摘要:

98 ABSTRACTS OF CHEMICAL PAPERS.Organic C h e m i s t r y .Tetrabromethanes. By R. ANSCH~~TZ (Re?.., 12, 2073-2076) .-Acetylene tebrabromide, prepared by the direct union of bromine aidacetylene, distils without decompositian a t 137" under 36 mm. pres-sure. It IS a colourless liquid, which refracts light powerfully, anddoes not solidify at, -224". It is converted into symmetrical ethylenedibromide (11. p. 110") by the action of zinc-dust. The dibromide:combines with 2 atoms of bromine t o form a teti*sbromethsne, whichis identical with acetylene tetrabromide. Unsymmetrical ethylenedibromide boils a t 93" , and readily passes into polymeric modifications.In the latter respect it differs from the symmetrical isomericle.The tetrabromethsne obtained by Bourgoin (AHH,.Chim. Pliys.,1873 [4], 29, 3 i 8 , and 1874 [ 5 ] , 2, 227) by the action of bromine or1dibromosuccinic acid, is considered by the author t o be probazblj-etlrglene perbromide. w. c. w.Ferro- and Ferri-cyanides of certain Tertiary Bases. 13sC. WURSTER and L. ROSKR (Bey., 12, 1822--1827).-The followingferro- and ferri-cyanides are precipitated on the addition of potassium€erro- and f erri-cyanides to a, concentrated solution of the correspondingsulphates.Nitrosodimethy ZCLiiiZii~e fen-ocycnnide, (NMe2.C6H~NO),H1Fecy6 + HzO,reddish-brown needles, blue by reflected light ; fer~ic,?/anitle(N&Ie,.C,H,NO)2€16FeCy,2 + GH,O, silky yellow needles. Nitroso-&met11 y 1 nzetcctol d i n e f errocyaiaide, viole t-brow n needles, containing5 mols.H20 ; the jerric?junicle, yellow needles, containing 4 mols. H20.B,.onzodinzeth1*1~t~tiliiie fewocyanide, silver-white plates, contain-ing 2 mols. H,O ; the .fei*ricpnide, Fellow crystals, containing 5H,O.nyo??zor1i17IethyInzetatcJIzr,idirie f k r o c y m ide, white crystals with 4H,O ;the .ferricya?tide, yellow crystals n i t h 9H,O.Din? ethl/Z(~rtlzotoZi~idirLe ferrocyaniclc, white anhydrous needles ; f e u i -cyanide, yellow unstable crystals, containing 9 niols. H,O.Di??~ethyZtnetatol,lcidirza ,fei roc?ymiide, white needles, containing 2H,O ;f e r ? * i c y m d e , yellow needles with 3H20.DinLethylpcxratuluiili~ze femxya?Lide, wliite powder, contaiaing 1 mol.H,O ; fee?.rzcya?iidr, yellow needles with 5H20ORGANIC CHEMISTRY.99T e t ~ ~ n ~ i a e t l , ~ ~ l , , i e € a ~ l ~ e n ~ l e , 2 e d i n n 2 ~ ~ ~ ~ fewonyanicle, pearly scales, contain-l1et.1.ai?zet~Ly~ai.ap1ie122Jlenedin?lzil.le fe!n*ocyanide, anhydrous whiteThe ferricyanides aye, as a rule, more sohble thau the ferrocyanides.N;trosodirn ethylmiZiue is deposited from an ethereal solution incmerald-green triclinic crystals, and frorii a solution i n benzene intiark-green triclinic prisms, containing a molecule of benzene of crys-tallisation, which is lost on exposure to tlx air, the crystal losing itsing I mol. H,O.scales.transparency. w. c'. w.Allyl Cyanide and the Products of its Saponification. ByA. PINNER ( B e y . , 12,2053-2058) .-When a mixture of equal volumesor" allyl chloride, alcohol, and water is treated with potassium cyanidefor several weeks at the ordinaq temperature, potassium chlorideseparates out, arid on distilling the supernatant liquid, t r i d l y Zamiize(C3H5)3N (b.p. 150") passes over. The residue in the retort, formstwo layers ; the lighter liquid on fractimation yields propylene cyanide(b. p. 252- 254') and etboxylsutyroiiitril CH,.CH(OEt) .CH,.CN(b. p. 173"), described by Rinne (Ber., 6, 389). Pyrotartaric acid isobtained by adding hydrochloric acid to the heavier liquid andextracting with ether.Potassium cyanide acts very slowls on ally1 chloride at the ordinarytemperatiire when alcohol is not present. The sole products of tliereaction are allyl cyanide and a small quantity of pyrot,artaric acid.Allyl cyanide dissolves freely in fumirig hydrochloric acid ; if thesolution is left a t rest for 12 hours and then neutralised witli sodiumcarbonate, an oily liquid and crystals of crotonamide (m.p. 159') areformed. When the hjdrochloric acid solution of allyl cyanide is ex-posed to a temperature of 50-60" for two hours, ammonium chlorideis deposited, and ,B-monochlorobutTric acid, CHMeCI.CH,.COOH, isproduced. This acid is very unstable; it boils with evolution ofhydrochloric acid a t 200".The formation of crotonic acid from allyl cyanide may be repre-sented by the following equations :-CH2 : CH.CH,.CN + 2H,O + HC1= CH,.CHCl.CH,.COOH + NH, ;CHMeCl.CH2.COOH = CHMe : CH.COOH + HC1.An attempt to isolate P-oxybutyric acid by saponifying allyl cyanidewith aqueous potash w a s unsuccessful ; crotonic acid was obtained.On saponification with cold liydrochloric acid, ethoxybutyronitril,CHMe.CII(EtO).CH,.CN, yields tthe amide of ethoxybutyric ucicl(in.p. 71"), and on treatment with warm hydrochloric acid it splitsup into ammonium chloride and ethoxybutyric acid (b. p. 213-220").By the action of alcoholic potash on the nitril, a mixture of ethoxy-and hydroxy-hutyric acids appears to be formed. w. c. w.Action of Bromine on Dichlorhydrin. By E. GRIMAUX andP. ADAM (Bu71. SOC. Chinz. [2], 32, 18--19).--This paper is devotedto an account of a repetition of Carius' experiments, in which his12 100 ABSTRACTS OF CHEMICAL PAPERS.results are confirmed. By the action of bromine on dichlorhydrin inmolecular proportions, a ketone of the formula CBr2Cl.C0.CH,Cl isformed, which on exposiire to moist air forms a hydrate containing4HzO.W. R.Mannitol as Bye-product in the formation of Lactic Acidfrom Cane-sugar. By DRAGENDORFF (Arch,. Pharnt. [ 3],1'5,47-49).-3 kilograms of cane-sugar which had been heated for three hourswith 15 grams tartaric acid and 13 litres of water, when allowed tostand for 10 days after being mixed with 14 kilograms levigatedchalk, 120 grains cheese, and 3,600 grams milk, yielded besides lacticacid, 150 grams perfectlg pure mannitol, identical with tlmt obtainedfrom manna. Attempts were made on other occasions to obtain alike yield under similar conditions, but they were unsuccessful.E. W. P.Sugar from the Date-palm.By P. H. Dfio~ (Bull. XOC. Chin2. [a], 32, 125--126).-This sugar has the following composition :-Saccharose .................... 87.97Glucose ...................... 1.53Levulose ..................... 0.18Gum ........................ 4.88Water and volatile matter . . . . . . 1.88Ash .......................... 0.50Mannitol, fatty matter, and loss. . 3.06100.00The sample analysed was undergoing mannitic fermentation, andcontained a filiform and a globular ferment, both much smaller thanthat of beer. The rotatory power of the gum was found to be[a],, = 193.32". A greenish fat was separable from the sugar by treatrnent with ether. w. I..By H. P. Ddox (B.dZ. SOC. Chim. [el, 32, 121--l%).--The nature of sugar which does not affect polar-ised light has not been as yet satisfactorily explained ; the author hasmade it the object of some experiments.When diffused through parch-ment paper it acquires a kvorotatory power, sensibly equal to that ofordinary inverted sugar, retaining the sanie reducing action on cupricsalts. Now pure sugar, when boiled with alcohol and hydrochloricacid in presence of water just sufficient to hydrate it, becomes inverted,and the solution has no action on polarised light. When this solutionis evRporated in a vacuum, the resulting colourless solid is neutral tolight when dissolved in water ; but when it is evaporated slowly incontact with moist air, a semicrystalline mass consisting of a mixtureof glucose and levulose remains, which acts on polarised light likeinverted sugar.When ordinary inverted sugar is dissolved i n strongalcohol and precipitated with other, the precipitate, although it re-duces Fehling's solution when dissolved in water, has no action onpolarised light, but may be converted into the active modification byslow evaporation. The author explains these facts as follows :-SoonNeutral and Inverted SugarORGANIC CHEMISTRY. 101after glucose has been dissolved in water, it has the rotatory power[aID = + 53*2:3", which slowly decreases after lapse of time. Itsalcoholic solution has also [.ID = + 5:3*23", but this does not decrease,whilst the rotatory power of levulose is [a]D = - M.37". When cane-sugar is inverted by boiling with water, a process which demands alengthened time, its laevorotatory power is zero a t first, but graduallyipcreases to - 21-52'.Saccharme is therefore inverted to neutral supw,which if dissolved in alcohol remains neutral, but if brought in con-tact with water slowly becomes hydrated, and acquires the power ofinfluencing polarisecl light, I n this manner, the author accounts forthe neutral sugar noticed by Mitscherlich, as existing in crude sugarand molasses, and which reduces Fehling's solution without affectingpolarised light. W. R.By W. HZIKTZ (Annalen, 198,87--90).--'tTrhen triacetonamine sulphate and pot.assium dichromateare dissolved in hot water, crystals of' dichromate of triacetonamineseparate out on cooling, but it may be more readily obtained by mixing4 parts of chromic acid with 7 parts of crystnllised triacetonamine.The crystals are extremely brittle, of a tabular form, and notl wellformed a t the ends.When heated they decompose into triacetonamine,and a brownish-red alkaline liquid, which, when treated with platinumchloride, yields acicular crystals of the triacetonamine platinochloride.Triacetonamine dichromate is soluble in alcohol, but not in ether.It gives off traces of water a t loo", but is decomposed a t a highertemperature, leaving pure chromic oxide. Analysis shows that itconsists of (CgH,,NO),Cr207.The normal chroniate is obtained by mixing soilitions of 1 part ofchromic acid with 4 parts of cryst,allised triacetonamine. It crystal-lises in small yellow prisms readily soluble in water.From a hotsolution of this salt crange-red crystals of the dkhromate are deposited.The normal chromate exhibits the same deportment as the acid saltwhen heated, but i t dissolves rno1-e readily in water. Its formula is( C g H 1 BN 0 ) ZC 1 - 0 4 . G. T. A.Triacetonamine Chrornates.Products of Oxidation of Di- and Tri-acetonamine., particu-larly Amidodimethylaoetic, Amidodime thylpropionic, andImidodimethylaceto-dimethylpropionic Acids. By W. HEINTZ(AnnuZen, 19 8, 42-87) .-By oxidation with potassium dichromateiiIld sulphuric acid, diacetoiiamine yields an amidovaleric acid (arnido-dimethylacetic acid), and an amidobutyric acid (amidodimethy lpro-pionic acid), the amouct of Lhe former being relatively greaher. Formicand acetic acids are also formed.When the aqueous solution of the arnidovaleric acid is heated withsilver oxide, siher n.rniclocli7nethlll~~oyionrrte is formed, but if silvernitrate is first added to the concentrated aqueons solution of the acid,and then a few drops of ammonia, a crystalline body is obtained whichconsists of a compound of 2 mols.of silver amidodimethylpropionatewith 1 mol. of silver nitrate and 1 mol. of water, which is expelled a t100". A compound acid can also be obtained by the action of alcoholand hydrochloric acid on amidodimethjlpropionic acid, which crjstalABSTRACTS OF CHEMICAL PAPERS. 102Iises in silky needles, and consists of C,H,,NO,Cl. A similar body isformed w;th nitric acid. Platinum tetmchloride combines with tht.coinpound of hydrochloric and aniidoJimeth~lpropioiiic acids to forma platinochloride, (C,H,,NO,.HCl),.PtCI,, which crystallises in thetricliriic system.Schneider's amidobii tyric acid, obtained from monobiitpric acid(Pogg.Am., 114, 627), is quite different, from the amidodimethyl-acetic acid described above, although the two are isomeric. It ispossibly amido-ethylacetic acid.The ainidovaleric acid obtained by Gorup-Besanea from the pancreas,and that prepared by Clark and Fitfig from rnonobromovaleric acid,are also quite different from the author's Amidodimethylpropionic acid.The points of difference between these compounds are given intabular form in the paper.The chief product obtained on oxidation of triacetonamine is imido-dimethylaceto-dimethylpropionic acid, a small quantity of amidocli-methjlpropionic acid being formed at the same time.G i a i d o d i m e t h y l a c e t o - d ~ n ~ e t l ~ ~ l ~ r o ~ ~ ~ ~ ~ ~ i ~ c acid,COO~,C(CI3,),.NH.C(CH,),.CH,.COOH,forms small colourless crgstals which have an acid reaction and a sourkaste, and are soluble in hot water, but nearly insoluble in alcohol.The aqueous solution gives no precipitate with lead acetate, mercurousxitrate.picric acid, mercuric chloride, or platinum tetraclilo~ide. Theacid volatilises without melting, leaving a small amount of carbona-ceous residue. It is anhydrous and dibasic, and forms compoundswith acids. A copper, silver, ammoniiirn, barium, and two zinc saltshave been prepared. It also forms a double salt with silver nitrate,Compounds of the acid with hydrochloric acid, nitric acid, and sul-phuriu acid have also been prepared, but a platinum double salt doesnot seem to exist.From the foregoing experiments the author concludes that the struc-ture of triacetonamine i s expressed by the formula-CgHiGAgNOI + AgNO3 + HZO.Action of Potassium Cyanide on Ammoniacal Derivativesof Chloral.By R. SCHIFF and S. SPECTALE (Gaxzeth, 9, 355-344).-When an alcoholic solution of chloralammonin and potassiumcyanide is digested for a short time on the wat;cr-bath, a violent reac-tion sets in, and the liquid entws into ebullition, evolving torrents ofhydrogen cpnicl'e. On evaporation it leaves a c~ystalline mass ofdichloracetamide, CCl,II.CONHz, the yield being so abundant that it,is certninly the most convenient method f o r preparing this substance.The authors consider the reaction to take place in three stages :-CCl,.CH(OH).NET, = CCI,: C(OH)NH, + HCl,CC12: C(OH)NH, + H.OH = CCI,H.C(OH),NH,,CC1,H : C(OH),NH, = CCl,H.CONH, f HZO.E t was thought possible that if compounds of chloral with the subORGANIC CHEMISTRY.103stituted ammonias were treated in the same manner, substances inigh tbe obtained whicli would throw some light on the constitution of:: cetylchloralalllnionia, which Schiff considers to beCCI,.CH (OH) NHBc ;whilst Pinner contei?_cis that its formula should be represented by theformula CCl,.CH( OAc)XH2. The results obtained, however, are corn-l)licated, although it seems probablc that compounds analogous i odichloracetamide are first found.Chloral combines directly with dichloracetamide, and the product,when recrystallised from boiling water, fmms large lustrous prisms(In.p. 105") exceedingly soluble in alcohol or ether. I f this sub-stance, GCla.CH(OH).NH.CO.CCl,H, is treated with potassium cyanidei n alcoholic solution as above described, it yields nothing but dichlor-ncetainide and potassi urn dichloracetate.With chloracetamide, howevei-, prepared ciircctly from chloral and:icetamide, potassium cyanide gives potassium chloride and acetate,:tnd a substance which iiiay be extracted by treating the crude productjivith ether. This forms colourless crystals (m. p. 120°) which are mode-1.3tely soluble in ether, alcohol, and hot water, but only very sparinglyi n cold water. The results of the analysis agree with the formula,Cl~H18C18N405.The authors consider it possible that the compound]nay be formed as follows :-2CCI2H.CONHAc + 2CC12H.CONH, +C2H60 = 2H20 + 2CClIH.C(KHAc) N.CO.CC1,H + @,H60 =C14H1RN4C1805, but 1iotr:itlistanding this substance gives Lieben'siodoform reaction, indicating the presence of alcohol, the formulagiven cannot be regarded as definitel>- eskiblished.Chloralbenzamide, CCl,.C€€(OH).NHBz, \\.hen treated m-it11 potas-sium cyanide in a similar nianner, gives rise to a white crjstalline sub-htclnce (m. p. 131"), very soluble i n dilute aJcolZol. The analyses leadto the formula CzoHllC14M40, but further investigation is necessary todecide the constitutioii of this compound.C. E. G.Action of Potassium Carbonate on Isobutaldehyde. By 3'.UBECH (Be)-., 12, 1744- 1747).--The thick liquid which the authorobtained by treating isobutaldehyde with potassium carbonate (Ber.,12, 193, this Journal, 1879, Abst., 520) is a polymeride of isobutalde-liycle, and has the sp. gr. 0.969 at 24", whilst the sp. gr. of ordinaryi$obutaldehyde is 0.795 a t 20". On distillntion i t yields isobutalde-Iiyde and condensation-products wliich appear to form an acid,C8FI,402, on oxidation. w. c. TV.Action of certain Reagents 0x1 Parisobutaldehyde. By I?.UEWH (Be?-., 12, 1747--1749).--Parisobutddehyde is deposited i ncrystalline needles, when a mixture of crude isobutaldehyde (contain-ing isohutyl alcohol and acetone) with ,&&h its volume of sulphuricacid, is left at rest for several days.A further yield niay be obtainedby heating the mother-liquor on a water-bath to expel acetone andunaltered isobutaldeliyde, and distilling the residue in a current ofsteam, when the parisobutaldehyde will crystallise out of the distillate.This compound is also formed when isobntaldchyde is distilled wit104 ABSTRACTS OF CHEMICAL PAPERS.small quantities of calcium chloride. Parisobutaldehyde is not attackedby a solution of soda ; clrromic acid mixture scarcely acts on the bodyat loo", but at 130" isobutyric acid is formed. By the action of potas-sium permanganate a t 130", parisobutalclehyde is converted intoacetonic acid, and a second acid less soluble in water, which formscrystals melting a t 125".w. c. w.Polymerides of Isobutaldehyde, By F. URECH (Ber., 12, 1749-1751) .-Parisobutaldehyde resembles paracetaldehyde in its proper-ties, and the viscous polymeric modification resembles aldol in manyrespects, but differs from it in so far that on distillation it not onlysplits up into water and higher molecular compounds, but a t the sametime yields isobntaldehyde. The author considers it probable ihat thissubstance is a mixture of two polymerides.CHMe,.CH( 0; €1) .CMe2.CO€I. ...........CHMe. CH;( OH) .H jC,H.CHMe. COH, .. . . .II. 11. w. c. w.Preparation of Ekheresl Acetates. By A. P. N. FRBNCHIMONT(Ber., 12, 3059).--The acetic derivatives of the carbohydrates and ofmannitol are easily prepared by heating the alcohols with four timestheir weight of acetic anhydride and a small piece of fused zincchloride.w. c. w.Some Neutral Ammonium Salts : Citrate, Phosphate, andPhotosantonate. By F. S E s r m I (Gazzetta, 9, 298-304) .-Thesesalts were prepared by dissolving the acids in a large excess of con-cen trated aqueous ammonia, and exposing the solutions over quick-limeunder a large bell-jar rendered air-tight by means of mercury. Inthis way the solution is concentrated in an atmosphere of ammonia,and deposits the neutral salt in crystals which were collected andanal ysed.Xriammonium Citrate.-The crystals are deliquescent, and have anammoniacal odour, decomposing o n eqposure to the air. When heated,they rapidly lose water and anmonia, and leave triarnmoninm citrate.Their composition is represented by the formula, CIHBOT( NH,),.H,O.Trianzmolzium Zhosphnte, P04(N.H,),.5H20.-The crystals were notBhsrp enough for goniome tric observation.They evolve ammonia onexposure to the air.Diaiirinonium Photosantonate, CI5H,,O4(NH4),.7H2O, is deposited incrystalline crusts on evaporating a solution of the acid in excess ofammonia as above described. Like the salts previously mentioned, ithas an odour of ammonia. C. E. G.l3y W. H)EINTZ (AnnaZen, 198, 91-94).When concentrated soliitiolns of .urea aiid platinum tetrachloride aremixed in such proportions that one atom of platinum is present foreach two molecules of urea, and the solution is concentrated ip a vacuumover sulphuric acid, a crystalline crust is formed on the surface of tholiquid.If this crust is constantly disturbed so as to expose fresh sur-Urea Platino-chlorideORGANIC, CHEMISTRY. 105fixes of the liquid, the crystals settle down to the bottom of the vessel.They are of a yellow colour, and often have the appearance of rectan-gular plates, although they are really rhoinbic prisms.Theyare soluble in alcohol but not in ether. They cont'ain two moleculesof water, and have the formula, (CH,N,O.HCl), + PtC14 + 2HzO.When heated, they do not change colour, but evolve much waterand carbonic anhydride, whilst ammonium platinochloride is formed,probably together with cyanic and cyanaric acids, and possibly aplatinum compound of guanidine.New Derivative of the Parabanic Series.By E. GRTMAUX (BuZZ.SOC. Chiin. [2], 32, 120--122).-When an intimate mixture of ureaand oxalylurea (parabanic acid) is heated at 12-5-130", the followingreaction takes place; the amide of oxalyl-biuretic acid beingformed-CO.NHIThey are extremely deliquescent, and eflloresce in dry air.G. T. A.NH . C 0. NH,>CO + C@(NHJz = CO'CO.NH 'NHG 0. c 0. NH, .The new body is very sparingly soluble in water, and is destroyedby prolonged ebnllition. .It dissolves in fitrong sulphuric acid, and isprecipitated by water as a, jelly.When boiledwith ammonia, it yields osalate and urea, along with a trace ofbiuret. W. R.I t gives a violet-pink colour with copper sulphnte.Crystalline Form of some Aromatic Compounds.By R.PANEUIANCO (Gazzetta, 9,354-364).-~~ibror)zobeizze?ze [Br : Br: -NO,: Br= 1 : 3 : 4 : 51.-Monoclinic system, a : b : c = 0.651845 : 1 : 0.369345 ;9 = + X : +*Z = 99.46". Forms observed, (OlO), (OOl), ( l l O ) , (Oll),(101), (121). Cleavage parallel to (101), perfect. Twin planesparallel to (101). The angle of the optical axes for ordinary light inoil is about 60"; (p<u) for the red. The cpystals are sensibly di-chroic.T,.ibr.omoainifltohenzene (m. p. 135.S0).-The crystals are sulphuryellow,and belong,to the triclinic sydx-m, u : 6-: c = Qi45t;O : 1: 0.45717.Forms observed, (OlO), (OOl), (1101, (110), ( l l l j , (111), (Mi). CIenv-age parallel $0 (001) perfect. The angle of the optical axes in oil isabout 74". Dichroism is rery distinct on the face (OlO), the tinh beingdeep lemon-yellow, and almost colourless.The kdichroism on (110)and (110) is sensibly the same.-Bromncetanilide, C,H,Br. NHAc.--Colourless crystals belonging tothe monoclinic system, a : b : c = 1.53838 : 1 : 1-43.539 T,J = + X : + Z=117.12". Observea forms, (LOO), (OlO), (001), (110), (210), (101),(102), ( T O l ) , (012). Cleavage parallel to (101) perfect, but inter-rupted parallel to (100). There IS a plane of maximum extinction,making an angle of about 52" with the plane of ~ymme-try (ordinarylight).systemu : b : c = 1.35i81: 1 : 1.75472 ; 7 = + X : + Z =. 125" 10'. ObservedNitrotoluidiize [CH:, : NO, : NH, = 1 : 2 : 41. -Monoclini106 ABSTRACTS OF CHEMICAL PAPERS.forms, (110)~ (OOI), (OII), (11.2)~ (772).Cleavage perfect part11c1to (001) ; lamine flexible. Twin plane observed parallel to (001).The plane of the optical axes is parallel to the plane of symmetry, andthe angle of t'he axes in oil is about 77" for red light. Dichroism isonly sensible in thin lamin= or in very small crystals.Ivilro;odobe?/ze?ie.--Tlie crystals are colourless and belong t o themonoclinicsysteni,a : 7) : c=2-2961 : 1 : 1.1297; T,I= +X : +Z=104" 28'.Observed combination, (loo), (001), ( LlO), (101). Cleavage per-fect parallel to (100).Potnssiuni 12.ityopJlettobrr,l1,1iate! [OH : KSO, : NO2 = 1 : 2 : 4].-Thecrystals examined were heatntilully perfect, and of a straw-yellow colonr.1 hey belong to the monoclinic system, a : 7) : c, = 1.704Sl : 1 : 1.52466 ;1) = + X: + Z-= 117'5%' 45".Combinstions observed, (loo), (110),(IOI), (101), (11 1). TheI h n e of the optical axes nialres an angle of about 4u with the axis cwith ordinary light. Rotatory dispersion (I)<"). 2Ha = 66" 10'for red light. The dichroism is d i s h c t , normal to bhe faces of thevertical prism and of the pinacoid L.001: the tints are bright yellow andalmost colourless,JIetJ/y/lumbeZZic CZC~LZ, C,H,(OH) (OMe).CH,. CH2.COOH.-The crys-tnls belong to the monoclinic system, a : b : c = 1.7151 : 1 : 3-50] 7 ;71 = + X : + Z = 93" 58'. Forms observed, (loo), ( O O l ) , (OlO), (110))(115)) (115), (015). There is a perfect cleavage par:tllel to ($07).Tlie plane of the optical axes is normal to the plane of F;ymmekry.In;t lamins obtained by cleavage, the angle of the.optica1 axes in air was106" 20' for red, and 107" for violet liglit (p<v).An account of the two 1 : 4 acetoluides lias already been publishedin this Journal (Abst., 1879,626).Action of Nitric Acid cn Tribromobenzene. By C. VUI:STKRand A. BERAN ( B e y . , 12, 1821-1 822).-WHen tribromoberczene istxeated with nitric acid (sp. gr. 1.534) at IOU", mononitrotribromo-benzene (m. p. 142.5") is formed, and on nitrating this substaiice witha mixture of nitric and sulphuric acids, clinitrotrihromobenz~iie is 01)-tiined in glistening needles (m. p. 192"). Attempts to prepare tri-nit1,otribrornobenzene by this method mere urrsuccessfiil.These results are in direct contradiction to those of Korner (G!nzzetf(r,1374, 422)) who states that when nitric acid acts on tribroinobenzeneno mononitro-derivLtise is produced, but that a mixture of di- andtri-nitrotribromobenzcnes is obtained.w. C. w.Twin plane observed parallel to (100).r iThe cleavage parallel to (301) is perfect.C. E. G.Cymene from Cumic Alcohol. By E. PATEHN~ and P. SPICA(Gazzettu. 9. 397-400) .-The synhhesis of pxramethylcuniene or isocy-mene recently effected by Jacobsen (Be?:., 12, 429), and the markedtlifference in properties between it and the known cymene, has con-firmed the authors in their opinion that the cumic compounds containjsopropyl, whilst cymene contains normal propy1, and has also removedall doubt as to the identity of the cymene obtained from camphor, fromclssence of cumin, and from cyrnyl alcohol by the action of zinc chloride,although in the last-named reaction there must have been a transfor-mation of the isopropyl group into normal propyl.In order furtheORGANIC CHEMISTRY. 