seems to follow the equation C6H,?O6 + 6 0 =GCH202, formic acid being the chief product.The author discussesthe bearings of this reaction on the constitution of dextrose, andinfers that it does not contain either an aldehyde or ketone group.J. K. C.A New Saccharin from Milk-sugar. By H. RILIANI (Ber., 16,2625--3629).-By the action of lime on milk-sugar and on maltose,Cuisinier (Monit. Xcient., 1882,520) obtained the lime salt of a lactone,C6H1005r which he named isosaccharin t.0 distinguish i t from Peligot'ssaccharin. I n preparing large quantities of isosaccharin, the authorhas discovered a new saccharin (metusaccharir~). 1 kilo. milk-sugaris dissolved in 9 litres of water, 450 grams of calcium hydrate added tothe cold solution, and the whole allowed to stand for six weeks withrepeated agitation ; the clear brown sslution is separated by a syphon,saturated with carbonic anhydride, and heated to boiling.On evapo-rating the filtrate to about 2 litres, an abundant separation of calciumisosaccharylate takes place, and, after 24 hoars, is filtered off andwashed with cold water. After leaving a portion of the filtrate forseveral months in a closed bothle, a crystalline layer separated a t thebottom, whilst mould formed on the surface of the liquid, and onpurifying the crystals, a calcium derivative Kas obtained very sparinglysoluble in cold water and crystallising in nodules or hard crusts con-sisting of microscopic prisms. It I s the calcium compound of a newsaccharinic acid, its formula being (C6H,,O6),Ca + 2H20 ; it loses itswater of crystallisation Gt 120-1:30"- On decomposing its solutionwith oxalic acid and evaporating the filtrate, moderately large colour-less rhombic crystals of m,etasnccharin are obtained, having a slightlybitter taste, and showing a perfectly neutral reaction. Its formula isC6HloO5, but its properties are very different from those of Peligot'ssaccharin and Cuisinier's isosaccharin ; it crystallises in the rhombicsystem : a : b : c = 0.6236 : 1 : 8988.I t s aqueous solution is laevorota-tory [a]= = -48.4, whilst sncchaibin and isosaccharin are dextroro-tatory. It softens at 135", becomes completely liquid at 142", and284 ABSTRACTS OF CHEMICAL PAPERS.after resolidifying, melts at 141-142”. It dissolves readily in coldwater, its solubility being intermediate between that of isosaccharinand of saccharin ; the solution becomes acid on standing,.probablythrough the formation of metasaccharinic acid. It is readily solublein alcohol, very sparingly in ether. Like saccharin and isosacchmin,it yields salts of the corresponding saccharinic acid by boiling withmetallic oxides o r carbonates; the copper salt, (C~HI~O~)&U 4- 2&0,forms greenish wart-like clust’ers of microscopic scales. On repeatlingthe experiment, tjhe author finds that calcium metasaccharin is aconstant product of the action of lime on milk-sugar. A. K. M.Elementary Composition of Wheat-starch, and the Actionof dilute Acetic Acid on Starch. By L. SCHULZE ( J . pr. C h e r ~ .[2], 28, 311--338).-The author has examined wheat-st,arch in themanner detailed by F.Salomon in his paper on potatwstarch (Abstr.,1882, ll83), f o r the purpose of satisfactorily deciding whether theformula C30HS2031, given by Naegeli, is correct. The results pointconclusively, in the author’s opinion, to the formula CT6H,,0,. Wheat-starch carefully washed first with dilute caustic soda, then with dilncehydrochloric acid, afterwards with water, and finally air dried, wasfound to consist of 79.696 per cent. plnre starch, 20.143 per cent.water, 0.061 per cent. ash, and 1.1 per cent. insoluble residue. Fourseries of experiments were carried out. 1. The conversion of the starchby hydrochloric acid (the reaction is incomplete with sulphuric acid)and estimation of the resulting dextrose by a copper salt (Allihn’smethod) ; 100 parts absolutely pure starch (or 127 parts air dried)gave 110.986 parts dextrose, whilst theoryrequires 111.1 parts for theformula, C6HIoO5.11. The conversion by hydrochloric acid and esti-mation of the dextrose by the ~ p . gr. ; the average of four determina-tions gave 111.4 parts dextrose per 100 parts chemically pure starch.111. The conversion by hydrochloric acid and the observation of theyotatory power of the resulting dextrose solution; the average offour determinations gave 111.85 pep cent. dextrose per 100 parts purestarch. 1V. The elementary analyeis 04 the purified air-dried starch,calculated from the a.mount chemically pare starch contained ; theaverage of six- combustions agrees with the formula C6HI0O5.Little being known of the action of dilute acetic acid on starch, andthat little being of a contradictory nalure, a number of experimentson various starches with various strengths of acid were made.Thebest results were obtained with rice-&arch in a 10 per cent. solutionwith 20 per cent. acetic acid. The resnlts show that by heating rice-starch with acetic acid f o r four houra under pressure, almost thewhole is converted in to dextrin (Bondonneau’s dextrin, a-modifica-tion), and only traces of dextrose are formed. By continued actionof heat, however, the dextrin is slowly converted into dextrose.A. B.Inulin in the Artichoke. By PISTONE and DE REGIBUS (Pharm.JourTa. [3), 14, 52).-The bracts of the artichoke, Cynura scolymus,were boiled with water mid pressed, the liquid filtered, and againboiled and filtered when hot.The solution when slowly cooled de-posited a white flocculent substance which, after being washed witORGANIC CHEMlSTRY. 285boiling water and alcohol, was proved to be nearly identical withSach's spherocrystals of inulin : it was not coloured by iodine, andwas laevorotatory. W. R. D.Chemical Composition of Woody Tissues. By N. SCHUPPE(Pharn~. Journ. [3), 14, 52).-The cellulose ohtained from the woodytissues of pine, poplar, mahogany, American and European nut, oak,a,nd alder, by treatment with nitric acid and potassium chlorate, hasthe same composition as pure cellulose, C6H,,06. The wood of theEuropean and American nut nearly coincides in composition withcellulose ; that of rna>hogany and oak has the formulac,,H,,o~~ = ~c,H,,o, + C ~ H , ~ ,and the wood of poplar and alder the formula C,HEI06 = C6Hln05 +Czl&O.The proportion of lignin to cellulose is fairly constant indifferent woods, 17.6 per cent. of lignin to 40.7 per cent. of cellulose.The author considers that lignin has the formula C19H1R08r which isnearly identical wit#h that of catechin, and hence obtains as an ap-proximate formula for woody fibre, 5C6H,,05 + CIgHl,08. Only atrace of gum was found i n the wood of conifers, but 3.25 per cent. inpoplar and 7-09 per cent. in alder.By R. BEHREND (Annalen, 222, 116--136).-1n studying the action oEsulphonic chloride on ammonia, Regnault ( J . pr. Chein., 18, 98)obtained sulphonamide, S02(NH,),, but was unable to separate it fromthe simultaneously formed ammonic chloride.Wenghoff er (J. pr.Ohem., 16, 448), in acting wit'h sulphonic chloride on aroiiiatic amines,obtained only chlorine-substituted amines. The author has studiedthe action of sulphonic chloride on secondary fatty nmines, whichbehave very differently. The action of sulphonic chloride on di-methylamine has been already descibed (Abstr., 1881, 716), as alsothat of sulphonic chloride on the hydrochloride of dimethylamine(Abstr., 1882, 164), whereby dimethylamidosulphonic chloride isformed. An equally good yield is obtained if crude trimethylarnineis employed; it is only, however, the dimethylamine in the latterwhich takes part in the reaction. If a chloroform solution of di-~nethylamidosnlphonic chloride is added to dimethylamine, tetra-methylsulphonamide is formed, which can be purified as above :-SOpC1.NMe2 + 2NHMez = (NMe,),SO, + NHzMezC1.Tetramethyl-sulphonamide is decomposed by g ~ e o u s hydrochloric acid a t 120",dimethylamidosulphonic chloride and dimethylamine hydrochloridebeing formed:-(NRfez)zS02 + 2HCl = S02C1.NMe2 + NHzMe2C1.Aniline and dimethylamidosulphonic chloride yield dimethylphenyl-sulphonamide, 3fe2N.SOaNH.Ph, crystallising in needles, and meltingat 84-85', was prepared. This body dissolves in sodium hydroxidewith formation of a sodium compound, NMez.S02.NPhNa, which isdecomposed by hydrochloric or carbonic acid, with reproduction ofthe sulphonamide. Similar compounds were prepared by employingparatoluidine instead of aniline.Dimethylamidosulphonic chloride isonly slowly acted on by cold water, but on heating it is principallyW. R. D.Action of Sulphonic Chloride on Secondary Amines286 ABSTRACTS OF CHEMICAL PAPERS.converted into dimethylsulphonamic acid, a small quantity of aciddimethylamine sulphate being formed a t the aame time :-(1.) SO,Cl.NMe, + H,O = OH.SO,NMe, + HCl.(2.) S02C1.NMe2 + 2H,O = OH.S02.0NH2Me2 + HCl. The ether ofthis acid was prepared by heating an alcoholic solution of dimethyl-amidosulphonic chloride with sodium ethglate :--S0,ClNMe2 +NaOEt = NaCl + SO,(OEt)NMe,. On reducing the amidosulphonicchloride with hin and hydrochloric acid, the following reaction takesplace:-SO,Cl.NMe, + 4Hz = SH, + NH,Me,Cl + 2H20, whilst withzinc-dust the tetm.rnethylsi~lphonarnide is formed :-S0,C1NMe2 +Zn= S0,(NMe2),+ ZnCl, + SO,.Diethylamidofiulyholiic chloride wasprepared in the same way as the corresponding methyl compound ; itis, however, far less active than the latter. By the action of dimethyl-amine on diethyEamidosulphonic chloride, the same dimetliyldiethvl-sulphonamide is formed as when diethylamine acts on dimethylamido-sulphonic chloride, as was to be anticipated from analogy with thesubstituted carbamides. P. F. F.Trimethylamine Auroehloride. By C. E. ZAY (Ga;azetta, 13,420---421).-This salt, originallv obtained, but not described, byVincent (BUZZ. SOC. C'him. [2], 27, 194), is easily prepared by addinga concentrated solution of aiiric chloride to a solution of trimethyl-amine hydrochloride, washing the resulting precipitate on a filter withether, which removes only the excess of gold chloride, whereas waterwould dissolve some of the aurschloride itself. The dried salt formsa crystalline mass having a fine chrome-yellow colour and an odour ofputrid fish.It is permanent in a vacuum, but slowly turns brown onexposure to the air. On heating it, the fishy odour becomes stronger ;a t 220" the salt melts, and at higher temperatures it decomposes,leaving metallic gold. The salt is anhydrous, and has the formulaNMe3HC1,AuC1,. It dissolves readily in water and in alcohol, but isinsoluble in ether. The aqueous solution, when allowed to evaporateat ordiiiary temperatures, leaves the salt in well-defined transparentbrown- y ellow crystals, likewise anhydrous. H.W.Tetramethylammonium Cyanide. By C. M. THOMPSON (Ber., 16,2338-2345) .-This componnd can be obtained by adding an excessof hydrocyanic acid to a strong solution of tetramethylammoniumhydroxide ; the solution when evaporated yields a brown crystallinemass, which may be obtained in prisms by recrystallisation from alcohol.The cyanide may also be prepared by decomposing: the double cyanideof silver and tetramethylammonium with sulphuretted hydrogen.This cyanide gives the reactions of cyanides, and is decomposed by theweakest acids, with liberation of hydrocyanic acid. It volatilises a t225-227" without melting, producing alkaline vapours having an(>dour of trimeth ylamine and carby lamine.Te tramethylam moniu mcyanide when saponified with caustic potash behaves like potassiumcayanide, yielding ammonia, formic acid, and a tetramethylammoniumcompound.Double salt of silcer cyanide with teti.amefhylammoniuIm cyan&ORGANIC CHEMISTRY. 287NMe4CN,AgCN, is obtained by adding silver cyanide to a warm solu-tion of tetramethylammonium iodide. It crystallises from hot alcoholin long, slender, colourless needles ; is slightly deliquescent, andinsoluble in ether. btmzene, light petroleum, and chloroforni ; it meltsat 211-212". This salt is also formed on adding silver cyanide toa solution of tetramethylammonium cganide. On distillation, thisdouble salt yields a residue of silver cyanide and a distillate contain-ing trimethylamine, carbylamine, and acetonitril ; this distillate,treated wit,h au alcoholic solution of trimethylamine ai;d silvercyanide, yields a solid compound containing both cyanogen and silver,which could not be proved t o be identical with the double cyanide ofsilver and tetramethylammonium.Acetonitril and trimet hylarniuedo not appear to combine. P. P. B.Hexmethylenamine. By L. PRATESI (Gazzettn, 13, 437-438).-It is known that trioxymethylene, C3H603, is easily converted byammonia into Butlerow's hexmethylenamine, (CH2)6N4, which whenCreated with silver nitrate gives a white crystalline precipitate, per-manent or nearly SO in diffused daylight when dry, decomposing withslight deflagration when heated.This precipitate, not hithertonnalysed, has been found by the author to contain 18.03 per cent.carbon, 3-46 hydrogen (mean of two analyses), 19.32 nitrogen, and40.60-40.73 silver, leading to the formula 2C6HI2N4,3AgNO3. Thiscompouud, slightly soluble in cold water, dissolves more freely inboiling water, but with partial decomposition, producing a specula^deposit of silver on the sides of the vessel. Prom a hot solution, itseparates on cooling in needle-shaped crystals.Isobutylbiguanide, C6H15N5 = C,H,(C,H,jN,, and its Com-pounds. By A. SMOLKA (Monatsh. Chem., 4, 813--832).-CqwicIsobutylguanide Xulphate, (C6H14N5)2C~,H2S04, is prepared by mixinga solution of cupric sulphate with a solution of isobutylamine (ofabout 20 per cent.) in such quantity as to form a dark-blue perfectJyclear liquid, mixing this solution with dicyanodiamide, and eitherleaving the mixture to itself at the temperature of the air, or heatingit in a sealed tube a t about 100".In the latter case, the salt separatesafter ten or twelve hours on the sides of the tube, as a dark-red gra-nular film, the liquid a t the same time assuming a red-violet colour.At ordinary temperatures, a lighter-coloured deposit is obtained afterabout a week, and the mother-liquors, if left over night in a vesselcooled by ice, deposit a small additional quantity of the compoundlighter in coiour than either of the preceding. The formation of thiscopper-compouiid is represented by the equation 2C2H4N4 + 2C,H11NThis sulpbate separates from solution at temperatures above 60" incrimson anhydrous grains ; from concentrated solutions a t ordinarytemperatures, in rose-red crystals with 1 mol.HzO ; and fyorn dllutesolutions at 0" in light rose-coloured crystals containing 3H,O. Thocrystal-water is given off slowly, but completely, a t 105-110" ; morequickly at 125-130". The salt may be heated to 140" without decom-posit ion.H. W.+ CUSO~ = ( C~H,~N~)~CU,H,SO~288 ABSTRACTS OF CHEMICAL PAPERS.The hydrooh,Zoride, (C6H,,N5)2Cu,2HC1 + &HzO, obtained by decom-posing the sulphate with barium chloride, crystallises in pale rose-redmicroscopic needles, of ten forming hemispherical or kidney-shapedgroups, and like the sulphate, bears a heat of 140" without decom-position. 1 part of this salt dissolves in 37.76 parts water, forming adeep violet solution: the salt is insoluble in alcohol.Zinc or ironimmersed in the neutral aqueous solution throws down the whole ofthe copper, leaving in solution the hydrochloride of isobutylbiguanide.The nitrate, (CsH,4Nz)zCu,2HN03, prepared by decomposing thesulphate with barium nitrate, remains, after evaporation of its solutionin a vacuum, in rose-red crusts and spherical groups, resemblingthose of the hydrochloride. When heated on platinum-foil, it decom-poses with glimmering combustion,. giving off vapours smelling ofisobutylamine, and leaving cupric oxide. It is much less soluble thanthe hydrochloride ; the aqueous solution is violet.Cupric Isoh uty Zbiguanide, ( C6H14N5)zC u, is best prepared by treatingthe hydrochloride or nitrate with soda-lye, whereupon it separates asa bulky rose-coloured precipitate, which, after draining and drying,forms a thick magma of rose-red silky needles, dissolving verysparingly in cold, somewhat more freely in hot water, with red-violetcolour, and remaining on evaporation over sulphuric acid in carmine-coloured crystalline granules.It is a strong base, exhibiting greataffinity for acids, including carbonic acid ; its aqueous solution has analkaline reaction, and it expels ammonia from sal-ammoniac on boiling.It dissolves readily in dilute nitric and hydrochloric acids, formingst first the corresponding salts of the copper-base, but if the acid isin excess, the copper is dissolved out and a salt of the non-cnpreonsbase is produced.SULPIIATES OF IsoBnTrLBIGnAN1DE.--The no?'mnz subhate,is prepared by triturating the corresponding salt of the copper-basewith water, rinsing it into a flask, and heating it in a water-bathwhile a slow stream of hydrogen sulphidc is passed through the liquidfor several hours.On filtering from the copper sulphide, and evap-rating, first on the water-bath and finally in a vacuum over sulphuricacid, the normal sulphate ia obtained in large limpid crystallinelamine, and, after recry stallisation, in transparent triclinic prismswhich are permanent in the air, but slowly effloresce in a vacuumover sulphuric acid, and melt and decompose when heated on platinumfoil. The crystals dissolve in 3.8 parts water at 16", forming a neutralsolution, which is precipitated by alcohol. The acid suZphute,C,Hl,N,,H,SO~,~HzO, crystallises in large transparent plates, muchmore soluble than the normal salt, and is precipitated from the soln-tion by alcohol.HyDltOCHLORiDES.-The normal salt, CEHI5N5,HCI, obtained by de-composing the warm solution of the nornial sulphate with bariumchloride, forms, after repeated crystallisation, long thin transparent1,rittle anhydrous prisms, soluble in 2.5 parts water a t 16*5", meltingn t 216", and decomposing whm more stl-ongly heated on platinumfoil.The acid salt, C,H15N5,2HHCl, crystallises with great difficultORGANIC CHEMISTRY. 289from its aqueous solution ; from alcohol, it separates in anhydrousneedles often grouped in feathery tufts, and is precipitated from itsalcoholic solution by ether. It is deliquescent, has an acid reaction,and melts at 194".The platinochloride, C6H,,N5,H2PtCL,H20,crystallises from alcohol in fan-shaped groups of yellow four-sidedplates ; from water in crusts composed of yellow needles.Issobutylbiguanide, C6HI5NI = C,H,( CaH,)N5, is obtained by decom-posing the normal sulphate with the requisite quantity of baryta-water, and, after evaporation in a vacuum over sulphuric acid, formsit thick uncrystallisable syrup. Its aqueous solution has a stronglyalkaline reaction, decomposes ammonium salts at a gentle heat, andwhen added to salts of most of the heavy metals, or to those ofAl, Mg, Ca, Sr, and Ba, immediately throws down the correspondinghydroxides, especially those of the three last-named metals.Itquickly absorbs carbonic acid from the air, and solidifies to a mass ofdeliquescent needles consisting of the carbonate.As regards the position of the alkyl-radicle in isobutylbiguanide, itmay be observed that, on heating the compound! with chloroform andalcoholic soda-lye, the corresponding carbylamine o r isocyanide isgiven off, and may be recognised by its characteristic odonr ; and asthe formation of isocyanides is very characteristic of amines, itappears not improbable that the alkyl is situated in an amidogen-rather than in an imidogen-group.If then biguanide be represented, as in the author's paper, by theformula NH,.C( NH) .NH.C(NH).NH,, its isohtyl-derivative musthave the constitution NH( CHzP#).C (NH).NH.C( NJ3).NH2, but ifbiguanide be correctly represented by Emich's formula(this Journal, 1888, AbsCr., 973), then! isobuityl-bignanide must be consti-tuted as shown by the formula NH : C(NB.CH,Pr@).NH.C(NHz) : NH.Acetyl-pyrroline and Pseudoacetyl-pyrroline. By G. L.ClAMlCTAN and M. DENNSTEDT (Gazzetta, 13, 455-465 ; and Ber., 16,2348--2357).--The crystallised body melting at 90" which R. Schiffobtained by heating pyrroline. with acetic anhydride (Abstr.,1878, 216) was regarded by him as acetyl-pyrroline, in which theacetyl-group took the place of the hydrogen in the imidogen-groupof the pyrroline-mslecuk, that is, as represented by the formulaz N / [ ; but the experiments described in the present papershow that in thre compound thus prepared the acetyl-group isdireclJy attached to a carbon-atom, as represented by the formula11 or HN// 11 For distinction, the latter of these *v H .CH \'CH.CHcompounds is designated as acetyl-pyrroline, the former as pseudoacetyl-pyrroline. These two compounds are formed together by the actionof acetic anhydride on pyrroline ; the latter, however, in much thelarger quantity. They m-.y b: prepared and separated by heatingNH : C(NHz).NH.C(NH,).: NHH. W.CH.CH'CH.CH 11,CH.CZ CKc.CNVOL. XLVI. 290 ABSTRACTS OF CHEMICAL PAPERS.pyrroline with acetic anhydride and recently fused sodium acetate inan oil-bath, and distilling the resulting black semi-solid mass in awater-bath under reduced pressure ; treating the yellow and browncrystalline residue thereby obtained with water ; and distilling it in acurrent of steam.An oil beavier than water then passes over, andwhen this oil begins to deposit crystals on cooling, the operation isdiscontinued. The red-brown liquid then remaining in the flask con-tains in solution nearly the whole of the pseudoacetyl-pyrroline, pro-vided the quantity of water is sufficient ; if not, more must be addedand the entire solution boiled with animal charcoal. The filteredliquid after 24 hours deposits the pseudoacetyl-pyrroline in very fineneedles several centimeters long, which are easily purified by two orthree crystallisations from boiling water. The remainder of thepseudoacetyl-pyrroline may be extracted froin the aqueous solution bymeans of ether.Pseudoacetyl-pyrroline melts at go", boils at 220°, and agrees in itsother physical properties with the body described by Schiff.It is not,however, resolved into acetic acid and pyrroline by boiling with potash,as stated by Schiff, but the solntion on cooling deposits a whitesolid mass, which is perhaps the potassium-compound ; it dissolves ondilution ,with water, and ether extracts from the solution unalteredpseudoacetyl-pgrroline. On mixing a solution of pseudoacetyl-pyrroline in boiling water with a strong solution of silver nitrate andadding a few drops of ammznia, a white crystalline precipitate isformed of the silver salt CbHzAc NAg. This reaction shows distinctlythat the acetyl-radicle has entered into the nucleus of the pyrroline,and that the imidogen-group NH has remained unaltered.By oxidation with potassium permanganate, pseudoacetyl-pyrrolineis converted into the potassium salt of an acid having the compositionC,H,NO, = C,H,(CO.COOH) 1 NH.This acid may be separatedfrom the solution by acidulation with dilute sulphuric acid, and onagitating the liquid with ether, evaporating the ether, and crys-tallising the residue from boiling benzene, the acid separates ingroups of slightly yellow needles, which give off their water in theexsiccator, and have tho composition of an acetyZ-~yrroZine-carboxl!Zicacid, C6H5N03,H20. Tho dehydrated acid has a deep yellow colour,dissolves in boiling benzene, and separates from the solution aft'ertreatment with animal charcoal, in groups of very thin yellow needles,which begin to decompose a t 113--115" without showing any fixedmelting point ; when immersed in water they instantly turn white.They are slightly soluble in cold water and dissolve in hot water,forming a slightly yellow solution, which gives a deep red colour withferric chloride, and does not precipitate normal lead acetate.Heatedwith slaked lime, it appears to yield pyrroline, as indicated by theodour of the escaping vapours, and the reaction with a deal-shavingmoistened with hydrochloric acid. A hi hly characteristic reactioncarmine-red solution being thereby produced, somewhat like a solutionof eosin. On adding a base, a greenish-yellow colour is produced,changing t o rcd on acidification.The aqueous acid treated withsilver nitrate yields a white crystalline precipitate of the saltis exhibited on boiling t,he acid with hy cf rochloric acid, a very deeORGANIC ClHEMlSTRY. 