107to elucidate this question, the authors endeavoured to convert cumicalcol101 into the pa r a i s o p ~ o ~ ~ y l m e t l i y l b e n e or isocymene of Jacobsenby a different method of treatment. Yor this purpose, pure cnmicalcohol was transformed into cuwyl clilorid~, C,H,( C,H,) .CH?CI, bysaturating i t with dry hydrochloric acid gas, separating the oily layerfrom the aqueous solution of hydrochloric acid, drying it, and rectify-ing. The pure chloride was thus obtained as a colourless liquid(b. p. 230"), which yielded cumic acid and a little terephtlialic acidon oxidnt,ion, showing that' the isopropyl group had not undergoriemolecular change.I n order to convert the chloride, C,H,( C,H,) .CH,CI, into isocpene,C6H4(C3H,).CEIs, it was dissolved in alcohol and treated with hydro-chloric acid and zinc.The product siibmitted t o fractional distillationyielded a hydrocarbon boiling a t I75-178", which when convei*tedinto tlie sulphoriic acid gave a barium salt having all the properties ofthat prepared from ordinary c p e n e . The sulphonamide also, yre-pared from the c~nienesulplionic chloride, melted at 114-115", theinelting point of cymenesulphonamide, whilst the corresponding deri-vative of isocymene melts a t 97-W'. It is evident, therefore, thatin the reduction of the chloride, not only is the cltlorine in the CH26'1group displaced by chlorine, but a t the same time tlie isopropjlgroup CH(CHJ~ is converted into normal propyl, CH,.CFI,.CH,.c. a. G.Diamylbenzene. By A. ATJSTIN (BdZ. SOC. C h n . [a], 32,12-13).This hydrocarbon was prepared by heating $50 C.C. of' benzene with50 grams of anhrdrous aluminium chloride fcr sonie days a t E G O ,gradually adding 250 C.C. of opticsllp active amyl alcohol.The product of this reaction, consisting chiefly of smj.lbenzene, wasmixed with a tenth ~f its weight of aluminium chloride, and boiledwith an eqnal volume of amyl chloride. The prodlict boiled between260" and 270", and on analysis gave numbers corresponding with theformula C6H,(C5H,l)2.It is a colourless aromatic liqnid, with a tasteiwenibling that of turpentine. It is very mobile. It does not solidifyat - 20". Its vapour-density was foundequal to 8-09 : theory, 7.55. It probably belongs to the metu series. w. R.Brornodirnethylaniline. By C. WURSTER a;d A. SCEIEIBE (BAT.,I t s sp. gr. at' 0" is 0.8868.12,1816-1819) .-According to the authors, the monobromoclimethyl-aniline (m. p. 55") which Weber (Eer., 10, 764) obtained by tlie actionof bromine on a solution of dimethylaniline in acetic acid, is not ittneta but a ~ T U compound, since on treatment with sodium nitrite i tdoes not yield a nitroso-derirative, but paranitrodimethylaniline (m. p.161.') and monobromomononiethylaniline nitrosamine. The lattersubstance crj'stallises in white needles (m.p. 74."), and is reduced bytin and hydrochloric acid to monoloromoniethylaniline. This base boilsa t 260°, and decomposes a t a higher temperature, forming a substancewhich dissolves in alcohol, with intense red coloration, and whichappears to be dimethylrosaniline.Metnbro?iiodiiizethyZa?L;li~ie.--B y the action of methyl iodide andsoda on metabromaniline, the cornpound of this base with methy108 ABSTRACTS OF CHEMICAL PAPERS.iodide is obtained in crystalline scales (m. p. 201). On dist,illation in avacuum, i t splits up into methyl iodide and metabrsmdimelthylaniline(In. p. ll', b. p. 259"). This compound appears ho yield a nitroso-derivative (m. p. 1 4 8 O ) , and is totally different from Weber's mono-bromodi met11 ylaniline.w. c. w.Parabromodimethylaniline. By C. WURST~ER and A. BERAN(Ber., 12, 1829).-By the action of methyl iodide and a solution ofsoda on pure parabromaniline, a compound of methyl iodide and para-bromodimethylaniline is obtained in w l h e crystals, which melt withdecomposition a% 185". By treating this substance with oxide ofsilver, parabromodimethylaniline (m. p. 55") is formed. It is iden-tical in every respect with Wcber's (Be?.., 10, 763) so-called metabro-modime t hy laniline. w. c. w.Action of Stzlphonic Chlorides on Amines. By W. M~CHLERand I<. METER ( R e r . , 12, 1791--1793).-A mixture of tetra-?n ethyldiadclod@ heuqlmet hnwe and dip heny idirncth y 1 nmidosulplt m e ,PhSO&H,NMe,, is formed by the action of dimethylaniline on ben-zenesulphonic chloride.Hassencamp (Ber., 12, 1275) observed theformation of methyl violet in this reaction, but the chief products,viz., the base and sulphone, appear bo have escaped his notice. Toobtain the sulphone, the tetranietbyldiamidodiplienylmethane, withwhich it is mixed, is removed by treatment with hydrochloric acid.On recrystallising %he residue from alcohol, it is deposited in whiteneedles (m. p. 82"), which are soluble in alcohol, benzene, and ether.The sulphone is decomposed by strong nitric acid, forrriing three nitro-benzenesnlphonic acids and peiitanitro-dimethylaniline (m. p. 127").By the action of paratoluenesulphonic chloride on dimethylaniline,t ol y ldirne t hy laniidopheny lsnl p hone, C,H,.S O2CGK1NMeb a blue colour-ing matter and a base are formed. 'l'he sulphone melts a t 95", issoluble in alcohol and ether, and yields a t,rinitro-derivatlve on nitra-tion. w. c. w.Action of Sulphonic Chlwides on Amines. By W. MICHLERand F. SALATHE (Beo-., 12, l'it39--1991).--Bg the action of cc-naphtha-lenesulphonic chloride (1 mol.) on dimethylaniline (2 mols.), a bluemass is .obtained, which, after saturation with ammonia and distilla-tion in a current of steam. to remove free dimetbylaniline, leaves amix t 11 re of f et ramethy lcl i(x?nidod iphen!llinetlzaize and a-w aphthy 1 d i m t h y 1 -( I n7 idopheiLylsuZphone, CIOH,. S0,.C,H4NMe?. By tileating the mixturewith dilute hydrochloric acid, the former compound is dissolrcd ; itmay be obtiined in white plates by precipit:itiou with ammonia andrecrjstallisation from alcohol.The residue insoluble in hydrochloricacid dissolves in alcohol, and on slow evaporation yields crystals of thesulphone (m. p. 91"), soluble in alcohol and cthcr, but insoluble inwater. This compound i s decomposed by fuming liydrochloric acid ai;180", forming aniline, naphtha;lene, methyl chloride, and sulphuricacid. By the action of strong nitric acid, it is converted into penta-nitrodimethylaniline, C6(N0,),NMe2 (m p. 127"), and P-nitronaph-thalenesulpliouic acid. @-naphtha lenesulplionic chloride and dimethylORGANIC CHEMISTRY. 109aniline yield t~trameChyldiamidodiphenylmethane, and P-naphthyl-dimethjldiamidophenylsulphone. The latter compound is decomposedby strong nitric acid into pentanitrodimethylaniline, and ,8-nitronaph-Dimethylmetatoluidine Derivatives.By C. WURSTER and C.RI E D E L ( B r . , 12 , 1 79 6-1 802) .--Nit rosodim e t hy hnet a t oZ uid i n e 7iyd ro-chloride is deposited on adding a saturated solution of sodiumnitrite to a solution of dimethylmetatoluidine in dilute hydrochloricacid. It 1s sparingly sduble in cold, but dissolves in hot water inpresence of hydroch1ori.c. acid, and crystallises on cooling in yellowneedles.The free base obtained by decomposing the hydrochloride withsodium carbonate cryshl'lises from ether in green plates or needles(m. p. 92"), soluble in benzene, chloroform, and water. It resemblesnitrosodimethylaniline in its reactions.Nitrosocresd is formed, together with dimethylamine when nitro-sodimeth ylmetatolu,idine is boiled with soda, and is precipitated onacidifying the alkaline liquid with sulphuric acid.Nitrosocresol crys-tallisLs in white needles (m. p. 14.5-150"), soluble in alcohol, benzene,chloroform, and glacial acetic acid, and sparingly sohible in boilingwater and in ether. The acetlyl-derivative forms prismatic crystals(m. p. Ye"), soluble in alcohol.Trzizifroo.esoZ is produced by the action of nitric mid on an aceticacid solution of nitrosocresol.Nitrodi?iLetl~ll1112etntol?Lid i i ~ a is formed when po tassictm perm,a,nganat eis added to ai- aqueous solution of nitrosodimethylmetatoluidine iiy dro-chloride, and may be extracted from the liquid with ether. It, c i y -tallises in long yellow needles (m.p. 84"). The corresponding ditiitro-derivative is obtained in yellow needle-shaped crystals (m. p. 107"),by adding nitric acid t o a solution of dimethylmetatoluidine in glacialacetic acid. If the nitration is carried on with dilute nitric acid, orif the mixtare of sulphuric and nitric acids is kept perfectly cold, threenitro-derivatives are obtsir_ed, viz., the mono-nitro (in. p. 84"), andtwo dinitros melting a t 107" and 168" respectively. The latter is lesssoluble in alcohol than the dinitro-compound, melting at 107".It issoluble in benzene, aniline, alcohol, and petroleum spirit. On treat-ment with sodium nitrite, the hydrochloric acid solution yields the nitro-samine in the form of an oil? liquid.Dimetl~?/ZtoZyle?ieclitr mine, obtained by the reduction of nitrosodimethyl-metatoluidine with tin and hydrochloric acid, crystallises in whiteprisms (m.p 28"), soluble in water, alcohol, ether, and chloroform.The acetyl-derivative melts a t 155".Tetyanzetlql toly lenedianeine, prepared by the action of hydrochloricacid and methyl alcohol on the preceding base a t 180", is an oilyliquid (b. p. 260"). It combines with methyl iodide t o form t h ecompound C6H3Me(NAIe2)?. (MeI), which crystallises in needles(m. p. 160"). On distillatioil, it splits up into methyl iodide and thefree base.Ferric chloride produces an intense blue coloration in an aqueoust,halenesulphonic acid. IV. c. w.Broinodi.lnethylrrzetutoliLidi7Le melts at. 98" and boils ah 276"1.10 ABSTRACTS OF CHEMICAL PAPERS.solution of tetramethyltolylenediamine. Sodium nitrite gives a similarreaction with an acetic acid solution of the base.To estirnate the metatoluidine in crude toluidine, the liquid tolnidineis first freed from paratoluidine by Binclscliedler's process (Ber., 6,448) , converted into hydrochloride, and tlie ortliotoluidine hydro-chloride removed by filtration; tlie filtrate is then evaporated todryness, converted into dimethyltoluidine, and precipitated as nitroso-dime t hylme tatoluidine hydrochloride.w. c. w.A Colouring Matter containing Sulphur from Parapheny-lenediamine. By A. KOCH (Ber., 12, 2069-2071).-By treating anacid solution of paraphenylenediamine hydrochloride successively withsulphuretted hydrogen and ferric chloride, a beetle-green crystallinemass is obtained, which has the composition C,,H2,,N,S,.3HCl + 4H,O.This compound is soluble in water anti alcohol, forming a violet colo-ration, which is dcstroj-ed by reducing agents and restored by exposureto the air.The free base, C21H,,N6S2, is depositcd in dark-brown scales, on theaddition of ammonia to the hydrochloride. The base is less solublethan the liyclrochloride.The sulphrcte, C,J3,,,N,S2.HI,SO4 + H?O, andthe oculate, CZIH2,N,S2.H2C,O4 + 4H20, form dark-green needles. The.~iitrrci'e, CL4H,,N,S2.2HNO3 + 4H20, crystallises in brown needles. Thehydrochloride forins doiible salts with the chlorides of zinc and mer-cury, viz., C,,H,,N,S,."HCl.ZnCI? + H,O and C,4Hz,N,Y~.2HClZ-IgCl,.w. c. w.Dirnethylparaphenylenediamine Derivatives. By C. JvE17STERand Id. SEADTPJER (Eel.., 12, 1~[~3-1807).-~~;t~o~z of Bromi?m-Whena, 10 per cent. solution of bromine in glacial acetic acicl is added to asomewhat more dilute solution of dii~~etliylpara~pheiiylenedialnine irlthe same solvent, a green substance is precipitated, which has the corn-position C8EllN,Br. The precipitate must be thoroughly washed wit11glacial acetic acid and with anhydrous ether, and it may be rapidlyrecrystallisecl froin hot alcohol. From this solvent it is deposited iiigreen scales (m. p. 146"), having a metallic lustre. The aqueous andalcoholic solutions of this substance exhibit an intense red colour,which is destroyed by cxposiire to the air or by the addition of sul-phurous acid.Action of Nitrous Acid o n Dinzethy7~.,nrnpI~e7,?~lenedia~,zine Et7~ormmte.--On the addition of sodium litrite to a solution of dimethyl-paraphenylenediamiIie ethoxninate in dilute hydrochloric acid, ;tyellowish-red nitro- product, Nnle,.C,H,( NO,) .NHCO.CO OEt, collectson the surface. By recrystallisation from acetic acid, it is obtained inred needles (m. p. 152"), freely soluble in benzene, but less soluble inether and boiling water. On reduction with tin and h~drochloric acid, ityields oxalic acid and dii?.Letl~yltria,niclobenze~.Le "Me, : NEE, : NH, =1 : 3 : 41.This base crystallises in colourless prisms (m. p. 42-44", b. p. 298'),soluble in water and petroleum ether. It forms a msnoacetyl-derira-tive, which is deposited from an aqueous solution in transparent prismsor plates, containing 1 mol.HZO, which begin to melt at 82". Theftu hydrous crystals melt a t 153"ORGANIC CHEMISTRY. 11 1Dimethvltriamiclobenzene is also formed by the reduction of Xerteu'sdiuitromehslaniline (ni. p. 87"), (Ber., 10, ?63 aid 995).TV. c. w.Tetramethylmetaphenylenediarnine. By C. WURSTER and H.' F.NORLEY ( B e y . , 12, 1814--1813).-0n the addition of soda to the pro-duct of the action of methyl alcohol and hydrochloric acid at 180' onphenylenediamine, teti.tcm,ethyl?net~t?herL!/lelled!'ccnziiLe separates out as ailuncrystallisable oil (b. p. 256" corr.), having a pcculiar odour. Tliehydrochloride forms hygrossopic crystals. The free base innitcs witiLmethyl iodide to form the compound C6H4(N&)2.MeI + H20, whiclidissolves freely in water, but is less solixble i n alcohol.It melts a t192" with decomposition into its constituents. Tetrainetl-tSlinet:i-plienylenediamine forms a liquid dibromo-compound, mid i s convertedby the action of nitric acid 011 its acetic acid solution into trinityotri-metEiylmetaplienylenecXiamine, a yellow crystalline body (m. p. l3a0),soluble in alcohol and in benzene. w. c. w.Action of Oxidising Agents on Tetramethylparaphenylene-diamine. By C. WURSTER and E. SCHOBIG (Ber., 12, 1807-1813).-The unstable blue compound, which is formed by the action of broni;nchon an acetic acid solution of tetrnmethylparaphenylenediamine, can b,.obtainecl i n the form of a microscopic crystalline precipitate by addingether to the mixture.Its solution in water niid in alcohol has a Iintense blue colour, which is destroyed by sulpliurous acid. The s~iln-stance can also be obtained as ferrocyanide, by adcling potassiuni ferri-cyanide to tetrarnethylphenylenedianiine sulphste, CloHIGN, +H6~'e2Cyl2 = Clo~,~N~.HiF'ecyG 4- H,PeCy,.The ferrocyanide forms blue needle-shaped crystals, having a metal-lic lustre.By the action of sodium nitrite on tetraiiiethvlpnPaplicn~lenc-ciiamine, tyiriietl~~Z~lieiiyZe~~edicr?r,i~LerLit~o,scL,/~~~~e is obtained, and a, b1uccolouring matter is produced, which, however, could not be isolated.The nitrosamine crystallises in greenish-yellow plates (m. p. 98"),soluble in benzene, chloroform, cther, and hot water.On reductionwith tin and hvdrochloric acid, it yields trirnethpll?nl.aphenyleile-diamine, Nl\1e2.C6H4.KU'HMe, an oily liquid (13. p. 265"), spm*inglJ-soluble in water. The acetyl-derivative crystallises in prisms containiugwater (m. p. 78").When au excess of sodium nitrite is added to an acid soliltion oftetramethylparaphenylenediamine, ? i i t y o t i . i n z e t l ~ l l l ~ ~ ~ i - ~ ~ l ~ e n ~ l ~ ~ ~nit~osaneine, NMe,.CBH3(NMe.NO) (NO,), separates out in orange-coloured needles (m. p. 87'), soluble in benzene and chloroform, bakinsoluble in water. On reduction with tin and hyclrochloric acid, tllijcompound yields tri9netl,yZtricrit?idobanzeiae, NNe2.C,H3(NHMc) NH2,which crystallises i n white needles (m. p. 90"' b.p. S94'), soluble ~ I Lwater. I t s diacetyl-derivative crystallises in white plates (m. p. 1%').Colouring Matters obtained by the Oxidation of Di- andTetra-methylparaphenylenediamine. By C. WURS TE R (L'w., 112,2071-20'72) .-The author proposes to represent the formation of tlxred and blue colouring matters obtained by the action of oxididiiigThe anhydrous crystals melt a t 95".TIT. c. wABSTRACTS OF CHEMICAL PAPERS. 112agents on di- and tetfra-metliylparaphenylenediamine respectively (Bw.,12,1803 and 1807), by the following equations :-H2N.CsH4.NMe2 + Br2 = HBr + M e N < ~ ~ ~ > N € I , B r .Dimeth ylparaphenylenediamine.hle2N.C6H,.NMe2 + Brl = MeN<2::>NMe2Br + HBr.Te tramethylphenylenedianiine. w. c. w.Action of Nitrous Acid on Nono- and Diethylenediphenyl-diamine.By H. F. M o i a ~ x (Ber., 12, 1793-1 796) .--The ethylene-diphenyldiamine used in these experiments was prepared by warmingFL mixture of ethylene bromide (1 mol.) with aniline (4 mols.) in alarge flask provided with an upright condenser. An active reactiontakes place, and on cooling, the contents of the flask solidify. Aniiinehydrobromide is dissolved oiit on heating tihe product with water,leaving the diamine, which may he obtained in glishiing scales(m. p. 6 T ) , by recrytallisation from dilute alcohol.Ethz)lenedi~~heri~~ldi'li itmmnzin e separates out, as a yellowish-green pre-cipitate on the addition of sodium nitrite to a solution of eth-ylene-diphenyldiamine in dilute hydrochloric acid.On rccrystallisationfrom acetic acid, it is obtained in scales (m. p. 157"), insoluble inwater, ether, and cold alcohol.Di~~itrosodieth~~leiied~hcnyldian~irze, obtained as a yellowish-greenprecipitate, yields, on reduction with tin and hydrochloric acid, diethy-lenedi~~~e.n?jZenetetl.an~i?.le, NH,.C6H4 N : ( C2H4), N. C6H*.NH2. Thisbase crj-stallises in glistening scales (m. p. 221'), sparingly soluble inether, alcohol, and benzene. Ferric chloride produces a violet colora-tion in solutions of its salts. w. c. w.Ethereal Oil of Origanum Hirtum and Cretan Oil of Mar-joram. By E. JAENS ( A ~ c h . Pharin,. [3], 15,1--19).-The essential oilof Orignnwn hi~tunz has an aromatic t,hyme-like odour, neutral reaction,and a sp. gr. of 0.951 a t 15' ; it is feebly lxtvorotatory (100 mm.pro-ducing a rotation of -0.40'). When treated with a 15 per cent. solu-tion of sodium carbonate, it dissolves, and on diluting the clear brownsolution with warm water, the greater portion of the hydrocarbon sepa-rates, leaving a phenol in solution. This phenol, C,,H,,O, whichamounts to half the oil, was proved to be carvscrol, as on chlorina-tion it yielded a chlorcymene, CH3 : C1 : C3Hi = [l : 2 : 41, which onoxidation yielded chlorparatoluic acid. The sodium, potassium, barium,calcium, magnesium, and silver salts of carvacrol sulphonic acid aredescribed ; Ohe barium salt crptallises with 5H,O, and appears to bedifferent from that, described by Pott, which has the composition(CloH,,O .SO,),Bs. The sulphonic acid, when distilled with manganesedioxide and sulphuric acid, yields thymoquinone. The melting pointof the carvacrol, 1*5-2", does nob appear quite to agree with thoseobtained by other investigators.It yields ordinary cymene whentreated with phosphorus trisulphide. In the acid solution, from whichthe carvacrol was separated, there appeared to be a small quantity oORGANIC CHEMISTRY. 1138 vohtile acid, which reduced silver solution (formic acid?). Thatportion of the oil which was separated by the addition of water to thesoda solution appeared to be a mixture of terpenes. Submitted t o dis-tillation, a third passed over a t 3 70-180" ; another third a t 180-190" ; the remainder at 250". Finally, the portion 172-176" (a quayterof the whole), wliich had an odour of oil of lemons, yielded, whentreated with sulphnric acid, a very small quantity of cymenesulphonicacid.The results of the investigation are, that oil of Origammz hi&mconsists of 50-60 per cent. of carvxcrol, the rest being a mixtnre ofterpenes. There also appears to be a small quantity of a phenol whichgives a reddish-violet colour with ferric chloride. This oil is thg onlynatural source of carvacrol, except, the oil of Tlzynzus serpy ZZum, whereit is present t o the amount of 3 per cent. Oil of Oriyanum CrPticzmzobtained from various sources, which had a deeper and more red-browncolour than that of Oriqnnwn hirtum, was also remarkable for the largeamount of carvacrol which it contained. All the specimens contained-the phenol (1-2 per cent.) which is coloured violet by ferric chloride.An oil prepared in France, having the name 01.o ~ i p z i GnZ7., containsno carvacrol ; it should t,herefore be distinguished from Cretsa oil ofmarjomm, this name being applied only to that from Greece and AsiaNilinor. Tests for identification which can be applied are: rnixirigwith 90 per cent. alcohol in all proportions ; production of a green orviolet colour by ferric chloride ; violent reaction with phosphorus penta-chloride, accompanied by evolution of hydrochloric acid gas, followedby the production of a blnish-red coloration. Those oils whichcontain 50 per cent. or more of carvacrol will produce a clear mixturewith half tileir volume of a 15 per cent. soda solution.E.W. P.Resorcinol and Orcinol Derivatives. By V. MRRZ and G.ZETTER (EPY., 12, 2035 --2049).-The best yield of trinitroresorciiiolor styphnic acid is obtained by nitrating resorcinoldisulphonic wit].For this purpose finely powdered resorcinol is added in small portionsat a time, to five times its weight of strong sulphuric acid a t 40" ; theclear red solution is heated a t loo", when it crystallises, forming athick paste. The acid mixture is poured into cdd water, and nitricacid diluted with 10 per cent. of water .is slowly added, care being takento avoid any rise of temperature. Towards the end of the operationfuming nitric acid is employed ; a t least twice the theoretical amountof nitric acid must be used for nitration. The product of the reactionis left a t rest for 12 hours, and then poured into ttwice its volume (ifcold water, when trinitroresorcinol separates out as it granular crystal-line mass (m.p. 174-c50).Trinitro-orcinol can be prepared by a similar method, but the yieldis not so good as in the case of trinitroresorcinol, only about 60 percent. of the theoretical yield being obtained. The mixture of orcinoland sulphuric acid is heated on a water-bath, but in order t o completethe reaction, the temperature must be raised to 150". In the processof nitration, it is necessary t o use rather dilute nitric acid, and t o coolthe mixture with ice. Trinitro-orcinol crystallises in long yellowneedles (m. p. 163.5").VOL. YXXVIII. 114 ABSTRACTS OF CHEMICAL PAPERS.Trihy~roxybenzoquinone is formed by the action of dilute hydrochloricacid (8-10 per cent,.solution) a t 140-150' on the hydrochlorideof amidodi-imidoresorcinol, prepared by the addition of ferric chlorideLo a solution of triamidoresorciaol hydrochloride (Schredey, Alznalen,158, 244). The crude product may be purified by solution in soda,and reprecipitation by hydrochloric acid. Trihydroxybenzoquinoneexists as a dark, almost black, amorphous powder, and also in the formof dark crystalline scales, which are sparingly soluble in the usualsolvents. The ammoniacal solution of this substance produces darkeoloured precipitates with salts of the heavy metals and alkaline earth-metals, e.g., (C6H0,),(Ba02)s ; CsH02(AgO)3.Acetic chloride attacks trihydroxybenzoquinone a t the ordinarytemperature, forming triacetoaypin,one, CgH02( O&)3, whieh is de-posited from a solution in hot acetic acid in small crystalline scales.The corresponding t i a i benzoyl compound, C6H02( OBz), has not yet beenobtained in a crystalline state.Bron2otrijiydrozy~uin,one, C6BrO2( OH)3,prepared by warming a solution of trihydroxybenzoquinone in aceticacid with bromine, is a brown nncrystallisable powder, sparinglysoluble in alcohol. It forms insoluble compounds with the heavymetals, e.g . , Pb,( C6Br02.03)2. Trihydroxytoh q i t i n one, CgMe02( OH),,is deposited in dark-coloured crystals when amidodiimido-orcinol hydro-chloride is heated with a 10 per cent. solution of hydrochloric acid a t140-150". The crude prodcct is purified by conversion into the tri-acetyl derivative, C,?A!IeO,( O h ) , , a yellow lust'rous crystalline powder,soluble in hot alcohol.When treated with a solution of soda. thisyields a brown liquid, from which pure trihydroxytoluquinone is pre-ciDitated on the addition of an acid. A This toluquinone dissolves in hot alcohol, forming a dark cherry-coloured solution. It forms with calcium, barium, and silver dark-coloured precipitlates, which are insoluble in water.Trinitroresorcinol dissolves in fuming sulphuric acid, but is not repro-cipitated on dilution with water. When air containing bromine vapouris passed through an aqueous solution of monosodium trinitroresor-cinol, C6H(N02)30Na.0H, a mixture of bromopicrin and nitrodibrom-ethylene, CBr, CH.N02, is formed.The latter on recrystallisationfrom chloroform is deposited in transparent, six-sided i*hornbic prisms(m. p. 112'), soluble in alcohol, ether, carbon bisulphide, and benzene.The solution stains the skin red. The addition of alkalis t o the alco-holic solution prodnces a transient red coloration ; nitrate of silver andlead acetate throw down from the red liquid a red precipitate, whichrapidly changes to the corresponding metallic bromide w. c. w.Compounds of the Hydrobenzoins and Stilbene. Series 11.By T. ZINCKE ( A n n a l e n , 198, 115--141).-This is an important paperon a probable case of true physical isomerism. It has been previouslyshown ( A n n u l e n , 182, 241 ; Chem. SOC. J., 1875, 453), that the twodiatomic alcohols obtained from stilbene, C,H,.CH : CH.c6H5, bythe addition of bromine, and converr;.ion of the bromide into the acetateor benzoate, and subsequent saponification, are respectively identicalwit11 the hydro- and isohydro-benzoin obtained from benzaldehyde bORGANIC CHEMISTRY. 11 5the action of hydrogenising agents.Although any two of the follow-ing formuh : I. CHPh(OH).C.HPh(OH) ; 11. CH2Ph.C(OH)2Ph ;111. CHPh (OH). CsH4.CH,( OH) , for these two alcohols would explaintheir isomerism, and simultalteous formation from stilbene or benzalde-hyde, yet such formulae would not agree with other reactions of thealcohols. So far, it has not, been possible to prove the existence of twoisomeric dibromides in crude stilbene bromide.On oxidation with chromic mixture, both alcohols behave exactlyalike, and give first benzaldehyde and then benzoic acid, together withsmall quantities of benzophenone, the formation of the latter beingclue to a secondary reaction.These facts show that the third of theabove formiilte is inadmissible for either alcohol.By oxidation with nitric acid, hydrobenzo'in gives first benzo'in,Ph.CO.CHPh(OH), and then benzil PhCO.COPh, from which i tfollows that it has the constitution represented by formula I. Amniannand Fittig (AnnaZen, 168, 75) found that isohydrobenzoln on oxida-tion with nitric acid, gave only resinous products ; the author, how-ever, finds that this oxidation gives first a substance which crystallisesin monoclinic crystals (m.p. YS"), and then a body crystallising inyellow needles (m. p. 78-81)". Both these compounds are still underinvestigation. From the above-mentioned results obtained by oxida-tion, it follows that the only possible formulae for hydro- and isohydro-benzoi'n are I and I1 respectively, and the latter on oxidation withnitric acid would give, first, CPh(OH),.COPh, or PhCO.CH,Ph, andthen benzil. The author, however, considers that fhe oxidation pro-duct (m, p. 98") is a physical isomeride of benzoin, and the product(m. p. 78-81') the corresponding physical isomeride of benzil : for inseveral subsequent experiments on the oxidation of isohydrobenzo'inwith nitric acid, hhese two bodies (m. p. 98" and 78-81') were notobtained, but only ordiTiary beTizo'in and benzd, the only differencebetween hydro- and isohydro-benzo'in in this respect being that withthe latter, the crude products were always resinous.On treatment with phosphorus pentabromide, both hydro- and iso-hydro-benzoin give exactly the same dibromide (m.p. 237"), which,with silver acetate or benzoate, gives in both cases the hydro- andisohydro-benzoate, and these on saponification yield again hydro- andisohydro-benzoln respectively, exactly as stilbene bromide does,By the action of phosphorus, pentacliloride hydrobenzoin gives twoisomeric dicblorides, C1,HI2Cl2 (m. p. 192" and 94"), whilst isolzydro-benzoin gives only one (m. p. 192') which is identical with the formerof the two just mentioned.a-Hydrobeiazozn diddoride, C,,H,,CI,, already described by Ammannand Fittig (Zoc.cit.), crystallises in needles or prisms (m. p. 192'),which are sparingly soluble i n alcohol, but easily soluble in toluene,ether, and chloroform, and sublime in plates.P-Hydrobemoh (or isolLydrubemoan) dichloride, CldH12C12, differs greatlyfrom the preceding compound in physical, but has exactly the samechemical properties. It dissolves easily in most solvents, and crystal-lises in four- or six-sided plates (m. p. 94"), and sublimes withoutdecomposition. When heated, both the a- and /?-chlorides undergo anost remarkable chaiige as regards melting point, in such a way that* .116 ABSTRACTS OF CHEMICAL PAPERS.they both apparently give a third dichloride (in. p. 160"), which ismore stable than the other two.The investigation of the anhydridesof hydro- and isohydro-benzoin has also proved the existence of a thirddichloride (m. p. 153"). The dichloride (m. p. 160') is, however,probably a mixture of the a- and P-chlorides, since on crystallisation it..may be separated into the a- and P-dichlorides.Both hydro- and isohydro-benzoin, when treated with phosphor11 strichloride, give on17 one dichloride, viz., that melting at 192". Byconversion into the acetate, and subsequent saponification and crystal -lisxtion from hot water, a-hydrobenzoin chloride (m. p. 192") is con-verted almost wholly into isohydrobenzoln, together with small qmn-tities of hydrobenzoin. Under similar circumstances, P-hydrobenzoin(or isohydrobenzoin) dichloride (m.p. 94') gives the same results. If,however, for the conversion of these chlorides into the alcohols, silverbenzoate is used in place of the acetate, then both cx- an3 ,@-chloridegive chiefly hydrobenzoxn, together with small quantities of isohydro-benzo'in.The author considers that the above facts cannot be explained by adifferent grouping of the atoms, and that hydro- and isohydro-benzoinmust have identically the same chemical molecule,C,H,.CH( OH) .CH( OH) .CJI,.In other words they are true physical isomerides. T. C.Compounds obtained from Hydro- and Tsohydro- benzoinby the Action of Dilute Sulphuric Acid. By A. BRFL~ER anrlT. ZINCKE (Awnalen, 198, 141--190).-This is a continuation ofZincke's investigation with regard to the isomerism of hydro- and iso-hydro-benzoin (see preceding Abstract).The authors advance the fol-lowing general rule :-" On abstraction of water, which can be effectedby various reagents, all diatomic alcohols, containing t h e OH-groupsattached to two neighbouring carbon atoms, give first oxides (anliy-drides or ethers) without any intramolecular changes, and then byfurther action of the reagent, ketones, or aldehydes, or both." Bothhydro- and isohgdro-benzoi'n mnst be considered as aldehyde- pinacones,thus :-c,H,.CH(OH).CH(OH).C,H,. By the action of dilute s d -phuric acid, zinc chloride, or hydrochloric acid both give two eom-poimds, the one crystalline and the other liquid. With hydrobenzoiiiithe yield is 20 to 25 per cent. of the former, and 50 to 60 per cent.ofthe latter, whereas with isohydrobenzoln the reverse is the case. Theformer compounds are anliyd rides-C6H,.CH CsH,.CH. 0. CH. CtjH5C,H,.CH C6Hj.CH.O.CH.C,jH,I >O, or more probably I Iand although chemically identical, they are physically (in inel ting poiirtand crystalline form) different. The liquid compounds appear to 17::identical both chemically and physica,lly ; they are ulJel~?ytlcx,CHPh,.COH, and their formation therefore can only be explained byintramolecular transference of the C,H,-group. By the continueORGANlC CHEMISTRY. 117action of the reagent, the abo-cre crystalline compounds are also cou-\erted into this aldehTde, and by oxidation b3th give the same pro-duct, C28H2204,Convenient methods of preparing hydro- and isohydro-benzo'in aredescribed. Benzoin by the action of sodium amalgam in dilute alco-holic solution gives not only hydrobenzoin (33 per cent.) but alsosmsll quantities of isohydrobenzoin (1 per cent.).I€!ydrobemch anhydride, C14H120, forms monoclinic.crystals (m. p.132"), which are easily soluble in hot akoho1, benzene, chloroform,a n d glacial acetic acid, and but sparingly soluble in light petroleum.It is not volatile in steam.Isoliydrobenzoik a d i y d d e , C14H,z0, forms brilliant monoclinic crys-tals (m. p. 102"), very similar in form to gypsum ; these become dullon keeping. It is more solubJe in alcohol than the h-ydrobenzoizl-(:o tiipound, buk behaves in a siniilar manner towards other solvents.Keither anhydride is attacked by sodium amalgam ; both give stil-belie bromide on treatment with bromine, and both when heated inscaled tubes at 260" yield benzaldehyde and stilbene, 2Cl4Hl,O =2C,W,O + C,,H,,.Heated with benzoic acid at 240", the hydroben-zoin anhydride gives very small quailtities of hydrobenzo'in benzoate(m. p:. 242'1, whilst the iso-compound gives only traces of isohydro-beiizoin. Treated with acetic anhydride in sealed tubes, both com-pounds yield small quantities of hydro- and isohydro-benzoin. HeatedM ith acetic acid a t 165", the hydrobenzoin anhydride is convertedinto hydrobenzoln acetate, whilst the iso-compound is but slightlyattacked even a t 230°, and besides benzaldehyde andl stilbene givesonly small quantities of isohydrobenzoin.On treating hydrobenzo'iu anhydride with phosphorus pentachloridea t 130", the same chloride, CI4Hl2Cl2 (m.p. 192"), is obtained as fromliydrobenzojin itself, together with but a small quantity of resin, andiione of the chloride of melting point 94". Isohydrobenzoln anhydriderinder similar circumstances gives, besides the chloride (m. p. lY2'),dso a resinous body (C28H2,0C12, m. p. 87" ?), which was far moreabundant than in the case of the hydrobenzoin compound. On saponi-tication, this re& gave hydro- and isohydro-benzo'in ; by recrystnllisa-tion, it was converted into the compound C,H,,OCl (m. p. 153"),which is more soluble in alcohol than the dichloride (m. p. 192").Both anhydrides on oxidation give a compound, C2sH,20,, togetherwith small quantities of benzoic acid and other products, amongstwhich there is one crystallising in needles or plates (m.p. 1 4 4 O ) ,which appears to be a reduction-product of the conipound C2bH22@3.This latter substance is easily saluble in benzene and chloroform, andbut sparingly soluble in light petroleum ; it is also difEcultly solublein cold, bnt more easily soluble in hot alcohol, and crystallises inneedles or plates (m. p. 155"). The formation of this body by theoxidation of hydro- and isohydro-benzoin anhydrides seems to showthat the formida of these latter is more probably C:8HL402 thanC,,H,,O. On oxidationwith chromic and acetic acirls, it, gives neitherI)enzoic acid nor benzopheiione, but a new compound (C,,H,,O, 014C2r;H.2,,0,?), which crystallises in plates (m.p. 98'). On reduction withphosphorus and hjdriodic acid, the compound C29H2203 gives dibenzy118 ABSTRACTS OF CHEMICAL PAPERS.(m. p. 52"), and a substance, CljH1?02, crystallising in needles (m. p.144'), sparingly soluble in water, but easily soluble in alcohol, ether,and benzene, and which on further oxidation give chiefly benzophenone.By reduction with phosphorus and hydriodic acid, hydro- and iso-hydro-benzoln anhydrides both yield dibenzyl, together with a smallquantity of an oil, thus showing that they are both derivatives of thesame hydrocarbon ; the oil on oxidation gave benzophenone. Diphenyl-aldehyde is obtained on heating either anhydride with dilute sulphuricacid at, 210': hydrobenzdn chloride (m.p. 182'), together withdiphenglaldehyde, is obtained by heating the anhydrides with stronghydrochloric acid a t 170". Benzoic chloride converts both anhydridesinto hydrobenzoin chlorides (m. p. 192"). All the above reactionsshow that the two anhydrides are almost completely identical, andthat the difference between them is probably of the same kind as that"between the corresponding alcohols. These results also on the wholepoint to the formula, CqBH2a0,, for the anhydrides, rather than to thesimpler formula, ClaHl,O.It has not yet been possible to decide finally whether the aldehydesobtained from hydro- and isohydro-benzoin, by the action of dilutesulphuric acid, are absolutely identical both physically and chemically,but it is very probable that they are.Both these aldehydes give benzophenone on oxidation, and not di-phenylacetic acid, and only by treatment with alcoholic potash was i tpossible t o convert them into the latter compound; even then, thechief prod11 cts were benzhydrol and diphenylmethane.These alde-hydes which the anthors consider on the whole to be identical, havethe composition of a diphenyl-aZdehyde, CI4H,,O; the product is acolourless oil, heavier than water, and insoluble therein, but easilysoluble in ether, alcohol, benzene, and chloroform. It boils at 315"with slight decomposition. On keeping for many weeks i t yieldsformic acid and benzophenone, and gradually becomes crystalline. Thecrystals from the hydrobenzoin aldehyde melt at 213", and thosefrom the iso-compound at 167".I n a second experiment, however,the hydrobcnzoh aldehyde also gave crystals melting at 167", and nota t 213" ; the change which here takes place is probably as follows : -(C,H,),CH.COH + 0, = (C6H,),.C0 + CH,02. Both the crystallinebodies on oxidation give beneophenones, and by treating the onemelting a t 167" with acetic chloride, a crystalline body (m. p. 125-130") is obtained. T. C.Physical Isomerism, with Special Reference to Hydro- andIsohydro-benzoin. By T. ZTNCKE (Annulen, 198, 191-203) .-Inthis paper the theories which have been proposed by Laubenheimer(Ber., 9, 7661, Lchmann (Zeits. f. Krystalloyraphie, 1, l l O ) , and Van'tHoff, to account for physical isomerism, are severally discussed, andthe author arrives a t the conclusion that the physical isomerism i n thecase of the hydrobenzoins cannot be satisfactorily explained by meansof any of them.Orthobrombenzoic Acid.By M. RHALIS (Annulen, 198, 99-2(C,Hs),CH.COH + 0, = (C&,),C C(c6&), + 2CH~0~, andT. CORGANIC CHEMISTRY. 119Il4).-This acid is best prepared by oxidising liquid bromotoluenewith potassium permanganate. Tt, crystallises from hot water incoiourless silky needles (ni. p. = 150" ; 148", Zincke, Ber., 7, 1502 ;138", Richter, Ber., 4, 459), which are sparingly soluble in cold water,but far more soluble than either the meta- or para-derivatives, fromwhich it is still further distinguished by being little or not at, all vola-tile in steam. It is easily soluble in alcohol, ether, and chloroform.When fused with potash it yields parahydroxybenzoic acid (?), andbut a trace of salicylic acid.The salt's of the alkalis and alkalineearths are easily soluble in water, and thme of the heavy metals butslightly soluble. The following salts were prepared and examined :-The potussium salt, C7H,BrOzK.2H,0 (m. p. 245) ; sodium salt,C7H4Br0,Na ; bariunz salt, Ba( C7H,13r02)2.2CzH,0 (from alcohol) ;calcium salt, (C7HiBr0,),Ca.SH,0 ; z i n c salt, ( C7H4Br02),Zn ; neutralcopper salt, (C7H4BrO2).Cu.HPO (m. p. = 25i" with decomposition)we crystalline, whilst the basic copyer salt, C7H4Br02.Cu.0H, silversalt and Zeud salt, (C7H,Br0z]2Pb.C2H,0 (m. p. = 176-180"), areamorphous precipitates.Meihyl orthobronzobenzoate, C7HIBr02.Me, is obtaizled as a colourlessliquid (b.p. = 246') by the action of methyl iodide on the silversalts.Ethyl orthobronzobenzoate, C7HaBrOz, is a colourless liquid (b. p. =2547.21Titl.o-orthohrornobe~~~~c acid, CsH,Br(NOz).COOH, is obtained bydissolving the bromobeneoic acid in cold friming nitric acid, and isidentical with the acid previously prepared by Burghardt (Rer., 8,560). It crystallises from hot water in brilliant needles (m. p. =lSO"), which are sparingly soluble in cold, but more easily in hotwater, and very easily in alcohol, ether, and chloroform, The bariumsalt [ C7H,Br (NO?) O,],Ba.5~HZO, crystallising in needles or prisms,and the silver salt were prepared. EtJLyl nitro-orthobronzobenzoats,CsH3Br(NOz).COBEt, crystallises in needles (m.p. = 66"), whichare insoluble in water, but easily soluble in alcohol and in ether.That nitro-orthobromobenzoic acid has the constitution-[COOH:Br: NOz = 1 : 2 : 51,was proved by converting it (by treatment with aqueous ammonia)into nitro-amidobenzoic acid (m. p. 2?do), which is identical with thatobtained by Valtenberg (Ber., 8,1217) from ethyl paranitrosalicylate.Now Kruse has shown that the nitro-group of this acid must be inthe meta-position in reference to the carboxyl-group, and hence theacid must have one of the two following constitutions :-[COOH:NHz: NO, = 1 : 2:3, or 1: 2 : 51,but the fact that nitro-orthohromobenzoic acid gives paranitranfine(m. p. 148") on treatment with alooholic ammonia pruves that thelatter of these is the true one.T. C.Baranitrophenylacetic Acid. By T. MAXWELL (Ber., 12, 1764---1768).-The riitrophenylacetic acid (m. p. 114") which Radziszewsk120 ABSTRACTS OF CHEMICAL PAPERS.(Ber., 2,209 and 3,648) obtained by nitrating phenylacetic acid is nota definibc compound, but a mixture of para' and ortho-nitrophe~~laceticacids, which cannot be separated by recrystallisation from alcohol.The mixed acids (m. p. 114") were converted into methyl saks anddissolved in boiling light petroleum, when pure methyl paranitro-phenylacetate was deposited in long glistening needles (m. p. 54"),leaving a mixture of methyl ortho- and 1,ara-nitropheiiylacctatcs inthe mother-liquor.Tlie paritnitro acid crystallises in silky needles (m. p. 152') solublein alcohol, ether, and benzene.On Oxidation, it yields paranitroben-zoic acid (m. p. 238'), and on reduction with tin and hydrochloricacid, amidophenylacetic acid.Ba<rium plx?.a?zitrophe.lzylacetate crystallises in yellow anhydrousneedles, freely soluble in water.The zinc salt forms ncedles containing one mol. H20, the siluev baltalso forms colourless needles, which are sparingly soluble in cold water.The salts of the alkalis are very soluble. Methyl pal.~~izt7.o~7LerLylucetatenielts a t 54", and is soluble in alcohol, benzene, and ether. The addi-tion of a few drops of alcoholic potash produces a beantiful violetcoloration in the alcoholic solution of this substance.The ethyl salt crystallises in thin plates (m. p. 65.5") soluble inalcohol ahd ether.w. c. w.Polymerised Non-saturated Acids. By R. Frwx (Ber., 12,1739--1744).-When methncrylic acid is heated a t 130' in sealedtubes, it is converted into a polymeric modification in the form of awhite hard mass resembling poitcelain in appearance. This substancedoes not dissolve in water, but slowly unites with it,, forming a cleartransparent liquid, from which the polymeride can be separated as acolourless gelatinous mass, by filtration. Attempts to ascertain theconstitution of thifi compound have been U ~ S U C C ~ S S ~ U I , since it is eithernot acted on by treatment with oxidising agents, or else completelydestroyed.Isatroipic acid obtained by heating atropic acid at a temperatureabove its melting point, is converted into anthraquinone and ortho-benzoylbcnzoic acid, Ph.C0.C6H,.COOH (b. p.127") when chromicacid is added in small portions a t a time, to an acetic acid solution ofthe acid.By the action of sulphuric acid on isatropic acid a t a temperaturenot exceeding SO", carbonic oxide and a monobasic acid, clliHlJ02, areproduced. The acid is deposited from an alcoholic solution in colour-less plates which melt a t 156", and decompose on distillation intocarlooriic anhydride and a liquid hydrocarboil, C16Hl, (b. p. 3'20'). Ifthe mixture of sulphuric and isatropic acids is heated a t 100", a sul-phonic acid, C,,H1,SO3 or Cl5HI2SO, is formed. This conipound,which can also be prepared by the action of sulphuric acid on the newacid, CI7HI4O2, is insoluble in water.It dissolves in acetic acid andcrystallises from this solution in transparent prisms, wliich melt withdecomposition a t 258".Tlie solution of the sulphonic acid in water containing sodium car-bonate may be preserved in thc dark without undergoing ally altcmORGANIC CHEMISTRY. 121tion, but on exposure to the light, the liquid rapidly becomes turbid,and deposits a yellow precipitate (m. p. 19:3"), soluble i n alcohol.Isatropic acid is decomposed by distillation, Tielding (1) a hydro-carbon, CI6H,, (b. p. 3%") ; (2) a monobasic acid, CI7H,,O2, crystal-lising in prisms (m. p. 163"), which is not identical with the pre-viously described acid of the same composition ; ( 3 ) a soluble acid,probably C17H,602, not yet obtained in the crystalline state. Fromthe preceding observations, the author concludes that the conversionof atropic into isatropic acid, may be best represented thus :-COOH.CPh: CooH'CPh : CH, 'HZ COOH.CPh<~$~~>CH.COOH2 mols.atropic acid. Isatmpic acid.I n iibe preparation of isatropic acid by the long-continued boilingof atropic acid with water, a second polymeride is formed. On re-crystallising the product froni acetic acid, the new acid is found inthe mother-liquor, from which it can be obtained iii plates (m. p. 205").It is converted into isatropic acid (ni. p. 237O) by exposure t o a tern-perature of 220" for some time.C'irLrzmzic acid can easily be polymerised, but the dibasic acid,C16H1606, corresponding t o isatropic acid, has not j e t been isolated.The monobasic acid, CI7Hl6O2, is formed by boiling a solution of cin-nitnic acid in 5 parts of glacial acetic acid with its volume ofsulphuric acid, or by treating, cinnamic acid with sulphuric aciddiluted with 1+ times its volume of water.I n the latter method, theliydrocarbon, CI6HE,, (b. p. 310-312"), described by Erleiinieyer as~7istyre?ie, and also investigated by Krnteau (Ber., 11, l260), is ob-tained as a bye-product. The acid, C,,H,,02, is a colourless amor-1)lious substance, insoluble in water, but clissolved by ether, alcohol,and acetic acid. Its calcium salt is insoluble in hot water.TIT. c. w.The Isomeric Nitrosalicylic Acids. By H. SCHIFF andF. MASINO (Gazxettn, 9, 318--327).-In the first part of the paper theiiuthors give an account of the various researches which have beenmade on the nitrosalicj-lie acid obtained by the action of dilute nitricacid on indigo, hitherto supposed to be homogeneous, and the nitro-salicylic acid from salicin or salicylic mid, which has been shown tobe a mixture of two isomerides, melting a t 125" (144" when anhydrous)and a t 228O respectively.The aukhors find, however, that the nitro-salicylic acid from indigo may also be separated into two portions, onemelting a t 125" and the osher a t 228". Tliis is e$ecteil by first con-verting the crude acid into ammonium salt, and aftep sepamting theresin, boiling the solution with excess of baryta-water. The bariumsalts thus obtained are then separated by frxctiorial crystallisation,the one containing the acid of melting point 2 W being least soluble.According to the authors, the acid which forms anhydrous crystals(m.p. 228") has the constitution [COOH : OH : KO, = 1 : 2 : 5].whilstthe acid cq-stallising with one H20 (m. p. 125') has the constitution[l : 2 : 31. From these results, it is evident that the acid obtainedfibom indigo, like that from salicia or salicylic acid, is a mixture of twoisomerides. C. E. G122 ABSTRACTS OF CHEMICAL PAPERS.Artificial Tannin. By P. FREDA (Gazzetta, 9, 327--332).-Theauthor has repeated the experiments described by Schiff (Gmzettn, 8,363, and this Journal, Abst., 1879, 646), but obtains totally differentresults, all t,ending to confirm the conclusion at which he had arrived,that the supposed digallic acid or artificial tamin of Schiff, obtainedby the action of araenic acid on gallic acid, is merclp an arsenicalcompound of gallic acid.He has anrtlysed the precipitate formed inquinine solution, and finds that it contains as much as 7-8 per cent. ofarsenic in different specimens ; when the arsenic is removed, none ofthe tannin reactions could be observed. The atathor's experimentsshow that arsenic acid, whether in aqueous or alcohol solution, does nottransform gallic acid into digallic: acid, but into an arsenical compound,which has some properLies in comrrion with tannin, arid that whenthis compound is freed from arsenic by hydrogen sulphide, gallic acidis regenerated. The author has observed also that the melting pointof gallic acid is much lower ( Z l O O ) when it is gradually heated thanwhen it is rapidly heated (240-2252"), probably owing to incipientdecomposition.C. E. 42.Amidobenzenedisulphonic Acids. By 0. ZANDER ( AnlzaZen,198, 1-29) .-( 1.) Pa?.ni~zi~obenzenedisull-'7Lonic or clisulpuhnnilic acid,C6H3NHz(SOsH),.'2H,@ [SOsH : SO,H : NH, = 1 : 3 : 41, is obtainedby the action of f urriing sulphuric acid on paramidobeiizenesulphonicacid (sulphanilic acid), and is also found in the mother-liquor left inthe preparation of sulphnnilic acid. It crystallises in srnall reddishneedles, which dissolve readily in water and alcohol, but, not in ether.Bromine throws down tribromaniline from an aqueous solut,ion of theacid. It forms normal and acid salts, the former of which dissolveeasily in water, the latter less readily, whilst both are insoluble ina1 cohol.Normal anznzonium paramido b enzenedisulp honate,forms small transparent yellowish hexagonal prisms. The acid saZt,C,H3(NHz) (S0,H). SO3N&2H20, crystallises in large white needles,which become reddish when exposed to the air.The noi-m,al potassium salt, C6HsNHz( SO3K),.H,9, forms very hardFellowish nodules, and the acid salt white silky needles.The salts of calcium, barium, lead, and silver, resemble thosedescribed, except that the acid calcium salt and both the silver saltsare anhydrous.Dinzo~araOenzeiiediszLZphonic c u d , C6H3( SO,H) : NzS03 may be ob-tained by the action of nitrons acid on an alcoholic solution of the:Lmidodisulphonic acid, but a better method of preparing it is byiiitration of an acid salt.The diazoparabenzenedisulphonates dissolve in cold water, and areprecipitated by alcohol %,-om +he aqueous solution.They do notexplode by percussion. Heated on platinum foil they burn brightly,leaving a carbonaceous residue. When heated with alcohol, or boiledwith water or with hydrobromic acid, they yield benzenedisulphonates,phenoldisulphonntes, and bromobenzenedisulphonates.Ainmoiiiuin d i a z o ~ a r u b e n z e n e d i ~ u ~ l ~ o ? ~ a t e , CGH,(NHaSO,) : N,SO,ORGANIC CHEMISTRY. 123prepared by passing nitrous acid into an ice-cold concentrated solutionof hydrogen-ammonium pararnidobenzenedisulphonate, forms whiteneedles. The potassium salt obtained in a similar manner is alsoanhydrous.The barizcm and cnlcium salts contain 2, the lead salt3 mols. of water of crywallisation.2Cletnbenxenedi.sz~lp~or~ic acid [ SO,H : SO,H = 1 : S].-When calciumcliazoparabenzenedisulphonate is heated with alcohol under pressure,nitrogen is evolved, and the free benzenedisulphonic acid is found inthe solution (this Journal, 1878, Abst., 409).Bromobe?2zei2ecZi~lplzolzic acid [SO,H : SO,H : Br = 1 : 3 : 41, isobtained by heating the salCs of the diaxodisulphonic acid with hydro-bromic acid, converting the potassium salt int'o the chloride, andheating the latter with water a t 150". It crystallises in slendertransparent, deliquescent needles, and seems to be identical withHeinzelman's /3-bromobcnzenedisulphonic acid and Nolting's bromo-benzenedisulphonic acid (see this Journal, 1878, hbst., 410, and ~ 0 1 .13, 895, 1195, and Ber., 7 , 1311).The normal salts dissolve readilyin water ; acid salts could not be obtained.Potassium bronzobenzer~ec7isu~l~onate, C,H,Br( S03K),.H,0, obtainedhg decomposing the potassium diazo-salt with concentrated hydro-bromic acid, crystallises in small white nodular masses.The bmizmz salt contains 4 mols. H,O. The silver salt is anhydrous.Bromobenzen~di.szcl~lio~L~~ c h l o d e , C6H3Br( S02C1)3, is formed by theIt melts a tB,.omobenxe.lzedisiclpl~onamide, C6H,Br( SO,.NH,),, obtained by warm-ing the chloride with strong ammonia, forms slender white needles(m. p. 238"), sparingly soluble i n cold, but readily in hot water.Actiow of Bronaiwe o n P~l.ar7LidiJbeiLzened~sz~l~~~l~aic Acid.-The pro-ducts are tribromaniline, dibromamidobenzenesulphonic and paramido-bromobenzenedisulphonic acids.ParcLniidobl.oinoben,zenedisulphonic acid, [ 60,H : SO,H : NH, : Br= 1 : 3 : 4 : 51, consists of masses of slender niicroscopical needles,which have sometimes a silky l i d r e .It dissolves readily in water,and forms normA1 and acid salts, of which the former are the moreso1 u ble.The aiimnoniunz salt, C,H,Br( NH,) ( S0,NH,)?.2H20, crystallises intransparent, bright yellow hexagonal prisms, which are decomposedwith explosive violence by concentrated nitric acid.The potassium salt resembles the ammonium salt ; the normal saltof bnriziin has 3, the acid 1, and the acid lead salt 5 mols.of H,O.The diazobi.omrJben~ene~i~zLZ~honi~ acid, C,H,Br ( S0,H) N,SO,. 2H,O,is obtained by the action of nitrous acid on bromoparamidobenzene-disulphonic acid in white tabular crystals, which are not explosive.They evolve nitrogen when their aqueous solution is heated. Thepotmsiu.r?z salt forms pointed microscopical prisms, and containsS mols. H,O.Uibron2u7nidobenren~disiLIphonic acid [SO, : Br : NH, : Br =1 : 3 : 4 : 5j, crystalliaes in pale reddish crusts, formed of prisms con-taining 2H20, which effloresce when exposed to the air. It is easilysoluble in water, sparingly in spirit.action of phosphorus pentachloride on the potassium salt.103- 105"124 ABSTRACTS OF CHEMICAL PAPERS.The b~c,i-iunz salt with 5H,O forms white crystals, whicli acquii-e a rcdt'int on exposure to air ; they are slightly soluble, and are decomposedat 180'.The ~ ~ ~ Z O - C O V L ~ O U ~ of this acid yields a c l i b i ~ o m o b e n z ~ n e s 7 ~ l ~ ~ ~ ~ ~ i i c acid,[SO,H : B r : R r = 1 : 3 : 51, and also a tribromo-acid [SO, : Br : Br : B r= 1 : 3 : 4 : 51.