291C,H,( CO. COOAg)NH, which dissolves in boiling water, and sepa-rates on cooling in colourless needles.ACETYL-PYRROLINE, C4H4N.C2H30 = A ' 11 is the oil whichpasses over on distilling with steam the product of the action of aceticanhydride and sodium acetate on pyrroline. It is purified by distilla-tion, and passes over between 160" and 200" ; a small portion whichdistils above that temperature and solidifies completely on coolingconsists of pseudoacetyl-pyrroline, which is slightly volatile withvapour of water. After a long fractionation of the liquid a t 160-200", a port,ion is obtained which boils constantly a t 176-180', thegreater part at 177-178'.This portion consists of normal acetyl-pyrroline. It may be obtained in larger quantity by the action ofacetic chloride on potassium-pgrroline.Acetyl-pyrroiine boils a t 177-178". It has a chayacteristic odour ;is nearly insoluble in water ; gives a white precipitate with aqueousmercuric chloride ; and dissolves in aqueous silver nitrate, which itreduces after some time, Its vapour reddens a chip of wood moistenedwith hydrochloric acid ; this acid also resinifies the compound. Acetyl-pyrroline dissolves in aqueous potash, and when boiled therewith, isquickly resolved into acetic acid and pyrroline.ACTION OF BROMINE ON PsEUDoACETYL-PYRRoLINE.-~chiff describesan addition-compound obtained by the action of bromine (1 mol.) onpseudoacetyl-pyrroline dissolved in glacial acetic acid.The authors,however, have obtained by this reaction only substitution-products.The action of bromine in molecular proportion on pseudoacetyl-pyrroline yields a mixture of compounds very difficult to separate.The following methods yield better results :-Monobromopsezl.doncetyl-pyrroline, C6H6BrN0 = C6H,BrffcNH, isformed, together with the dibromo-compound, by dissolving pseudo-acetyl-pyrroline (10 g.) in a slight excess of glacial acetic acid, andadding bromine (14 g,) dissolved in a small quantity of the sameliquid, whereupon a white precipitate is formed, consisting ofC6&BrNO, while C6H,Br2N0 remains in solution.The monobromo-compound crystallises from boiling alcohol in small white needles,which turn yellow on exposure to light, and melt at 118-120'.Dibromopse.lcdoacetyZ-pyrroline, CaH5Br2N0 = C4HBr,.zNH, is pre-pared by adding 2 mols. bromine to 1 mol. of the base, both dissolvedin glacial acetic acid, pouring the liquid into water, and dissolvingthe resulting white precipitate in boiling alcohol with addition ofanimal charcoal. The filtered liquid on cooling deposits small whiteneedles, which after a few crystallisations melt at 145-147', andhave a composition approximating to the formula C,H,Br,NO, butstill contain small quantities of a less highly brominated compound,from which the authors have not yet been able to separate it.Thepure dibromo-compound is, however, easily obtained by evaporatingthe alcoholic mother-liquors to dryness, and crystallising the residuefrom boiling water, in which it is sparingly soluble, with addition ofanimal charcoal. The liquid on cooling deposits the dibromo-corn-pound in small white needles, which turn yellow on exposure to light,CH.CH cN\c, H. c$x 292 ABSTRACTS OF CHEMICAL PAPERS.and after a few crystallisations melt at 143-144". The mother-liquors contain traces of unaltered pseudoacetyl-pyrroline. Themono- and di-bromo-compounds dissolve readily in aqueous potash,and are precipitated therefrom unaltered on addition of an acid.Penta bro mopseudoacety 1- p yrro line,C6H2Br5N0 = C4Br3(C2Br2HO)NH,is formed on adding bromine (4 mols.) to a solution of pseudoacetyl-pyrroline (1 mol.) in glacial acetic acid, and gently heating theresulting red liquid on the water-bath to complete the reaction.Thesolution, if an excess of glacial acetic acid has been avoided, depositsthe pentabromo-compound on cooling in small colourless needles,which may be purified by a few crystallisations from boiling glacialacetic acid. They melt at 200". The mot.her-liquor contains lesshighly brominated compounds, which may be precipitated by water.The sixth disposible atom of hydrogen in pseudoacetyl-pyrrolinecannot be replaced by bromine by working in the manner abovedescribed even with larger quantities of bromine; but this finalsubstitution, might perhaps be effected by heating in sealed tubes.H.W.Derivatives of Pyrocoll. By G. L. CIAMICIAN and P. SILBER(Bey., 16, 2388-2399) .-TetrabromopyrocoZZ, Cl,Br4H2N20,, obtainedby heating pyrocoll with bromine in sealed tubes at loo", is insolublein most solvents save glacial acetic acid, from which it crystallises insmall yellow needles ; it is decomposed at 250". When heated withcaustic potash, it is converted into dibromopyrrolcarboxylic acid,Octochloride or Perchloride 0 f PerchloropyrocoZZ, c,,H6( Cl8)N2o2.-In a former communication (Abstr., 1€?82, 875) one of the authorshas shown that pyrocoll is converted by the action of phosphoruschloride into perchloropyrocoll, CloC16N,02, and two other bodieshaving the formulae C~oC11,N20 and CaCl72JO.This latter compoundthe authors regard as perchloride of perchloropyrocoll, and assign t oit the formula CI0Cll4N202, double that assigned to it in the previousmemoir. It crystallises from glacial acetic acid in large cubical crys-tals, which can be easily separated by mechanical means from the flatprisms of the compound C10CI&T20.By the action of zinc on a solution of perchloride of perchloro-pyrocoll in dilute acetic acid, tetrachloropyrroline, C4CI4NH, is formed.It crystallises from light petroleum in long silky needles, melting atl l O o , easily soluble in alcohol and ether, but only sparingly in water.It is very volatile, and emits an odour resembling that of tetraiodo-pyrroline. In its properties it resembles those of a weak acid, andgives a white precipitate with ammoniacal solutions of silver nitrate.In explanation of the formation of this substance, the authorssuppose, first, that the perchloride takes up water to form the tetra-chloride of trichloropyrroline-carboxylic acid, and that this is thenresolved into carbonic anhydride and tetrachloride of trichloro-pyrroline ; the latter is converted into tetrachloropyrroline by nascenthydrogen. This series of reactions is represented as follows :ORQANIC CREAMISTRY. 293(1.) C~OCI~(CI,)N,O~ + H?O = 2C*CI,(COOH) (CI4)NH.(2.) C,C13(COOH) (C1,)NH = ( 7 0 2 + C,CI,H(CI,)NR.(3.) CaC13H(Cl,)NH -!- 2H = CkC1,NH + 3HC1.When perchloride of perchloropyrocoll is heated with dilute aceticacid in sealed tubes at 130", it is resolved into hydrochloric acid, car-bonic anhydride, and a compound having the formula CIC1,O,NH,which is eit,her a dichloromaleimitle or dichlorofumarinzide.Theformation is represented by the following equations :-(1.) CloC&(CI,)N?02 + 2H2O = 2CaC13H(CI,)NH + COZ.(2.) C~Cl~H(C1~)NH + !AH20 = C4ClZOLNH + 5HCl.(Comp. this vol., p. 176.)This same imide is obtained by the action of chlorine on snccin-imide at 160". It crystallises from water in long needles melting at179". With ammoniacal silver nitrate solutions, it gires a precipi-tate of an argentic ammonium compound, C4C1,02N.NH3Ag. A com-pound, which is either monochlorofumarimide or monochloromaleim-ide, C4C1H0,NH, is formed, together with this dichloro-derivative,when succinimide is treated with chlorine.It crystallises in largecolourless shining leaflets melting at 131".Caustic potash converts the imide C4CI,02NH into a deliquescentacid, which is easily soluble in alcohol, ether, and benzene, and is pro-bably dichloromaleic acid, C,Cl,H,Oa. When heated, it yields a com-pound less soluble in water, probably the anhydride. When thedichloromale?mide is heated with water in sealed tubes at 125", i tis resolved into carbonic anhydride, ammonia, and a-dichloracrylicacid.The conversion of the perchloride of perchloropyrocoll intodichloromale'imide suggested the possible synthesis of tetrachloro-pyrroline from the imide, which the authors have carried into effectIJY acting on the imide with phosphorus pentachloride, taking up withether, and subsequent treatment of the ethereal extract with zinc-dust and water.P. P. B.Oxymethylene and Formaldehyde. By B. TOLLENS (LanduJ.Versuclas.-Stat., 29, 355-392) .-The preparation and properties offormaldehyde have been studied by numerous authors. The chiefinterest which attaches to this subject is that very possibly formalde-hyde is the first assimilation-product of carbonic anhydride in thevegetable organism, and is afterwards converted by polymerisationinto the various carbohydrates which form the greater prupo~tion ofthe plant substance. The author made use of Hofmann's method,the oxidation of methyl alcohol by platinum foil. The best resultswere obtained when the water-bath in which the methyl alcohol washeated was kept at the temperature of 54--55".The quantity formedwas, however, always small? and averaged about 2 per cent. of thetotal distillate ; i t was estimated by an ammoniacal solution of equalparts of silver nitrate and caustic soda. The distillates can be con-centrated by further distillation, but the richest product obtained bythis method only contained 11.3 per cent. formaldehjde. By dryin294 ABSTRACTS OF CHEMICAL PAPERS.over sulphuric acid pure oxymethylene may however be obtained,although this method is attended with considerable loss. The vapour-density of oxymethylene was determined, and found to correspondwith the formula CH,O. Various ammoniacal solutions of silvernitrate were used for the exact quantitative estimation of oxymethy-lene, but no perfectly satisfactory method could be found.Heated with alkalis or alkaline earths, oxymethylene yields methylalcohol and formic acid.When the crude distillate of formaldehydeis heated with baryta-water, a yellowish precipitate is thrown down ;after freeing this from barium, an amorphous syrup is left behind,which strongly reduces Fehling’s solution, and on analysis gives num-bers approximating to the formula C,H,,O,. When it is heated withsulphuric acid, formic and lactic acids are. formed ; the latter was con-verted into its zinc salt and analysed. The syrup has no action onpolarised light, does not undergo fermentation, and yields no lamulicacid when treated with mineral acids. I n these properties it agreeswith the methylenitan obtained by Butlerow.In certain preparations of this syrup, small crystals were obtained,but the author is of opinion that they were due to the presence ofethyl alcohol, as they were never formed when perfectly pure methylalcohol was employed.J. K. C.Thioaldehyde and Carbovaleraldine. By L. GUARESCHI (Gaz-zettu, 13, 500).-When thioaldehyde is oxidised with potassium per-manganate it yields sulphuric, acetic, and ethglidenesulphuric acids,together with oxy sulphides, including the compound CsHI2S20,. Byoxidising the same body with zinc permanganate, the author obtainedsulphuric acid, acetic acid, and the oxysulphides c6H,,S3o5, C6H12Ss0,,and C6H,,S302. The formation of ethylidenesulphuric acid and theoxysulphides points to the conclusion that solid thioaldehyde containsthree CzH4S-groups joined together by salphur-atoms, as representedCHDIIe-S-MeHCS -CHMe- Sby the formula 1 I .C a r b o v a l e r a l d i n e is converted by ferric chloride into thiocyanicacid ; by potassium permanganate into hydrocyanic, sulphuric, andvaleric acids ; and by ferric chloride and excess of hydrochloric acidinto thiocarbamic acid.It therefore behaves like carlsothialdine, andmay be regarded as the thiocarbamate of t-alerilidene,NH,.CS.S.N(CH.CH,.CHMe),.These and preceding experiments tend to confirm the generalformula NH,.CS.S.N(C,H,),, proposed by Mulder for the ca,rbothi-aldines. H. W.Preparation and Reactions of Crotonaldehyde. By S. B.NEWBURY (Arner. Chew,. J., 5, 112--114).-Aldehyde (1 vol.) orparaldehyde is mixed with water (1 vol.) and concentrated hydro-chloric acid (2 vols.), the liquid being cooled during mixing, andthen allowed to remain for some days at the ordinary temperaturenntil the mixture bas become quite dark and opaque.On neutralisinORGANIC CHEMlSTRY. 295i t with sodium carbonate, it yields a thick oily layer, which after somehours becomes thick and opaque. The neutralised liquid is separatedfrom the oily layer, repeatedly shaken with ether, the ethereal liquidevaporated, and the residue distilled under a pressure of 2 cm. ofmercury, when nearly pure a.ldol passes over between 90" and 110" ;the maximum yield of crotonaldehyde is obtained when this aldol isheated in an oil-bath at 140".Pure crotonaldehyde boils at 105".As shown by Kekul6 (this Journal, 1872, 616), crotonaldehyde yieldsdichloropseudobutylene when treated with phosphoric chloride. Bythe action of bromine on this chloride, dichZoro23sezcdobutyZene bromide,CMeHBr.CHBr.CHClp, is obtained as a heavy oily liquid, which isdecomposed when heated above 100'. On boiling it with dilutepotassium carbonate, carbonic anhydride is evolved,. but the removalof the halogens is only partial. A fraction, 115-120", gave numbersapproximating to those required for C4&BrC10. Cro tonaldehydeunites directly with bromine to foPm a heavy oily liquid of the for-mula CHMeBr.CHBr.CI€O. Its vapour is very irritating. It is decom-posed when heated. Attempts to replace the bromine by hgdroxyl-groups were unsuccessful. A.J. G.Nonoic Acids from different Sources. By E. SCHMIDT (Ber.,16, 2590).-An examination of the nonoic acids obtained from thefollowing sources shows that they are identical and of normal consti-tution :-1, from normal octyl alcohol from heracleum-oil ; 2, fromthe oxidation of oleic acid; 3, from the oxidation of methyl nonyl'ketone ; 4, from the distillate of the leaves of Pelmgonezcm rosezcrn;5, from the fusel-oil of beet-molasses ; and 6, from undecylenic acid.A. K. M.A New Acid Isomeric with Crotonic Acid. By R. FITTIG andF. ROEDER (Ber., 16, 2592-2593).-A further study of the acid pre-viously obtained by the authors (Abstr., 1883, 730) leaves little doubtas t o its being vinylmalonic acid, CH, : CH.CE(COOH)2.It combineswith hydrobromic acid to form bromethylmdonie acid, which is de-composed by boiling water into hydrobrornic acid and bzctyro Zactom-carbozyZic acid, COOH.CH<Co6>CH2; CH at 120" this is decomposedinto carbonic anhydride and butpolactone. The properties of theacid, CaH602, obtained by the distillation of vinylmalonic acid differfrom those of isocrotonic acid. It crystallises at a low temperature,melts at 18-19', and boils at 180-181". The authors think it pro-bable that the formula CH, : CH.CH2.COOH, represents the constitu-tion of this new acid and not that of isocrotonic acid, and that theisomerism of the latter with crotonic acid is of the kind frequentlyobserved amongst unsaturated acids and unexplained by our presentformuh; this is confirmed by the results obtained by Friedrich(Abstr., 1883, 968) from the chlorisocrotonic acids. A.K. M.Preparation of Glycollic Acid from Glycerol. By H. EILIANI(Ber., 16, 2414-2416).-The author has already shown that severalglucoses and nearly allied compounds yield glycollic acid whenoxidised by silver oxide, and has recommended the oxidation of in296 ABSTRACTS OF CHEMICAL PAPERS.verted sugar as a method for preparing this compound (Annulen, 205,191). The acid can, however, be more easily obtained by oxidisingglycerol with silver oxide in presence of an alkali. For this purpose10 grams of glycerol are mixed with 200 C.C. of water and 6 grams ofslaked lime added, to this the oxide of silver obtained from 60 gramsof silver nitrat.e is next added, and the whole heated at 60" for somefou.hours. The product is hreated with carbonic anhydride andfiltered ; on wnce&rating the filtrate, calcium glycollate separatesout. P. P. B.Optically Active Glyceric and Lactic Acids. By J. LEWKO-wi rscH (Bey., 16, 2720-2721) .-Solutions of ammonium glyceratean1 ammonium lactate exposed to the action of Penicilliuin gluucumfor several weeks become opt,ically active. The glgceric acid solutionbecomes laevo- and the lactic acid solution dextro-gyrate. The opticallyactive acids have not yet been isolated. w. c. w.Tribasic Aluminium Oxalate. By MATHIEU-PLESSY (Compt.rend., 97, 1033) .-An aqueous solution of oxalic acid attacks alu-minium at 2Q0°, ,and also attacks tribasic aluminium sulphate, theproduct of the action being an oxdate of the composition-Cz03,AML,2H,O,which may be regarded as kaolin in whieh oxalic .acid has replacedsilica equivalent for equivalent, thus furnishirrg a further example ofthe analogy between carbon and silicon.C. H. B.Monethyl Oxalate. By R. ANSCH~~TZ (Ber., 16, 2412-2414).-This compound, which has hitherto remained unisolated, is obtainedby heating equal quantities of dehydrated oxalic acid and absolutealcohol at 135." After cooling, the crude oxalate is decanted from theoxalic acid and submitted to rectification under reduced pressure.Monethyl oxalate, C204HEt, is a transparent, colourless liquid, sp. gr.at 20" = 1.2175 (water at 4' = 1) ; it has a strongly acid reaction ; bywater, it is resolved into ethyl alcohol and oxalic acid. It boils at117" under a pressure of 15 mm., and decomposes when distilled underordinary pressure, forming ethyl formate and diethyl oxalate, thus :HzO, Monethyl oxalate can also be prepared from crystallised oxalicacid and alcohol by a method similar to the One used by the authorand Pictet in preparing the et%ereal salts of tartaric acid.C20,EtH = H.COOEt + CO,': BC,O,EtH = CZOdEtz + CO, + CO +P.P. B.Identity of Isopropylsuccinic Acid with Pimelic Acid fromCamphoric Acid. By E. HJELT (Rer., 16,2621-2623).-0n oxidis-ing isopropylsuccinic acid, no terebic acid was formed, as might beexpected if the assumed constitution of this acid is correct. Whentreated with alkaline potassium permanganate in calculated quantitya portion becomes completely burnt, another portion remaining un-atbacked.When heated with nitric acid (4 : l), it remains unalteredORGANIC CHEMISTRY. 297I n its properties, isopropylsnccinic acid agrees with pimelic acid, andthe properties of its salts are also identical with those of the salts ofthe latter acid, as described by Hlasiwetz, Grabowski, and Rachler.It dissolves readily in water and in ether, melts at 114", and yieldsan anhydride a t higher temperatures. The calcium salt, C7Hlo04Ca,is anhydrous, and is precipitated as a sandy powder ; the barium saltis very readily soluble ; the silver salt is sparingly soluble. Theidentity is further confirmed by a crystallographic examination of thisacid, the measurements closely agreeing with those of Ditscheiner andZepharovich. A.K. M.Reduction of Pyrotartaric Chloride. By E. HJELT (Ber., 16,2624) .-Saytzeff having obtained butyrolactone by the reduction ofsnccinic chloride (Annulen, 171,258), the author has tried the reactionwith pyrotartaric chloride. This is a colourless oil boiling at 190-195" ;it is gradually decomposed by water with formation of pyrotartaricacid. When its ethereal solution is acted on by glacial acetic acidand sodium-amalgam, the ether-extract evaporated, treated withwater and potassium carbonate, and then extracted with ether, aneutral oil is obtained boiling for the most part at 203-205". It hasnot been obtained pure, the analytical results agreeing only approxi-mately with the formula C5H802 ; it has an odour like that of a lac-tone, dissolves in 5-6 parts water, and does not solidify in a freezingmixture of ice and salt.Boiled with barium hydroxide solution, it.yields a gummy barium salt, which when dried at 100" has a composi-tion agreeing with the formula (C5H,03)3Ba.The constitution of the chlorides which yield lactones may beassumed to be analogous to that of phthalic chloride. A. K. M.Ethyl Dicarbontetracarboxylate. By M. CONRAD and M.GUTHZEIT (Ber., 16, 2631--2632).-This is best prepared by addingthe calculated quantity of sodium t o a mixture of ethyl chloromalo-nate (19.4 grams) and ether (free from water and alcohol). Afterabout 20 hours, the ether is separated by distillation, the unalteredsodium removed, and the product mixed with water ; the ethyl dicar-bontetracarboxylate obtained is purified by crystallisation fromalcohol.When it is heated in sealed tubes with alcohol and hydro-chloric acid, first at 150" and subsequently a t 190°, fumaric acid isformed according to the equation :-(COOEt,),C C(COOEt), + 4H20 = 4EtOH + 2COz +COOH.CH : CH.COOH.By the action of zinc-dust and hydrochloric acid on an alcoholicsolution of ethyl dicarbontetracsrboxylate, ethyl acetylenetetracar-boxylate melting a t 76" is produced :-(C00Et)zC : C(C0OEt)Z + Hz = (COOEt),CH.CH(COOEt)2.A. K. M.Attempts to obtain Tartronic Acid from Glycerol, and Tar-taric Acid from Erythrol by Electrolytic Oxidation. By D2 98 ABSTRACTS OF CHEMICAL PAPERS.BIZZARR~I and G.CAMPANI (Gazzettn, 13, 490-492) .-The experimentsdid not lead to the expected results. H. W.Antimony Tartrates. By F. W. CLARKE and C. S. EVANS (Ber.,16, 2379--2387).