( 2 .) O,.t7rni72idobenzenetlisulylionic acid is obtained from orthamido-benzenesulphoiiie acid by the action of fuming sulphuric acid at170-180", slid is identical with disulphanilic acid. It crystallises inslender red microscopical needles, soluble in water, and forms normalwnd acid salts. Bromine precipitates tribromaniline (m. p. 118.5')from dilute aqueous solutions of the acid.The potolssiuni, bai-imz, and lend salts have been prepaiwl.The ban'um ~iaeobenze72edisul~~,7L'oncLte is obtained by the action ofnitrous acid on a cold concentrated solution of the barium salt of thenmido-acid.( 3 .) ~~etai?iiJobenze?LediszL~honic acid, C,H,(NH,) ( SQaH)n.4Hr0, isformed from metamidobenzenesulphonic acid by heating it withfuming sulphuric acid a t 180". It forms rhombic octohedrons, easilysoluble in water arid in alcohol ; it slowly absorbs moisture on exposureto the air, and quickly effloresces over sulphuric acid. When heated, itmelts in its water. of crystallisation and decomposes, leaving an easilycombustible carbonaceous residue. Concentrated nitric acid causes itto deflagrate. I t forms normal and acid salts, of which the latter areless soluble than the formw.The salts of ummo?zizm, potassium, barium,and Zead have been prepared, and resemble ih general characters thesalts previously described. The acid potassium salt is anhjdrous.When metamidobenzenedisulphonic acid is acted on by iiitrous acida diazo-acid is formed, which yields salts with potassium, &c. Whenthe potassium salt, C,H,(KSO,) N,SO,, is heated with alcohol under1~ressure, a new body is formed containing an acid, which the authoriiamcs oxef~yZbeiizeiiediszi12Jho71 ic acid, C',H,(E:tO) (SO,HI>?. Thc potas-i i i ~ ~ salt of this acid crystnllises in slender, yellow transparentneedles, soluble in water, and precipitated by alcohol from the aqueoussolution as a white pomder, redissolving in water with B yellow colour.The B c o .i z ~ ~ n . salt crystallises with 2H20, when the solution is rapidlyevaporated, otherwise with 3H,O.The c l i Z o d e , C,H,(EtO) ( S02C1)2, obtained from the acid bytreatment with phosphorus pen tachlorlde, forms white hexagonalIilates (m. p. 106--108"j, soluble iu benzene, apparently -forming ac ompound with it. Strong ammonia converts the chloride into the( i m i d e , which crystallises in nodular groups of needles (m. p. 233').This behaviour of the diazo-compound with alcohol is similar t othat of orthnmidotoluene-parasulplionic acid described by Hayduch(Aima7en, 172, 215).The b,-o7?zobeiixenedi~~~l~onic acid, CGH,Br(S0,J3),, is formed whenliydrobromic acid acts 011 the diazobenzenedisulplionates (obtainedfrom the acid metamidobenzenedisulphonates).It consists of slender,w-liite deliquescent, needles, and forms sparingly soluble normal salts,resembling in general characters those previously described.~ ? l . o i , z o ~ e i i x e , ~ c d ~ s ~ ~ ~ ~ ~ i ~ ~ ~ ~ c cldoritle, C6H3Br(SOLC1), melts at 104"ORGAKIC CHEMlSTRY. 125R~o~~znbeizzeiteciisi~l~h.onrcn~irie, C,H,Br(SO,.NH,),, formed by theaction of ammonia on the chloride, forms slcnder silky needles(m. p. 210').Synthesis of Phenylnaphthalene. By IT. SMITH ( B e y . , 12,2049--2053).-The -author has recently shown that when a mixtureof bromobenzene and naphthalene is pa?sed through a red-hot tubecontaining pumice stone, phenylnaphthalene, CloH7P11, dinapllthyl,and diphenyl are formed. An increased yield of phenylnaphthalene i qeffected by distilling the crude product, and again passing the firstportion of the distillate mixed with a fresh portion of naphthalenethrough the red-hot tube.The new hydrocarbon crysiallises in coloudess transparent scalesG.T. A.(m. p. 95' corr.), and probably has the constitution rm \w \/ w. c. w.Action of Iodine on Oil of Turpentine. By H. E. ARMSTROKGBer., 12, 1756--1759).-When turpentine oil is heated in a retoytwith one-fourth its weight of iodine, no apparent change takes placeuntil half the liquid has distilled over ; a t this stage hydriodic acid andiodine vapours are given off. The distillate is now poured back intothe retort, and the distillation continued. These operations arerepeated until iodine vapours are evolved as soon as the distillation iscommenced ; the product is then distilled in a current of steam.Thcresidue consists of colophene ; the chief portion of the distillate boilsbetween 155-lGO0, 17.5-180", and a t 170" ; it contains cymene and amixture of two hydrocarbons of the composition Cl,)H20, one of whicliboils a t about 160°, and the other a t about 170". Cymene is the onlyhydrocarbon of the benzene series which is produced by this reaction. w. C. w.Formation of Resin, and Chemistry of Ethereal Oils. B.vDRAGENDORFF (,49.ch. Pliarm. [ 31, '15, 50-54) .-Of the two theorie;that have been proposed for the formation of resins, the author con-siders that the oxidation theory is the correct one. It Kas found thatthe oil of PinuspzcnziZio, when kept for a yea8r in a flask, deposited 3crystalline resin having the eomposition C,,H,,O, ; it is hence inferred.that all resins are produced by the oxidation of hydrocarbons.Thepresence of water does not appear to aid the formation of the resin.Certain oils after they have been kept for some time will no longermix to a clear solution with excess of alcohol, although a small quttn.tity of alcohol produces no turbidity. This turbidity is due to theprecipitation of the resin which was dissolved in the oil.This theory is opposed to experiments made by Godeffroy and Lie-bermann ( Z e i f s . Oest. Apt., 15, 583), in which they fonnd that oilfreshly prepared from green juniper berries, became turbid on additionof alcohol. The author, however, found that oil of unripe juniperberries, prepared by himself, did not become turbid ; he can, therefore,account f o r the results of Godeffroy only by the supposition that theoil from green junipers cxidises more rapidly than that prepared fromthe ripe berries.E. W. P126 ABSTRACTS OF CHEMICAL PAPERS.Action of Zinc-dust on Resins. By G. L. CIAMIC~AN (Gazzetta,9, 304--318).-The first two sections of this paper describing theproducts obtained from abietic acid and from elemi-resin, have alreadyappeared in this Journal (Abst., 1878, 438, and 1879, 69). The thirdtreats of the action of zinc-dust on gum ammoniac. The resin afterbeing separated from the gum by means of alcohol is distilled withzinc-dust in a current of hydrogen, when it yields about 45 per cent.of an oily liquid.By distilling this in a current of steam, and byrepeated fractional distillation, it maT be separated into four por-tions-one boiling at 136-138", which gives isophthalic and tere-phthalic acids on oxidation, and is st' mixture of meta- and para-xylenes, C,H,, ; the second (b. p. 160') is m e t a ~ z e t h y Zet~ylbenzeile,CsH,, : the third, boiling a t 190-192", the methyl etJLer of orthoethyZ-pheizol, C,H,.MeO, which when heated with hydriodic acid yieldsmethyl iodide and orthoethylphenol, C,H,,O. The phenol i,q oxidisedto salicylic acid by fusion with potash, and does not appear to beidentical with any of the known ethylphenols (comp. Anmdeiz, 102,166 ; 156, 211 and 251 ; 170,. 345). The fourth fraction (b.p. 235)is a homologue of benzene of the formula c113H20, and on oxidationwith chromic mixture yields acetic and propionic acids and a smallquantity of benzeic acid. C. E. G.Formation of Complex Glucosides, B-y H. SCHIFE~ (Bey., 12,2032-2035).-Metarnidobenzoic acid dissolves in a warm aqueoussolution of helkin. On evaporating the liquid, a transparent, fluo-rescent, glass-like substance remains, which can be obtained in colsur-less plates (m. p. 149") by recrystallisation from alcohol. This com-pound has the composition c13~1607. C7H&02, orCHO. (CH.OH),CH,.O.C,H,.CH(OH),.NH.C6H,.COOE.By boiling with acids it is decomposed into glucose, an amido-acid, andan aldehydeyhenol. Similar crystalline compounds are fcrmed whenthe hydrochlorides of amidocinnamic and amidosalicylic (1 : 2 : 3 and1 : 2 : 5 ) acids are added to a solution of helicin in dilute soda.Theyare purified by recrystallisation from alcohol, and have the compositionC l s H ~ 6 0 , . C , o ~ 1 3 ~ ~ 2 and C1,H,605.C7H,Na respectively.Unstable substances having the general formulaare obtained by dissolving helicin in an aqneons solution of amido-benzoic acid, glycocine, leucine, &c., ssturatidg with sulphurous oxide,and evaporating the liquid over sulphuric acid.These compounds slowly lose a portion of their sulphurous oxidea t the ordinary temperature; they resemble the compounds of thealdehydes with acid potassium sulphite in their behaviour with diluteacids. w. c. w.Economical Process for Prepring Bibasic Quinine Citrate.By J?.Do1To-SCIuHm1 ( G ~ z z e t t u , 9, 2bS-%5).--Two processes arORGANIC CHEMISTRY. 127at present employed for the preparation of quinine citrate, either bydissolving quinine in boiling water by the aid of ciitric acid, or byadding the requisite quantity of sodium citrate solution to quininenulphate dissolved in 40 parts o€ boiling water. On cooling, quininecitrate crystallises out. The author finds it much more economicalfiiqst to prepare calcium citrate by neutralising boiling lemon- juice withlime, washing the precipitate with boiling water, and, after drying,decomposing it with quinine sulphate. For this purpose 100 gramsof quinine sulphate are dissolved in 3 litres of boiling water previouslyacidified with 3.669 grams sulphuric acid, 32.685 grams 05 the drycalcium citrate are added, and the whoie boiled for half an hour.Oncooling, the clear solat’ion deposits quinine citrate in t u f t s OF needles,which may be purified by recry stallisation. The mother-liquors yielda further quantity of the citmte on evaporation. C. E. G.Piperidine. By R. SCHIFF (Gazzetta, 9, 333-335) .-Consideringthe supposition that pipsridine is a methylcrotonylamine as the mostsimple, the author determined to make attempts to reduce it, in hopesof obtaining normal methylbutylamine, but not succeeding,. he thentried the reduction of a bromine derivative. He found that acetyl-piperidine in chlorofoym solution absorbed a molecule of bromine withavidity, b u t no crystalline compound could be obtained from it, neitherdid the aetion of reducing agents lead to any satisfactory result.Hethen prepared phthaZylpiperide, C6H,( C0.NC5H,,),, by the evaporatioiiof an alcoholic solution of piperidine (2 mols.) and phthalic anhydride(1 mol.). It forms large transparent crystals which readily unite withbromine, producing the compound C,H,( C0.NG,H,,),Br4 ; this crys-tallises in long colourless needles, very soluble in water or alcohol, butinsolubie in ether. When treated with potash, it does not yield mono-bromopiperidine as might be expected, but all the bromine is removed,and the original compound is regenerated: silver oxide acts in asimilar manner. From this it would seem improbable that the doublebond in piperidine exists between two carbon atoms, but rather that itis between a earbon atom and a nitrogen atom.C. E. G.Alkaloids of Alstonia Constricts.'' By OB ERLIN and SCHLAG-DENHAUFFEN (Phamn. J. [l’rans. [ 3 ] , 10, 1059-1060) .-The bark wasexhausted smccessively with ether, alcohol, and water, which took LIP1.038, 27.740, and 1.375 per cent. respectively, but no examinationwas made of the alcoholic or aqueous extract. The orange-colouredresidue left on evaporation of the ethereal extract was taken up withdilute hydrochloric acid (1 : ZOO), treated with animal charcoal, andprecipitated with ammonia. The dried precipitate was then exlinustedwith ether, evaporated, taken up with dilute acid, and reprecipitated,repeating these operations un ti1 all colouring matter was removed.It was finally obtained in silky tufts of lustrous needles by recrysta,lli-sation from ether.It is soluble in ether, alcohol, ehloroform, benzene,acetone, and light’ petroleum, moderately soluble in boiling water, butinsoluble in the cold. It dissolves readily in dilute acids, and is pre-cipitated by the same reagents as the other alkaloids. It is easilysoluble in concentrated sulphuric, nitric, or hydrochloric acids, withou128 ABSTRACTS OF CHEMICAL PAPERS.any perceptible coloration, but on dilutin9 these solutions with water,a beautiful blue fluorescence is prodnced. Coilcentrated sulpliuricacid and potassium dichromste coiour the crystals of an intenqe blue-green, passing to violet and then to purple ; on adding water a crimsollsolution is obtained.The er;hereal mother-liquors from which the alstonine had ,crystal-lised left an amorphous alkalo'id on evaporation, whirh the authorspropose to call a 7 s t o ~ i c i n ~ .It resembles alstonine in many points, bntis oiily spaxingl~ soluble in boiling water. It dissolves in concentrateriEiilphuric and hydrochloric acids with a greenish-brown t i n t ; whilstwith nitric acid i t gives a splendid crimson-red. The acid solutions ofthe amorphous alkaloid do not exhibit fluorescence. The authors areof opinion that alstonine and alstonicine niay possibly be related inthe same way that yuiriiiie and quinicine are.By P. SPICA (Girxzetta, 9, 28s-289) .-Thisplant, called " erva de ibbisi " in the Sicilian dialect, i s used by thepeasantry to prepare a decoction which is taken in cases of intermit-tent fever : it is an herbaceous plant of the labiate order, having anaromatic odour, and somewhat pungent taste. I n order to ascertainto what the active properties of the plant were due, the residue lefton evaporating the alcoholic extract of the plant was washed with coldalcohol t o free it as much as possible from chlorophyll, then dissolvedin boiling alcohol, precipitated with an alcoholic solution of leadacetate, and filtered boiling.After .separating the excess of lead byadding ammonia carbonate to the clear liquid, it was concentratedand precipitzted with xater. The substance was further purified bytreating its alcoholic solution with animal charcoal and again pre-cipitating with water.The white gelatinous product was sepasatedby means of ether into two compounds, one of which, moderatelysoluble in ether (m. p. 204-5205"), gave numbers agreeing with theformula C31H5R01, or, with less probability, C9H,,0. The other sub-stance, which is much less soluble in ether, especially in the cold,does not melt even at 250", and above that temperature it is decom-posed ; the results of t h o analysis agree 11 it11 the formula C,,H,,O,.The more soluble substance acquires a greenish-yellow tiiige whenboiled with dilute sulphuric acid, but otherwise remains unclianged :a minute quantity dissolves, but the solution does not reduce Fehling'stest, althoiigli when evaporated at 100" it blackens and emits an odourbetween that of wax and caramel.This is only a preliminary notice,the author iiitending to exanline the plant more ca,refully as soon ashe can obtain a sufficient quantity.C. E. G.Satureja Juliana.C. E. G.Carica Papaya and Papayatin. By J. PECKOLT ( P ~ w ) ~ z . J .TYnrLs. [3], 10, 343- 346, and 383-386).-'I'he author gives a detaileddescription of the C a ~ i c a y a p a p , or papaw tree, its growth and cul-tivation. The trees are dicecious and herniaphrodite ; the herma-phroditte variety is called Mawno macho (male mamao), the fruitbearing variety Hamao femea (female mamao), and a cultivated varietyof the latter Mmricro melao (papaw-bearing mamao).Fruit.-The fruit is gathered in the full-grown but unripe condiORGANIC CHEMISTRY.129tion, when it contains a considerable quantity of a milky juice, whichdisappears almost entArely on ripening, and in the “ mamao macho”‘ isfound a caoutchouc-like substance; i‘n the “mama0 femea,” a softyellow resin; and in the “mamao melao,” a dark reddish-yellowfatty oil ; these substances doubtless originated from the milky juice.The ripe fruit contained no free acid. The analyses of the fresh fruitof the three varieties freed from acid gave the following numbers :-Mamao Mamao Mamaofemea. melao. macho.Caoutchouc-like substance ....... - - 0-0460.165 - Soft yellow resin .............. -Reddish-yellow fat ............ - 0.020 -Albumino‘ids. . . . . . . . . . . . . . . . . . 1.070 0.500 0.735Sugar ....................... 3.238 3.580 8.333Pectinous matter ...............1.315)0.075 12.3320.083 I Citria acidMalic acidDextrin, &c.. ................. 5.503JWater ...................... 85.351 92.500 89.444Cellulose ..................... 3.180 2.920 5.091combined with o.020 } o.483basesThe fresh fruit of the “ mamao femea” gave 1.239 per cent. of ash,and the dried fruit, 8.457 per cent. It contains a large amount ofsoda, pobash, and phosphoric acid.Seeds.-The examination of the seeds is not-yet completed, but a de-tailed account of the method of analysis is given. They are found tocontain :-An oil, Papaya oil; Ca~icin, an oil-like substance, with adisagreeable taste and smell, soluble in ether and alcohol; an acidsimilar to palmitic acid, Carica fat acid; a crystalline acid, Yapuyicacid, insoluble in cold water, but soluble in hot water and alcohol ; aresin acid having an irribating and bitter taste, insoluble i n water andether, soluble in alcohol and alkalis ; and a soft resin similar to thatfound in the fruit flesh of the “ mamao femea.”Milky Juice.-This juice occurs in all parts of the plant, but in quan-tity only in the unripe fruit.I t is extracted with difficulty, the methodbeing to make longitudinal incisions through the skin of the growingfruit, and as soon as one wound ceases to yield any juice, another ismade ; the gathered f r u i t yields ouly a few drops of juice. The milkresembles sheep’s milk, has a strongly acid reaction, and gelatiniseswhen mixed with three times its volume of water ; it is without smell,and its taste is astringent and bitter: its sp. gr.= 1.023 a t 20”.Analyses of the milk were made in various ways.(I.) The milk was repeatedly shaken with ether until nothing morewas extracted. The ethereal solution, on evaporation, left a residue ofwax, Hamao wax. The residue, insoluble in ether, was treated withalcohol, which extracted a resin, and the insoluble portion was treatedwith water and filtered ; a caoutchouc-like substance remained on thefilter ; the filtrate mas treated with absolute alcohol, when a white pre-cipitate of yapayotin was thrown down, which, when dried over cal-VOL. XXXVIII. 130 ABSTRACTS OF CHEMICAL PAPERS.cium chloride, formed an amorphous powder. The alcoholic filtratecontained a small quantity of extractive matter; 7.845 per cent.ofpapayotin was obtained by this method.(11.) A quantity of the milk was evaporated to dryness, and themass exhausted successively with ether, alcohol, and rectified spirit ; theinsoluble residue was dissolved in water, and alcohol rodded to thesolution, when a light-brown precipitate separated out of pnrnpopnyoti~~,(5.338 per cent.), a substance formed by the decomposition of papayotinby heat.(111.) The milk was mixed with four times its volume of water, fil-tered from insoluble matter, and the filtrate treated with absolutealcohol. The precipitate was dried over calcium chloride, and con-sisted of snow-white paprtyotin to the amount of 3.762 per cent.(IT.) The milk was exhausted repeatedly with warm water; theaqueous extracts concentrated, filtered, and precipitated with absolutealcohol ; 4.304 per cent.of papayotin of a greyish colour was obtained.(V.) The aqueous extracts of the milk were treated with leadacetate, the precipitates decomposed with sulphnreited hydrogen, andthe filtered solution treated with absolute alcohol, in one case withoutand in another after concentration. A difference in the coloar of thetwo products was all that was noticed.MzUc jro7n the Xtem.-The stem yields but a small quantity of milk,which had more the consistency of crcam than that from the fruit. Itcontains 3*9(il per cent. of snow-white papayotin.Green Leaves.-The leaves yield 33 per cent. of a green juice, whichis treated with absolute alcohol and filtered ; the residue washed freefrom chlorophyll, and exhausted with water ; the solution which con-tains impure paparotin is precipitated with basic lead acetate, andthe precipitate treated as in No.V. A yield of -117 per cent. isobtained.I n the preparation of papayotin, strong heat should be avoided, toobtain an active product of a white colour. The best papayotin isobtained by method I or 111, or from the stem; the most advan-tageous source, however, is the leaves, notwithstanding the smallyield, since they can be obtained in large quantities. Papayotin is anamorphous, snow-white, non-hygroscopic powder, without smell, butwith a sliglitly sweet, saline, astringent taste. It is insoluble in ether,alcohol, chloroform, and petroleum spirit, but soluble in glycerol andin water, nitric acid, and hydrochloric acid.Sulphuric acid coloursi t yellow; potash and soda colour it brown, and ammonia, yellow.An aqueous solntion gave the followin? reactions :-White precipitateswith alcohol, lead acetate, mercuric chloride, tannic acid, and sodiumcarbonate ; with silver nitrate, a whit’e turbidity, which, on standing,forms a deep yellow precipitate and a brown solution; iodine soh-tion, a light-brown precipitate ; ferric chloride, slight yellow preci-pitate ; with phosphoric acid, on standing, a white precipitat,e; withTrommer’s sugar-test, a beautiful violet-blue, which, after boiling,became red-violet.Papayotin readily dissolves roasted meat ; 28 gram dissolved2 gram meat in 10 minutes.Parapnyotin has no action on cookedmeat, even when heat is applied. Papayotin coagnlates milk verORGANIC CHEMISTRY. 131rapidly, as do those milk-juices of other Brazilian plants which havean acid reaction.The fruit of the Cucrica papaya is used as a food, and the syrupformed by boiling the juice of the ripe fruit with sugar as a sedativeand expectorant. The milky juice taken internally causes intestinalinflammation, but in small doses is given as a vermifuge, as are alsothe seeds. It is also used as a wash for the skin.These results confirm those of Wittmack and Roy.Lithofellic Acid and some Lithofellates. By G. ROSTER(Gazzetta, 9, 364-393) .-The finely-powdered oriental bezoar is ex-tracted with boiling alcohol, and the filtered solution allowed to eva-porate spontaneously, when it deposits the impure lithofellic acid incrystalline crusts. This, after recrystallisation, is converted into thesodium salt by neutralising the alcoholic solution with sodium carbo-nate, evaporating to dryness, and extracting the sodium lithofellntefrom tlie residue by treatment with boiling absolute alcohol. Thesodium salt is converted into the corresponding barium salt by decom-posing it in aqueous solution, with a slight excess of barium chloride,and may then be purified by recrystallisation.Barium Zithofellate, C40H,,Ba0,.10H,0, may be obtained from itsaqueous solution in very perfect prismatic crystals, as much as 4 em.long; they have many lateral faces, and are terminated by rhom-bohedral summits. The measurements show that they do not differmuch from the rhombohedric system. The crystals (m. p. 185') con-tain 10 mols. of water of crystallisation, of which they readily lose 4in a dry atmosphere, and tlie remainder a t 150'. The salt is verysoluble in boiling water and in alcohol. Its rotatory power in aqeuoussolution, as determined with r2 Wild's polaristrobometer, is [a]D = + 19*6So, a t a temperature of 15'.Lithofellic acid, C20H3604.H20, is easily prepared from the bariumsalt by precipitating it in dilute solution with hydrochloric acid, andwashing the precipitate with boiling water until the washings nolonger give a precipitate with silver nitrate. Prepared in this way, itis a white crystalline powder (m. p. 203', corr.), which may be obtainedin distinct crystals from its alcoholic solution. The general appearanceof these crystals is that of a hexagonal prism ; but accurate measure-ments show that they are more complicated, and that they do notbelong to the rhombohedric system, as stat'ed by Hoppe-Seyles, but tothe clinorhombic. The specific rotatory power of the acid in alcoholicsolution is [a]D = + 13-76", as determined with a Wild's polaristro-bometer.Sotlium Zithofellate, obtained by neutralising pure lithofellic acidwith sodium carbonate and evaporating the aqueous solution, forms agummy trarisparent mass, of pale yellow colour. It is exceedinglysoluble both in water and in alcohol ; its solutions have a very bittertaste. Its concentrated alcoholic solution, on cooling, deposits thesodium salt in microscopic crystals, consisting of stellate croups ofslender needles. Its rotatory power a t a temperature of 14.5" is [a+ + 18.16'.L. T. 0's.In recrystallising the crude precipitated barium lithofellate, a resi-k 132 ABSTRACTS OF CHEMICAL PAPERS.noid substance remains behind, apparently the barium salt of a newacid, but which the author has not as yet investigated.The author considers that although lithofellic acid differs from thebile acids, and especially from cholalic acid in its crystalline form, inits behaviour with acids and with alkalis, and in its action on polarisedlight, it should yet be classed witlh them, considering the ratio of thecarbon and hydrogen, its dextroretory action, and its behaviour withPettenkofer's reagent. C. E. 6.Diastase, By M. BASWITZ (Bey., 12, 1827--1831).-The authorpreviously stated (Bey.,, 11, 1443, and this Journal, 1878, Abst. 903)that the presence of carbonic acid is favourable to the conversion ofstarch into sugar by diastase. He now finds that diastase acts onsome specimens of commercial starch equally well in the absence ofcarbonic acid.Potato paste, rye meal, and barley extract contain a body whichenables the diastase to convert the starch into sugar without the pre-sence of carbonic acid.The ackion of diastase on starch is not affected by increased ordiminished pressure. The most favourable temperature is about 50" :above 60°, very little sugar is formed, the ferment being destroyed ;whilst below 45" the formation of sugar takes place but slowly, althoughthe maximum amount will be formed i E the experiment is carried onfor a snficient length of time.The quantity of sugar foymed increases when the amount of diastaseused is increased, but the increase is not proportional to the addi-tionel diastase. w. c. w

ISSN:0368-1769    

DOI:10.1039/CA8803800098

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

132 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Fermentation aocornpanied by firmation of HydrogenSulphide. By P. M~QIJEL (Bull. XOC. Chinz. [2], 32, 127-138).-A peculiar organism, existing in sewage water, has the power of con-verting not only combined, but even free sulphur into hydrogen sul-phide. When placed in water containing solid albumin, this fermentcauses the sulphur to be evolved in combination with hydrogen, untilthe amount of gas has increased t o 60-7’0 C.C. per litre of liquid. Theorganism then dies. But if the solution be made alkaline with ammo-nia, soda, potash, or lime, about twice as much hydrogen sulphide isproduced, before the ferment ceases to act. The sulphur contained i nindia-rubber is also evolved by this organism, and if the hydrogen sul-phide be prevented from amcumulating in the liquid, which can beaccomplished by passing a current of carbonic anhydride through it,the evolution goes on as long as sulphur is present.A litre of water,to which had been added sulphur, 4 per cent. of normal urine, and atrace of the ferment, evolved 0.236 gram of sulphur combined withhydrogen in two days. To the naked eye, solutions undergoing thisfermentation are almost limpid; the ferment, seen under the microscopeVEGETABLE PHYSIOLOGY AND AGRICULTURE. 133forms elongated or circular cells of less than a thousandth of a milli-meter i n thickness. It is capable of existing in media free fromoxygen. W. R.Bacillus Ureae. By P. MIQUEL (BUZZ. SOC.C h h . [2], 32,126-127).-This ferment, which exists in sewage, belongs to the class namedAiicerobies by Pasteur ; it resists exposure for some hours to a tempera-ture of 95-96', and causes urea to disappear from urine. It alsoremoves urea rapidly from a solution of pure urea to which a littlegelatin has been added.Researches on the Bleeding of Vines. By E. RoroNDr andA. GHIZZOKI (Bied. Centr., 1879, 527-530).-After giving the resultsof his analyses of the sap of vines cut in April and May, the firstnamed author remarks that on the average a litre of vine-sap contains0.147 gram of solids, and 0*052 gram of ash, the red sorts yield-ing, however, more solids than the white; the time of cutting does notseem to have any influence on the quantity of phosphoric acid andpotash contained in the sap.Ghizzoni's investigations lead him to theadditional conclusion that sap taken from a lower part of the plantcontains more mineral and less organic matter than that taken fromupper parts. J. K. C.Composition of the Kernels and Husks of the Seed ofGleditschia Glabra" By 5. MOSER (Bied. Centr., 1879, 388).-W. R.The author obtained the following results :-Non-nitrogenousWater. Protei'n. Fat. extract. Fibre. Ash. Sand.Kernels.. 10.90 20.94 2'96 51.68 10.66 2-77 0.09HLIS~S . . 1.24 4.54 3.67 60.70 1980 300 0.05After boiling with dilute sulphuric acid, it wits found that 41.4 percent. of the kernels had been converted into dextrose.Tannic acid was found bo be present in the husks to the extent of7.7 per cent.Ash of Different Parts Of the Vine.By E. RoTomr (Bied.Centr., 1879, 530-532) .-The following briefly noticed investigationsof the mineral constituents of the musk, branches, and leaves of t h evine relate to the products of two vine hills in the neighbourhood ofAsti, on each of which were planted three kinds. The anthor gives theresults of his analyses in tabular form, and infers from .them thaf thecomposition of the ash varies with the locality rather than with thesort of vine; potash is found in greatest quantity in the ash of themust (60 to 70 per cent.), and in the least ( 6 per cent.) in that of theleaves, the latter also being poorest in phosphoric acid, and very richin lime and silica.Agricultural Chemistry in Japan.By E. KINCH (Chem. News,40, 195, 196).--This is a, shorf accoun& of the collection of soils,J. K. C.Soda Is absent in dl the samples analysed.J. K. C134 ABSTRACTS OF CHEMICAL PAPERS.manures, and agricultural products, shown by the Imperial College ofAgriculture, Japan, a t the International Exhibition, a t Sydney.Accompanying the collection is a report containing analyses of thegreater number of the products, from which Mr. R. Warington hasselected those of the principal foods, such as rice, soy beans, sweetpotato, large radish, sea-weeds, tea, and saki. The last, a fermentedliquor prepared from rice (this Journal, 1879, Abst., 413), contains from11.33 to 15.0 per cent. of alcohol, and the free acid, reckoned as aceticacid, amounts to 0.20 t o 0.27 per cent.Besides these, the reportcontains analyses of manures, including lime, wood-ashes, nitre, wastevegetable substances, and residue from various manufactures, fishmanure, bone superphosphates, excrement of birds, and hair. Thereis also a summary of the principal dye-stuffs and their methods of pre-paration, and the a,nalyses of the most important. The different oilsand waxes form the concluding section of the catalogue.L. T. 0's.Method of Selecting Beet for Seeding. By D. IBLED (Bied.C'entr., 1879, 535--536).-This is usually done by taking the specificgravity of the whole root ; but on account of the difficulties connectedwith this plan, the author suggests that pieces be cut out of the root,about one third from the top; these do not differ greatly in specificgravity from the rest of the root, and should be placed in a bath ofsalt of 105", only those roots the cuttings from which sink being usedfor seed.J. K, C.Relation of the Colour of Clover Seed t o its Value. ByG. HABERLANDT ( B i e d . Clenty., 1879, 532-534).--The autlior dividesclover seed into two groups, the one comprising the yellow and violetbeing more valuable and less altered by keeping than the other group,in which he includes the brown and gray seeds. J. K. C.Absorptive Power of Soil-constituents for Gases. By G.ANMON ( B i e d . Centr., 1879, 511--515).-The substances used in theseexperiments were sand, aluminium silicate, calcium carbonate, hy-drated oxide of iron, gypsum, clay, and humus, all powdered to variousdegrees of fineness.The author tried the effect of aqueous vapourand ammonia on these substances a t various temperatures ; his experi-ments showing that the most favourable temperature for absorptionlay between 0' and lo", and that the quantity absorbed varied directlywith the fineness to which the substance had been powdered. Thefollowing are the numbers obtained, 100 C.C. of each substance beingused, and &he water being calculated by volume in the state of gas :-Cubic ccntimetres of water-rapour condensed byH y clrated CalciumAt Humus. iron oxide. Quartz. carbonate. Kaolin.-10" C. 12717 12973 2026 208 53780 14206 47332 2198 4258 537510 36504 99712 1185 4775 644720 26789 98990 277 962 154130 16497 54753 99 233 133VEGETABLE PHYSIOLOGY AND AGRICULTURE.135Of ammoiiia gas at 0" C. the following quantities were absorbed :-By hydrated BJ carbonateBy humus. iron oxide. By quartz. of lime. By kaolin.29517 38992 938 1552 2447Part of the ammonia was converted into nitric acid by the oxide ofiron. Carbonic anhydride was absorbed in very small quantity, exceptin the case of hydrated oxide of iron, from which the gas could notbe expelled by air, as was the case in the other inaterials employed.By treating the soil-constituents with marsh-gas, empyreumaticsubstances were formed which prevented the experinients in this direc-tion being completed. The condensation was greatest in the case ofhydrated oxide of iron. Treatment with sulphuretted hydrogen wasfollowed by a separation of sulphur in the case of all the substancesemployed: the greatest increase in weight was observed in gypsum.Oxygen was not absorbed by quartz, carbonate of lime, or kaolin:humus even lost in weight by exposure to the gas ; 100 C.C.of gypsumabsorbed 1189, and 100 C.C. hydrated oxide of iron absorbed 665 C.C.of oxygen. The condensation power for nitrogen was greater, as isshown by the following numbers :-100 C.C. of~~~ ~ ~ THydrated carbonateHumus. iron oxide. Sand. of' lime. Kaolin. Gypsum.23986 24 3803 813 10253 Absorbed c.c.1 126In this case also nitric acid was found i n the aqueous extlract fromthe hydrated oxide of iron.To show the influence of oxide of iron on the absorption of nitrogenbF the soil, the author made the following determinations, in whichferruginous sand and clay, and the same substances freed from.iron byhydrochloric acid, are compared in t*heir absorptive power for nitro-gen :-of nitrogen100 C.C. of sand 100 C.C. of kaolin -- r A \Containing iron. Pure. Containing iron. Pure.Absorbed. . 217 101 1687 816 C.C. o€ nitrogen.J. K. C.Experiments on the Manuring of Barley. By P. WAGNER andW. ROHN (Bied. CYeilh-., 1879, 515--519).-The soil in which theseexperiments were carried ouc was a sand containing I$ per cent. ofIiurnLis, the phosphate being applied in the following experiments o mday before, and tlie nitrogen (in the form of Chili saltpetre) the dayafter sowing. The followirig table shows the quantities of manureapplied per hectare and the yield obtained :-Corn. Stra-w.Kilos.KiIos.(1.) Unmanured.. ...................... 4420 3770(2.) 20 kilos. nitrogen .................. 5280 4890(3.) 30 kilos. soluble phosphoric acid, ..... 4570 449136 ABSTRACTS OF CHEMICAL PAPERS.corn. Straw.Xilos. Kilos.(4.) 50 kilos. soluble phosphoric acid with20 kilos. ni%rogen.. ............... 5320 4920(5.) 50 kilos. phosphoric acid in the formof freshly precipitated calcium phos-phate, and 20 kilos. nitrogen ...... 5600 5110(6.) 50 kilos. soluble, with 43 kilos. insolublephosphoric acid in form of phospho-rite, with 20 kilos. nitrogen ...... 5970 5370(7.) 35 kilos. soluble, and 30 kilos. insolublephosphoric acid as above, with 20kilos. of nitrogen .................5660 5350(8.) 50 kilos. soluble phosphoric acid in theform of phosphate of potash, with20 kilos. nitrogen.. .............. 6170 6500It is 'evident from the above that although the aolub?e phosphoricacid yielded poor results, the use of saltpetre proved very advantageous.The reason of this may be looked for in the fact that the soil was sovery poor in lime as not to be able to arrest the phosphoric acid duringits.percolation through the soil after rains, thus only a dmall qaantityof it came into actual contact with the roots of the barley. This wasof conrse different in the cases of experiments ( 5 ) , (6), and (7), wherepart at least of the phosphoric acid was applied in the insoluble form,and larger yields were the resnlt.With regard to experiment (8),the authors do not explain whether'the remarkable yield obtained wasthe result of the way in which 'the phosphoric acid was combined, orof the presence of potash.Manuring Experiments With Oats. Ry C. XENSSEN (Bied.Centr., 1879, 519--523).-A field was marked off into eleven plots of975 square metres each ; of these'two were not manured, the remain-ing nine being treated with quantities of manure of various sortsequal in value commercially. The table following shows the various.manures used and .the resulting produce : -J. K. C.Quantity Yield inappliedper hectare. Grain. Straw.Kilos. Kilos. Kilos.Chili saltpetre ............... 19 201 268Unmanured ................ - 151 190Bone meal.................. 25 181 227Bone meal siiperphosphate ..... 2.5 173 216Ammoniacal superphosphate . . 22 177 199Peruguano ................ 16 181 209Unmanured .......... *_. .... - 168 194Bone guano superphosphate . . 31 194 242Animal manure.. ............ 17.5 172 213Stable dung ................ 1100 194 233Mejillon guano superphosphate 29.5 170 200- Chaff.Kilos.29182121201 7161 718231ANALYTICAL CHEMISTRY. 137The above tables show that Chili saltpetre, and next to it stabledung and bone guano superphosphate, produced the best yields. Fur-ther researches are necessary to establish any conclusions from theabove results. J. K. C.Manuring of Beetroot. By 0. VIBRANS (Bied. Centr., 1879,525).-The object of these investigations was to ascertain the value ofthe potash contained in molasses lees a!ud charcoal residues as amanure. The action of several other well-known manures was tried,with results not differing much from the ordinary.. From his experi-meiits the author draws the conclusion that the potash of the charcoalresidues is in a form which can be more readily absorbed by the beetthan the potash of the lees. J. I(. C.Manuring of Beetroot. By B. BODENBENWR (Bid Centr., 1879,523--524).-Samples of the sugar-beet taken from plots of Iand towhich various manures had beea applied, were tested for sugar a tdifferent periods of their growth. The seeds were sown on the 9thof May, and from the 1st of Angust t o the 14th of September theplants were subjected to quaiitifative investigation. On the resultsof his researches the author makes khe following remarks :--Nitrognnwhen applied as manure in the form of Chili saltpetre, delays theripening of the root to a cnnsidcrable extent, and lessens the per-centage of sugar, although the yield by weight o$ the root is muchincreased. Phosphoric acid and guano give very favourable resultsas regards the percentage of sugar in the yield. 5, K. C