-When antimony trioxide is dissolved in a consider-able excess of tartaric acid, and the solution evaporated, it yields a welldefined crystalline salt. It is not, however, always easy to obtain thiscompound, gummy amorphous masses being obtained in some cases.These crystals prove to be arztirnofiy trihydric tartrate,This salt crystallises in rosettes of white needles, easily soluble inwater. It is strongly acid, decomposing carbonates with evolution ofcarbonic anhydride. The normd aiztimon,y taytrate, 8b2( C4H40s)3,6H20,is obtained by adding sodium carbonate to a solution of the trihydrictartrate, and then precipitating with alcohol ; it forms a heavy whiteprecipitate, easily soluble in water.I n the cold, sodium carbonatehas no action on it, but on boiling, a white precipitate is formed.Attempts to prepare double salts from antimony trihydric tartratewere unsuccessful.By evaporating to dryness a saturated solution of antimony trioxidein tartaric acid, a non-crystalline residue was obtained having thecomposition Sb( OH)H,(C4H,06),, which may also be represented asSb(C4H,06)20H. Its aqueous solution when treated with alcoholyields a white precipitate of a compound Sb2(C4H~06)20.6H20.When the aqueous solution of this tartrate is allowed to evaporate,it yields a yellow scaly mass containing 16.39 per cent.of water, andwhen heated a t 170” loses another molecule of water, and leaves ayesidue of two molecules of Sb~C4H,06. These results indicate theexistence of two salts, having the formulse sbCaH306 and SbC4H,0,respectively.The results of this invest,igation indicate the existence of two seriesof antimony tartrates, one derived from ortho-antimonic acid, Sb(OH),,and the other from antimony trioxide, SbzO3; the constitution ofthese salts is represented as follows :-Sb ( C 4H4O 6 ) JH394HZO ,Of these, the antimony trihydric tritartrate (111), the antimon7 tri-tartrate (TI), and the antimony ditartmte, are described in the fore-going. The probable existence of 11, antimony dihydric ditartrate, isalso demonstrated. Attempts to prepare the compounds I and IVhave not yielded altogether satisfactory resultaORGANIC CHEMISTRY.299The aut,hors consider that in its tartrates, antimony behaves just asany other trivalent metal, and the supposed existence in them of aradicle (SbO) is altogether unnecessary. There are ca.ses, as for in-stance in tartar emetic, where the Sb atom and the oxygen atom areunited, still the composition of these may be explained without pre-supposing the existence of the radicle (SbO). Tartar emetic may berepresented as derived from a tartarantimonious acid, thus :-Sb-CaHjO6K0’ ‘0\ /Sb-C,H,O 6 K\ /Sb--C,HaO6Ha view by which the composition of barium antimony tartrate and ofthe double salt of strontium antimony tartrate and strontium nitratecan be easily explained, as shown in the following formulae :-Oxidation of Benzenecyanide.By W, A. NOYESSb-CC,H406-Sr-N030’ ‘0\ /Sb-C~H*O6-S1’--NO3P. P. B.Derivatives with Potassium Ferri-(Arrter. Chem. J., 5, 97--105).-The pre-sence of negative atoms or groups in many benzene derivatives exertsa powerful influence on the oxidation of hydrocarbon groups attachedto the same benzene ring. Experiments, so far, seem to show that ahydrocarbon-group in the ortho-position relatively to the negativeatom or group, is not oxidised at all, or only in small amount, bychromic acid ; that nitric acid can oxidise a group in the ortho-position, but if there is a choice, will, in preference, oxidise groups inthe rneta- or para-position.Caustic potash, in the one class of com-pounds for which it has been used, oxidises groups in the ortho-position ; potassium pernianganate in alkaline solution oxidises groupsi n all three positions, but where there is a choice would seem to oxidisethe group in the ortho-position by preference.I n order to ascertain i f another alkaline oxidising agent wouldbehave ~imilarly to the two last mentioned, the author has investigatedthe action of potassium ferricyanide in alkaline solution on the nitro-and bromo-toluenes. Ortho-, nitro-, and paranitro-toluene are bothreadily oxidised to the corresponding nitrobenzoic acids, there beingno indication as to which is oxidised more easily. Para-bromo-toluene is only oxidised with great difficulty with alkaline ferri-cyanide, whilst orthobromotoluene appears to be scarcely attacked.For comparison, toluene was treated with alkaline ferricyanide, andfound to be only slightly attacked by it.A. J. G.Metaisopropylmethylbenzene. By H. E. ARMSTRONG and A. I(.MILLER (Bey., 16, 2748--2750).-When pure metaisocymene is dis-solved in warm sulphuric acid, and the solution neutralised wit300 ABSTRACTS OF CHEMICAL PAPERS.barium carbonate, the barium salt of a metaisocymenesulphonic acidis deposited, and the mother-liquor contains a more soluble salt, whichreadily crystallises in prisms of the composition ( ClOH~,SO3),Ba +9Hz0. According to Kelbe (Anlzaleia, 210, 30) the p barium salt isdeposited fi-om the concentrated syrupy solution in glistening phtescontraining 1 mol.H20. The calcium salt resembles the barium saltand cryst,allises with 5g mols. H,O. The potassium salt forms longprisms containing Z+ mols. H,O. w. c. w.Action of Chlorine on Boiling Cymene. (Preliminary Notice.)By G. ERRERA (Gazzetta, 13, 421--422).-The action of chlorine oncymene vapour gives rise to a liquid resolvable by a few fractionaldistillations into three portions, the first passing orer below l95", andcontaining a considerable quantity of unaltered cymene, the secondboiling at 225-229', the third above 255". This last portion israpidly decomposed by boiling, but on distilling it with steam, a heaT-yoily liquid passes over, apparently consisting of a mixture of di- andmono-chlorocjmene. The more abundant fraction, boiling a t 225-229", is a liquid heavier than water, decomposing on distillation, withevolution of hydrochloric acid, and consisting, as shown by analysis,of monochlorocymene or cymyl chloride, CIOH13CI, identical wit'h t h a twhich Patern6 and Spica obtained by the action of hydrochloricacid on cymyl alcohol* (Abstr., 1880, 106).Cymyl chloride, heatedin a reflux apparatus with lead nitrate, is converted into cumicaldehrde, which in its turn is oxidised to terephthalic and cumicacids.Cymyl chloride is decomposed by boiling, yielding hydrochloric acidand a fluorescent hydrocarbon, C,,H24, of very high boiling point.H. W.Two Butyltoluenes Occurring in Rosin Spirit. By W. KELBEand A. BAUR (Ber., 16, 2559-2566).-Kelbe (Abstr., 1881, 809)obtained a hydrocarbon of the formula CllH16 from rosin spirit; thisyielded isophthalic acid on oxidation, and he therefore assumed it tobe either a methylbutylbenzene or an ethjlpropylbenzene.Theauthors now find it to be nietaisobutyltoluene, C6H4Me.CH2.CHMe?, andthey have also obtained an isomeric hydrocarbon, namely, parabzityl-t o l w n e . Metaisobutyltoliiene, obtained on heating its lead sulphonatea t 150" with concentrated hydrochloric acid, is a colourless stronglyrefracting liquid of agreeable odour, boiling at 186-188". Its sul-phonic acid cryst allises in small very deliquescent scales, melting at75-76". The barium salt, (C, ,Hl,S03)2Ba,H20, forms small lustrousscales, sparingly soluble in cold, more readily in hot water, very spar-ingly in absolute alcohol ; the lend salt, ( CllH15S03)2Pb,3H,0, formslarge nacreous plates, much more readily soluble in hot than in coldwat,er ; the potassium salt, C11H15SOBK,HP0, crystallises in lai-ge mode-rately soluble nacreous plates, and tbe sodiurn salt, CIIH15S0,Na,H20,i n easily soluble lustrous needles; the copper salt, (C11H,5S03)2Cn,4H20,crystallises in large blue lustrous plates, readily soluble in water.* Commonly, but incorrectly, called cumic alcohol or cum$ alcohol j the propername of the radicle C,,HI3 is cymyZ.-H. WORGANIC CHEMISTRY.301MetaisobutyltoluerLesuZl,honarnide, C11H15.SOz.NH2, crystallises in smalllustrous scales melting at 74-75'.Parabuty ltoluene, C6H4Me.C4H9, is separated from the crude meta-isocymene by crystallising the barium sulphonates from 50 per cent.alcohol, in which barium yarabutyltoluenesulphonate is much morereadily soluble than the metaisocymene salt. Parabutyltoluene (b.p.176-1 78") is a colourless, highly refracting liquid of agreeable odour ;dilute nitric acid oxidises it to paratoluic acid. The barium sulplLonn.te,( C11H15SOJ)2Ba,H20, forms small scales, sparingly soluble in water ;the lead salt, ( C,,H15S0,),Pb,3H20, crystallises in small lustrous scales,sparingly soluble i n cold, readily in hot water; the potassium sult,C11H15S03K,1~H,0, in small, lustrous, easily soluble scales ; the sodiumsalt, CL1H15.S03Na,2H20, in small wart-like crystals, readily soluble inwater, and the copper salt in readily soluble bright blue wart-likecrystals. Pnrabuty lto luenes.u@hnnarnide, Cll H15.S02NH2, forms largenacreous plates melting a t 113", and sparingly soluble in hot water.With potassium permanganate, it yields parutolylsulphonatninic acid,COOH.C6H3Me.S02NH,, melting a t 242O, sparingly soluble in water,almost insoluble in ether and in alcohol.Metaisobutyltoluene, identical with the hydrocarbon contained inrosin-spirit, can be obtained synthetically from isobntyl bromide andtoluene, in presence of aluminium bromide.Reductions with Zinc and Ammonia. By W. G. MIXTER(Amer. Chenz. J., 5, l-g).-Powdered zinc, with aqueous or alcoholicammonia, and a small quantity of platinic chloride solution, forms avery gentle reducing agent, of which, so far, but little use seems tohave been made.It waR used for the reductions in the preparation ofthe bodies described below.A. K. M..N. C6Hi.NHAcParazoxyacetaizilide, 0' I , obtained by the reduction\N.c,H~. N H A ~of paranitracetanilide in alcoholic solution, forms minute hair-likeparticles of a light golden-yellow colour, melts at 275-278", issparingly soluble in boiling, nearly soluble in cold alcohol. Theammoniacal mother-liquor from the preparation of this substance con-tains azo-acetanilide, C16Hl,N,Oz ; it will be described in a future paper.By boiling parazoxyacetanilide with alcoholic potash, it yields parazo-ozyaniline, O/ 1 , as a fibrous mass which melts at 182-184", and is readily soluble in alcohol. The hydrochloride cry stalliseswell from water, and is sparingly soluble in alcohol. The sulphateseparates on adding sulphuric acid to a dilute solution of the base.The platinochloride, C12Hl,N40,H2PtCls, forms long brownish-redncledles. By reduction with ammonium sulphide, or with tin andhydrochloric acid, azoxyaniline yields paraphenjlenediamine, showingthat the azoxy- and amido-groups occupy the [l : 41 positions.N.C,H,.NHz'N .c6 Hq . N H,N.CCH4.NH.E , obtained by the reduction Metazoxybenzannilide, 01 / IN. C6H4. NHE302 ABSTRACTS OF CHEMICAL PAPERS.of metanitrobenzanilide, forms a light powder of pale yellow colour ;it melts at 272", and is insoluble or nearly insoluble in alcohol, ether,and benzene. The mother-liquor, after renewed digestion with zinc,yielded the substance NHE.C6H4.NH2, described by Bell (thisJournal, 1874, 900).A. J. G.Action of Ethyl Acetoacetate on Phenylhydrazine. I. BgL. RNOR.R (Ber., 16, 2597--2599).-This reaction is similar to thatbetween ethyl acetoacetate and aniline, yielding a new class of com-pounds, the properties of which closely resemble those of a-meth-ry-hydroxyquinoline (see p. 334). According t o Fischer, phenylhydrazineand ethyl acetoacetate, a t the ordinary temperature, yield an oilycondensation-produc t with liberation of water ; this compound musthave the formula PhN,H CMe.CH,.COOEt. When heated on awater-bath, it yields alcohol and a substance, CloHloNzO, whichresembles carbostyril in many of its properties. It melts at 127", canbe distilled unchanged, and shows both basic and acid properties ; it isa stronger acid than carbostyril, dissolving in ammonia and in alkalinecarbonates.To prepare it, 100 grams of phenylhydraeine are added to125 grams of ethyl acetoacetate, the water which forms is separated,and the oily product is heated for about two hours on a water-bath,until a portion is found to solidify on cooling, or on the addition ofether. The warm mass is poured into and stirred with ether, whichremoves colouring matter, and the white crystalline product is thenwashed with ether and dried at 100". The yield is quantitative andthe product pure. It is almost insoluble in cold water, ether, andlight petroleum, more readily soluble in hot water, and very readily inalcohol. It crystallises from hot water in hard prisms, and by theslow evaporation of its alcoholic solution can be obtained in crystalsof diamond lustre.It yields crystalline precipitates with salts ofmost of the heavy metals, the ultramarine blue cobalt salt, and theorange-yellow uranium salt, being especially characteristic. Its con-stitution remains to be explained. An anhydride, C20H,,N40, isformed, when it is heated with an excess of phenylhydraeine ; thismay be prepared as follows : ethyl acetoacetate (50 grams) is mixedwith phenylhydraeine (60-70 grams), the water which forms Bepa-rated, and the oily product heated to boiling in an oil-bath until asolid mass is obtained; on boiling this with alcohol, the anhydride isobtained pure. Heated to 250-260" it turns brown and decomposesbefore melting.It is insoluble in most of the usual solvents; is inmany respects similar to carbostyril; dissolves in acids and bases,from which it is reprecipitated on neutralisation; it is insoluble inacetic acid and in ammonia, and is precipitated by carbonic anhydridefrom its alkaline solution, so that it apparently contains a hydroxyl-€PUP. A. I(. M.By 0. WIDMANN (Ber., 16,'3576-2587) .-By the action of acetic anhydride on amidohydroxy-propylbenzoic acid (the externaJ application of heat being avoided),acetamidohydroxypropylbenzoic acid is formed (see p. 31 7), but if theamido-acid is boiled with an excess of acetic anhydride, and the latterA New Group of Organic BasesORGANIC CHEMISTRY. 303then separated by repeated evaporation with alcohol, a reddishcoloured oil is obtained crystallising from alcohol in rhombic plates,melting a t 218", and insoluble in water.Its hydrochloride isextremely soluble in water, sodium acetate reprecipitating the baseC12H13N03 in white needles. The same compound is formed on boil-ing acetamidohydroxypropylbenzoic acid with hydrochloric acid, andalso when acetamidopropenylbenzoic acid is boiled with hydrochloricacid. The author names it methylcuinazonic acid; it dissolves readilyin dilute acids, forming salts, and also in concentrated sulphuric acid.On distillation, it yields a tarry product having an odour like that ofindole, but when cautiously heated, white needles sublime. By theaction of potassium nitrite on a solution of the hydrochloride, nitrousacid is liberated, whilst needles of free methylcumazonic acid sepa-rate.When heated in a tube with ethyl iodide, it yields a syrupysubstance which could not be obtained in a pure state. By evaporat-ing a solution of the base in dilute sulphuric acid, the acid sulphate,Cl2HI3NO3,H2SO4 + H20, is obtained in slender, white, silky needles,very readily soluble in water ; it loses its water of crystallisation at100-140". The hydrochloride crystallises in needles. The platino-chloride, (C,,Hl,N03)2,H2PtC16, forms lustrous four-sided plates orcubical crystals, very readily soluble in water. By the action ofsodium-amalgam on a solution of methylcumazonic acid in sodiumhydroxide, the compound C12H15NO3 is produced ; it is very sparinglysoluble in ether and alcohol, crystallising from the latter in slenderneedles, which melt a t 246" and sublime a t higher temperatures.This substance is identical with a.cetamidocumic acid,C6H3Pr( NHffC), COOH,prepared by the author from nitrocumic acid.With the object ofeliminating an acetyl-group from methylcumazonic acid, it was boiledwith hydrochloric acid and with alcoholic potash, but with negativeresults. Judging from its formation from amidohydroxypropyl-benzoic acid or its acetyl-derivative, methylcumazonic acid might beCMeaassumed to have the constitution COOH.C6H/ I -, but this for-"Acmula does not explain the basic character of the substance, nor thedifficulty of displacing the acetyl-group : the formulais equally unsatisfactory. Its reactions and properties can, how-ever, be satisfactorily explained ou the assumption that its constitu-tion is-CH CMe2/\ AHC C 0I II I CO0H.C C CMe y&\304 ABSTRACTS OF CHEMICAL PAPERS.ie., that it is formed by the abstraction of the elements of a moleculeof water from acetamidohydroxypropylbenzoic acid, the carbon-atomof the propyl residue uniting with the oxygen-atom of the acetyl-group.A substance of this constitution must be a tertiary base,contains no acetyl-group, and might yield acetamidocumic acid onreduction. Its formation from acetlamidopropenylbenzoic acid is moredifficult t o explain, the yield in this case being also less satisfactory ;the hydrochloric acid may perhaps first form an addition-compoundwith the propenyl-group, the chlorine then separating again, but inunion with the amido-hydrogen. I n support of the above constitu-tion, the author mentions the analogous formation of Ladenburg'scondensation-products from orthamidophenol, and the acid anhydrides(Ber., 9, 1524) as, for example, C6H4\ /O\ @Me.NThe name '' methylcumazonic acid " is intended to implv that thissubst,ance is derived from cumic acid, and that it contains both nitro-gen and oxygen, " cumazone " being the hypothetical parent substanceCMe, C6&<N: CH>o*CMe2.0 Ethybztrnaxonic acid, COOH.CsH3<N : cEt>, is obtainedboiling amidohydroxypropylbenzoic acid with an excess of propionicanhydride, and crystallises from alcohol in small lustrous well-formedpyramids, melting at 202" ; it is readily soluble in alcohol, insolublein water.The hydrochloride crystallises in white needles, extremelysoluble in water. The acid sulphate, C13H15N03,H2S04, also cryst(a1-Zises in extremely soluble white needles. The free base dissolvesreadily in very dilute sulphuric acid.Plzenylcumazonic acid, C,,H15N03, is formed on heating amidohp-droxypropylbeczoic acid with an excess of benzoic chloride a t 100-120", as long as hydrochloric acid is evolved, boiling the productwith alcohol and subsequently with water. It melts a t 219-220",is insoluble in water, and separates from alcohol in transparentcrystals of the formula 2C17H15N03 + EtOH. The acid sulphate,C1,H15N03,H2S04 + 2H,O, forms lustrous, colourless, elliptical plates,insoluble in water.Compared with the methyl- and ethyl-derivatives, phenylcnmazonicacid is a weak base.A. I(. M.Orthonitrophenyl-p-alanine. By A. EINHORN (Bey., 16, 2645-2651) .-In describing the lactone of orthonitrophenyl-p-lactic acid(this vol., p. 65), the author mentioned that it was converted intosalts of the Eydroxy-acid by warming it with alkaline hydrates orbarjta. Whcn heated with ammonia solution, it gradually dissolves,and on cooling white crystals separate ; these, after recrystallisation,melt a t 197". The product, C9H10N204, has the composition of ortho-nitrophenyz-P-alanine, but it neither forms metallic salts, nor does itcombine with acids, In order to be able to compare i t with ortho-nitrophenyl-P-alanine, the author prepared the latter by dissolvingorthonitrophenyl-/?-bromopropionic acid in an excess of ammonia, auORGANIC CHEMISTRY.305leaving the solution a t rest. Crystalline scales gradually separate,and on recrystallisation from water or alcohol needles are obtainedmelting at 197". The composition, CSH,,N,04, and mode of prepara-tion of the product show it t o be orthonitrophenyl-p-alanine ; it dis-solves readily in water. alcohol, acetone, and glacial acetic acid, moresparingly in ether, chloroform, light petroleum, and carbon bisul-phide. It dissolves when heated with dilute sodium carbonate solu-tion, but not more readily than in water, and separates unchanged oncooling. When boiled with sodium or barium hydroxide, it does notyield salts, a partial decomposition taking place with formation ofammonia ; attempts to obtain copper and silver salts were also unsuc-cessful.Orthonitrophenyl-P-alanine crystallises unchanged fromdilute or concentrated hydrochloric acid. Sulphuric acid (1 part acidand 1 part water) dissolves it- in the cold, but decomposition sets inafter a time. On warming it with concentrated sulphuric acid, a bluesolution is obtained, and on pouring this into water a blue dye is pre-cipitated agreeing in its reactions with indoin. It is converted intothe orthonitro-p-lactic acid by boiling with nitrous acid. The perfectcoincidence of these properties with those of the compound obtainedby the action of ammonia on the lactone, prove the identity of thetwo substances.The acetyl-derivative, CllH12N205, is prepared bydissolving orthonitrophenyl-P-alanine in boiling acetic anhydride ; itcrystallises from alcohol in splendid prisms molting at 141-143" ; itcrystdises unchanged from hot water, is insoluble in cold sodium car-bonate and alkali solutions, hut%oa boiling with the latter, is decom-posed with formation of orthonitmphenyl-e-alanine. It does notyield salts when boiled with copper hydroxide o r silver hydroxide,is insoluble in cold hydrochloric acid, but dissolves in hotl concentratedsulphuric acid to a blue solution, which has a strong odour of aceticacid. When the alanine is boiled for about three hours with aceticanhydride, the latter separzted by distillation, and the residue crys-tallised from alcohol; a substance, C,,H,,N,Oi, is obtained crystallisingin needles melting a t 172'.It is assumed to be the Zactam of orthowitro-phenyZ-P-acet?lla7aiLine, NO2.C6H,.CHQNZ>CO. It is decomposedby dilute soda solution, with evolution of ammonia and formation oforthonitrocinnamic acid. If equal quantities of the alanine andsodium acetate are boiled with acetic anhydride, and after remot-al ofthe latter the product is crystallised from alcohol, the above lactamseparates, whilst the solution contains a small quantity of a secondsubstance, which is probably the lactam of orthonitrophenllZ-P-al~~ine,N02.C,H,.CH<N.g> CH CO. It crystallises in transparent, stronglyrefracting, vitreous prisms, melting at about 80°, but it has not, yetbeen obtained pure.It is moderately soluble in hot water, and is notaltered by alkalis or acids.From the chemical beha,viour of orthonitrophenyl-6-alanine, andfrom its ready production from the lactone or orthonitrophenyl-p-lactic acid and ammonia, the author concludes that it is not an amido-acid, and he gives the following equation to express its formation :-CH,VOL. XItVI. 306 ABSTRACTS OF CHEMICAL PAPERS.NO2. C6H4. C H. C H2 CH2.CO 1 I + NR3 = N02.C6H,.CH/ 10-CO 'NH3.OA. K. M.Synthesis of Methylene-blue. By R. M~HLAU (Bey., 16, 2728-8730).-When nitrosodimethylaniline acts on dimethylaniline inpresence of strong hydrochloric acid, the hydrochloride of the baseC1,HI9N3 is obtained. The base crystallises in prisms which melt at215".'Methylene-blue is produced ,by reducing the hydrochloridewith sulphuretted hydrogen and oxidising the product with ferricchloride. The base CL6H19N3 is decomposed by reducing agents, suchas zinc-dus t, into paramidomethylaniline and dimethylaniline. Bay oxidising these products of reduction, dimethylaniline-green isformed.Sulphuretted hydrogen converts dimethylaniline-green into leuco-dimethylaniline-green and methylene-white, and by alternate rednc-tion with sulphuretted hyCrogen and oxidation with ferric chloride,dimethylaniline-green is converted into methylene-white and methy-lene-blue. As methylenedwhite has the constitutionRS'NH(C6R,NMe2)2,the hydrochloride of methylene-blue is probablyw. c. w.Metanitrophenylthiocarbimide. By H.STRUDEMANN (Bey., 16,2331--;?335).-The production of this compound by the action of hotglacial acetic acid on metanitrothiocarbamide has dready been de-scribed (Abstr., 1883, 801). In this communication, the author givesan account of a detailed examination of the reaction taking dace inits production, which may betiom :-I. NHPh.CS.NH.CJ&.NO, + + S O H .11. NHPh.CS.NH.C6H,.NO2 + + AcOH.represented by the follo&.. equa-&,O = CSNPh, + NO2.C6H4.NHAc?G20 = CSN.C,H,.N02 + NHPh&The presence of ph en yl tbiocarbimide, metani t roacetanilide, me ta-nitrophenylthiocarbimide, and acetanilide was satisfactorily demon-strated amongst the products of the reaction. TWO other substancesare also produced, via., metanitrodiphenylthiocarbamide melting a t160-161", and a substance having the same composition as metanitro-phenylthiocarbimide ; the formation of the former resulting from t,heaction of water on metani trophenylthiocarbimide, thus :-2(CSN.C6H..NOz) + 2H2O = CS(NH.C6Ha.KO2)2 + CO2 + H2S.Phenylt'hiocarbimide undergoes a similar change when heated withwater in sealed tubes a t loo", giving diphenylthiocarbamide, carbonicanhydride, and sulphurctted hydrogenORGANIC CHEMISTRY. 307These secondary reactions show that in the preparation of meta-nitrophenylthiocarbimide, distillation in a current of steam should beavoided, and the purification by crystallising from glacial acetic acidand carbon bisulphide is to be preferred.Metanitrophenylthiocarbimide is also formed by the action ofglacial acetic acid on dinitrophenylthiocarbamide.It crystallises inlong flexible needles melting a t 60*5", and boiling a t 275-280' ; i t issoluble in alcohol, ether, benzene, and carbon bisulphide. Attemptsto reduce the " nitro-group " have failed ; the alcoholic solution ofthis ccmpound yields nitraniline when treated with sulphurettedhydrogen.The following derivatives of metanitrophenylthiocarbimide hayebeen prepared :-Metunitrophen ylparatolyl thiocarbarnide,NOz.CsH4.NH.CS.NH.C6H4Me,pale yellow needles melting at 173", and sparingly soluble in water,benzene, and ether, easily soluble in alcohol and glacial acetic acid.Metanitrop ken y Zparaomjp heny It hiomrbam ide,NO,.C,Ha.NHzC S.NH.CGHa.OH,crystallises in white needles me1 ting at 152".Metnnitrophenylorthoni-trol3arntolylthioccnr~am~~e, N02.C~H4.NH.CS.NH.C6H3Xe.N0, [ 1 : 2 : 41,crystallises in yellow needles melting a t 188".Orthonitroparatolylthiocarbamide. By H. STEUDEMANN (Rer.,16, 2336--2338).-Keither of the isomerides of metanitraniline appearto form isomerides of metanitrophenylthiocarbamide ; and of its homo-l o p e s , othonitropratoluidine alone yields a thiocarbamide.Orf honitroparatoly~henylthiocnrbamide, NO?.MeC,H,.NH.CS.NHPh ,is obtained by acticg on an alcoholic solution of orthonitropara-toluidine with phenylthiocarbimide ; it melts a t 143", and is easilj-soluble in alcohol and glacial acetic acid. It is isomeric with thenitrophenjlparatolylthiocarbamide melting a t 173", described in thepreceding Abstract.Ortlioi~itropar~tolylthiocarbimide, CSN.C6H31\~e.N02, obtained byboiling the solution of the above compound in acetic anhjdride withwater ; phenylthiocarbimide, ncetanilide, and nitro-acetotoluide areamongst the products of this rea2tion.It crystallises in broadneedles, which melt a t 56-57', and resemble metanitrophctnylthiocar-bimide in its properties. When heated with water, it forms hydricsulphide, carbonic anhydride, and d.initrodi2,aratol!jIth~o~a~b~inid~i,CS.[NH.C6H2Me(N02)2]2, which is also obtained by acting on nitro-toluidine with nitrotolylthiocarbimide. It mtlt,s at 207", is soluble inglacial acetic acid, and when heated with acetic anhjdride is resolvedinto orthonitroparatolylthiocarbimide and nit roacetotcluide.Orthorlitropnrntolylethi/lthiourethun,e, EtO.CS.NH.C,H,Ne.NO,, form-ed by slow decomposition of the alcoholic solution of orthonitropara-tolylthiocarbimide, melts a t 95.5".Orthoiiitronzanoparnto ly 1 thiocar banzide, NH,.C S . NH C,,H,Me .NO,, 017 -tained by dissolving the thiocarbimide in ammonia, forms a citron-yellow powder melting a t 176".P. P. B.Y 308 ABSTRACTS OF CHEMICAL PAPERS.Ort h onitrodipar at o 1 y 1 t hiocar ba mid R ,N02.MeC6H3.NH. C S.NH.CsH4 Me,formed by mixing alcoholic solution of paratoluidine and nitro tolyl-thiocarbimide, crystallises from alcohol in needle-shaped crystalsmelting at 169".An Isopicramic Acid. By C. W. DABNEY (Amer. Ch,en7. J., 5,20--30).-~-BenxoylarnidosaZicyZic acid, C6H3(NH&) (OH).COOH, isobtained, together with two other substances not yet fully investi-gated, by the action of benzoic chloride on a-metamirlosalicylic acid.It forms a white powder, melts a t 252", is readily soluble in aceticacid, sparingly in hot wa'ter, insoluble in chloroform, behzene, andlight petroleum.The barium salt, (C14H,,04N),Ra + 6Hz0, formssmall colourless needles readily soluble in water. The calcium salt,(C14Hl,04N)2Ca, forms little blunt needles of satiny lustre. The nitra-tion of the acid was accompanied with some difficulty, pure nitricacid acting on it with ungovernable violence ; finally, by dissolvingthe substance in 20-30 times its weight of acetic acid, adding fivedrops of nitric acid to each 100 C.C.of liquid, and heating to 80°, thenitration was effected. The resulting compound was, however, notthe nitro-acid expected, but benzoy713arcc.midoclinitroplie~~o1,C6H2(NOz)?(NHB;) .OH,small quantities of benzoic acid and picric acid being also formed.It crystallises in glistening yellow plates, gives off red vapours a t150", and then melts a t 250". It is readily soluble in glacial aceticacid, somewhat less in alcohol, benzene, and naphtha, sparingly solublein water. It acts as a strong acid, forming salts which crystallisewell, and yield deep bluish-red solutions.C6Hz(N02)2(NH~).0K + HzO,forms light red needles with a splendid golden-yellow lustre; theanhydrous salt is of a dark brick-red colour. The barium salt,(C13H,N,06)2Ba + 3H20, crjstallises in slender bright red needles.The calciiinz salt, ( Cl&T\T,O6)dh + 4&H20, crystallises in glisteningyellowish-red scales or plates.The lead salt, (C13H,N,0a)2Pb, is oh-tained by precipitation as a dark red crystalline mass. When heatedwith moderately dilute hydrochloric acid at 130" for 12 hours, benzoyl-pnrnmidodinitrophenol is resolved into benzoic acid and diorth0?2itro-p - a m idophenol or isopicrarnic acid,This crystallises in dafk brown plates or needles, melts apparentlywith some decomposition at 170°, is sparingly soluble in cold water,soluble in benzene and naphtha, readily soluble in hot water or inalcohol ; the solutions have a cherry-red colour. It appears to com-bine with acids, dissolving in them to form yellow solutions, but thecompounds so formed could not be isolated.It unites with alkalis,forming crystalline salts, whose solutions are of a deep bluish-redcolour. The pofassizim salt, C6H2(N02)2(NH2) .OK, crjstallises inbluish-black needles, and is very soluble in water. Both acid andP. P. B.The pofassiiwb salt,C6H2(N02)?(NH,).0H [OH : NO2 : NH2 : NO, = 1 : 2 : 4 : 61309 ORGANIC CHEMISTRY.Picramic Acid [OH : NH, : NO,: N 0 2 = l : 2 : 4 : 6 ] , m . p . 1 6 5 0 . -Crystallises from water in orange-red needles, from chloroform inblood-red scales. Soluble in alco-hol. 100 parts water a t 22" dis-solve 0.14 part acid; solubility inhot water about the same. Solu-tions orange-red in colour.Potassizm Xn It.-Red translu-cent rhombic tables.Benzoylpicrafizic A c i d , m.p.220".--Greenish - yellow needlessparingly soluble in alcohol.Isoyicramic Acid [OH : NO,: N H , : N 0 2 = 1 : 2 : 4 : 6 ] , m . p .1 7O0.-Crystallises in bundles offine brownish-yellow needles, hav-ing a golden lustre when moist,very readily soluble in alcohol.100 parts water at 22" dissolve0.082 of acid : a t just below theboiling point 0.812 part of acid.Solutions bluish red.Potassium SaZt. -Bluish-blackneedles.Benzoylisogicramic A c i d , rn. p.250".-Iteddish plates of goldenlustre, soluble in alcohol.Triamidophenol. By E. BAMRERGER (Bey-, 16, 2400-2403) .-Triamidophenol hydrochloride was prepared by reducing piciic acidwith tin and hydrochioric acid and precipitating the tin from theproduct with zinc.The hydrochloride so preparrd was next convertedinto the trit~crt!/Z-fl.iamidophel-Lol, CeH,( NH&),.OH, by heating i t withacetic anhydride and sodium acetate. This compound crystallisesfrom water in white leaflets melting a t 263". It is sparingly solublei n benzene and acetone, but more easily in alcohol, water., or glacialacetic acid. It is easily soluble in alkalis and ammonia, and is pre-cipitated from these solutions by acids.It WRS next? attempted t o nitrate this acetjl compoiind, with theresult, however, of producing the quinone,which is also produced when the acetyl compound is treated withweak oxidising agents snch as dilute nitric acid or ferric chloride.This quinone crpstallises from glacial acetic acid in golden-yellowleaflets melting at 268", sparingly soluble in alcohol and water.The corres~ionding quinol, viz., tetrncetnmidodihydroxj phenjlquinol, [ CRH(OH),( NHAc)?],, is obtained by treating the qii inonesuspended in water with hydrogen sulphide.It crystallises fromalcohol in colourless needles. P. P. B310 ABSTRACTS OF CHEMICAL PAPERS.Condensation Products of Paranitrobenzyl Alcohol. By A.RASLER (Ber., 16, 2714-2720) .-The nitrobenzyl alcohol used int'hese experiments was prepared from paranitrocinnamic acid. Thebest results are obtained by dissolving 103.5 grams of methyl nitro-cinnamate i n 1400 grams of sulphuric acid, and gradually adding135.5 grams of potassium nitrate t o the solution, which must be kepta t a temperature between 60" and 70".When the reaction is com-plete, the mixture is left at rest for six hours, and afterwards pouredinto 10 times its volume of ice water. The precipitate is treatedwith a 3 per cent. solution of sodium carbonate, washed, arid re-crystallised from hot water. To convert the nitrobenzaldehyde intothe alcohol, one part of the powdered aldehyde is dissolved in 5-6parts of 15 per cent. soda solution. After 12 hours, the solid pro-duct is dissolved in a small quantity of water and extracted withether. The alcohol is deposited from the ethereal bolution i n crystalsmelting at 92". From 80 to 90 per cent. of the aldehyde is convertedinto alcohol. Nitrobenzyl alcohol was also prepared from t h e ace-tate.When a solution of nitrobenzpl alcohol in benzene is treated withstrong sulphuric acid, two condcmsation products are formed.The one,dinitrodibei?xyZbenzene [C,H,(NO,),CH,]zC,H,, is sparingly soluble inthe usual solvents with the exception of benzene, in which i t istolerably soluble. It forms needle-shaped crystals which soften at140" and melt a t 146". The other, para-mononitro ~iiwl2erzylnzetl~ane,C6H4(N02).CH2Ph, melting a t 31°, is freely soluble in benzene, ether,and alcohol. It is deposited from the alcoholic solution in prisms.Chromic acid converts monodiphenylmethane, in acetic acid solutiori,into pal.a-monoizit~obenzo~~henonc., CsH4(NO2) CO. Ph, melting a t 138".It is freely soluble in benzene, in hot water, and in boiliiig alcohol.On reduction with t<in and hydrochloric acid, mononitrodi:,henylme-thane is converted into naona?,zidodi~heny.lin ethane.This base formswhite crystals melting at 34", which rapidly change on exposure tothe air. The sulphate, hydrocliloride, and zinc chloride are crystal-line salts. By means of the diazo-reaction i t can be converted intopara-monhydroxydiphenylmethane, C6H4(OH).CH2Ph, which is iden-tical with the compound Paterni, obtained by the action of zinc-duston phenol and benzyl chloride (Her., 5, 288, 435 ; 15, 1.53).By dissolving para-mononitrodiphenylmethane i n fuming nitric acid,a diriitro3lphenylmethane is obtained which melts at 175". It has amusk-like odour, and is perhaps identical with Doer's isodinitrodi-The yield is about 75 per cent. of the theoretical.phenylmethane (Re,.., 5, 795).w. c. w.Action of Aromatic Hydroxy-acids on Phenols. By A.3IlCHAEL ( A m e r . Chem. J., 5 , 81--97).-Phenol and salicylic acid donot react on each other when heated either in open vessels or sealedtubes, but on addition of dehydrating agents, best stannic chloride, areaction is readily effected, the products being paradihydroxybenzo-phenone and a new substance, salicylphenol, the former appearing toowe its formation to parahydroxybenzoic acid contained in the salicylicacid usedORGANIC CHEMISTRY. 3112 4SulL'ry ?pheno I , C6H4( OH). co. C6H,.0 H, crystallises from hot wateror alcohol in pale yellow plates, from benzene in pyramids withsymmetrically truncated end-faces. It melts at 143 -144", is nearlyinsoluble in cold, moderately soluble in hot water, readily soluble inalcohol and benzene.It dissolves readily in alkalis, yielding metallicderivatives. The sodizcnz compound, C&60 (ONa)?, forms stellategroups of needles, very soluble in water and alcohol ; the siZver com-pound, C1,H60(OAg), + H,O,. is obtained as a bright yellow pre-cipitate, sparingly soluble in water. The me:*cury compound formsreddish-yellow needles, the ferric silk is obtained in brown fern-shapedcrystnls, the copper salt crjstallises in groups of greenish-yellowrhombic plates, the lead salt was obtained as an amorphous yellowprecipitate which melts in boiling water. 1)iacettl~snZicyZ~henoZ,CI3H8O (O,G)?, prepared by ,heattng a mixture of salicylphenol, aceticanhydride, and sodium acetste, crystallises in long concentricallygrouped white needles, melts a t 84-83', is sparingly soluble in cold,moderately soluble in hot water, readily soluble in hot alcohol orbenzene. From its formation from salicylic acid, one hydroxjl-groupin salicylphenol must be in the ortho-position to the carbongl-group,and as parahydroxy benzoic acid occurs largely amengst the productsof its decomposition by fusion with sodium or potassium hydroxides,it is most probable that the second hydroxyl-group is in the parn-position.O~.tho-yuru-dihyclroxyd~phen~lcu~binol, C6H,(OH) .CH( OH) .C6H4.0H,is obtained by the action of sodium-amalgam on an alkaline solutionof salicylphenol, and is precipitated on saturating the liquid withcarbonic anhydride, as a white amorphous powder vphich could not hecrystallised.I t becomes strongly electric on rubbing, is insoluble i ncold, sparingly soluble in hot water, readily soluble in cold alcohol,the solution, on evaporation, yielding an oil that does not solidify onstanding. It dissolves readily in alkalis, yielding metallic derivatives.Like the corresponding dipara-compound (Annulen, 202, 132) itgives an intense violet-blue coloration when heated with mineralacids.Sulicylresorcinol, C6H,(OH) .co.C,H,(OH),, is obtained in smallquantity: by heating a mixture of salicylic acid and resorcinol a t195-200" for 15 hours. It crjstallises from alcohol in glitteringyellow scales, melts at 133-134", and resolidifies at 116-117"; itvolatiiises slowly in a current of steam.I t is insduble in cold,sparitigly soluble in hot water, readily soluble in alcohol, benzene, orin alkalis. Acetic anhydride converts it into an acetyl-derivative ; anoil which solidifies partially on long standing. Reduction withsodium-amalgam gives a substance resembling the dihydroxydiphenyl-carbinols. I n presence of dehydrating agents (best zinc chloride) thereaction between salicylic acid and resorcinol takes rather a differentcourse, the product of the action being salicylresorcinol ether,This compound crjstallises in long bright yellow needles, melts a312 ABSTRACTS OF CHEMICAL PAPERS.146-147", is insoluble in cold, sparingly soluble in hot water. It isalso formed by the action of zinc chloride on salicylresorcinol.Fusedwith alkalis, it yields salicylic acid and. resorcinol. Its metallic deri-vatives are characterised by their inso1ubilit)y in water. A so/Ziumcompound, CI3H,O3Na,NaOH, is obtained by the action of sodiummethylate on the ether. It crystallises in long lemon-yellow needles,and on long washing with cold water is completely decomposed intosodium hydroxide and salicylresorcinol ether. A mono-sodium-derivative could not be obtained in a state of purity. The author con-siders it very probable that the disodium-derivative has the compositionas from its behaviour with water it must be regarded as a derivativeof the ether and not of salicylresorcinol. Acet~lsalicylresoi-cilzoletlLer, C&L< O->C6H3.0Ac, crystallises in white prismatic needles,melts a t 167-168", is sparingly soluble in water, readily soluble iu.hot elcohol.coXaZicyZorcinoZ ether, C6H,<&,>C6H2Me.0H, 0- is prepared by heat-ing a inixt,ure of salicylic acid, orcinol, and zinc chloride.It crystal-h e s in straw-coloured silky needles, melts at 140°, is insoluble inwater, soluble in hot alcohol. Fused with alkalis, i t yields salicylicacid and orcinol. The sodizmz derivative, CIIO3HSNa + 1&H20,crystallises in long yellow needles ; a disodium-compound could not beobtained. AcetyZsaZic,ylorciiaoZ ether, ClaH9O3Z, crystallises in longneedles, and melts a t 151-152'.Conversion of Hydrocarbons into Aldehydes by the Actionof Chromyl Dichloride. By A. ETARD (Cyompt. rend., 97, 909-911).-The author repeats, in reply to Paternh and Scicliilone, thatpure cumene yields cumaldehyde when the compound which it formswith chromyl dichloride is decomposed by water.When a 10 per cent.solution of mesitylene in carbon bisulphide ismixed with a similar solution of chromyl dichloride, a precipitatc isobtained of the composition C6H3MeZ. CH( OCrCIz.0H)2, and when thisis decornposcd by water it yields mesitylaldehyde in almost tlieoreticalquantity. I t boils a t 220-222', and oxidises rapidly on exposure toair, yielding mesi tylenic acid.Aniyl-toluene, boiling a t 213-218", when treated in a similarmanner a t 45", yields a precipitate of the compositionCGH4Me. C6H, (OC rCI2.OH)?,and when this is decomposed by water, a mixture of two isomericaldehydes of the composition Cl2Hl6O is obtained.Phenetoil, in the same manner, yields a substance C,H,O, ; ortho-cresol yields C,H603 ; and paracresol, C,,H,,O,. These substancesapparently resemble the quinones in character.They dissolve inalkalis, but are insoluble in acids. Styrolene also forms a definitecompound with chromyl dichloride, but it has not j e t been examined.A. J. G.C. H. BORGANIC CHEMISTRY. 313Action of Benzaldehyde on the Mononitro-derivatives ofthe Paraffins. By B. PRIEBS (Ber., l6,2531).-When nitromethaneand benzaldehyde in molecular proportions are heated with zincchloride in a sealed tube a t 160", phenylnitroethylene, CHPh CH.N02,melting at 56-5-57', is produced: Ph.COH + CH,.NO, = H20 +CHPh : CH.NO1.I n the same way nitroethane and benzaldehgdeyield a phenylnitropropylene, CHPh": C'hle.N02, melting a t 64".-A. K. M.Ammonia-derivatives of Benzil. (Preliminary Notice.) ByF. R. JAPP (BOY., 16, 2636-2640).-According to Zincke and Henius,(Ber., 16, 889) the compounds imabenzil, benzilimide, and beiizilani,obtained by Laurent, have the forrnulx? C4?H3,N2O4, C42H&X204, andC,H,,N,O, respectively. The author refers to previous communica-tions (this Journal, Trans., 1883, p. 12, and Rer., 15, 2413), in whichhe has shown that the formula of azobenzil (benzilam) is C,,H,,NO,and not C42H30N202, as Zinin assumed (Anrmlen, 34, 190). Its vnpour-density also excludes the formula proposed by Zincke and Henius.When heated with concentrated hydrochloric acid a t 250", i t yieldsbenzoic acid, ammonium chloride, and a resinoils mass, If oxidisedby chromic mixtm=e, benzoic acid is obtriined in almost the theoreticalamour,t required by the equation C2,Hl,N0 + O2 + 3H20 =3C,H,O, + NH,, showing that three benzenjl groups must be presentin the compound.Moreover, azotenzil is closely analogous in itsbehaviour to benzenylamidophenanthrol, the constitution of which isknown. These facts leave little doubt as to the correctness of theconstitutional formula previonsly assumed by the author (Zoc. cit.).According to Zincke, the conversion of be?,-? il,hzide into azobenzil bycold concentrated sulphuric acid, consists in the removal of oxygen,and as the latter does not appear in the free state it must be assumedto oxidise a part of the substance.This, however, is not in accordancewith the fact that the change is very complete, and the author thinksit far more probable that water is eliminated, which might occur inthe following manner, if beiizilimide be assumed to have the formulaC?lH17N02r thus : C2,H17N0, - H20 = C,,H,,NO. This formula alsoagrees better with the results of analysis than that given by Zincke.PhC-0,The constitution, 11 )C(OH)Ph, is suggested, according toPhC.NHwhich benzilimide would also be a condensation-product of benzalde-hyde and b e n d with ammonia. The author agrees with Zincke thatimabet/ziZ has the formula C.izH32N,04 ; the halved formula wouldrequire that half the benzil taking part in the reaction should bedecomposed, but the yield of imabenzil is too great for this.More-over, on boiling it with dilute sulphuric acid, almost exactly the sameweight of benzil is obtained: C4,H31N,04 + 2H20 = 3C,aH1,@2 +2NH3, this being the reverse of Zincke's method of forming it. Ima-benzil contains therefore neither benzoic acid nor benzaldehyderadicals, and must be derived from 3 mols. of benzil.Action of Nitriles on Benzil. By F. R. JAPP and R, C.TRESIDDER (Ber., 16, 2652--2654) .-On adding acetaldehyde andA. K. M314 ABSTRACTS OF CHEMICAL PAPERS.benzonitrile to well cooled concentrated sulphuric acid, Hepp andSpiess obtained a compound of the formula CI6Hl6N2O2; CzHAO +2C7H5N + HzO = Cl6H,,NZO2. The authors find that a! similar re-action takes place with benzil and propionitrile.Finely powderedbenzil is suspencled in four times its weight of concentrated sulphuricacid, and propionitril gradually added, the mixture being agitatedand cooled. After remaining a t rest €or some hours, it is pouredinto water and the white product washed with ether and crystal!isedfrom boiling alcohol. It forms lustrous colonrless needles of theforrriula C20H22NZ03, melting at 197": C14Hl,,02 + 2C,H5N + H20 =C20H22N203. On boiling it with dilute sulphuric acid, it yields benzil,propionic acid, and ammonia: C20H22N20, + SH& = C14H1002 +;IC,H,.COOH + 2NH3. When benzill and benzonitril are treated asabove described, the product consists of two compounds, which can beseparated by crystallisation from alcohol.The more soluble com-pound forms colourless prisms melting a t 168", which crystallise withhalf a molecule of alcohol, 2C28H22N203 + C2H60 : CltH1002 + 2C&N + H20 = C29H22N20J. The second substance, C2,HzlNOs, is nearly in-soluble in alcohol and in most of the iisual solvents, but can bepurified by crystallisation from boiling benzene, when i t is obtained inmicroscopic prisms melting a t 225". Its formation probably takesplace thus: 2ClrH,002 + C7H5N +i B20 = C2eH2LN03 + PhCOOH.When it is heated with concentrated hydrochloric acid a t 150°, it isdecomposed, benzil, benzoic acid, and atnmonia being formed, pro-bably according to the equation C2,H2,N03 + 2H20 = C14H1002 +C7H602 + C7H60 + NH, ; the authors did not succeed in confirmingthe formation of benzsldehgde.Acetic anhydride, a t 150", has noaction on the substance. A. K. M.Substituted Benzoic Acids,, and the. Nature of the Hydro-gen Atorris in Benzene. Part I. By H. H~BNER (AnnuZen, 222,67-115).