ISSN:0368-1769    

DOI:10.1039/CA8803800132

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 137A n a l y t i c a l Chemistry>Apparattls for Estimating Oxygen in the Atmosphere. ByF. FISCHER (Ber., 12, 1696--1698).-The oxygen in the atmosphereis determined by measuring the diminution in voltlrme which takesplace when $L copper spiral is heated to redness, by means of il galvaniccurrent in il known volume of air. A descrirhion of the apparatusand full d e t a h of the process employed aye i i v e a in thcL&iginalpaper. w. c. w.Quantitative Estimation of 'Oxygen dissolved in Water. ByF. TIEMANN and C. PRNJSSE (Ber., 12, 1768--1789).--The authorshave examined three methods of determining the amount of oxygendissolved in water, viz. : -1. Mohr's volumetric process (Mohr's titrirmethode) in which sodaand a standard solution of ferrous sulphate are added to 500 C.C.of thewater, which must be heated to 40" ; after an interval of half an hourthe precipitated ferrous hydroxide is dissolved in sulphuric acid, andthe unoxidised ferrous salt determined by titration with potassium per138 ABSTRACTS O F CHEMICAL PAPERS.mangsnate. From the amount of ferrous sulphate oxidised by thewater, the quantity of oxygen is easily calculated. The results obtainedby this method are invariably too low.2. Gccsonzetwk Method.-In order to expel the dissolved gases fromthe water, a slightly modified form of Reichardt's apparatus (Zeits.And. Chem., 11,271, and this Journal, 26, 412) is employed. I n pre-sence of combustible gases, e.g., marsh-gas, the oxygen is determinedby absorption with potassium pyrogallol, but when the mixture con-tains only oxygen, nitrogen, and carbonic anhydride, the latter isremoved by a solution of soda, and the oxygen estimated by explosionwith hydrogen.This method yields excellent results, but requirescomplicated apparatus. I n certain cases when the water is boiled toexpel t'he pses, there is a risk of a part of the oxygen not beingevolved, owing t o its having oxidised some of the constituents of thewater.3. The process of Schiitzenberger and Risler (Bull. Xoc. Chim., 19,153, and 20, 145) is very accurate, and seems to be the best adaptedfor general use. I n this method, the oxygen is determined by theamount of indi6o-white it converts into indigo-blue. Standard. solu-tions of ammoniacal copper sulphate, sodium hyposulphite, Na2S02,and indigo-carmine are required.Tho standard copper solntion is prepared by dissolving 4.469 gramsof CuSOa + 5H20 in water, adding excess of ammonia, and dilutingto a litre with water free from air ; 10 C.C.of this solution are equiva-lent to 0.0014336 gram, or 1 C.C. oxygen at 0' and 760" mm. Thehyposulphite solution is prepared by treating with zinc-dust forfive minutes a soluticn of commercial sodium hydrogen sulphite,which haas been diluted to sp. gr. 1.25. The liquid isnow mixed withten times its volume of boiled water, separated from the zinc-dust byciecantation, and transferred to stoppered bottles, milk of lime beingadded until a slightly alkaline reaction is produced. The precipitatedzinc oxide is allowed t o settle, and the supernatant liquid is rapidlyfiltered.To standardise the hyposulphite, 10 or 25 C.C. of the standardammoniacal copper solution are brought into a Woulf's flask, fromwhich the air is displaced by a current of pure hydrogen. The hypo-sulphite is added from a burette, the point of which passes through acork in the tubulus of the Woulf's bottle. The exact point when theblue copper solution is completely decolorised by the hyposulphite iseasily observed. After this experiment, the hyposulphite is dilutedwith water free from air until 5 O.C. are required to reduce 10 C.C. ofthe copper solution.The indigo solution is prepared by dissolving 100 grams of com-mercial indigo carmine paste or commercial indigotin (sodium indigosulphate) in 2 litres of water.I t s strength, which should equal thatof the ammoniacal copper solution, is determined by titration withh osulphite.'!he apparatus required for the determination consists of a three-necked Woulf's bottle, of 1 $ litres capacity, which stands in an evapo-rating basin, containing warm water. Each tubulus is provided witha double-bored cork; through +,be first pass athermometer and a glasstube, connected with an apparatus for generating pure hydrogen. ThANALYTICAL CHEMISTRY. 139second contains two drawn out pieces of glass tubing, which areattached by means of a caoutchouc tubing to the burettes containingt'he standard hyposulphite and indigo solutions. The upper end ofthe hyposulphite burette is provided with a tube containing pumicestone soaked in potassium pyrogallate.A funnel fitted with a stop-cock, and a glass tube bent twice at right angles, and dipping intowater, pass through the cork in the third tubulus.About 250 C.C. of warm water free from air, and 30-40 C.C. of theindigo solution, are brought into the flask, from which the air isexpelled by a current of hydrogen. The contents of the flask must bekept at a temperature of 4.5" during the experiment. Standard hypo-sulphite is added until the indigo is bleached'. 250 C.C. of the waterto be examined are now brought into the flask through the tap funnel,care being taken to prevent the admission of air. The mixture is wellshaken, and hyposulphite added until the blue colour is destroyed.From the C.C. of hyposulphite used, the quantity of oxygen may a t oncebe calculated, e.g., 4.2 C.C.hyposuiphite are equivalent to 10 C.C. of thestandard copper solution = 0.0014336 gram, or 1 C.C. oxygen.28.8 -4.26-85 C.C. of oxygen at 0" and 760 mm. Three oxygen determinationsin succession may be made without changing the apparatus ; but sincethe hyposulphite changes rapidly, its strength must be determined bytitration with ammoniacal copper solution every time the burette isfilled. w. c. w.250 C.C. water required 7.2 G.C. hyposulphite, or 28.8 per litre, ~ -Water Analysis. By A. MGLLER (Arch. PJ~m-712. [3], 15, 25-27>.-The residue obtained by evaporating the water is usually heated to120-140". This temperature is insufficient to remove the crystal-line water of magnesium and calcium sulphates, therefore the solidmatter is always reported boo high.It is advisable therefore alwaysto add a known weight of sodium carbonate, aiid subsequently toiieutralise after sdparation of the earths according to the processdescribed in Ber., 1870. E. w. P.Estimation of Sulphur in Natural Sulphides. By A. COLSOX(BUZZ. SOC. O'hhn. [2], 32, 115--116).-The rnethod described is par-ticularly applicable to estimation of sulphur in pyrites. The sampleis placed i n a platinum boat near the sealed end of a piece of combustiontube, the other end of which is closed with a double- bored india-rubbercork. Through one of the holes a tube passes to the end of the corn-bustion tube, and conveys oxygen to the sulphide, whilst the resultingsulphurous anhydride escapes through the other tube into soda. Thesulphurous acid may be estimated by the iodine process, and the sul-phuric acid by baryta, or if a standard solution of soda, be used, theportion remaining unneutralised may be estimated with standardacid, and the total sulphur deduced by calculation.W. R.Testing for Nitric Acid in Presence of Nitrous Acid. By. A.PICCINI (Guzzefta, 9, 395--396).-l'his method is useful for detectin140 ABSTRACTS OF CHEMICAL PAPERS.minute quantities of nitrates in the presence of large quantities ofnitrites, and is founded on the property urea has of decomposing thelatter in acid solution. Urea is added to the Rolution containing thenitrate, and it is then gradually added to another solution of urea indilute sulphuric acid.As soon as the evolution of nitrogen due to thedecomposition of the nitrites has ceased, some iodised starch is added,and then a fragment of zinc, when a blue coloration is produced if anynitrate is present.Analysis of Superphosphates By E. WEIN., L. R~SCH, and J.LEBMANN (AnnaZen, 198, 290--307).-As adverse criticisms have beenmade against the process which was adopted a t the Magdeburg Con-ference in 1872 for the extraction of soluble phosphoric acid fromsuperphosphates, the authors have investigated the different pointsobjected to- and some of the methods which have been proposed to besubstituted for it. I n their opinion the differences which frequentlyarise in the analysis of superphosphahes are to be attributed entirelyto a vant of uniformity in preparing the aqueous solution, and not tothe method that may be employed for the determination of thesoluble phosphoric acid.a.The time necessary for Digestion.-In the opinion of Abesser, Jani,and Narcker (Zeits. Anal. Chem. 12, 239), a digestion of the super-phosphate in water for a few minutes is suEcient, as by digestion fora longer time more soluble phosphoric acid may be obtained than wasoriginally present, as such, probably owing to the action of free sul-phuric acid on the phosphate.On the other hand, too low results are possible either from a trans-formation of mluble monocalcium phosphate into insoluble dicalciumosphate, or, in the presence of oxides of iron and alumina from theWith these statements the authors entirely disagree.Their experi-ments prove that although in some cases a shorter time may suffice,yet with all kinds of superphosphates, whether containing much orlittle iron oxide and alumina, a digestion in co€d water for two hoursgives the most accurate results.b. The Extraction, oj* the Solubls Phosphoric Acid by Washing theSuperphosp1tnte.e on a Filter udziclz is connected with a Bunsen’s Pump.-This method has been recommeiided by Fresenius, Luck, and Neubauer(Zeits. Anal. Chew, 7, 304) ; and by Marcker, who states that the re-duction of the soluble phosphoric acid is thereby avoided. Theauthors, however, obtained results from mine different kinds of super-phosphates which were from -06 to 825 p.c. too low, arising no doubt,as explained by Erlenmeyer, from the decomposition on the filter ofthe monocalcium phosphate owing to the absence of free phosphoricacid. In the presence $of excess of free phosphoric acid, this processwas accurate, and this is believed to explain Fresenius’s results,which were obtained with a snpepphosphate containing 5.83 p. c. freephosphoric acid.c. The quantity of Water zoh4ch i s nscessary for Complete Extraction.-With the exception of a slight increase in the amount of solublephosphoric acid from superphosphates containing much oxide of ironC. E. G.The points investtigated were as follows :-ormation of insoluble phosphates of these bases. f ANALYTICAL CHEMISTRY. 141and alumina, no advantage is gained by increasing the quantity ofwater above that used in the Magdeburg process.The authors’ results, therefore, confirm the accuracy of the Magde-burg method, which consists in digesting 20 grams of the superphos-phate in a litre of cold water for two hours.Superphosphates from Pure Tricalcium Phosphate.By E.WEIN (Annalen, 198, 307-318).--In order to ascertain the cause ofthe differeme in the results obtained by the methods described in theprevious paper, similar experiments were made with calcium super-phosphates which had been prepared by the action of sulphuric acid onpure tricslcium phosphate in such a manner as to obtain superphos-phates of three kinds, a, b, c .The soluble phosphoric acid was in all cases debermined by themolybdic acid method.a.Superphosphates which wwtain, nauch Free Pl~osphoric Acid(11.35 p. c.).-A very short period of digestion in water is sufficientto extract the whole of the soluble phosphoric acid. An increase inthe quantity of water (1000 C.C. for 2Q grams) is unnecessary. Correctresults are obtained by washing the superphosphate on a filter-pump,but the quantity of wash water required before the filtrate is freefrom acid, that is, before the extraction is completed, is considerablygreater than 125 C.C. for five grams, as stated by Marcker.b. Xupe~phosphates containing only a Xmall Quantity of Fvee Phos-phoric Acid (.05 p. c.).-It i s necessary to continue the digestion inwater for two hours to be certain that the extraction is completed.Washing on a filter-pump gives results which are considerably too, lowf o r the reasons stated in the previous paper.c.Superphosphates with no Free Phosphoric Acid.-Digestion in waterfor two hours is also necessary ip this case : the filter-pump methodis wholly inapplicable.I f superphosphates, which contain mono- and di-calcium phosphatesbut no free acid, are treated with more than the usual q,uantity ofwater, e.g., with 5 : 1000, then more soluble phofiphoric acid is obtainedthan when the same superphosphate is digested for two hours in the wayrecommended, that is 20: 1000. This result is due to the solubility ofthe dicalcium phosphate. The opposite results obtained by Watten-berg ($.fir Landuj;irfl&, 1879,27-52) on this point are stated to bedue in all probability to the presence of free phosphoric acid whichthe author found could only be removed with great difficulty from amixture of mono- and di-calcium phosphates.The decomposition of monocalcium phosphate which occurs accord-ing to Erlennieyer (Bey., 9, 1839) when it is treated with a smallquantity of water is too trifling to affect the results.The conclusions therefore arrived a t i n the previous paper are con-firmed.A. J. C.Estimation and Separation of Manganese, By J. VOLHARD(Anqcalen, 198, 318--364).-The volumetric method proposed byGuyard (Bull. Xoc. Chint. [2], 1, 88) for the determination of manga-nese in a manganous salt by titrating the neutral and very dilutesolution with a standard solution of potassium permanganate, has notA.J. C.The results are as follows :142 ABSTRACTS OF CHEMICAL PAPERS.been found to give exact results on account of the precipitate which iscaused by the permanganate being always of an uncertain and variablecomposition, and because of the extreme difficulty in ascertaining tbeend of the reaction. Guynrd stated that the whole of the manganesewas precipitated as 1\InO,.Mn,O,.The author shows that if a salt of calcium, magnesium, barium orzinc, be added to a solution of mangsnous salt, the whole of the man-ganese is precipitated by potassium permanganate as dioxide ;* more-over, the end of the reaction can be very readily observed, as the precipi-tate settles rapidly and the supernatant liquid becomes quite clear.Thereaction occurs according to the equation, 3Mn0 + Mn207 = 5MnO2.The salts of all strongly basic metallic oxides which are not sus-ceptible of oxiclation, have a similar action. Alkaline salts to a greatextent obscure the end of the reaction.Prefatory to describing the modified process, the author’s opinionsare expressed on several points more or less connected with it.Titmtion of the Solution of Potnssium P m n nngcinate.-Objections aremade against most of the usually adopted methods for standardisingthis solution. The use of the double salt of iron and ammonium isspecially objected to on account of the difficulty of obtaining it freefrom ferric salt.Methods are described by which it can he standardised by deter-mining the manganese in it, either as sulphate or as oxide, Mn304.I n either case the permanganate is reduced by sulphurous or hydro-chloric acid, and the manganese after precipitation by ammoniumcarbonate is converted into sulphate, or into oxide by igniting thechloride with mercuric oxide.The mercuric oxide used for this purpose is prepared by precipita-tion (with pure sodium hydrate) from the chloride which has beensublimed from a mixture of the chloride with one-tenth its weight o€oxide; thus prepared, it can be similarly employed with great ad-vantage for the conversion of most inetallic chlorides into oxides ;and to precipitate ferric or alnminic oxide, when in solution as chlo-ride, free from alkalis, but not from alkaline earths ; also to separateferric oxide completely from manganese.To any of the methods above mentioned, the author prefers t o stan-dardise the permanganate solution by means of a, solution of potassiumiodide in presence of hydrochloric acid, deteymining the liberatediodine in the usual way with standard sodium thiosulphate and calcu-lating the manganese from 80 mgrms.0 = 3 x 55 = 165 mgrms. Mn.The solution of permanganate must be free from chlorates, and thewater used in the process from nitrites. The solutions required arepotassium perrnanganate containing 3.833 grams per litre, 1 C.C. =2 mgrms. Mn; sodium thiosulphate prepared by dissolving 30.061 gramswith addition of 3 grams of ammonium carbonate in 1 litre of water,1 C.C.= 2 mgrms. Mn, and a solution of potassium iodide approxi-mately equivalent to 55 grams free hydriodic acid per litre.* Kcssler has previously used zinc chloride for the same purpose in precipitatingt~ maiiganous salt with bromine (Zeits. Anal. Chem., 1879, 1-144, and this Journal,1879, 341, Abst.). Pattinson subsequently found that ferric chloride had a similaraction (this Jownul, 1879, 365, Trans.).-A. J. CANALYTICAL CHEMISTRY. 143Separation of Iron from Manganese.-Iron is the only metal which,if present in large quantity, hinders the determination of manganeseby this method. I n preference to any other method, the author sepa-rates the iron from manganese by precipitation with zinc oxide, whichcan be prepared for this purpose by igniting ordinary zinc white andlevigaiing it with water.In the absence of iron or in the presence of a small quantity of it,the process is as follows :-The solution of manganous salt is mixed with about 1 gram of zincsulphate and diluted so that 100 C.O.docs not contain more than0.25 gram &In, and if the solution is neutral 2 t o 3 drops of nitricacid (1.2 sp. gr.) are added; if acid, it is neutralised with sodiumcarbonate (free from sulphite) and nitric acid then added as before.The solution is heated to boiling, and the solution of permanganateadded until the colour remains permanent. Properly performed, thetitration occupies from twelve to fifteen minutes. A blank experi-ment must be made with the solution of zinc sulpliate.Metallic alloys, wrought iron, and steel, are dissolved in a mixtureof 3 vols.of sulphuric acid (1.13 sp. gr.) and 1 vol. of nitric acid(1.4 sp. gr.). Substances dissolved in hydrochloric acid are evaporatedto dryiess with sulphuric acid, and then taken up with water. Spiegel-eisen or ferromanganese is dissolved in nitric acid, tlie solution thenevaporated to dryness, and the residue heated until the nitrate isdecomposed and carbonaceous matter is burnt off. The residue isdissolved in hydrochloric acid, and this acid expelled with sulphurjcacid as before described. I n a11 cases, the greater part of the acid isneutralised with sodium carbonate or sodium hydrate (free from man-ganese), then zinc oxide is added until the supernatant liquid is milky,showing that the whole of the iron has been precipitated.The oxide of iron precipitate generally settles so rapidly that it isunnecessary to filter, and a portion of the liquid can be taken of'f withst pipette and the manganese determined as before.Sepration of JIa?zgaqLese from other ildetcils in a Xtrowgly Acid Xolir-tiow,.-Manganese is usually separated from other metals by precipita-tion in a slightly acid or neutral solution by means of lead dioxide,chlorine, or bromine.It has been found possible to do this in astrongly nitric acid solution, with lead oxide as a precipitant, in amanner which is described by the author; but the rneihod is notrecommended, and the following is considered preferable :--The solu-tion of mangnnous compound is heated to boiling with strong nitricacid and pure mercuric oxide.Chlorine or bromine water is addeduntil the oxidation is completed, which is shown either by the solutionbeing red or' becoming quite clear. In this manner, from a solutioncontaining 0.5 gram pure manganous snlphate and 15-20 C.C. nitricacid (1.2 sp. gr.), and about 1 gram mercuric oxide, the nianpnese iscompletely precipitated in 15-20 minutes. The precipitate is thenheated to redness to expel mercuric oxide, and can be weighedeither as oxide or as sulphate. If cobalt, nickel, zinc, calciurr~,magnesium or potassium are present, the precipitate should be dis-solved and rcprecipitated.Precrpitstiorb of Xanysnese by Oleidisiizg Ageuts.-The author dis144 ABSTRACTS OF CHEMICAL PAPERS.cusses the formation of the precipitate which is produced when anoxidising agent is added to a solution of manganous salt, and heexpresses the opinion that permanganic acid is most probably thefirst result of the oxidation, and this combines with the manganousoxide, so that the whole of the manganese is precipitated as dioxide(“ hyperoxide ”).* In furtherance of this view, it is shown that eitherpermanganic acid or dioxide can be obtained as the result of theoxidation ; in fact, Crum’s Best for manganese depends on producingthe one, viz., perma,nganic acid, in presence of nitric acid, leaving nomanganous oxide in solution, in which case the solutios retains thecolour of permangnnic acid.Crum7s test is best performed by heating almost 130 boiling 10 C.C.of a solution made from equal.parts of nitric aci‘d (sp. gr. 1.2) andwater containing a little plumbic dioxide, then adding the dilute soh-tion of manganese compound ; the coloration occurs immediately evenin presence of chlorides. It has been proposed’ to use Crum’s testfor the quanhitative determination of manganese, but it cannot beused when the amount of manganese in solution exceeds 100 mgrms.,as this appmrs to be the maximum that can be oxidised to permanganicacid wikhout precipitation of oxide.Titration with potassium permanpnate as above described is con-sidered to be quite as delicate for the detection of minute quantitiesof manganese. A. J. C.Experiments with Scheibler’s Method of Analysing RawSugar. By H.WICHELHAVS, K. EISSFELI), and K. STAMMER (Bied.Centr., 1879, 542).-Scheibler’s method consists in boiling the rawsugar with a saturated alcoholic solution of sugar, and weighing theresidue. After numerous experiments with various kinds of rawsugar, it was found that o n the average Scheibler’s method gavefairly good results, no variation being greater than one and a half percent. J. I(. C.Estimation of Sugar in Beet Juice. By C. BITEMAN (Arch.Pharm. [ 3 ] , 15, 63-69).-1n the manufacture of sugar from sugar-beet, there always appears to be a loss of sugar during the filteringand concentration of the juice. This loss is, however, only apparent,as the amount of sugar is estimated by the polariscope, and is coil-sequently affected by the presence in the raw juice of dextrin, arabicacid, and asparagin ; these being dextrorotatory cause the amount ofsugar to appear greater Ohan it, really is. The total amount of sugarin the roots is sometimes deduced from the amount of sugar in the juiceas follows :-If the sugar i n the juice amounts to say 12 per cent. andthe mark 5 per cent. of the roots, then the percent’age of juice is 95per cent., and the percentage of sugar in the roots is 12 x 0.95 = 11.4.This calculation takes for granted that the amount of sugar in thewhole of the juice coincides with that found in the sample, that is, thatthe cells of the root contain a homogeneous liquid. This hypothesis the* Wright and Luff (this Journal, 18’78, 513) have shown that the precipitateproduced on adding bromine t o manganous chloride containing excess of causticsoda, consists of dioxide mixed with a certain amount of lower oxide.-A. J. CTECHNICAL CHEMISTRY. I45author combats, and quotes in corroboration Yicinsky, Heintz, andScheibler, who state that every porlion of the juice in the root mustnot be considered as holding equal quantities of sugar in solutionthat in the root there is water containiiig no sugar, and which mustbe considered as water of organisation. The conclusion drawn is, thatthe present method of determining the amount of sugar in sugar-beetis very unsatisfactory. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8803800137