-I. Metanitrobenzoic acid melting at 142" is prepared byadding finely powdered benzoic acid to nitric acid (sp. gr. 1*5), andthen boiling for 24 hours. I t is separated from the orthonitrobenzoicacid simultaneously formed, by means of the sodium salt, which ismore soluble in the case of the ortho-acid. The preparation ofdimefanitrobenzoic acid melting at 205", by the action of a mixtureof strong sulphuric and fuming nitric: acids on benzoic acids, has beenalready described (Abstr., 1828, 148). The same acid may also beobtained from the above metanitrobenzoic acid by the action of amixture of strong sulphuric and nitric acids.The preparation ofthe same dinitro-acid from parst'oluidine was made known byW. Staedel (Abstr., 1881, 724). Paraorthonitrobenzoic acid,CsH3(COOH)(N02)2 [l : 2 : 41,is prepared by heating paranitrobenzoic acid with a mixture ofequal volumes of the strongest nitric and commercial sulphuricacids at 170". The acid is purifiei by means of its barium and leadfialts : iC melts a t 179". This nitration has since been studied byClaus and Halberstadt (Abstr., 1880, 647), who find that a seconddinitrobenzoic acid is simultaneously formed. Prom the above iORGANIC CHEMISTRY. 315appears that the NO?,-group in entering into mononitrobenzene-deriva-tives principally replaces those hydrogen a t o m which are in themeta-position, irrespectively of any oxatyl-, methyl-, or amido-groups,which may be already present in the molecule.11.The preparation of metanitrometamidobenzoic acid melting a t208" has been already described (Abstr., 1878, 148). Metamidoben-zoic zcid is prepared by passing sulphuretted hydrogen through anarnrrioniacal solution of metadinitrobenzoic acid until the solutionyields no precipitate with hydrochloric acid. The acid crystalliseswith 1 mol. H20, and melts a t 228". By heating the dry hydro-chloride of this acid with barium hydroxide, dimetamidobenzenemelting a t 60" is obtained. This shows that the dinitrobenzoic acidmelting a t 204", which is the chief product of the nitration of mono-metanitrobenzoic acid, has the two nitro-groups in the meta-positionrelatively to each other.The nitramidobenzoic acid melting a t 208" was converted by meansof the diazo-compound into metanitrobenzoic acid melting at 142",and this again, by means of tin and hydrochloric acid, into metamido-benzoic acid melting a t 172.5".The same metanitramidobenzoicacid melting a t 208" was converted by means of the diazo-compoundinto metsnitrochlorobenzoio acid melting a t 147" ; then, by means ofzinc and hydrochloric acid, the latter was. converted into metamido-chlorobenzoic acid melting at 216", and this again, through the diazo-cornpoiind, into metachlorobenzoic acid melting a t 153". Thus boththe nitro-groups in the dinitrobenzoic acid are shown to be in themeta-position.These experiments and results may be thus brieflytabulated :-[I : 3 : 5.1Dimetimitrobenzoic acid.. . . COOH aNOz pNO,Metrariitramidobenzoic ,, . . . . COOH d o z PNH,Metanitrobenzoic ,, .... COOH aNO2 Ha-Metachlorobenzoic ,, . . , . COOH aCl Ha/%&!etachlorobenzoic ,, . . . . COOH H pClMetanitrochlorobenzoic ,, . . . . COOH aNOz PClMetamidochlorobenzoic ,, . . . COOH aNH, BCl111. When metachlorobenzoic acid is acted on by fuming nitricacid, two nitrochlorobenzoic acids are produced. As it may beassumed that the nitric acid acts in the same way as on metabromo-benzoic acid, tl ie two acids must be metachlororthonitrobenzoic acids.The two acids are separated by repeatedly boiling them with smallquantities of water until the undissolved portion (a-metachloronitro-benzoic acid nielting at 235") no longer melts under water.Thesolution contains the ,!?-metachloronitrobenzoic acid melting at 137".The properties, both of the acids themselves and of their respectivesalts, are quite distinct, thus demonstrating that in monosub-ptituted benzenes there are two atoms of hydrogeu in the ortho-position.IV. Hitherto for the preparation of a- and p-orthonitrometn-brvniobenzoic acid, purified bromobenzoic acid from bromine andbcnzoic acid has been employed (Bey., 8, 558; Abstr., 1878, 748)316 ABSTRACTS O F CHEMICAL PAPERS.Owing to the difficulty of separating the products of such an action asthat of bromine on benzoic acid, the suspicion might arise that theseisomeric bromonitrobenzoic acids had been formed from different bro-mobenzoic acids.In order to obviate this objection, pure metanitro-benzoic acid was converted into metamido-, and then into metabromo-benzoic acid, and this on treatment with nitric acid yielded the a- andP-orthohitrometabromobenzoic acids as with the ordinary bromoben-zoic acid. To prepare t'he a-orthobromome tabroniobenzoic acid, theabove a-orthonitro-acid was coiiverted into the diazo-compound, orrather into the diszoimido-compound, >N, as itproved to be, and the latter into the dibromobeiizoic acid, which meltsat 147".To prepare the metsbromo-8-orthobromobenzoic acid, the abovep- orthonitro-acid was first converted into the metabromo-p-orthamido-benzoic acid.The further conversion of the latter, by means of thediazo-compound, into dibromobenzoic acid, is attended with niuchdifficulty. The hydrobromide of the amido-acid is first prepared,treated with nitrous anhydride in the cold, and finally boiled. Themrztabromo-p-orthobromobenzoic acid melts a t 153".The two isomeric bromamidobenzoic acids were also convertedinto amidobenzoic acid by means of sodium-amalgam. In bothcases, the same amidobenzoic acid melting a t 144", and identical withanthranilic acid or orthamidobenzoic acid was obtaiued, thus confirm-ing the already demonstrated existence of t w o ortho-hydrogen atomsin mono-substituted benzene.That the existence of two isomeric metabromorthonitrobenzoicacids depends on the different relationship between the bromine- andnitro-groups, Wafs shown by converting these acids into dibromoben-zene. The P-compound was found to yield paradibromo-, and thea-compound orthodi bromobenzene, thus :-CO0H.CeHjBr.N =ClOOH.C,H,Br.NHMetabromo-P-orthoni trobenzoic acid.Metabmino-a-orlhonitrobenzoic acid.[COOH: NO,: Br = 1 : 2 : 31.[ COOH : Rr : Hr = 1 : 2 : 31.[COOH: NO,: B r = 1: 2 : 51.[COOH: B r : Br = 1: 2 : 51.Metabromo-l3-orthobromobenzoic acid. Metabromo-n-orthobromobenzoic acid.Paradibromobenzene.[Br : Br = 2 : 51.Orthodibromobenzene.[Br : Br = 2 : 31.P. F. F.Nitrohydroxypropylbenzoic Acid and its Derivatives. By0. WIDMANN (Bey., 16, 2567--2575),-This acid, together with someof its derivatives, have been already described by t3he author (Abstr.,1883, 330).The n~nmonium salt, C,,H,,N0,.NH4 + 2H20, formslustrous needles extremely soluble i n water ; the silver salt,CmHioNO&g t QHz0,separates from a warm solution in needles, and from a cold solution inwell-formed prisms or rhombic plates, sparingly soluble in cold, morORGANIC CHEMISTRY. 317readily in warm water ; the calciim s d t , (C,oH,,NO5),Ca, crystallisesin sparingly soluble white rreedles, the barium salt, (CloHloN05)~Ba +GH20, in highly lustrous needles, 1 part of the latter salt (anhy-drous) dissolving in 11 parts water at 13". The lead salt,(CioHioNO5)J'b + 5HzO,forms short lustrous prisms very sparingly soluble in water, and thecopper salt, ( C~,H,ONO~)ZCU + l+HzO, bluish-green prismatic orcubical crystals, also very sparingly soluble in water, although readilyin alcohol, from which it crystallises in small green slender needles.Nitroacefoz~~,.oy,?/lbennoic acid, C6H,(N02) (CMe,.O%).COOH, is ob-tained when nitrohydroxypropylbenzoic acid is heated with an excessof acetic anhydride in sealed tubes a t loo", the solution repeatedlyevaporated with alcohol, and the oily product crystallised from a mix-ture of ether with a little alcohol.It forms colourless rhomboidalpyramids melting a t 131-133", and extremely readily soluble inalcohol, ether, and the usual solvents, almost insoluble in water.Salts of Nitropro~en!ilbenzoic Acid. -The nmnzoiaizcin snlt is ex-tremely soluble in water, and crystallises a t ordinary temperatures inwhite needles, C,,H,NO,.NH, ; the silver salt, CloHHN04Ag, formsclusters of white needles, or on rapidly cooling its hot solutio~~, slenderwhite feathery needles, very sparinglv soluble in cold, more readily inwarm water ; the calcium salt, (CloH,N04),Ca + ZHZO, separates inclusters of slender white needles, very sparingly soluble in water ; thebarium snlt, (CloH,NOd).?Ba + 3&H20, crjstallises in small white con-centrically grouped needles, very sparingly soluble in cold, much morereadily in warm water; the copper salf;, (CloH8NOp)2Cu + HzO, ob-tained by precipitating the ammonium salt with copper sulphate,forms a bluish-qreen precipitate ; it begins to decompose above loo",whilst long white needles sublime, insoluble in water, readily solublein potash, and melting at about 150".rlmidohydl.oxy~rop?/lbe?~zoic acid,C,H,(NH,) (CMe,.OH).COOH, is prepared by dissolving the nitro-acid ( 5 grams) in an excess of ammonia, and gradually adding a solu-tion of ferrous sulphate (40 grams). The mixture is supersaturatedwith ammonia, warmed on a water-bath, and the nearly colourlessfiltrate treated witth acetic acid and repeatedly extracted with ether,from which, after purification, the amido -acid crystallises in colourlesslustrous prisms, wliich do not melt atl 270". It is almost insoluble inbenzene, readily soluble in alcohol, very sparingly in ether, and mode-rately soluble in water ; i t possesses very feeble acid as well as basicproperties ; it yields amidopropenylbenzoic acid when boiled withhydrochloric acid.AcetcLmidolLydrox~pro~~lbenzoic acid, NAcH.C6H3~CMe,.0H).COOH,is obtained by the action of acetic anhydride (1 mol.) on amido-hydroxypropylbenzoic acid (1 mol.), the two substances reactingviolently with great evolution of heat, the product soon solidifying toa hard brittle mass.It is very sparingly soluble in boiling alcohol,from wliich it separates as a white crystalline powder, which does notmelt a t 280". A midopropenylbenzoic acid, NH2.C6H3(C3H,).COOH, isprepared from the corresponding nitro-compound by reduction wit3 18 ABSTRACTS OF CHEMICAL PAPERS.ammonia and ferrous sulphate. It crystallises in long white lustrousneedles melting a t 93-94', and is readily soluble in ekher, alcohol,chloroform, and benzene, sparingly in light petroleum and in water.It may also be obtained by boiling amidohydroxypropylbenzoic acidwith hydrochloric acid. On evaporating the solution.the hydro-chloride is obtained, and may be decomposed by sodium hydroxide,and the acici separated by the addition of acetic acid. The hydro-ch7oride, COOH.C,H:,(C,3H,) .NH,Cl, crystallises in long colourlessprisms, very readily soluble in water, and Fields a readily solubleplatinochloride. The ncetate, COOH.C,H,(C3H5).NH2,KZOII, crystal-lises in short colourless well-formed prisms, melting a t about 160",with evolution of gas and formation of a substance of very high melt-ing point; this behavionr is due tao the presence of water of crystal-lisation. Considerable evolution of heat takes place when aceticanhydride (1 mol.) acts on amidopropenylbenzoic acid, and acetundo-propenylbenzoic ucid, NAcH.CsH3( CaH,).COOH, is formed.It crystal-lises from dilute alcohol i n white flat needles melting at 210-212O.If an excess of acetic anhydride is used, the second amido-hydrogenseems to be replaced, the product melting a t 215-216". Acetamido-propenylbenzoic acid is sparingly soluble in boiling water, fromwhich it crystallises in long needles; it is insoluble in cold, butsoluble in boiling dilute sulphuric acid, from which it crystallisesunchanged ; it is also insoluble in cold hydrochloric acid, and on boil-ing. dissolves with difficultv and with Dartial sanonification and forma-tigu of the hydrochloride &f a new cokpound (see p.303).A. K. M.Conversion of Active Mandelic Acid into Inactive. By J.LEWKOWITSCH (Ber., 16, 2721-2722).-When lwomandelic acid isheated a t 160" in a sealed tube for 30 hours, it is conrerted intobenzaldehyde and inactive mandelic acid. By means of the cincho-nine salt, the inactive acid can be split up into the two optically act'ivevarieties. When paramandelic wid is exposed to t,he action ofschizomycetes, the dextromandelic acid is decomposed, but the laevo-acid remains. w. c. w.Dipyrogallopropionic Acid. By C. B~TTINGER (Ber., 16, 2404-2412) .-By treating pyroracemic acid and pyrogallol with con-cenkrated sulphuric acid, a mixture of this acid and its anhydride wasobtained from which the former was separated by its greater soh-bility in water.The aqueous solutions, on spontaneous evaporation,leave a red resinous mass, which is easily soluble in glacial acetic acid,acetone, and alcohol. It is decomposed by heat, leaving the anhy-dride, and melts at 162". The composition of this acid is expressedby the formula C15H,,08. It dissolves in ammonia and alkalis, form-ing blue solutions, in which barium chloride, calcium chloride, andcopper sulphate produce dark-blue precipittates.Meth~ldi~yrogallo~ro~ionate is obtained by heating the acid withpotash, methyl iodide, and methyl alcohol a t 120". It is a dark-brownpowder melting below 100".Dipyrogallopropionic acid with acetic anhydride, yields a diacetylORGANIC CHEMISTRY. 319derivative, C,,H,,Ac,O, ; this when treated with bromine yields apentabromo-derivative, C15H6Br5Ac207.I)ipyrogallopropionic acid treated with bromine in glacial acetic acidsolution, yields a mixture of a tribronio- and pentabromo-derivative.A?Lh!Idrod~~.l/rogallo~ropionic acid, C'15H1?07, is obtained by heatingthe acid at 100".It forms a reddish-brown powder soluble in hotwater and dissolving in ammonia to a violet-coloured solution.When heated with acetic anhydride, it yields a diacetyl-derivative.Bromine reacts with a solution in glacial acetic acid or chloroform,forming a tribromo- and pentabromo-snhydropyrogallopropionic acid.D D R 1. L . U .Properties of Ethylic Phenylsulphonacetates. By A. MICHAELandA.M. COYEY (Amer. Chem. J., 5,116-119).--Ethylicphei~ylsulplzon-acetate, PhSO,.CH,.COOEt, is obtained by the action of ethyl chlor-acetate on an alcoholic solution of sodium phenylsulphonate, thcmixture being heated for 4-5 hours on the water-bath, the alcoholdistilled off, the residue extracted with water, and the insoluble oilallowed to stand for some time, when it crystsllises, and is purifiedby crystallisation from alcohol.Ethylic phenylsulphonacetate crystal-lises in clusters of long prisms, melts a t 45", is insoluble in water,spa.ringly soluble in cold, soluble in hot alcohol. Boiled with alkalis,it yields the metallic salts, which, on treatment with acids, give thefree acid.Sodium has little action on the ethyl salt; sodium ethylate, on thecontrary, readily reacts, a mixture of the substances in molecularproportion dissolved in absolute alcohol soon solidifying to a mass ofwhite needles of ethyl sodium p henylsulphonacetate,PhS02:CHNa.COOEt.This is sparingly soluble in cold, moderately soluble in hot alcohol,readily soluble in water ; on -acidifying, the origindl ether is precipi-tated.Ethylic benzylphenylsulphon acetate, Ph S 02.CH (CH,Ph).COOE t, isprepared by the action of benayl chloriae on the preceding compound ;it forms short white prisms, melts a t 95-96', is insoluble in water,readily soluble in hot alcohol. Heated with alcoholic sodium ethyl-ate, it yields a sodium derivative which when treated with benzylchloride gives the dibenzyl derivative melting at 101 8". On heating themonobenzyl derivative with excess of alcoholic caustic soda in aclosed tube a t 100" for several hours, i t yields cinnamic acid, accord-ing to the eqnation, CsH5.CH,.CH(S0,Ph).coo~t + 2KOH =C,H,.CH : CH.COOK + PhS0,K + EtOH + OH,.These results show clearly that an acid radical snch as PhS02, hasas decided an effect as an actyl-group in rendering the hydrogen ofthe CH,-group to which it is attached sufficiently negative to bereplaceable by metals.Oxidation of Substitution-products of Aromatic Hydro-carbons.Experiments with Derivatives of Naphthalene. ByI. REMSEN and W. J. COMSTOCK (Amer. Chenz. J., 5, 106--lll).-TheA. J. G320 ABSTRACTS OF CHEMlCAL PAPERS.lead snl ts of a- and 6-napli thalenesulphonic acids mere treated directlywith phosphorous pentachloride and ammonia, and the aniides SOobtained submitted to oxidation. Satisfactory results were obtainedonly when potassium permanganate was employed as the oxidisingasgent.I n wutral solution, or in alkaline solution with excess ofpermanganate, phthalic acid and sulphophthalic acid are obtained,whilst in alkaline solution with the permanganate not in excess of theamo 11 n t theoretically required, s ulpb amine ph thnlic acids are obtained,together with a small quantity of phthalic acid.a-Su7phophthalic acid could not be obtained pure in the free state ;the barium salt, (C8H/ Baa + 8H20, crystallises in aggre-gates of small clear and transparent plates. It loses 7 mols. H20below 150". The hydrogslrlead salt, C,jH,(COOH) <g$:>Pb + l&H20, crystallises in smallp i s m s ,a-Sulphaminephthalic acid was not obtained free.Potassiuma-anhydrosulphamin ep hthalat e, C6H3( COOK) <:gz> NH + HzO,cq-stallises in needles, is soluble in alcohol and water, insoluble inether. Silves. 61~1~~12a7nine~Z~tlznZafe, C6H3(GoOH) (SOzNHz).C00,4g,forms colonrless necdles, is soluble in hot watei-, does not lose inweight a t 180", but appears to suffer deeomposition when heatedmuch at that temperature.Uipotassizcm 6 sulplzophtl~aZate, C6H3(S03K) (COOK).COOH +2H,O, forms small prismatic crystals, readily sol able in water, nearlyinsoluble in alcohol. Pdtassium P-sulphamine~hthalate,CGH,(S02NH,) (COOK).COO~ + 2$H20,crystallises in radiating groups of silky needles 0f.a light straw colour,and is readily soluble in# water.It is sparinsrly soluble in boiling water.A. J.G.Aniluvitonic Acid. By C. BOTTINGER ( B e y . , 16, 2357-2359) .-The hydrochloride of t,his acid suspended in chloroform and treatedwith bromine, forms a red oily liquid which, after being wasbed withchloroform and then with water, forms a reddish-yellow powder, losingbromine on exposure to tbe air. This same oily bromine addition-product is obtained by heating the hydrochloride with bromine in sealedtubes at 120°, but substitution-products are formed a t the same time.Artilucitonic acid lydrobrornide is obtained by spontaneous evapora-tion of its aqueous solutions in beautifully iridescent large prismatictabular crystals, containing 2 mois. H20, whilst from hot saturatedsolutions it crystallises in long spikes containing Q a mol.H?O. Itsaqueous solutions when not too dilute give a yellow precipitate withplatinum chloride. When the hydrobromide is mixed with lime anddistilled, it yields meth~-lquinoline.When the hydi-ochloride of aniluvitonic acid is heated with phthnlicanhydride and zinc chloride, i t gives a brownish-yellow colouring matterof a basic character, the hydrochloride of which reacts with methyORGANIC CHEMISTRY. 321iodide, yielding a brownish-red powder, which crystallises from alcoholand ether in yellow needles, and is probably a methylated derivativeof aniluvitonic acid. P. P. B.Cymenesnlphonic Acids.A reply to Claw (Bey., 16, 1297).By E. PATERB~ (Ber., 16, 2713).-"Oakbark Tannic Acid." By C.BOTTINGER (Rer., 16, 2710-.L713).-In reply to Etti (Abstr., 1883, 995), the author maintainsthat the tannic acid contained in oakbark must have the compositionC,9H160,n, as it forms a bromine substitution-product, C19H1QBr2010,which yields a perdaeetic derivative. Strong hydrochloric acid at200" decomposes the dibromo-derivative into carbonic acid, water, andthe compound C3RH1R013, from which a tetrabrominated derivative wasobtained. The tannic acid contains 1 ketone oxygen-atom. Whendibromotannic acid is acted on by bromine, 4 hydrogen-atoms areeliminated, but only two of them are replaced by bromine. andC19H10Br4010 is produced. This body also yields a pentacetic deriva-tive.Phlobaphen and '' oak-red" have the composition C38H26017, fit-e ofthe hydrogen-atoms being replaceable by acetyl.No methyl chlorideis formed when the compound is converted into C36H22011 by the actionof hydrochloric acid a t a high temperature. Phlobaphen yields twobromine derivatives, C,H,,Br,017 sparingly soluble in alcohol, andC.7sH,6Br100,7 freely soluble in alcohol. Seven hydrogen-atoms in thefirst body can be replaced by acetyl.It is reducedby hydriodic acid, and yields ethers when treated with alcoholiciodides and potash. On oxidation with potassium permanganate, theether is converted into carbonic, oxalic, and acetic acids, and a solidcompound which is decomposed by hydrochloric acid a t 190" into ethylchloride and pyrogallol.From these facts, the author concludes that the tannic acid fromoakbark is a condensation-product of an aldehyde, C,H,.CO.CH,.CHO,with tannin.w. c, w.Phlobaphen does not contain a ketone oxygen-atom.Diphenylparaxylylrnethane and its Products of Oxidation.By W. HEMILTAN (Ber., 16, 2360--2379).-D1$:l~enylparaxylylrnethane,CHPh,.C6H3Me9, is obtained by heating together benzhydrol, paradxylene, and phasphoric anhydride. It is a solid, crystallising fromcther in large shining transparent prismatic crystals, which melt a t92", and are easily soluble in alcohol, ether, benzene, and glacialacetic acid. Like triphenylmethane, it yields colouring matterssimilar t o roeaniIine., by successive nitration, oxidation, and reduction.On careful oxidation with chromic mixture, it Tields a resinous mass,which is partly soluble in conccntrated soda solution ; the residue,when extracted with boiling alcohol, yields methyldiphenylphthalide,the first homologne of dipbenylphthslide described by Baeyer (Abstr.,1880, 650).>CO, crystallises from Ale t IL y 1 dip hen y &I h t R aTid e , P hz C < __ __YOL.XLVI. zc 6H3b1 322 ABSTRACTS OF CHEMICAL PAPERS.alcohol in large shining prismatic crystals, is sparingly solubIe incold, more easily in hot alcohol. It melts at 179", and sublimeswithout decomposition at 360".Tol~ldiphenylrnethanecarbox~l~c acid, CPh2( OH) .C6H,Me.COOH, isobtained by first heating methyldiphenyiphthalide with alcoholic soda,and then reducing the resulting sodium tolyldiphenylcarbinolortho-carboxylate, CPh,( OH).C6H3Me.COONa, with zinc-dust ; the solutionso obtained is decomposed by an acid, when the tolyldiphenylmethane-carboxylic acid separates out as a white curdy precipitate.It crys-tnllises from a mixture of alcohol and ether in large transparenttables, insoluble in water, but soluble in alcohol, ether, &c. ; it meltsat 21'7" and distils without decomposition. It is a strong monobasicacid, forming well-defined salts, which are mostly insoluble in water,but soluble in alcohol. By careful oxidation, it is easily reconvertedinto methyldiphenylphthacde..CPh--.Methylpheny Zanthranol, CeH3Me< 1 >C,&, is obtained by theC(OR)action of concentrated sulphuric acid on tolyldiphenylmethane-carboxylic acid, a formation exactly analogous to that of phenyl-anthranol (Baeyer, loc.cit.). It crystallises from alcohol in lightyellow shining tables which melt at 156". It is soluble in ether, hotalcohol, and glacial acetic acid, insoluble in solutions of caustic alkalis,and of the carbonates of the alkali metals, but soluble in boilingalkalis.CPh(0H) Methylpheny Zoxanthranol, C,H3Me<--,o-_>C6H4, formed by osi-dising methylphenylanthranol with chromic acid. By crystallisationfirst from glacial acetic acid, and then from alcohol, it is obtained incolourless rhombic tables melting at 195", and soluble in alcohol, ether,and glacial acetic acid, but insoluble in caustic alkalis. Like phenyl-oxanthranol (Baeyer, loc. cit.), it dissolves in concentrated sulphuricacid, forming a purple solution, which becomes dark violet onwarming. By reducing agents, it is converted into mebhylphenyl-anthranol.ing methylphenylanthranol with zinc-dust.When crystallised fromalcohol or glacial acetic acid, it forms tufts of yellow crystals whichmelt at 119"; its ethereal alnd alcoholic solutions exhibit distinctgreenish-blue fluorescence. It forms a compound with picric acid,and when treated with sulphnric acid, is converted into a soluble snl-phonic acid.~ulyzdi~henylmethane, CHPh,. CbH4Me, is formed by distilling bariumtolyldiphenylrne thanecarboxylate with baryta. It cry stallises inlong thin needles, united in globular masses, melting at 6P, andvolatile without decomposition at temperatures above 360". It iseasily soluble in alcohol, ether, benzene, and glacial acetic acid ; itssolutions exhibit well-defined blue fluorescence, which is observablein the crystals also.The crystals of this hydrocarbon exhibit theremarkable property of giving out an intensely blue light whenChromic acid converts it into the oxanthranolORGANIC CHEMISTRY. 32 3rubbed. In its chemical behaviour the hydrocarbon resemblestriphenylmethane and diphenylparaxylylmetkmne. On oxidationwith chromic mixture, it yields a Eriphen~learbinoEcarbo~~lic acid,CPh,(OH).CsH4.COOH, melting rut 160-162".This hydrocarbon is the third known, having the fornulaE. and 0. Fischer obfained one conta,ining the methyl-group, sym-metrically disposed as regards the methane residue, vie., in the posi-tion [l : 41 (Animlen, 194, 242).A second one has also been obtainedby these chemists from leucaniline; it melts a t 59-59.5", and onoxidation yields a carbinol melting a t 150". In this hydrocarbonthe position of the methylgoup to the methane residue is supposedto be the unsymmetrical one, viz., [1:3]. The author contends thatthis hydrocarbon is an ortho-compound, and that the tolyldiphenyl-methane described by him is in reality the meta-compound, inasmuchas the acid from which it is formed can only have the constitution[C'HPh, : Me r C'OOH = 1 : 3 : 61,and consequently the tolyldipbenylmethane formed from it musthave the constitutional formula [CHF%, : Me = 1 : 31. The portionof the products of oxidation. of methyldiphenylphthalide, which issoluble in soda, contains the sodium salts.of tolyldiphenylcarbinol-metacarboxyIic acid and triphenylmethaneanhydrocarboxylic acid.Toty Wiphey Z c ~ b i n o ~ ~ ~ ~ e t a c n r b o z y l i ~ acid,CPh&OH) .CsH3Me. GOOH,crystallises from hot glacial acetic acid in small leaflets ; it is sparinglysoluble even in hot alcohoI and gracial acetic acid, and insoluble inthe cold ; it melts at 250-255", and is at the same time resolved intowater and a yellow non-crystalline product. It forms well-definedcrystalline salts, most of which are insoluble in water. Heated withacetic anhydride, it is partially converted inta an acetic compound,c,iHu(Ac)03-C6H@ 0 0 H) > c 0,-- O- Triphersy lmetlzcone-annhy~ocarFoxy lic acid, CPh,<is obtained from the mother-liquors obtained in the purification of thetolyldiphenylcarbinolmetacarboxylic acid, from which it diff ers bybeing much more easily soluble in alcohol and gIacial acetic acid: itcrystallises in two distinct forms- from its solutions in the lattersolvent ; by quickly cooling the hot sakurated solution, it is obtainedin silky needles, and by slow eva-porntion in transparent tablets ; bothforms melt at 244-246", and distil at higher temperatures withoutdecomposition- It is a monobmic acid, forming salts which as a ruleare easily soluble in water.When distilled with excess of causticalkalis, it yields benzophenone and benzene, the latter being a secon-dary product of the decomposition of terephthalic acid and benzoic:acid. This decomposition is exactly analogous to that which pheno?-phthale'in undergoes under similar conditions.Trip henjjlmet hanediccwbozg lie m i d , CHPfr,.C6H3( C OOH) *. - T h isacid is obtaiued by treating the solution of triphenylmethar=eanhS-2 324 ABSTRACTS OF CHEMICAL PAPERS.drocarboxylie acid in caustic soda with zinc-dust, and filtering fromexcess of zinc, then decomposing the solution with hydrochloric acid.The white curdy precipitate so obtained is next crystallised fromglacial acetic acid, when it forms slender needle-shaped crystalsmelting a t 278-280", and easily soluble in alcohol, ether, andglacial acetic acid. It is a dibnsic acid, forming salts which aregenerally soluble in water ; the silver salt is insoluble in water andalcohol. When distilled with an excess of an alkali, it yields triphenyl-methane.On oxidation, it is converted into triphenylmethane-anhydrocarboxylic acid. It dissolves in cold cancentrated sulphuricacid, forming a greenish-yellow solution, which on warming changesfirst to green, then 'indigo-blue, violet, and finally msumes an intensepurple. P. P. B.Carbonyldiphenyl Oxide and Hydroxyphenylene Ketone. ByR. RICHTER (J.pr. Chem. [a], 28, 273--309).-In this paper a moredetailed account (Abstr., 1882, 618) is given of the ketones obtainedoriginally by Kolbe and Lauternann'(Annalen, 115, 197) by the actionof phosphorus oxychloride on the basic and neutral sodium salts ofsalicylic acid.CarbonyZdiphenyZ oxide, CO( C6HJ20, is best prepared by theaction of phenyl phosphate on sodium salicylate :Ph3POq f 3C6H4(0HjCOONa = 3C0(C6H4),0 + Na3P04 + 3H,O.It is obtJained from alcoholic solution in white crystals, which melta t 173-174", and sublime readily.It is soluble in hot alcohol,benzene, and chloroform, less soluble in cold alcohol and et'her, andquite insoluble in water. This ketone is also formed by distillingphenyl phosphate with sodium meta- or para-hydroxybenzoate (withphosphorus oxychloride the reaction is quite different) ; by acting onpotassium methyl salicylate with phenyl phosphate ; by distillation ofneutral or basic sodium salicylate with phosphorus pentoxide ; by dyydistillation of sodium chloro-salicy late ; by the action of chlorosahcyhcchloride on basic sodium salicylate, C6HICl.COC1 + C6H4(ONa).COONa= NaCl + C02 + CO(C,H,),O; and lastly by the action of phos-phorus oxychloride on sodium ortho-phenylbenzoate.The ketonecharacter of the compound was demonstrated by the action ofhydriodic acid and of zinc-dust ; and also by fusion with potash, whenit is decomposed into salicylic acid and phenol.Methylenediphenyl oaide, cH2(C6H4), lo, is prepared by the actionof hydriodic acid on the ketone, and forms white crystals, soluble inalcohol and ether, sublimable, m d melting a t 98.5". It is easilyoxidised again to ,the ketone by dilute nitric acid. By the action ofphosphorus pentachloride, a bibasic acid of %he formula ( C,,H90)PO3is formed, crystallising in needles, and melting a t 255-260". Theammonium and silver salts were prepared ; the latter is insoluble inwater.Dilute nitric acid decomposes it into phosphoric acid and theoriginal ketone. Bromine gives a subshitution-product with methylene-diphenyl oxide, and fuming nitric acid a dinitro-derivative of theketone.CarbonyZdi%Yydroxyd~henyZ, CO(C6H,.0H)2, is formed as an interORGANIC CHEMISTRY. 325mediate compound on fusing carbonyldiph enyl oxide with potash.With strong bases, it forms salts in which one atom of hydrogenis replaced by the metal, but with alcohol and acid radicals, a t hightemperatures, it forms compounds in which two hydrogen atomsare replaced. The author has prepared the barium and ammo-nium salts, and2lso a mono- and a di-methyl ether, an acetyl-corn-pomd, Cj13H:303AC2, and a benzoyl compound.In his opinion thissubstance is not an acid containing the group-COOH, as Merz andWerth have supposed (Ber., 14, 192), since no ether could beobtained by long action of hydrochloric acid on the substance dissolvedin absolute alcohol, and from the nature of the above-mentioned saltsand ether, the two hydroxyls are not of the same kind', but are similarin character to those in the glycols. Dilute nitric acid convertsthis substance into the original ketone. On heating it with fuminghydriodic acid and amorphous phosphorus, meth ylenediphenyl oxideis first formed by reduction, and finally the phosphoric acid compound,C,,H&.PO(OH),. Ib differs from the ketone i n bebg completely de-composed by funiing hydrochloric acid a t 200' into phenol andcarbonic anhydride.By reduction with sodium-amalgam, a crystallinesubstance, C26H1803, is formed. Since acetic anhydride decomposesit into the ketone and methylenediphenyl oxide; its formula may berepresented as ( C 12Hs 0) " C 0By oxidation 'with chromic acid in glacial acetic acid or by perman-ganate of potash, the ketone is slowly but completely decomposed. Itforms a dibromo-substitution product with bmmine, and with nitricacid, a-carbonyldinitrodiphenyl oxide, melting a t 145-150", aiidp-carbonyldinitrodiphenyl oxide, melting a t 260".Hydrozydiphenylene ketone, CO<A-6;H4--> .-This ketone isformed by the action of phosphorus oxychloride on neutral sodiunisalicylate, and differs in being easily soluble in alcohol, ethei., andalkaline carbonates.It forms colourless needles melting at 91". It canalso be obtained by the action of phosphorus oxychloride on methylor ethyl salicylate. By treating a mixture of Gasic sodium salicylateand ethyl salicylate with phosphorus oxychloride, a mixture of thetwo ketones is obtained. Distilled over red-hot calcium oxide, i t isdecomposed into diphenylene oxide and diphenyl ketone. Over red-hot zinc-dust, it yields a substance smelhg of diphenyl, soluble incaustic soda and reprecipitated by acids, and crystallising in beautifulcolourless plates. The melting point of this substance is 51" ;diphenyl, melting a t 71", was also obtained. This ketone is notreduced by zinc or sulphuric acid, or by fuming hydriodic acid andphosphorus.Chromic acid completely oxidises it. The author hasprepared a mono- and a di-nitro-derivative, also a disulpho- and amonobromo-substitution compound.Action of Phosphorus Ozyddoride o n Neutral Potassiwn Salicylateamd Sodium Neta- and Pura-hydroxyhenz0ates.-The action on potas-sium salicylate is the same as on the sodium salt. Sodium meta-hgdroxybenzoate gives a yellow crystalline acid, melting and decom-posing a t 285". The para-salt grves a chlorinated sublimable orC H (OH32 G ABSTRACTS OF CHEMICAL PAPERS.crystalline compound, melting and distilling a t 105". These reactionswill form the subject of future research.Among& the products of the action of phenyl phosphate on sodiumsalicglate were found phenylbenzok acid melting a t 110-lll",diphenyloxide melting a t 27-28"., and a substance, which the authorsupposes may be phenylene oxide (C6H40).A. B.Unsymmetrical Tetraphenylethane. By R. ANSCH~~TZ (Ber.,16, 2377-2379) .-By the action of aluminium chloride on a solutionof stilbene bromide in benzene, a Letraphenylethane is formed,which is found to be identical with that obtained from unsymmetricaltetrabromethane, benzene, and aluminium chloride (Ber., 16, 1435),and also with that obtained by the reduction of P-benzopinacoline.The formation of this compound by these three reactions is repre-sented by the following equations :-CH2Br.CRr3 + 4c6H6 = CH2Ph + CPh, + 4HBr.CPh,.COPh + 2H, = CPh,.CH,Ph + HzO.CHPhBr.CHPhBr + 2CsH6 = CPh,.CH,Ph + 2HBr.The formation of an unsymmetrical te tmphenylethane fromsymmetrical stilbene bromide is apparently due to an intermolecularchange taking place in the stilbene bromide, and brought about bythe action of the aluminium chloride on this substance.P. P.B.Bromine-derivatives of P-Naphtholazobenzene. By I;. MAR-GARY (Gazzetfa, 13, 438-440) .-The author prepared P-naphtbolazo-benzene by the action of diazobenzene chloride on an alkaline solutionof @naphthol, whereby a brown crystalline mass was formed, havinga green metallic reflex, and after a few hours the whole of the colour-ing matter separated at the surface of the liquid. P-Naphtholazoben-zenc forms red-brown needle-shsaped crystals, soluble in acetic acid,light petroleum, alcohol, and benzene, and melting at 125-126",differing thereby from Typke's a-~~aphtholazobenzene (Ber., 1877,p. ISSO), one modification of whieh melts a t 266", and the other a t175".With the view of determining whether the action of bromine on/j-naphth olazobenzene gives rise to a monobrominated derivative, andwhether the substitution takes place in the benzene- or in the naphthol-group, the author heated that compound dissolved in acetic acid withbromine in the proportion required to form a monobromo-derivative,whereupon a brown crystalline mass separated, which after two crys-tallisations from alcohol yielded orange-red silky needles melting a t160-161", and having the composition C6H4BrN : NCloH6.0H orC,H,N : NCIoH,Br.OH. In this respect P-naphtholazobenzene differsfrom the a-compound, which, according to Typke, does not yield amonobi~omo-derivati~e when similarly treated.This being established, the position of the bromine in the moleculemay be de terinined by subjecting the monobromo-cdmpound to Nietzki'sreaction for the preparation of the amidonaphthols : for if the bro-mine replaces an atom of hydrogen in the naphthol-group, the producORGANIC CHEMISTRY. 327will be a bromamidonaphthol, whereas if the substitution takes placein the benzene-group, the result will be the formation of bromanilines.Experiment showed that the reaction took place in the manner ]actmentioned, the products being parabromaniline and amidonaphthol,the presence of which latter was demonstrated by converting it,according t o Liebermann and Jacobsen's method, into naphthaqui-none.As a confirmation of this result, the author diazotised para-bromaniline, and treated &naphthol with the product, obtainingthereby a body agreeing in crystalline form and melting point withthe above-described product formed by direct bromination.H. WProducts of the Decomposition of Santonous Acid. By S.CANNIZZARO (Gazxetta, 13, 383--395).-This acid heated in a streamof carbonic anhydride at 330-320", gives off a few gas-bubbles, andyields a liquid distillate together with a crystalline substance satu-rated with oil, which condenses in the neck of the retort. At 360" afresh portion of liquid acid is obtained, together with a crystallinematter and a considerable quantity of viscid yellowish oil ; and on con-tinuing the heating a t a temperature above 360" till nothing is leftbut a small carbonaceous residue, an oil distils over similar to thatabove mentioned, and bubbles of combustible gas are given off.The portion which distils up to 360" contains water, santonous acid,propionic acid, dimethylnaph thol dihydride, CI2Hl4O, dimethylnaph-thol, ClnH120, arid an oil resolvable by potash into propionic acid anddimethylnaphthol dihydride, consisting therefore of the propionicether of the latter.The portions which distil above 360" consistchiefly of this ether, together with a small quantity of dimethylnaph-thalene, CI,H12. The residue left in the retort when the heat has notbeen raised above 300", and has been discontinued after water, san-tonous acid, and traces of other products have passed over, is ananhydride of santonous acid, which solidifies to a transparent brittleresin not perceptibly soluble in alcohol or ether : it dissolves, however,when heated for some time with alcoholic potash, and on evaporatingthe alcohol and replacing it by water, an alkaline solution is obtained,from which carbonic acid does not separate any phenol, and hydro-chloric acid throws down santonous acid.This acid is also found inthe residue left after heating to 360". I f the temperature has beenraised from that point to 400°, the residue consifits of a mixture ofCl2Hl20 and C12H,,0; but if it has been raised above 400", theresidue is small in quantity, and does noh contain any determinableproduct.The formation of these products appears to take place as follows :1.Part of the santonous acid C15H2003, is resolved into water and theanhydride CI5Hl,O,. 2. A small portion of the santonous acid iscarried over unnlt,ered by the aqueous vapour, and another portion issplit u p into propionic acid and dimethylnaphthol dihydride, Cl,H2,0, =CsH,02 + C,2H,40. 3. When all the water that can form has beengiven off, the anhydride, C,,HI8O2, is transformed by the action ofheat into the propionic ether of dimethylnaphthol dihydride328 ABSTRACTS OF CHEMICAL PAPERS.4. The dimethylnaphthol which is formed in variable quantity, andthe small quantit,y of dimethylnaphthalene obtained towards the endof the process, are secondary products of the decomposition of themet hy lnap h t hol di h ydride.Dimethylnaphthol dihydride, C,,H,,O = H2,C10H5Me2.0H, is pre-pared by decomposing its propionic ether with alcoholic potash,evaporating the alcohol, saturating with carbonic anhydride, and dis-tilling in a current of steam.When purified by solntion in alcoholand precipitation with water, it crystallises on cooling i n very slendeysilky needles, which after two or three recrystallisations melt con-stantly a t 113". It is very soluble in ether, alcohol, benzene, andpetroleum, especially when hot, nearly insoluble in cold water. It isvolatile, and distils unaltered with vaponr of water. When treatedwith phosphorus pentasulphide, it gives up 1 mol. H20, and is con-verted into dimethylnaphthalene, Cl2H1,, identical with that which isobtained from dimethylnaphthol, and therefore analogous in constitu-tion to Glaser's dibromonaphthalene melting at 81".When heatedwith sulphur in a test-tube, it is partly decomposed, with evolution ofhydrogen sulphide and formation of dimethylnaphthol, CIoH,Me2.0H,melting a t 134".The results above described, and those previously observed byCannizzaro and Cameluthi (Abstr., 1883, 77), may be explained byregarding santono-us acid a s a tetra- substituted derivative of nnph-thalene tetrahydride, H,C,,H8, represented by the formulaH4,CloH4Me, (OH) ,CH,.CH,. COOH,which is that of a tetrahydride of dimethylhydroxynaphtlhylpropionicacid. On heating it, two out of the four additive hydrogen-atoms art:detached, and employed in separating the propionic acid residue, theproducts thereby formed being dimethylnaphthol dihydride and pro-pionic acid, thus-H,, Cl0H4MeZ(OE€) .CH2.CH,.CQOH = H,,CloB*Mez( 0H)H +CH,.CH2.C OOH.The resinous substance formed by elimination of a molecule ofwater from santonous acid may be regarded as an inner anhydride,in which the propionic residue, having lost its acid hydroxyl, hasattached itself to the phenolic oxygen, as in the phenolic ethers, achange which may be represented by the following equation :-H4,CloH,Me,(OH).CH,.CH2.COOH = H,O +- 0 . c o -H4, CioHJfez< CH,. CH,>When this anhydride is heated, two out of the four additivehydrogen-atoms may be supposed to separate the propionic residii efrom the naphtholic nucleus, leaving it attached by the oxygen as anacid radicle, and thereby forming the propionic ether of dimehhyl-naphthol dihydride, CH,.CHT,.CO0.C,oH4Me2,H2.H. W.By J. STRASBURGER ( Ber.,16, 2346-2348).-Mononitrophenanthraquinone, obtained by nitra-Derivatives of PhenanthraquinoneORGANIC CHEMISTRY. 329t i n g phenanthraquinone (Anschuta and Schultz, Ber., 9,1404 j, yieldson nitration a dinitrophenanthraqninone, which is converted byoxidising agents into the a-dinitrophenic acid melting a t 253", and inwhich Schultz has shown that both nitro-groups occupy the para-posi-tion (Ann,aZen, 196, 29). Hence mononitrophenanthraquinone musthave the constitutional formula Cf6H4<CO>CGHS.NOZ [4]. coParamononitrodiphenic aeid,COOH.C6Hd.C6H&NOZ).COOH [ 2 : I : 4 : 21,is obtained by oxidising the above mononitrophenanthraquinone.Itforms yellow prismatic needles melting at 217". On reduction withtin and hydrochloric acid, it yields an amido-derivative ; the hydro-chloride of this, when distilled with lime, yields lJara-amitioJEiAorene,,CH2, which crystallises from alcohol in pale-brown needlesCeH*,1NH? . CGH3melting at 123".Hydrocyanides of the Diketones, and their Saponification.(Preliminary Notice.) By F. R. JAPP and N. H. J. MILT,EE (Bey., 16,2416-2418) .-When benzil hydrocyavhide, prepared according toZinin's method, is treated with hydrochloric acid gas, it yields asubstance crystallising from benzene in pale yellow needles meltinga t 1%", and having the formula C16H1?N20, also an acid containingnitrogen, which crystallises from water in prisms melting a t 185".Yhenanthrapuinone H y droc yanicle, C lcH80z (HCN) .-I? h enan t h raq ui -none is treated with aqueous hydrocyanic acid (30 per cent.HCN),and the solution filtered from unaltered phenanthraquinone. Thenew compound separates in slender needles which easily decomposewhen moist. It is freed from phenanthraquinone by washing withchloroform, and then dried over concentrated sulphuric acid. Whensaponified with hydrochloric acid, it yields a cornpound crys tallisingfrom benzene in colourless silky needles, which melt a t 241", and havethe composition C,,H,,NO. At the same time an acid of the formulaC,,H1,NO2 is formed ; this melts at 183", and its.constitution is pro-ba bly-P. P. B.C6H4.. C. COOHCsH,.C.CH,.NHZ I IIThe compound CuHl,NO is probably the laetame o r lactime of thisacid. P. P. B.Anthracene-carboxylie Acid from Methybthraquinone.By E. BORNSTEIN (Ber., 16, 2609--2613).