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

TECHNICAL CHEMISTRY. I45 T e c h n i c a l C h e m i s t r y . Burning o€ Fuel in House Stoves. By F. FISCHCR (Dim$. yolyt. J., 233, 133--136).-During the 18 months previous to January, 1879, 56 patents for house stot-es were taken out in Germany. What is required of the house stove is that it should raise and keep the temperature of a room about 15" t o 20°, ard that as cheaply and conveniently as possible. The usual plan of putting coal into home stoves is to do so after the fire has burned down, the result being that much coaibustible gas is distilled off, which thus produces waste of heat-giving material, besides using up part of the heat from another portion of the fuel for the distillation ; and again when the heat rises sufficiently high to ignite these gases, a proper supply of air is frequently not allowed t o enter the fire, so that much waste is caused by incomplete combustion, zccompanied by the formation of soot and carbonic oxide.The stove acts best when the fuel burns from above downwards, as the hydrocarbons which are distilledfrom the fresh coal a t the bottom burn when they reach the top of the fire. Too much atmospheric air should, however, not be admitted. The coal should be separated from the sides of the stove by a layer of fire-clay, to prevent loss of heat, and so to avoid the resultling loss of fuel from imperfect combustion. The habit of wetting the coal is a very objectionable one. The author endeavoured to determine the loss of heat consequent on the above-mentioned conditions, employing different kinds of stoves, and different sorts of fuel.He analysed from time to time the gases which passed up the flue during the combustion, and noted the temperature in the flues and in the room, and the force of the current in the chimney. He embodies his results in a number of tables ; as examples, the following are given. In one experiment, calculating from the amount of air required to burn the fuel, the heat produced by the combustion, and that carried off by the flue gases, the author arrived st the conclusion that 40 per cent. of the total fuel value of the coal was carried off with the smoke gases, even when the fire was carefully managed. In a second experiment, when the same coal and stove were employed, but in which the current of air in the flue was much increased, it was found that 80 per cent.of the heat was carried off by the smoke gases, VOL. XXXVI1I. 1146 ABSTRACTS OF CHEMICAL PAPERS. The tliird experiment was made with an iron stove, 0.5 meter high, lined with fire-proof stone, the smoke gases rising by one side of a, partitioned pipe or trunk, nearly to the roof of the room, descending to the level of the stove by the other side, and again rising to the roof and making their escape into the chimney. All the joints about the stove were closed by a mixture of soluble glass, asbestos, and clay. In this experiment, Piesberg anthracite was used as fuel, and the loss of heat, calculated as above mentioned, was 15 per cent. of the total fuel value of the coal. The temperature of the smoke a t the fire- hole and a t the exit into the chimney at the roof mere measured by pyrometers, and the loss of heat which was given to the air of the room between these two points was very great.The influence which the opening of the doors of the stove have on the loss of heat is great, as shown by the results obtained from burning coke in the iron stove. When the door of the ash-kole was partly opened, the loss amounted to 1 7 per cent., and when closed, to 6 per cent., but when the ash-hole door was completely opened, and the fire-place door partly opened, the combustion became very vigorous, the temperature of the gases in the flue rose rapidly, so that the tlher- mometer had to be removed, whilst in propovtion to the incl.eased draught the amount of carbonic auhydride diminished, and the loss in heat corresponded to about 40 per cent.of the fuel value. The draught ranged between 2.5 and 4.4 mm. W. T. Salts obtained from the Mother-liquors of ihe Brine-springs of Volterra. Ey A. FUNARO (Gaxxettcn, 9, 289-293).-In a note on these brine-springs (Gazzetta, 8,71, and this Journal, Abst., 1878, 652) the author suggested that they might be utilised for the extraction of potash salts. Experiments have been made with this object, and analyses are given :- 1. Of the residue left on evaporating the mother-liquors. 2. Of the salt obtained by the evaporation of the mother-liquor to 3. Of the salt left on evaporating the moiher-liquors from 2. 4. Of the salt obtained by lixiviating the residual salt with fresh mother-liquors, evaporating, azain 1ixiviat;n: the residue, and so on, by which means the proportion of sodium chloride is greatly diminished.I n this way it is easy to obtain a salt coatailiing 17-18 per cent. potassium sulphake, and consequently but little inferior to the " Kalisalz '' of Stasslurt. C. E. G. two-thirds of its volume. Lead Fume, and a New Process of Fume Condensing. By A. FRENCH (Chem. News, 40, 163--16G).-This paper describes n series of experiments made by the author and Messrs. H. 5. and J. Wycliffe Wilson wiifh a view to discover a good process for conden- sing fumes of lead, silver, and other metals, wltich volati1;se in the smelting and refining operations. Not only does the loss of lead by sublimation amount to hundreds of ions in a year at many works, but the injury which is done to health mid vegetatiori is very great. The various methods of coiidensjng fiimes whch have been tried in this and other countries may be classed as follows :-TECHNICAL CHEMISTRY.147 1. Deposition of the fume by its own gravity in long flues with or without the addition OF a series of settling chambers, placed either near to or a t some distance from the furnace. 2. Filtering through flues, towers, or chambers containing brush- wood, coke, coarsely woven fabric, or similar porous material, using water either in a constant or intermitlent shream to keep the filhers irom becoming choked. 3. The use of water, either in the form of steam or in showers of drops or jets, projected with some considerable degree of force into and across the current of smoke.4. Processes based on the inverse of the precedins principle, viz., passing the smoke under and through a depth oE water, either in great rolumes, as in the old Stagg's condenser, or in a more or less comminuted condition. As to the physical nature of the lead fumes and their deportment nnd er varying conditions of temperature and friction, experiments have proved that as the vaporised lead cools, i t assumes the condition oE a vast number of minute isolated particles. Lead fume appears to have no definite composition, as the proportions of its constituents vary in every specimen. The lead varies from 35-65 per cent. Lead fume, besides silver, invariably contains a little gold ; usually from Q to 1 per cent. of the quantity of silver. Platinum and iridium have also been found in the fumes on several occasions.The greatest deposition of lead fume takes place, as might be ex- pected, near the furnace, and the fume is most abundant whenever the gases have suffered the greatest friction and fall in t'emperature. The author, in the next place, discusses the various methods of condensing fumes as classitied in the above manner, and points out the objections they are subject to. He then describes a new apparatus for condensing these fumes. Copper-wire gauze, having about 15 meshes to a lineal inch, is used in the apparatus, the meshes being about one-twentieth of an inch wide. A number of gauze diaphragms are arranged one above the other in horizontal planes, and a t small distances apart. The whole apparatus is submerged in water, the smoke being equally distributed under the diaphragms by means of tt horizontal series of perforated pipes.The gauze diaphragms do not add much to the resistance which the smoke current bas to overcome i n its passage through the apparatus : three of the size mentioned above add about half an inch of water pressure. The depth of water usually employed is '7 inches above the perforated pipes, and with this dep1,h the water-gauge indicates a resistance of about 10 inches, one half inch only of which is due to the gauze, the remainder befng due t o the depth to which the smoke depresses the water a t the inlet passages. The ascending gases set up an upward current of water through the gauzes, and to promote a steady circulation of this, a return passage is provided.Each square foot of area of the diaphragm space is capable of passing about 40 cubic feet of smoke per minute, and when a blast furnace is employed for smelting lead-ore about 1 foot of area will be required for each ton of ore smelted in 24 honrs. During the past six months, almost daily assays have been made of the smoke before it entered and after it left the condensers a t the145 ABSTRACTS OF CHEMICAL PAPERS. Sheffield Srnelting Company’s works. With a few exceptions these have exceeded 95 per cent. of fume caught. I n a few cases aa much as 99.5 per cent. of the metallic contents olc the smoke has been caught. After the lead has been removed ;?om tbe smoke, the large quantity of sulphurous acid which is usually contained in it may be recovered in a very simple manner.The gases can be mixed with a little air, if enough of oxygen is not already present, and then propelled by means of a steam jet through a heating apparatus similar to the hot blast heaters used in iron smelting works, amd the hot sulphyrons acid, steam, and air passed through common salt, accordin to Hargreave’a process. By this means lead or copper smoke wi5 be rendered not more pernicious than that from ordinary chimneys. Any arsenic or zinc which reaches the condenser is dissolved in the water, and thus separated from the lead fume, which subsides to the bottom. The apparatus was tried with hydrochloric acid vapour, and condensed 97.73 per cent. ; of common salt vapour, it condensed 93 pel- cent. A Roct’s blower is used with iron revolvers for forcing the smoke through the apparatus ; from 2+ to 3-hoi~e power is amply sufficient to work a condenser large enough for a furnace to smelt 15 tons of lead-ore per 24 hours.The weight of a condenser for that size of furnace is 18 cwts. The smoke should be cooled to about 120-130” F. by passing it through iron pipes, or any other kind of flue. This is necessary to prevent rapid evaporation of the weter with which the condenser is supplied. It is also very important to cool the smoke as far as possible, so as to have a smaller volume to pass, and thereby save both power and cosh of a larger apparatus. By E. KLEBS (Bied. Centr., 1879, 541).- The author heats the milk to a temperature of 65-70”, whereby the fresh taste is preserved. D. B. Preservation of Milk. J.I(. C. Composition of LiGrains’’ from Malt. By A. MARKL (Bied. Centr., 1879, 388).-Malt, weakly dried, gives “ grains ’’ richer in starch than when it has been more strongly dried. 100 pasts of grains obtained by the infusion process contained :- Fresh. I ~~~ ~ Strongly From gently. Stronger. dried malt. Water.. .... 79.3 79.1 78.6 Albumin. . . . 4.1 4.7 5.4 Fat ........ 0.4 0.3 0.4 Fibre ...... 6.2 7.8 9.4 Starch .... 9.5 6.7 5.3 Ash ........ 1.1 1.3 1.2 J. H. C.TECHNICAL CHEMISTRY. I45T e c h n i c a l C h e m i s t r y .Burning o€ Fuel in House Stoves. By F. FISCHCR (Dim$.yolyt. J., 233, 133--136).-During the 18 months previous toJanuary, 1879, 56 patents for house stot-es were taken out in Germany.What is required of the house stove is that it should raise and keepthe temperature of a room about 15" t o 20°, ard that as cheaply andconveniently as possible.The usual plan of putting coal into home stoves is to do so after thefire has burned down, the result being that much coaibustible gas isdistilled off, which thus produces waste of heat-giving material, besidesusing up part of the heat from another portion of the fuel for thedistillation ; and again when the heat rises sufficiently high to ignitethese gases, a proper supply of air is frequently not allowed t o enterthe fire, so that much waste is caused by incomplete combustion,zccompanied by the formation of soot and carbonic oxide.The stove acts best when the fuel burns from above downwards, asthe hydrocarbons which are distilledfrom the fresh coal a t the bottomburn when they reach the top of the fire.Too much atmosphericair should, however, not be admitted.The coal should be separated from the sides of the stove by a layerof fire-clay, to prevent loss of heat, and so to avoid the resultling lossof fuel from imperfect combustion. The habit of wetting the coal is avery objectionable one.The author endeavoured to determine the loss of heat consequenton the above-mentioned conditions, employing different kinds ofstoves, and different sorts of fuel. He analysed from time to time thegases which passed up the flue during the combustion, and noted thetemperature in the flues and in the room, and the force of the currentin the chimney. He embodies his results in a number of tables ; asexamples, the following are given.In one experiment, calculating from the amount of air required toburn the fuel, the heat produced by the combustion, and that carriedoff by the flue gases, the author arrived st the conclusion that 40 percent.of the total fuel value of the coal was carried off with the smokegases, even when the fire was carefully managed.In a second experiment, when the same coal and stove were employed,but in which the current of air in the flue was much increased, it wasfound that 80 per cent. of the heat was carried off by the smoke gases,VOL. XXXVI1I. 146 ABSTRACTS OF CHEMICAL PAPERS.The tliird experiment was made with an iron stove, 0.5 meter high,lined with fire-proof stone, the smoke gases rising by one side of a,partitioned pipe or trunk, nearly to the roof of the room, descendingto the level of the stove by the other side, and again rising to the roofand making their escape into the chimney.All the joints about thestove were closed by a mixture of soluble glass, asbestos, and clay.In this experiment, Piesberg anthracite was used as fuel, and theloss of heat, calculated as above mentioned, was 15 per cent. of thetotal fuel value of the coal. The temperature of the smoke a t the fire-hole and a t the exit into the chimney at the roof mere measured bypyrometers, and the loss of heat which was given to the air of the roombetween these two points was very great.The influence which the opening of the doors of the stove haveon the loss of heat is great, as shown by the results obtained fromburning coke in the iron stove.When the door of the ash-kole waspartly opened, the loss amounted to 1 7 per cent., and when closed, to6 per cent., but when the ash-hole door was completely opened, andthe fire-place door partly opened, the combustion became very vigorous,the temperature of the gases in the flue rose rapidly, so that the tlher-mometer had to be removed, whilst in propovtion to the incl.easeddraught the amount of carbonic auhydride diminished, and the loss inheat corresponded to about 40 per cent. of the fuel value. The draughtranged between 2.5 and 4.4 mm. W. T.Salts obtained from the Mother-liquors of ihe Brine-springsof Volterra. Ey A. FUNARO (Gaxxettcn, 9, 289-293).-In a note onthese brine-springs (Gazzetta, 8,71, and this Journal, Abst., 1878, 652)the author suggested that they might be utilised for the extraction ofpotash salts.Experiments have been made with this object, andanalyses are given :-1. Of the residue left on evaporating the mother-liquors.2. Of the salt obtained by the evaporation of the mother-liquor to3. Of the salt left on evaporating the moiher-liquors from 2.4. Of the salt obtained by lixiviating the residual salt with freshmother-liquors, evaporating, azain 1ixiviat;n: the residue, and so on,by which means the proportion of sodium chloride is greatly diminished.I n this way it is easy to obtain a salt coatailiing 17-18 per cent.potassium sulphake, and consequently but little inferior to the" Kalisalz '' of Stasslurt. C.E. G.two-thirds of its volume.Lead Fume, and a New Process of Fume Condensing.By A. FRENCH (Chem. News, 40, 163--16G).-This paper describes nseries of experiments made by the author and Messrs. H. 5. andJ. Wycliffe Wilson wiifh a view to discover a good process for conden-sing fumes of lead, silver, and other metals, wltich volati1;se in thesmelting and refining operations. Not only does the loss of lead bysublimation amount to hundreds of ions in a year at many works,but the injury which is done to health mid vegetatiori is very great.The various methods of coiidensjng fiimes whch have been tried inthis and other countries may be classed as follows :TECHNICAL CHEMISTRY. 1471.Deposition of the fume by its own gravity in long flues with orwithout the addition OF a series of settling chambers, placed eithernear to or a t some distance from the furnace.2. Filtering through flues, towers, or chambers containing brush-wood, coke, coarsely woven fabric, or similar porous material, usingwater either in a constant or intermitlent shream to keep the filhersirom becoming choked.3. The use of water, either in the form of steam or in showers ofdrops or jets, projected with some considerable degree of force intoand across the current of smoke.4. Processes based on the inverse of the precedins principle, viz.,passing the smoke under and through a depth oE water, either ingreat rolumes, as in the old Stagg's condenser, or in a more or lesscomminuted condition.As to the physical nature of the lead fumes and their deportmentnnd er varying conditions of temperature and friction, experimentshave proved that as the vaporised lead cools, i t assumes the conditionoE a vast number of minute isolated particles.Lead fume appears tohave no definite composition, as the proportions of its constituentsvary in every specimen. The lead varies from 35-65 per cent.Lead fume, besides silver, invariably contains a little gold ; usuallyfrom Q to 1 per cent. of the quantity of silver. Platinum andiridium have also been found in the fumes on several occasions.The greatest deposition of lead fume takes place, as might be ex-pected, near the furnace, and the fume is most abundant wheneverthe gases have suffered the greatest friction and fall in t'emperature.The author, in the next place, discusses the various methods ofcondensing fumes as classitied in the above manner, and points outthe objections they are subject to.He then describes a new apparatusfor condensing these fumes. Copper-wire gauze, having about15 meshes to a lineal inch, is used in the apparatus, the meshes beingabout one-twentieth of an inch wide. A number of gauze diaphragmsare arranged one above the other in horizontal planes, and a t smalldistances apart. The whole apparatus is submerged in water, thesmoke being equally distributed under the diaphragms by means of tthorizontal series of perforated pipes. The gauze diaphragms do notadd much to the resistance which the smoke current bas to overcomei n its passage through the apparatus : three of the size mentioned aboveadd about half an inch of water pressure. The depth of water usuallyemployed is '7 inches above the perforated pipes, and with this dep1,hthe water-gauge indicates a resistance of about 10 inches, one halfinch only of which is due to the gauze, the remainder befng due t o thedepth to which the smoke depresses the water a t the inlet passages.The ascending gases set up an upward current of water through thegauzes, and to promote a steady circulation of this, a return passage isprovided.Each square foot of area of the diaphragm space is capableof passing about 40 cubic feet of smoke per minute, and when ablast furnace is employed for smelting lead-ore about 1 foot of areawill be required for each ton of ore smelted in 24 honrs.During the past six months, almost daily assays have been made ofthe smoke before it entered and after it left the condensers a t th145 ABSTRACTS OF CHEMICAL PAPERS.Sheffield Srnelting Company’s works.With a few exceptions thesehave exceeded 95 per cent. of fume caught. I n a few cases aamuch as 99.5 per cent. of the metallic contents olc the smoke has beencaught. After the lead has been removed ;?om tbe smoke, the largequantity of sulphurous acid which is usually contained in it may berecovered in a very simple manner. The gases can be mixed with alittle air, if enough of oxygen is not already present, and then propelledby means of a steam jet through a heating apparatus similar to thehot blast heaters used in iron smelting works, amd the hot sulphyronsacid, steam, and air passed through common salt, accordin toHargreave’a process.By this means lead or copper smoke wi5 berendered not more pernicious than that from ordinary chimneys.Any arsenic or zinc which reaches the condenser is dissolved in thewater, and thus separated from the lead fume, which subsides to thebottom. The apparatus was tried with hydrochloric acid vapour, andcondensed 97.73 per cent. ; of common salt vapour, it condensed 93 pel-cent.A Roct’s blower is used with iron revolvers for forcing the smokethrough the apparatus ; from 2+ to 3-hoi~e power is amply sufficientto work a condenser large enough for a furnace to smelt 15 tons oflead-ore per 24 hours. The weight of a condenser for that size offurnace is 18 cwts. The smoke should be cooled to about 120-130” F.by passing it through iron pipes, or any other kind of flue. This isnecessary to prevent rapid evaporation of the weter with which thecondenser is supplied. It is also very important to cool the smoke asfar as possible, so as to have a smaller volume to pass, and thereby saveboth power and cosh of a larger apparatus.By E. KLEBS (Bied. Centr., 1879, 541).-The author heats the milk to a temperature of 65-70”, whereby thefresh taste is preserved.D. B.Preservation of Milk.J. I(. C.Composition of LiGrains’’ from Malt. By A. MARKL (Bied.Centr., 1879, 388).-Malt, weakly dried, gives “ grains ’’ richer in starchthan when it has been more strongly dried. 100 pasts of grainsobtained by the infusion process contained :-Fresh.I ~~~ ~ StronglyFrom gently. Stronger. dried malt.Water.. .... 79.3 79.1 78.6Albumin. . . . 4.1 4.7 5.4Fat ........ 0.4 0.3 0.4Fibre ...... 6.2 7.8 9.4Starch .... 9.5 6.7 5.3Ash ........ 1.1 1.3 1.2J. H. C