-One part of the crudemethylanthraquinone (Abstr., 1883, 70) crystallised from alcohol ismixed with concentrated sulphuric acid (6 parts), water (1 part)added, and then powdered potassium dichromate (24 parts) in smallquantities a t a time. The mass must be continually stirred duringthe reaction, which is very violent, a.nd after all the chromate hasbeen introduced the product is heated for some time a t about 110330 ABSTRACTS OF CHEMICAL PAPERS.120", water being added if necessary.When cold, the product iswashed, boiled with dilute ammonia until the ammoniacal odour dis-appears and the filtrate acidulated, when the anthmyuinonecarboxylicacid is precipitated. The residue insoluble in ammonia is a mixtureof anthraquinoue and methylanthraquinone. The anthraquinone-carboxylic acid is wnrmecl with an excess of dilute ammonia andtwice its weight of zinc-dust gradually added; the filtrate is darkyellow by transmitted light, and exhibits a strong blue fluorescence.On the addition of a iniiieral acid, anthracenecarboxylic acid isthrown down as a voluminous yellow precipitate; it is sparinglysoluble in cold, more readily in hot alcohol, the solution showing anintense blue fluorescence. It crystallises from alcohol in small yellowscdes, soluble in glacial acetic acid, sparingly in chloroform, andalmost insoluble in benzene and carbon bisulphide ; it melts a t about%SO", and sublimes, forming small scales and needles.The alkali saltsare readily soluble in water, the barium salt almost insoluble. Theethyl derivative cryst'allises in white scales melting a t 13P-135",ehowing that the acid is identical with the anthracenecarboxylic acidubtained by Liebermann and Bischof (Abstr., 1880, 399), in whichthe carboxyl-group has the same position as the hydroxyl-group inhydroxyanthraquinone. The chloride, CI5H90C1, forms a yellow solu-tion with benzene, showing an intense green fluorescence, and yieldingthe chloride in nodules on evaporation ; it also dissolves readily inchloroform, carbon bisulphide, ether and alcohol, and is readily de-composed by boiling with water. The amide, CI5HllNO, crystallisesfrom glacial acetic acid in lustrous pale yellow scales, insoluble inwater, benzene, carbon bisulphide, and chloroform ; it is sparinglysoluble in alcohol, from which it crptallises in slender yellow needles,melting at 293--295".Its solutions show a blue fluorescence. Bythe action of sodium-amalgam or of hydriodic acid and amorphousphosphorus on the acid, hydro-derivatives are obtained. When analcoholic solution of the acid is warmed with sodium-amalgam, andacetic acid added from time t o time to diminish the alkalinity, thesolution becomes gradually decolorised. The dihydro- and tetrahydro-tcnthrac~necarboxylic acids obtained are separated by crystallisationfrom alcohol, the former, C15HI2O2, separating first in star-like groupsof colourless scales readily soluble in the ordinary solvents ; it showsa faint blue fluorescence both in solution and when dry ; its alkalisalts are readily soluble, those of the alkaline earths and heavy metalssparingly soluble ; it melts at 203".Tetrahydroanthracenecarboxylicacid, C15H,402, is more readily soluble in alcohol than the last-men-tioned acid, and crystallises in colourless lustrous rhombic platesmelting a t 164-165", and showing no fluorescence. By the action ofhydriodic acid (sp. gr. 1.7) and amorphous phosphorus a t 220--230",n mixed product is formed, and on fractionally crystztllising it fromalcohol, hexhytZroanthrace~~ecnrbozy Zic acid, C,,H,,O,, is obtained melt-ing at 232"; i t crystallises from benzene, chloroform, and carbonbisulphide in slender colourless needles, and from alcohol in nodules ;i n solution, it shows a faint blue fluorescence.The more solublefractions melt between 150" and ZOO", and appear to contain the tetra-hydro-acid. A. K. MORGANIC CHEMISTRY. 331Phellandrium Aquaticum. By L. PESCI (Gaxzettn, 13, 496).-This plant yields an essential oil, about 80 per cent. of which consistsof a terpene (PheZZanthreTte) boiling a t 103-104" under a pressure of80 mm., and a t 171-172" under 766 mm. Sp. gr. 0.8553 at 10".Refractive index for D = 1.481. Rotatory power [a]= = - 16-74.The author has not succeeded in obtaining pure hydrochlorides.Phellanthrene heated a t 140-150" in sealed tubes is converted into atransparent neutral solid substance, soluble in ether, insoluble inalcohol, melting- a t 86", isomeric with the liquid, but differing from itin having a strong dextrorotatory power.By A.BE'YER (Arch. Plzurnb. [3], 21, 283--288).-Glad-stone has shown that the carvol obtained from dill-oil agrees in its prin-cipal physical properties with the carvol from caraway oil. Fluckigerfound that the carvol obtained from German mint-oil, Mentha crispa,differecl from the carvol from the other two sources in being stronglylsevorotatory. The author has re-examined the carvol obtained fromthese three oils. To obtain it, the crude oils were distilled, theportion of the caraway oil distilling a t 223", those of the Germanmint-oil at 215--230", and 200-215" being employed.The crudedill-oil was used without distillation. The hydrogen sulphide com-pounds, (C,sH,40)2,SH2, were first obtained in the crystalline stateand recrystallised from a mixture of three parts of chloroform and oneof alcohol. The yield from caraway oil was 8 per cent., that fromdill-oil 40 per cent., whilst the first fraction of the mint-oil yielded 50per cent., the second fraction 30 per cent. All the hydrogen sulphidecompounds melted a t 187". The specific rotatory power [a]= at 20" ofthe compound from caraway oil was + 5.53, from dill-oil + 5.44, frommint-oil - 5.55. No crystallographic difference in the compoundscould be detected. By the action of hydrogen sulphide on an alcoholicsolution, all the three compounds were converted into the amorphousthiocarvol ( C,oH,4S)2,SH,. The carvol obtained from all the hydrogensulphide compounds agreed in boiling point and density ; and thespecific rotatory power of carvol from caraway-oil and dill-oil wasnearly the same, being dextrorotatory ; the carvol from mint-oil,however, was lavorotat,ory ( [ c c ] ~ = - 62-46 at 2").The carvol from mint-oil was distilled from metaphosphoric acid,the resulting careacrd dissolved in potash solution, filtered, decom-posed with sulphuric: acid, and tho carvacrol, CI0Hl40, was dried overcalcium chloride.Theboiling point was 230-231'; sp. gr. a t 4" 0.975, specific rotatorypower 0. The crystalline barium salt of carvacrolsulphonic acid wasalso prepared.It was thus shown that the carvacrol from IEVO-rotatory carvol is identical with the carvacrol from dextrorotatorycarvol. A small quantity of a hydrocarbon boiling at 168-171" wasobtained from the mint-oil. it was lavorotatory, and appeared to bea terpene. W. R. D.H. W.Carvol.It solidified a t - 20" to a crystalline mass.Cinchocerotin. By A. HELMS (Arch. Pharm. [3], 21,279-233).This substance was exhibited by its producer, Kerner, a t the exhibi-tions at Paris in 1858 and a t London in 1862. I t had been deposite332 ABSTRACTS OF CHEMICAL PAPERS.in copper tubes through which hot alcohol was passed after havingexhauded a mixture of calcium hydroxide and South Americancalisaya bark.The brown mass yielded two different substanceswhen treated with alcohol, the first and larger constituent was awhite crystalline body, for which the author proposes to retain thename cinchocerotin, the second a light yellow substance of which onlya small quantity was obtained. The first constituent is representedby the formula C27H4802, aud melts a t 130". It is dissolved by theordinary solvents, and when oxidised with chromic mixture, yieldsbutyric and acetic acids, fogether with an acid which was obtained incrystals melting a t 72". This the author proposes to call cinchocero-tic acid, C,oH,,02. Cinehocerothi is not attacked by alkalis, and isprobably allied to betulin and cerin in constitution. The second con-stituent of the crude mass is decomposed a t 230' without melting,and when heated with glacial acetic acid forms a crjstalline acidmelting a t 54", which is easily soluble in alcohol, ether, and lightpetroleum.It farms sparingly soluble metallic salts. A furtherexamination of this constituent was not possible owing to the smallyield. W. R. D.Piscidin, the h t i v e Principle of Jamaica Dogwood. By E.HART (Amer. Chena. J.., 5, 39-40).-Fluid extract of Jamaica dog-wood was mixed with lime, left at rest for half an hour in itwarm place, filtered, and water added to the filtrate from which, after2-3 days, crystals of piscidin, separate. After purification, it is ob-tained in nearly colourless microscopic crystals of the formula C29H,a0,,and melting at 192" (uncorr.).It is. insoluble in water, slightlysoluble in ether or cold alcohol, much more soluble in boiling alcohol,readily in benzene and chloroform. lit dissolves in strong hydro-chloric acid, and is reprecipif ated by water apparently unchanged.It does not seem to be a glucoside, and gives no precipitate with leadacetate. The alcoholic solution is neutral in reaction. A. J. G.Action of Nitaic Acid on Teucrin. By A. OGLiAr,oRo (Gazzettn,13, 498).--ln his memoir on Tezccrium fiucticans (Abstr, 1879, 728),the author showed that teucrin, the glucoside of this plant, whentreated with dilute nitric acid, is converted into a monobasic acid,C8H802, melting at, 180". Further experiments on this acid and itsderivatives have shown that it is identical with anisic acid,H.W.Saponin from (' Saponaria officinalis." By C. SCHIAPABELLI(Guzzetta, 13, 432--430),.--The analyses hitherto made of saponinobtained from different plants are not very concordant, the resultsvarying indeed from 47.52 per cent, C and 7.16 H (Overbeck) to52-63 C and 7-48 H (Rochleder and Schwarz). Moreover the experi-ments of the last-named chemist lead t o the conclusion that thecarbohydrate obtained i n the first instance from saponin by decom-position with acids, is not grape-sugar, but a body convertible intothah sugar by the further action of acids,-and consequently that.saponin is not a glucoside but an amylo'id. To throw further light onthis matter, the author has endeavoured to determine whether thORGANIC CHEMISTRY.333products extracted from different plants and included under thename of saponin, are really identical, and in the present paper hedescribes the results obtained with saponin from Saponaria q@cinaZis.The root of this plant, dried and coarsely pounded, was boiledfor three days in a reflux apparatus with alcohol of 90" ; after whichthe boiling alcoholic decoction was separated and left for some daysin a cool place, whereupon the sides of the vessel became coatedwith a copious yellow flocculent deposit which, when freed fromcolonring matter 5y treatment with a warm mixture of alcohol andether, consisted of saponin, shill however very impure. Treatmentwith alcohol and animal charcoal still lefh it contaminated with about3 per cent. of mineral matter.It was therefore dissolved in thesmallest possible quantity of water ; the cold solution was precipitatedwith saturated baryta-water ; the resulting barium saponate, afterwashing with baryta-watter, was suspended in water and decomposedby a current of carbonic anhydride, then heabed to the boiling point,and filtered ; the filkrate evaporated to a syrup ak, a gentle heat wasprecipitated with alcohol ; and the still yellowish saponin was furtherpurified with alcohol of 90 per cent. The substance thus obtainedstill contained barium salts, to remove which it was dissolved in waterand treated with dilute sulphuric acid, added drop by drop ; and thefiltered liquid, aRer concentration at a gentle heat, was precipitatedwith alcohol and ether, these operations being repeated a second andR third time, and the product finally purified with boiling alcohol of90 per cent.in quantity n o t sufficient t o dissolve it completely. Thealcoholic solution evaporated in a vacuum left perfectly white flocksof pure saponin, wkich were washed with ether and dried over sul-phuric acid.Saponin thus prepared gave, as the mean result of five analyses,52.65 per cent. carbon and 7.36 hydrogen, agreeing nearly with theformula C32H5401R, which requires 52 86 C and 7-44 H, Saponin fromC*YypsophiZa was found by Rochleder to contain 52.65 carbon and 7.34hydrogen.Pure saponin is a very white amorphoiis inadorous powder, whichexcites sneezing when inhaled by the nostrils ; it has a pungent dis-agreeable taste, and is poisonous ; dissolves very freely in water, butis insoluble in ether, benzene, and chloroform, and only slightly solublein alcohol.Heated on platinum-foil, i t decomposes, emitting an odourof burnt sugar, and leaving P porous residue difficulh to burn. Saponinis laevogyrate, like most glucosidcs ; specific rotatory power [a]= =-7 30 : it is the lmsf optically active of all known glecosides,Saponin, as already observed, is remarkable for the power of itsaqueous solution to dissolve salts which are insoluble in water. Whenits aqueous solution, mixed with lead aeetate, is precipitated byhydrogen sulphide and filtered, the liquid which passes through isblack from dissolved lead sulphide, which may be precipitated from itby adding a small quantity of alcohol.A boiling aqueous solution ofsaponin dissolves barium carbonahe (up to 10 per cent.), which may beprecipitated by sulphuric acid ; nevertheless harium sulphate is slightlysoluble in aqueous saponin. This property of dissolving salts throwsgreat dificnlty, as already observed, in the way of purifjing saponin334 ABSTRACTS OF CHEMICAL PAPERS.This substance likewise dissolves gases, and incloses them mechani-cally. A dilute aqueous solution of saponin forms on agitation a verypersistent froth.An aqueous solution of saponin mixed with hydroxide of potassium,barium, or strontium, yields precipitates of the corresponding com-pounds. The barium compound has the composition-Products of Decomposition of Haponin.-An aqueous solution ofsaponin was heated on a water-bath with dilute sulphnric or hydro-chloric acid, the liquid being filtered after two hours, in order toremove the flocculent substance which separated, and thereby preventits further decomposition by the acid ; the filtered solution was thenagain boiled, the new precipitate separated, and these operationswere repeated a third time.The three precipitates thus obtainedagreed very closely in composition, giving as the mean result of theiranalysis, 60-G5 per cent. carbon and 8.22 hydrogen, numbers agreeingnearly with the formula C40R66018, which requires 61.06 carbon, 8.38hydrogen, and 3-56 oxygen. The decomposition of sapnin by diluteacids may therefore be represented by the equation-The compound C40H66015 is called by the author s a p o n e t i n , to dis-tingnish it from the snpoyenz'n of Rochleder and others, which was notof constant composition.Saponetin is a whitish microcrystallinesubstance, insoluble in water, alcohol, and ether,The glucose formed by the action of dilute acids on saponin isdextrogyrate, its specific rotatory powep being [a]= = +52-48. It isfermentable, has a saccharine taste, and has not yet been crystallised,its solution, after concentration to it syrup, having remained for sixmonths without giving any sign of crystallisation. Further experi-ments are however required t o determine whether it is a peculiar sugardistinct from dextrose, or whether the difference between its opticalrotatory power and that of the latter is due to some other cause.H.W.New Synthesis of Quinoline-derivatives. I. By L. KNORR(Ber., 16,2593-2596).--Ry the action of ethyl acetoacetate on aniline,Oppenheirn (Bey., 9, 1098) obtained diphenylcarbamide, alcohol, andacetone. Different results are obtained on modifying the conditions ofthe experiment. At the ordinary temperature a layer of water sepa-rates after some days, whilst a heavy oil is formed which appears tobe the condensation-product PhN CMe.CH&OOEt. Aniline andethyl acetoacetate react more readily when the mixture is heatednearly to the boiling point. When the mass becomes dark yellowthe reaction should be interrupted ; the product is then treated withconcentrated sulphnrie acid, diluted with water, and alkali added,when hydrox~methylqzkinoline, C:loH,OM (m.p. Beo), is precipitated.The author explains its formation thus :ORGANIC CHEMISTRY. 335PhNH, + COMe.CH,.COOEt - H20 = PhN : CMe.CH,.COOEt;PhN : CMe.CH,.COOEt + HzO = PhN CMe.CH1.COOH + Et.OH ;.N CMe.PhN : CNe.CH2.COOH - H,O = C H ' \CH. '\c(oH,//If the reaction be conducted in a sealed tube a t 120°, a, substance ofthe formula C,,H,,NO, (m. p. 81") can be isolated, and is probablyanilacetoacetic acid, PhN : CMe.CH,.COOH ; it yields hydroxy-methylquinoline when treated with sulphuric acid. Hydroxymethyl-quinoline is sparingly soluble in water, more readily in hot alcohol,insoluble in ether ; it has both basic and acid properties, but is pre-cipitated by carbonic anhydride from alkaline solutions ; i t forms acrystalline sodium salt, hydrochloride, sulphate, and platinochloride.When distilled with zinc-dust, it yields a-methylquinoline, and maytherefore be designated ~~-hydroxy-a-methylquinoline.A.K. &I.Condensation-products of Methylated Quinofines and Pyri-dines. By E. JACOBSEN and C. L. REIMER (Bey., 16, 2602-2608).-It has been shown by the authors (Abstr., 1883,922) that a yellow dye,CI8Hl1NO2, is formed by the action of phthalic anhydride on quin-aldine, or on crude coal-tar quinoline, and that similar dyes are alsoyielded by the homologues of quinaldine and by pyridine. Furtherinvestigation shows that the substance obtained from pyridine is dueto the presence of picoliue, and that pure pyridine, like pure quino-line, is not acted on by phthalic anhydride.They conclude thatTraub's quinophthalone (Ber., 16, 297) is also most probably derivedfrom a methylquinoline, and that i t is either identical or isomericwith quinoline-yellow, Cl,HllNO,. Paramethylpui?ao~hthIr.lone,C,9H,,NOz, is obtained by heating paramethylquinaldine with phthalicanhydride and zinc chloride at 200°, boiling the melt with hydro-chloric acid and crystallising from alcohol; it forms long gold-colonred needles melting at 203", and resembling quinoline- yellow.It is insoluble in water, sparingly soluble in alcohol, readily in glacialacetic and concentrated sulphuric acids; it dyes silk and woolalmost exactly like quinoline-yellow. The paramethylquinaldine canbe obtained from pamtoluidine and aldehyde by h e b n e r and Miller'smethod, and purified by fractional distillation and by means of thesparingly soluble chromate ( C,1Hl,N)z,HzCr20,.It melts at 55" andboils at 259-261". When coal-tar pyridine ifi heated with phthalicanhydride and zinc chloride at 200°, and the product treated with hotdilute hydrochloric acid, the greater portion (containing undteredpyridine) dissolves, whilst the residue, after crystallisation fromglacial acetic acid and from alcohol, yields bright yellow silky scalesof pyrophthaZone melting above 260" with partial decomposition. Itis almost insoluble in water. sparingly soluble in alcohol, readily inglacial acetic acid. Its formula, C,HSNO,, indicates its derivationfpom picoline present in the pyridine, thus: C,H,N + CJ&O, =C14H,N0, + H20, and experiment proves that it cannot be obtainedfrom perfectly pure pyridine, whilst coal-tar picoline gives anabundant yield. A second substlance, apparently of the same com336 ABSTRACTS OF CHEMICAL PAPERS.position ns pyrophthalonc, is also formed ; i t is, however, more readilysoluble in alcohol, and crystallises from glacial acetic acid in slenderorange-red needles, melting below 200" ; i t seems probable thereforcthat two diffwcnt picolinev exist in coal-tar.Both of these phtha-lones from picoline dye silk and wool yellow, but much fainter tilaiiqu i nu1 ine-yellow .The fact that only methylated pyritlines and quinolincs react withphthalic acid indicates that i t is the hydrogen of tlie methyl-groupwhich becomes substituted, and not that of the pyridine nucleus aswas previously assumed. I n this case quinoline-yellow will have theforniu1;t C,H,N.CH : C202 : C6H4. This view is supported by thebehaviour of the phthalones on oxidation ; for if the snbstitutiontook place in the pyridine nucleus, pyridinecarboxylic acids (orquinolinecarboxylic acids) would be expected to result from the de-composition of tlie phthalyl-group.On heating qninoline-yellow withnitric acid (sp. gr. leg), phthalic acid is prodnced, together withresinous substances, and a second acid containing nitrogen ; this latteracid is sparingly soluble in water, very readily in mineral acids, Asubstitnce of sitnilar properties is obtained when a mixture of chromicmcl sulphuric acids is employed, the product in this case, however,contains no phthalic acid.On neutralising with barium hydroxideand evaporating the filtrate, a sparingly soluble barium salt is obtainedyi~ltliiig an acid which crystalliscs in colourless needles melting at157''. I t discolves very readily in hot, less so in oold water, and I-eryreadily in mineral acids ; i t forms a platinochloride, crystallising inyellowish-red prisms, and when hcated with lime emits an odourresembling that of quinoline. I t is probably a new quinolinemono-carboxjlic acid. Pyrophthalone is also very readily oxidised by nitric:Lcid, yielding phthalic acid and a n acid containing nitrogen, whichhowever has not yet bnen examined.When quinalcline (1 mol.) is heated with benealdeliyde (1 mol.)and zinc chloride at 160-170", the prodiict dissolved in hot con-centrated hjdrochloric acid, and ponsed iiito water, the hydmchlorideof a solid base (benz~/Zidenepuinaldine) is precipitated in yellowishneedles.The free base, C17Hl?N, is insoluble in water, sparinglysoluble in cold, readily in boiling alcohol, from which i t crydallises incol~urless lustrous needles melting a t 99-100". At a higher tempera-ture, it sublimes without decomposition, its vapour having an odoiirresembling that of quinoline. Its formation takes place thns :-C,o€€9N + CiH,O = CLiH13N + H,O. Tts salts are sparingly solublein cold water; the acid chromate, C17H13N,H2Cr207 + 29H,O, formsslender reddifih-jellow needles sparinply soluble eFen in boiling water.The same base is produced by the action of benzal chloride on quinal-(line in hhe presence of zinc chloride.Benz3-lideriequinaldine can bereadily oxidised, nitric acid (sp. gr. 1.4) yielding a mixture 0f severalacids, from which paranitrobbenzoic acid could be isolntd. Whenoxidised with chromic and sulphuric acids, benzoic acid is formed.I'icoline also yields R condensation-product wiLh benzaldehyde analo-gous to t h a t obtained from quitiddine, whilst pure pyi.icline is notattacked. It is probable therefore that in these reactions the substi-tution also takes place in the rnethj1-group, and that benzyildencORGANIC CHEMISTRY. 337quinaldine has the constitution C9H6N.CH : CHPh. Benzylidene-quinaldine is identical with the base obtained by Wallach and Wusten(Abstr., 1883, 1037).A. K. M.Preparation of Quinaldine on the Large Scale. By G.SCHULTZ (Ber., 16, 2600--2601).-When aldehyde is added to anaqueous solution of aniline hydrochloride, and the two are allowed toreact in the cold, the hydrochloride of a solid base is produced, andon melting this, either alone, o r better, with zinc chloride, it is con-verted into quinaldine. When paraldehyde, metal, aldol, and similarsubstances arc employed in place of tbe aldehyde, and other primaryaromatic bases in the place of aniline, compounds are obtainedwhich yield bases analogous to quinaldine when melted with zincchloride. From the product of the action of free aniline on aldehydea solid base has been isolated, apparently identical with the above.By boiling w<th hydrochloric acid both are decomposed (althoughnot readily) into aniline aud aldehyde, and then converted into quin-aldine.The composition of these bases appears to be far from constant,and to vary with the relative proportions of the components. Fromparaldehyde and aniline hydrochloride, a base was obtained which,after solution in benzene and precipitation with alcohol, had the corn-position CI,H,,N,, whilst a base obtained in another way had theformula ClaHlsNa, agreeing with Schiff's ethylicienediphenamine.A. K. M.Sparteine. (Preliminary Notice.) By 0. BERNHEIMER (Gazzetta,13, 451--454).-This base, C,,H,,N,, was first obtained from S p a & mscopnrium by Stenhouse in 1881, who determined its composition, andwas afterwards examined by Mills, who showed that it is a tertiarydiarnine.Ths spsrteine examined by the author was prepared fromSpnrtiunz scopnrium by a slight modification of Stenbonse's method ;it distilled to the last drop at 180-181" under a pressure of 20 mm.Its solution in alcohol at 96" has a specific rotatory power [a]== - 14.6 for a concentration of 23.88 a t 26". It bears a heat of 200"without alteration, but becomes partially carbonised a t higher tern-peratures ; is not decomposed by heating in sealed tubes with hydro-chloric acid. Bromine acts strongly on sparteine at ordinary tempera-tures, even when i t is largely diluted with ether, forming an undefinedresinous mass.On gradually adding 3 p r t s iodine dissolved in ether to an ethericsolution of 1 part sparteine, the iodine is decolorised, and a black pre-cipitate is formed, which when separated, washed with ether t o removefree iodine, and dissolved in boiling alcohol, separates on cooling inbeautiful green needles, having the compobition C15H,6N213.Thiscompound is insoluble in cold water and alcohol, but dissolves readilyi n those liquids when heated ; it is insoluble in ether, permanent inthe air, and yields free sparteine when heated with potash.Spnrteine (as snlphate) oxidised with potassium permanganateyields a small quantity of a volatile acid, having the odour of thefatty acids, together with a non-volatile acid having the compositionof a p!/ritfinem~nocarboz?lZic acid, C5H4N.COOH ; and on distilling asalt of this acid with lime, a volatile base is obtained having all theVOL.XLVI. 2 335 ABSTRACTS OF CHEMICAL PAPERS.properties of pyridine.ments as soon as he is in possession of a larger quantity of material.H. W.The author intends to continue his experi-By A. CLAUS and E. A.MERCK (Bey., 16, 2737--.9i"78).-Aniline, toluidine, qninine, cinchoni-dine, and strychnine, dissolve in aqueous hydrocyanic acid. Anexcess of acid renders the solution ver-y unstable. The salts have notbeen isolated, as ,they are decomposed by evaporation in a vacuum.Although the bases are completely withdrawn from these liquids byether, the solutions are not mere mechanical mixtures, since theyyield double cyanides with mercuric cyanide ; e.g., when mercuriccyanide is added to a solution of aniline hydrocyanide, white tabularcrystals, NH,Ph,HCN + Hg(CN)2, are deposited, which dissolve inwater, alcohol, and ether.When mercuric cyanide is added to tetramethylammonium iodide,two salts are formed, viz.,.a white salt of the compositionfreely soliible in waier, and a yellow salt, NMe4.CN,HgICN, sparinglysoluble in water.The white salt slowly changes into the yellowisomeride a t the ordinary temperatme, more rapidly at 200".TetraniethylammoniatrrL cyanide, NMe,.CN, prepared by the action ofbarium cyanide on tetramethylammonium iodide, has been describedby C. Thompson (this vol., p. 286). The clear crystals of the saltbecome opaque a t 150", decrepitate at 215", and melt at 295".Thesalt can be volatilised s?t> 225-250" without melting. With mercuriccyanide it forms a double salt, NMe,.CN,Hg(CN),, crystallising inprisms melting at 275". The corresponding silver salt,NMe4. CN,AgCN,has been described by ThompFon. Tetramethylammonium cyanidedissolves cobalt cyanide and ferrous cjanide, forming tetramethyl-ammonium cobalticyanide and ferrocyanide respectively. The lattercompound has been described*by Barth (Bey., 8, 1484). The formercrptallises in yellow plates, and resembles the potassium cobalti-cyanide in its properties.Cinchonitiine ethylcyanide, C,9H22N20,EtCN, prepared by the notionof barium cyanide on cinchonidine ethylsulphate, forms white crystal-line needles, which are decomposed by carbonic acid, and rapidlyabsorb moisture from the air.It is soluble in water but insoluble inether and chloroform. The crystals melt with decomposition a t 140".Quinine ethyZct,anide, C2"H24N202, EtCN, crystallises in needles solublein alcohol. The crystals melt at 90" and begin to decompose a t 95".Strychnine ethy1cyanide, C2,H2,N202,EtCN, is less hygi*oscopic andmore stable than the quinine and cinchondine compounds. It dissolvesCaffe'ine Methhydroxide. By E. SCHMIDT (Bey., 16, 258'7-2588).-In the hopes of obtaining an insight into the constitution ofcaffeine. the author submitted caffeine niethhydroxide to the action ofhydrochloric acid. He previously showed (Abstr., 1883, 872 and 873)Hydrocyanides of Organic Bases.XMe,I,Hg(CN),,freely in water, but is less soluble in alcohol.w. c. wORGANIC CHEMISTRY. 339that caff e'ine and theobromine yield the same decomposition-productswhen treated in this way, but the reaction threw no light on the con-stitution of these substances. Caff elne methhydroxide,C,HloN40,,MeOH + H20,is readily obtained by the action of moist silver oxide on caffeinemethiodide (Zoc. cit.). When it is dissolved in f Liming hydrochloricacid, and left for 14-20 days t o evaporate spontaneously, amalic acidseparates, with simultaneous formation of methylamine and formicacid, the production of amalic acid being, however, due t o a secondarydecomposition of the dimethyldialuric acid first formed. A consider-able portion of the caffeine methhydroxide is also converted intocaffeine methylchloride, C,H,,N,O,,MeCl, whilst a smaller portiongives rise to secondary reactions.Cafielne methhydroxide suffers no appreciable change on continuedheating above its melting point (137-138"), but is completely decom-posed when submitted to dry distillation in a current of hydrogen, caf-feine being produced.Water decomposes it at about '200", with formationof carbonic anhydride and methylamine. With a solution of bromine inchloroform, it yields a readily decomposible addition-compound whichis decomposed by water into hydrobromic acid, methy lamine, choles-trophane, and allocaffehe. This last substance is probably methyl-apocaffelne, since it is decomposed into carbonic anhydride andmethylcaffuric acid when boiled with water.By the action of hydro-chloric acid and potassium chlorate, caffeine methhydroxide yieldsdimethylalloxan, allocaffehe, amalic acid, cholest,rophane, and methyl-amine ; with chromic mixture it yields carbonic anhydride, formicacid, cholestrophane, and methylamine. Nitric acid (sp. gr. 1.4)decomposes it at ordinary temperatares, with violent evolution ofcarbonic anhydride and formation of methylamine and cholestrophane.Baryta-water also decomposes it in the cold. A. I(. M.Quinine Phenolsulphonate. By P. GIUBLEO (Arch. Pharm. [3j,21, 298).-This salt can be obtained by dissolving quinine in phenol-sulphonic acid and by decomposing solutions of lead or bariumphenolsulphocates with a solution of quinine sulphate. The salt,which crystallises with difficulty, contains 52 per cent.of quinine,20 per cent. of phenolsulphonic acid, and 28 per cent. of water.W. R. D.Berberine. By E. SCHMIDT (Bey., l6,2589).-The formula of thisbody, according to Fleitmann, is C42H36N209, according to Kemp,C4,HE,,N2@,, according to S tas, C4iH3RN2010, according to Henry,C4?.HX8N2010, and according to Serrius and Hlasiwetz, C,oHliNOa,4~E120.From numerous analyses of the free base, the hjdrochloride, nitrate,and sulphate, the author assigns t o it the formula C2,H1,N04,4H20.Analyses of Hla~iwet~z and Gil m's hydroberberine (AnnuZen, Snppl., 2,l g l ) , its hydrochloride and nitrate confirm their formula, C,H,,NO,.From its behaviour with ethyl iodide, hjdroberberine must be a tertiarybase. Berberine is converted into berberine hydriodide by treatment2 a 340 ABSTRACTS OF CHEMlCAL PAPERS.with ethyl iodide.The hydroxide obtained from hydroberberineethiodide forms colourless needles melting at 165" ; it yields crystallinesalts with hydrochloric, nitric, and sulphuric acids, and with platinicchloride. On oxidising berberine with alkaline permanganat e, a bi basicacid, CI0Hl0OG + 2H20, melting at 1 6 5 O , is obtained apparently identicalwith hemipinic acid.By 0. BERNHEIMER (Gazzetta, 13,342-347).-When berberine is heated in a retort with five times itsweight of potassium hydroxide, it blackens, intumesces, and gives offammonia, together with a small quantity of an oily liquid which, onexamination, was found t o be qainoline. Froin the residue in theretort, two acids were isolated, which were found to have all theproperties ascribed to them by Hlasiwetz and Gilm ; the author is atpresrnt engaged in studying their constitution.When hydroberberine is heated with methyl iodide a t 100" in aclosed tube, a yellow crystalline mass is obtained, which may be puri-fied by repeated crystallisation from boiling methyl alcohol.It crys-tallises in the trimetric system: a : b : c = 1.10332 : 1 : 1.78880.Observed forms, 001, 111, 113 ; combinations, 001, 111, 113 ; cleavageperfect, 001. The hydroberberine methiodide, C,oH21N04,MeI, is spar-ingly soluble in water or alcohol in the cold, but readily when heated.When the iodide suspended in water is treated with silver oxide, ityields the corresponding hydroxide, which may be obtained in crys-talline crusts, C2,,HZ1NO4,MeHO + H20, on evaporating the solution.It is strongly basic, and liberates ammonia from ammonium chloride.It dissolves in cold alcohol, but is insoluble in ether.On addinghydrochloric acid to its aqueous solution. the chloride is precipitatedas a crystalline powder. The plntinochloride crystallises in beautifullustrous plates, soluble in boiling alcohol. When heated in a sealedtulle at l50", the hydroxide is decomposed, with elimination of metlijlalcohol. From these results, the author infers that hydroberberine,like berberine itself, is a tertiary base.When berberine is heated with methyl iodide and methyl alcohol,it yields a methiodide, CmHIiNO4,MeI, in stellate groups of slenderneedles.On treating this with silver oxide, the correspondinghydroxide is obtained, very bimilar in its properties to the hydrober-berine compound.Fleitmann (AnnaZen, 59, 176) in his paper on berberine mentionsth9 formation of the hydrochloride of a base containing sulphur. Theauthor, followitig E'leitmann's directions, added yellow ammoniumsnlphide to a solution of berberine hydrochloride, collected the redprecipitate, dissolved i t in warm water, and added hydrochloric acid ;llydrogen sulpliide was evolved, and on examining the solution i t wasfound to contain berberine hydrochloride, but no trace of sulphurettedbase. The red precipitate mentioned above is probably a persulphideof berberine.On treating hydroherberine with iodine, both in chloroform solution,a brownish precipitate is obtained consisting of berberine hydriodide,C2nH,iN04,HI.It is easily purified by crystallisation from dilutealcoho 1. C. E. G.A. K. M.Derivatives of Berberine.The platinochloride is a yellow powderORGANIC CHEMISTRY. 341Alkaloids of Angustura Bark. By KOERNER and C. BOHRINGER(Gazzetta, 13, 363--367).-1n this preliminary notice the authors,after some historical details as to the introduction of the bark, statethat it contains aromatic substances and several alkaloids, the amountof the latter varying in different specimens from 0% to 1 per cent. Thealkaloids are mostly in the free state, and may be ext'racted directlyfrom the bark by means of ether. After the ethereal extract has beenwashed with dilute potash solution, the addition of oxalic acid ordilute sulphuric acid gives a yellow crystalline precipitate of thecorresponding salt of one of the alkaloids, cusparine, whilst otheralkaloidal Ral ts remain in solution.The precipitated cusparine salt is moderately soluble in boilingalcohol, and, on cooling, crystaliises out in slender needles of amagnificent greenish-yellow ; this colour is not removed by repeatedcrystallisation, or by treatment Kith animal charcoal, and other saltsof the alkaloid, obtained from the yellow precipitate by decomposition,are also intensely yellow. If, however, the free cusparine, C19H17N03,obtained from these coloured salts, is crystallised several times fromlight petroleurn, and then reconverted into the salt, this is found to becolourless.The author has been unable to ascertain the cause of thisyellow coloration. The a1 kaloid crystallises from light petroleum intufts of slender needles melting at 92"; it is moderately soluble inether, more readily in alcohol. The sulphate, oxalate, and hydro-chloride of the base are but sparingly soluble in water ; the acetate ismuch more soluble, but the solution is decomposed if largely diluted ;the tartrate dissolves readily. The platinochloride was obtained as anorange-yellow crystalline precipitate.When treated with potassium hydroxide, cusparine splits up, yield-ing a new alkalo'id and the potassium salt of an acid which seems tobe an aromatic derivative ; the acid is sparingly soluble and crystal-lises readily.The alkalojid crystallises from alcohol, in which i t isvery sparingly soluble, in minute, very brilliant, colourless needles ;it decomposes a t 250" without melting. An attempt to decomposethe cusparine in a similar manner by the action of hydrochloric acidfailed, as it began to carbonise eren a t 100".I n the mother-liquors from which the cusparine was originallyprecipitated as sulphate or oxalate, another alkaloid is found, to whichthe authors have given the name of gaZ@ezne, C2,H21N0,. The free basecrystallises from light petroleum in white needles melting a t 115.5".It may be obtained in well-formed transparent prisms from its solu-t,ion in ether or alcohol. All the salts of this alkaloid are moresoluble than those of cusparine ; several of them are of a magnificentgreenish-yellow like uranium salts. The sulphate crystallises inlarge prisms with 7 mols. H20, which it loses in part on exposure tothe air ; it melts a t 15", and at 100" undergoes decomposition, yield-ing the sulphate of another alkaloid and a crystalline nitrogenoussubstance which melts a t 196". The platinochloride crystallises inprisms with a triangular base.Besides cusparine and gallipehe, the authors have found amtheralkaloid which melts at 180", and is very sparingly soluble in ether342 ABSTRACTS OF CHEMICAL PAPERS.It crystallises f7om alcohol and furnishes salts, the solutions of whichhave a blue fluorescence.The property these alkaloids have of being transformed into otheralkalo'ids with simultaneous formation of acids, is interesting, andmay throw some light on the constitution of vegetable alkaio'ids ingeneral. C. E. G.Ptomaines. By A . SOLDAINI (Gazzettn, 13, 325).-In order toobviate the difficulties usually met with in the extraction and purifi-cation OF ptoma'ines, the author digests the putrid viscera with alco-hol acidified with oxalic acid ; the solut'ion is distilled down to removealcohol, taken up with water, and the acid solution agitated withbisulphide of carbon and w-ith ether. It is then rendered alkaline bylime, and the bases are removed by ether, chloroform, &c. The variousextracts are purified by fractional distillation in a current of hydro-gen. The author describes the ptoma'ines as colourless liquids, easilyalterable in contact with air, and all more or less soluble in water:some are soluble in ether, others in chloroform. They have apleasant odour, and the higher the boiling point the stronger thebasic properties. It is not known as yet whether these compoundsare amides, amines, or true alkaloids.The so-called Ptomaines in Relation to ToxicologicalResearches. By F. Mamo-Zuco (Gaxzstta, 13, 431--433).-Theauthor's experiments were made on a variety of fresh animal sub-stances, viz., white and polk of egg, brains, lungs, heart, liver, spleen,and blood, several methods being employed, with strict attention toall the conditions indicated by their respective authors. The resultof these experiments was the extraction of a base which exhibited allthe usual reactions of the alkaloids, b u t had the constitution of anammonium hydroxide, and in those cases in which an aurochloridecould be prepared and analysed, was found to be identical in compo-sition with neurine. In one iostance traces were also found of theso-called " animal quinine.''To determine the origin of this neurine, the author applied themethods above mentioned to the lecithins (prepared by Streeker'smethod from egg-yolk), and found that these szbstances behave inthe same manner as, for example, a mass of brain, egg, lungs, &c.On applying the same method to the albumin remaining after com-plete extraction of the lecithins, the result was purely negative.Hence it is clear that the so-called ptomajines obtained in the extrac-tion of fresh animal substances, originate, not as is generally supposed,from sudden alterations of the prote'ids, but from the splitting up ofthe lecithins under the influence of acids or alkalis.As neurine hydrochloride is not decomposed by sodium bicarbonate,the author was able to determine the toxicological question in casesof the extraction of alkaloids from substances in which putrefactionhas not yet commenced. The hydrochlorides of the alka'loid and ofthe so-called ptomaines, simultaneously extracted, are dissolved inwater, and the liquid, rendered alkaline with sodium bicarbonate, isC. E. GORGANIC CHEMISTRY.agitated with the solvent. The neurine then remains dissolvedwater as hydrochloride, and the alkalo'id may then be extractedThis has been demonstrated by all the experiment's made asdescribed, and by others on yolk of egg mixed with strychnine.H.Selmi's Ptomahes. By F. MARTNO-ZUCO (Gaxzetta, 13,451).--Tn this paper, the author describes a number of experiments,chemical and physiological, tending to establish the conclusion indi-cated in the preceding preliminary notice, as to the identity of thesebases with neurine. The most characteristic chemical reactionsobserved in both cases are :343in thealone.aboveW.441-With Phosphoric acid .- slight brown coloration on heating.,,,,,,,,Platinic cliloride .- no precipitate, but deposition of yellowishMercuric chloride : white precipitate.Auric chloride .- yellowish precipitate, and after a short time,reduction of metallic gold.Iodised potassium iodide : red-brown precipitate, which, how-ever, soon redissolves. H. W.crystals after a short time.Compounds of Silver with Albumino'ids. By 0. LOEWRer., 16, 27O7-2nl9) .-On warming silver albuminate with excess ofan ammoniacal solution of silver nitrate, a reddish- brown precipitateof variable composition is deposited. It is purified by solution indilute ammonia and reprecipitation with dilute sulphuric acid. It isinsoluble i r i water and alcohol, but dissolves in. alkalis and in dilutesulphuric acid. in the compound is the same asit is in peptone. When the compound is digested with baryta-wateror hydrochloric acid, metallic silver is deposited, and a substanceresembling peptone remains in solution. The silver is not precipitatedfrom an ammoniacal solution of the compound by sulphurettedhydrogen at the ordinary temperature. I n many respects this red-brown compound resembles the substance obtained by the action of adilute arnmoniacal solution of silver on the albumin in the living cellsof the alga, Xpirogyra. The latter compound, however, is insoluble indilute sulphuric acid, and is not even decomposed by sulphurettedhydrogen i n warm solutions.A compound containing as much as 82.4 per cent. of silver wasobtained by adding potash to the ammoniacal solution of silver nitrateand albumin. It is a silver-grey powder, insoluble in water and indilute acids. It dissolves in ammonia, yielding a deep orange-coloured solution.The author regards these substances as compounds of varyingquantities of molecular silver with partially oxidised silver albumi-iiate. w. c. w.The ratio of C toPermanence of Carbonic Oxide Haemaglobin. By E.SALFELD (Arch. Pharm. [ 31, 21, 289) .-The absorption-spectrum ofthis conipound was obtained from venous blood 14 days after death,and again after the lapse of one month. The blood was treated wit344 ABSTRACTS OF CBEMTCAL PAFERS.ammonium sulphide, to reduce oxy-haornaglobin, before examination.After two months, the absorption-spectrum of carbonic oxide hEma-globin was not observed.Gelatin Peptone. By P. TATARINOFF (Compt. rend., 97, 713-714).-Pure gelatin is digested with artificial gastric juice a t 40°, andwhen solution is complete, the liquid is saturated with calciumcarbonate, boiled, filtered, concentrated, and precipitated by alcohol.After 24 hours, the precipitate is dissolved in cold water, filtered anddialgsed after addition of a few drops of hydrochloric acid. Thepiirified solution t'hus obtained is concentrated, and the peptone pre-cipitated by alcohol. It has the composition :-I... ...... 50.00 7-26 17.5711.. ....... 49-53 7.00 17.69These numbers show that gelatin undergoes no great alterationunder the influence of gastric juice, but appears to combine with theelements of water, like the albuminoYds. The same body is obtainedby the prolonged digestion of gelatin at8 a somewhat higher tempera-ture with somewhat stronger hydrochloric acid and without anypepsin. C. H. B.W. R. D.C. H. N

ISSN:0368-1769    

DOI:10.1039/CA8844600277

出版商:RSC    

年代:1884

数据来源: RSC