ISSN:0368-1769    

DOI:10.1039/CA8803800145

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

149 General and P h y s i c a l Chemistry. New Galvanic Couple. By A. NIAUDET (Compt. rend., 89, 703 --708).-This couple consists of a plate of zinc for a positive, and a plate of carbon, surrounded with pieces of carbon, for a negative electrode : the former is immersed in a solution of common salt, and the latter in a solution of chloride of lime in a porous cell. The chloride of lime acts as a depolariser, the hydrogen decomposing the hypochlorous acid, forming water and hydrochloric acid, which unites w ~ t h the zinc or lime, forming salts which ape very soluble and good conductors, As zinc is not attacked by chloride of lime, the action takes place only when the circuit is closed; so that with D broken circuit, a couple may be kept for any length of time. When sodium chloride is used, %he electromotive force is greater than with any other solution, being 1.6 volts, and 1.5 after standing for some months.The depolarising action of chloride of lime is not com- plete, as is the ease with eopper sulphate, and with a slight external resistance the elechomotive force slightly diminishes if the current con- tinues ; but it regains its former strength on standing. The internal resistance is reduced to a minimum by bringing the plates as close together as possible. To prevenh the smell of the bleaching powder being disagreeable, the porous cell is closed with a cork. Determination of the Density of Vapours which Attack Porcelain at a Red Heat. By V. MEYER and H. ZUBLIN (Bey., 12, 2204-2205) .-The apparatus used for determining the vapour-density of those bodies which attack porcelain, consists of a, platinum cylinder 245 mm.in length and 26 mm. diameter, to which is soldeved, by means of the oxyhydrogen blowpipe, a platinum tube 400 mm. long and 7 mm. in diameter. To protecb the cylinder from the aetion of the furnace-gases, which would permeate the platinum walls, it must be surrounded by a Berlin porcelain tube, glazed inside and out, Specific Heats and Melting Points of the Refractory Metals. By J. VIOLLE (Compt. rend., 89, 70%-703).-The specific heat of iridium, which has been determined up to a temperature of 1400", is found to increase regularly with the temperature according t o the formula Ct, = 0.037 4- 0.000006 t. The melting p i n t determined by the calorimetric method (this Jonrnal, A b t ., 1879, 294) is found to be 1950". The specific heat of gold remains nearly csnsltant between 0" and 600", but increases constantly bemeen 600" and its melting point : according to Regnault, the specific heat of gold = 0.0324 between 0" and loo", and is nearly the same a t 600°, but according to the author it is a little less a t loo", namely, 0.0316. At 900" it is 0.0345, an4 0.0352 at 1020". L. T. 0.73. 60 cm. long. w. c. w. VOL. XXXVlII. nL150 ABSTRACTS OF CHEMICAL PAPERS. The melting points of the different metals determined by the author are- Silver ................ 954" Gold ................ 1035 Palladiiim ............ 1500 Platinum ............ 1775 Iridium .............. 1950 L. T. 0's. Copper .............. 1054 Decomposition of Seleniuretted Hydrogen by Mercury, By BERTHELOT (Compt.rend., 89, 684) .-Seleniuretted hydrogen, when kept in contact with mercury for some time at the ordinary tempera- ture, is decomposed, with formation of mercuric selenide ; under similar circumstances, sulphuretted hydrogen has no appreciable action on mercury, it being only at 550" that decomposition takes place. This difference may be due to the difference in the heat of formation of the two hydrides. H2 + S solid = H,S disengages + 4.6 cal. H, + Se solid = H,S,absorbs - 5.4 ,, A similaz case is met with when hydrobromic and hydrochloric acids are treated with mercury ; the latter acid is decomposed only at high temperatures ; the former slowly at the ordinary temperature, the heats of formation from the elements in the gaseous state being HBr = + 13.5, BC1 = + 22.In all such cases, the decomposed bodies being analogous and com- parable with one another, their decomposition is easier the less heat disengaged in t8heir initial formation. Combinations of Phosphine with the Haloi'd Acids. By J. OGIER (Conzpt. rend., 89, 7U5-708).-PI~a.sphine hydrochloride (phos- phonium chloride), PH4C1, is obtained by mixing equal volumes of phosphine and hydrochloric acid, at a temperature of I@, and submit- ting them to a pressure of 20 atmospheres, when small crystals similar to those of the bromide deposit on the sides of the vessel. At 20" a liquid is obtained which, on cooling, deposits crystals. A mixture of equal volumes of the two gases under the ordina'ry pressure, deposits crystals when cooled to -30" to - 35".Phosphilze hydrobromide (phosphonium bromide), PH4Br. The heat of formation of this body is measured by decomposing it with water, when PH3HBr + water = PH, gas + HBr dissolved, absorbs -3.03 cal. By deducting from this number, representing the thermal action of water on 1 equiv. of PH4Br, the heat of solution of hydro- bromic acid in water (+20*0), and changing the signs, the heat dis- engaged by the union of the two gaseous bodies is obtained. PH, gas + HBr gas = PH,Br solid disengages + 23.03 cal. The heat of formation of this body is determined like that of the hydrobromide, PH,HI + water = PH, + HI dissolved, absorbs -4.77 cnl. By deducting the heat of solution of HI in water and changing the sign, L. T. 0's. Phosphine hydriodide (phoephonium iodide), PHJ.GENERAL AND PHYSICAL CHEMISTRY.151 we get PH3 gas + HI gas = PHJ solid disengages + 24.17 cal. By directly measuring the heat evolved by the union of the two gases, +24.2 cal. was obtained. The author corrects an error made in the calculation of the heat developed in the formation of phosphine (ibid., 87, 210, and this Journal, Abst., 5,1879) due to the heat of formation of gaseous water instead of solid water being used. The corrected calculation stands thus :- 1st Series. P + H, disengages x 5(H + 0) ,, A = + 172.5 cal. PH, + 81Br ,, B = + 254.6 ,, 2mi? Series. P + 0, = PO5 disengages C = + 202.7 (Thomsen) 1(H + Br) disengages D = + 236.0 (Berthelot). From which x = (C + D) - (A + B) = + 11.6 cal., therefore P + H, = PH, gas disengages + 11.6 cal.Similarly, Pa + H = P2R solid disengages 17.7 caI. As + H3 = AsH3 gas absorbs 36.7 ,, The heat of formation of phosphine is less than that of ammonia. By comparing the heats of formation of ammonia and phosphine com- pounds we find- HC1 gas + NH, gas = NIP,Cl disengages 42.5 cal. HBr ,, + NH, ,, = NH4Br ,, 45.6 ,, HI ,, + NR3 ,, NHJ ,, 44.2 ,, PH3 + HBr = PH4Br ,, 23-0 ,, PH3 f HI = PH4Br ,, 24.1 ,, Starting from the elements themselves, we get- N + E4 + c1 N H4 + Br (liq.) = NH4Br ,, 81.7 ,, P (sol.) + HP + Br (Tiq.) = PH4Br ,, U.1 ,: P (sol.) + HP +- P (sol.) = PHJ ,, 29.5 ,, = NHaCl disengages 91.2 cal. N + Hi + I (sol.) = NHJ ,) 65.1 ,) The heat developed by the formation of ammonium cyanide and ammonium sulphide are- HCN + NH3 = NH,CN disengages 20.5 cal.H2S + NH, = NH4HSt 23-0 ,, As a reducing agent, phosphine hydriodide is not as effectual in some cases as hydriodic acid, on account of the loss of energy which takes place in its formation. L. T. 0’s. Thermic Study of Succinic Acid. By P. CHROUSTCHOFF COW,^^. rend., 89, 575--582).-The following numbers represent the heat evolved by various salts of succinic acid when dissolved in 400 C.C. of water :- m, 2152 ABSTRACTS OF CHEMICAL PAPERS. C4H404Na, = 8.4 C,H4Na,04.6H,0 = - 11.0 CaHpOaK, = 0.2 C4H4O,K?.H,O = - 3.4 CpH*O,HK= - 7.6 CdH,O,H.NH, = - 4.9 From these may be calculated the heat evolved by the combina,tion of the solid salt with water. I n the case of the soda salt, it becomes 10.8; with the potash salt, 2.2 units. Succinic acid dried at 110" gives by solution in 500 C.C.at 11" an absorption of heat equal to 6.4 units. The heat of neutralisatioh by alkalis made with a solution containing 4 of an equivalent of acid gave as follows, everything being dissolved, a :id remaining dissolved :- With soda 26.4; with potash 26.4; with ammonia 22.9. By increasing the relative proportions of suecinie acid t o alkali, the numbers mere slightly altered: thus with 2 mols. of acid to 2 mols. of potash, 27-25 units were obtained ; with 3 mols. of acid to 2 mols. of potash, 24.76 anits; with 2 mols. of acid t o 2 mols. of ammonia, 24.7 units. The number found by Thomsen for the 'heat of neutralisation of succinic acid was 24.8 units ; the author considers that this number is incorrect. The foregoing numbers may, if required, be referred to a reaction between the solid constituents.With soda 40.02 ; with potash 46.37 ; with ammonia gas 39.42. As regards the amount of heat evolved on neutralisation, snccinic acid occupies a position intermediate between beneoic and tartaric acids. Acetic acid. ......... 18.3 21-9 18.5 Benzoic acid ........ 17.4 2 2.5 17.0 + succinic acid ...... 20.01 23-19 19.7 + oxalic acid ........ 26.5 29.4 24.41 6 tartaric acid ...... 22.9 2 7.3. Sulphuric ,, ...... 34.7 40- 7 33.8 NaHO. KIIO. NH, gas. - By determining the heat of solution of the anhydride, and of the hydrated acid in potash, the heat of combination of the anhydride with water was obtained by difference: CpHf,Od = 20-06 ; CaH403 = 29.78 ; difference = 9-22 units. If the heat of solution of the hydrated acid in water be deducted from the heat of solution of the same acid in potash, the number of units obtained should be equal t o the heat of neutralisation by potash i n solution.Heat evolved on solution in potash = + 20.06 9 , 9 , water = - 6 4 -- Difference = 26.46 This indirect verification of the number 26.4 supports the author's wsults as against Thomsen's figure, 24.8.INORGANIC CHEMISTRY. 153 Succinic acid appears to be completely displaced from its combiim- tiow by sulphuric acid ; but doubtful results only were obtained in the case of hydrochloric acid, further data are in fact required respect- ing the heat evolved or absorbed in diluting succinic acid and its salts. J. W.149General and P h y s i c a l Chemistry.New Galvanic Couple.By A. NIAUDET (Compt. rend., 89, 703--708).-This couple consists of a plate of zinc for a positive, and aplate of carbon, surrounded with pieces of carbon, for a negativeelectrode : the former is immersed in a solution of common salt, andthe latter in a solution of chloride of lime in a porous cell. Thechloride of lime acts as a depolariser, the hydrogen decomposing thehypochlorous acid, forming water and hydrochloric acid, which unitesw ~ t h the zinc or lime, forming salts which ape very soluble and goodconductors, As zinc is not attacked by chloride of lime, the actiontakes place only when the circuit is closed; so that with D brokencircuit, a couple may be kept for any length of time.When sodium chloride is used, %he electromotive force is greaterthan with any other solution, being 1.6 volts, and 1.5 after standing forsome months.The depolarising action of chloride of lime is not com-plete, as is the ease with eopper sulphate, and with a slight externalresistance the elechomotive force slightly diminishes if the current con-tinues ; but it regains its former strength on standing. The internalresistance is reduced to a minimum by bringing the plates as closetogether as possible. To prevenh the smell of the bleaching powderbeing disagreeable, the porous cell is closed with a cork.Determination of the Density of Vapours which AttackPorcelain at a Red Heat. By V. MEYER and H. ZUBLIN (Bey., 12,2204-2205) .-The apparatus used for determining the vapour-densityof those bodies which attack porcelain, consists of a, platinum cylinder245 mm.in length and 26 mm. diameter, to which is soldeved, bymeans of the oxyhydrogen blowpipe, a platinum tube 400 mm. longand 7 mm. in diameter. To protecb the cylinder from the aetion ofthe furnace-gases, which would permeate the platinum walls, it mustbe surrounded by a Berlin porcelain tube, glazed inside and out,Specific Heats and Melting Points of the Refractory Metals.By J. VIOLLE (Compt. rend., 89, 70%-703).-The specific heat ofiridium, which has been determined up to a temperature of 1400", isfound to increase regularly with the temperature according t o theformula Ct, = 0.037 4- 0.000006 t. The melting p i n t determined bythe calorimetric method (this Jonrnal, A b t ., 1879, 294) is found tobe 1950".The specific heat of gold remains nearly csnsltant between 0" and600", but increases constantly bemeen 600" and its melting point :according to Regnault, the specific heat of gold = 0.0324 between 0"and loo", and is nearly the same a t 600°, but according to the authorit is a little less a t loo", namely, 0.0316. At 900" it is 0.0345, an40.0352 at 1020".L. T. 0.73.60 cm. long. w. c. w.VOL. XXXVlII. n150 ABSTRACTS OF CHEMICAL PAPERS.The melting points of the different metals determined by the authorare-Silver ................ 954"Gold ................ 1035Palladiiim ............ 1500Platinum ............ 1775Iridium .............. 1950 L. T. 0's.Copper ..............1054Decomposition of Seleniuretted Hydrogen by Mercury, ByBERTHELOT (Compt. rend., 89, 684) .-Seleniuretted hydrogen, whenkept in contact with mercury for some time at the ordinary tempera-ture, is decomposed, with formation of mercuric selenide ; undersimilar circumstances, sulphuretted hydrogen has no appreciable actionon mercury, it being only at 550" that decomposition takes place.This difference may be due to the difference in the heat of formationof the two hydrides.H2 + S solid = H,S disengages + 4.6 cal.H, + Se solid = H,S,absorbs - 5.4 ,,A similaz case is met with when hydrobromic and hydrochloric acidsare treated with mercury ; the latter acid is decomposed only at hightemperatures ; the former slowly at the ordinary temperature, theheats of formation from the elements in the gaseous state being HBr = + 13.5, BC1 = + 22.In all such cases, the decomposed bodies being analogous and com-parable with one another, their decomposition is easier the less heatdisengaged in t8heir initial formation.Combinations of Phosphine with the Haloi'd Acids.By J.OGIER (Conzpt. rend., 89, 7U5-708).-PI~a.sphine hydrochloride (phos-phonium chloride), PH4C1, is obtained by mixing equal volumes ofphosphine and hydrochloric acid, at a temperature of I@, and submit-ting them to a pressure of 20 atmospheres, when small crystals similarto those of the bromide deposit on the sides of the vessel. At 20" aliquid is obtained which, on cooling, deposits crystals. A mixture ofequal volumes of the two gases under the ordina'ry pressure, depositscrystals when cooled to -30" to - 35".Phosphilze hydrobromide (phosphonium bromide), PH4Br.The heatof formation of this body is measured by decomposing it with water,when PH3HBr + water = PH, gas + HBr dissolved, absorbs-3.03 cal. By deducting from this number, representing the thermalaction of water on 1 equiv. of PH4Br, the heat of solution of hydro-bromic acid in water (+20*0), and changing the signs, the heat dis-engaged by the union of the two gaseous bodies is obtained.PH, gas + HBr gas = PH,Br solid disengages + 23.03 cal.The heat offormation of this body is determined like that of the hydrobromide,PH,HI + water = PH, + HI dissolved, absorbs -4.77 cnl. Bydeducting the heat of solution of HI in water and changing the sign,L.T. 0's.Phosphine hydriodide (phoephonium iodide), PHJGENERAL AND PHYSICAL CHEMISTRY. 151we get PH3 gas + HI gas = PHJ solid disengages + 24.17 cal. Bydirectly measuring the heat evolved by the union of the two gases,+24.2 cal. was obtained.The author corrects an error made in the calculation of the heatdeveloped in the formation of phosphine (ibid., 87, 210, and thisJournal, Abst., 5,1879) due to the heat of formation of gaseous waterinstead of solid water being used. The corrected calculation standsthus :-1st Series.P + H, disengages x5(H + 0) ,, A = + 172.5 cal.PH, + 81Br ,, B = + 254.6 ,,2mi? Series.P + 0, = PO5 disengages C = + 202.7 (Thomsen)1(H + Br) disengages D = + 236.0 (Berthelot).From which x = (C + D) - (A + B) = + 11.6 cal., thereforeP + H, = PH, gas disengages + 11.6 cal.Similarly, Pa + H = P2R solid disengages 17.7 caI.As + H3 = AsH3 gas absorbs 36.7 ,,The heat of formation of phosphine is less than that of ammonia.By comparing the heats of formation of ammonia and phosphine com-pounds we find-HC1 gas + NH, gas = NIP,Cl disengages 42.5 cal.HBr ,, + NH, ,, = NH4Br ,, 45.6 ,,HI ,, + NR3 ,, NHJ ,, 44.2 ,,PH3 + HBr = PH4Br ,, 23-0 ,,PH3 f HI = PH4Br ,, 24.1 ,,Starting from the elements themselves, we get-N + E4 + c1N H4 + Br (liq.) = NH4Br ,, 81.7 ,,P (sol.) + HP + Br (Tiq.) = PH4Br ,, U.1 ,:P (sol.) + HP +- P (sol.) = PHJ ,, 29.5 ,,= NHaCl disengages 91.2 cal.N + Hi + I (sol.) = NHJ ,) 65.1 ,)The heat developed by the formation of ammonium cyanide andammonium sulphide are-HCN + NH3 = NH,CN disengages 20.5 cal.H2S + NH, = NH4HSt 23-0 ,,As a reducing agent, phosphine hydriodide is not as effectual insome cases as hydriodic acid, on account of the loss of energy whichtakes place in its formation.L. T. 0’s.Thermic Study of Succinic Acid. By P. CHROUSTCHOFF COW,^^.rend., 89, 575--582).-The following numbers represent the heatevolved by various salts of succinic acid when dissolved in 400 C.C. ofwater :-m, 152 ABSTRACTS OF CHEMICAL PAPERS.C4H404Na, = 8.4 C,H4Na,04.6H,0 = - 11.0CaHpOaK, = 0.2 C4H4O,K?.H,O = - 3.4CpH*O,HK= - 7.6 CdH,O,H.NH, = - 4.9From these may be calculated the heat evolved by the combina,tionof the solid salt with water.I n the case of the soda salt, it becomes10.8; with the potash salt, 2.2 units. Succinic acid dried at 110"gives by solution in 500 C.C. at 11" an absorption of heat equal to6.4 units.The heat of neutralisatioh by alkalis made with a solution containing 4 of an equivalent of acid gave as follows, everything being dissolved,a :id remaining dissolved :-With soda 26.4; with potash 26.4; with ammonia 22.9.By increasing the relative proportions of suecinie acid t o alkali, thenumbers mere slightly altered: thus with 2 mols. of acid to 2 mols. ofpotash, 27-25 units were obtained ; with 3 mols. of acid to 2 mols. ofpotash, 24.76 anits; with 2 mols. of acid t o 2 mols. of ammonia,24.7 units.The number found by Thomsen for the 'heat of neutralisation ofsuccinic acid was 24.8 units ; the author considers that this number isincorrect.The foregoing numbers may, if required, be referred to areaction between the solid constituents.With soda 40.02 ; with potash 46.37 ; with ammonia gas 39.42.As regards the amount of heat evolved on neutralisation, snccinicacid occupies a position intermediate between beneoic and tartaricacids.Acetic acid. ......... 18.3 21-9 18.5Benzoic acid ........ 17.4 2 2.5 17.0 + succinic acid ...... 20.01 23-19 19.7 + oxalic acid ........ 26.5 29.4 24.41 6 tartaric acid ...... 22.9 2 7.3.Sulphuric ,, ...... 34.7 40- 7 33.8NaHO. KIIO. NH, gas.-By determining the heat of solution of the anhydride, and of thehydrated acid in potash, the heat of combination of the anhydride withwater was obtained by difference: CpHf,Od = 20-06 ; CaH403 = 29.78 ;difference = 9-22 units.If the heat of solution of the hydrated acid in water be deductedfrom the heat of solution of the same acid in potash, the number ofunits obtained should be equal t o the heat of neutralisation by potashi n solution.Heat evolved on solution in potash = + 20.069 , 9 , water = - 6 4--Difference = 26.46This indirect verification of the number 26.4 supports the author'swsults as against Thomsen's figure, 24.8INORGANIC CHEMISTRY. 153Succinic acid appears to be completely displaced from its combiim-tiow by sulphuric acid ; but doubtful results only were obtained inthe case of hydrochloric acid, further data are in fact required respect-ing the heat evolved or absorbed in diluting succinic acid and itssalts. J. W

ISSN:0368-1769    

DOI:10.1039/CA8803800149

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 153 Inorganic Chemist rg. Silicon Nitride. By P. SGH~~ZENBERGER (Compt. rend., 89, 644 -646) .-The composition of the silicon nitrides discovered by Sainte- Claire Deville and Wohler, not having been experimentally determined, the author has sought to prove the existence of two compounds by the following experiments :- By heating crystnllised silica with gas carbm in a blast furnace for some time, a mass is obtained consisting of unaltered silica, a white substance soluble in cold concentrated hydrofluoric acid without evolu- tion of gas, and a green substance which is insoluble in hydrofluoricacid and caustic alkalis, and, after successive treatment with hydrofluoric acid and dilute potash, is obtained as a green infusible powder : this is riot attacked by water or by solution of caustic alkalis, but i s dissolved by potash a t a red heat with formation of potassium silicate and evolution of hydrogen and ammonia.The analyses agree with the formula (SiN),. The white substance soluble in hydroflnoric acid cannot be obtainecl in the pure state, but most probably it has the formula Si3N4 ; this is rendered probable by the fact that 011 heating (SiN), in a current of' chlorine, it loses 22 per cent. of its weight of silicon, and a white sub- stance, soluble in hydrofluoric acid, is, left, The equation, (SiN)4 + ClA = SiC1, + Si3N4, represents the loss of 22.4 per cent. of silicon. By passing ammonia gas into a flask containing silicon tetrachloride, a very light white powder is obtained soluble in water with separation of Si(H0)4; when heated in a current of hydrogen, amramium chlo- ride sublimes. The results of analyses compare fairly with those required by the formula Si,N,,Cl,H.Its formation may be expressed thus: 8SiCl4 + 10NH8 = Si,N,,Cl,H + 29HC1, and its decomposi- tion by water, thus: Si8NloCl3H + 16H20 = 8Si02 + + 3HC1. When heated to bright redness in a current of ammonia, a white powder is obtained which, is not attacked by water, and only slightly soluble in alkalis; its formuTa is Si2N3H.. These experiments show the existence of two silicon nitrides, one (SiN), corresponding to CN, the other probably of the formula SiJV,. L. T. 0'3. Action of Metallic Nitrates on Nitric Acid. By A. Dmm (Con2pi. rend., 89, 576-579) .-Ammonium nitrate dissolves readil2 in fuming nitric acid, forming a, liquid which does not solidify at 5" ; below this temperature crystallisation takes place, when the ther- mometer immediately rises to 18". The crystals melt regularly a t 18", but generally exhibit the phenomenon of surfusion, in which canditioii154 ABSTRACTS OF CHEMICAL PAPERS.a crystal of ammonium nitrate will not determine solidification. The composition of the salt is NH4N0,.2HN0, ; when melted the liquid closely resembles nitric acid, but does not fume in the air ; it is capable of dissolving a large quantity of ammonium nitrate to form the salt NH4N03.HN03, melting at 9" ; this latter remains liquid at 4", and a crystal of the di-acid salt does not induce crystallisation. The same compounds are produced when dry ammonium nitrate is placed in an atmosphere containing nitric acid vapour.Potassium nitrate, in like manner, produces the salt KN03.2HN0,, melting at -3" ; when carefully cooled the whole will remain liquid at -lo", bnt the temperature rises to -3" its soon as crystallisation sets in. The monacid salt, KNO,.HNO,, could not be prepared. Thallium and rubidium nitrates also combine with nitric acid to form the salts T1N O3.3HNO3 and RbN0,.5MN03 respectively ; their melting points are not given, but in general properties they resemble t lie potassium and ammonium salts previously described. J. W. Action of Metallic Nitrates on Nitric Acid. By A. DITTE (Cowpt. rend., 89, 641--643).-The author has shown (see previous abstract) that aertain metallic nitrates combine with nitric acid to form acid salts. There are, however, other salts which behave dif- ferently.Magnesium nitrate, M,q(NO,),GH,O, for example, which contains 6 mols. of water of crystallisation, melts and begins to decompose when heated ; under certain circumstances, however, when heated, it yields a syrnpy mass, which suddenly solidifies, evolving a large amount of heat; it consists of Mg(N03)23H20. It is decom- posed by heat, leaving a residue, from which is separated by water a nitrate having the composition MgO.Mg(NO,), ; this decomposes without me1 ting, leaving magnesia. I f the decomposition of the neutra'l nitrate be stopped the moment nitric oxide begins to be evolved, a deliqaescent mass is obtained, which dissolves in nitric acid, and on cooling deposits transparent prisms, consisting of Mg(N03)2.2Hz0. The basic nitrate, when treated with nitric acid,.yields the neutral salt, but owing to the quantity of water set free it is impossible to obtain acid salts ; the aukhor therefore proposes to saturate a solution of the neutral salt with nitric anhydride, which will combine with the water, and thus a solution of the anhydrous salt in nitric acid will be obtained. To this group besides magnesium nitrate belong the nitrates of manganese, aluminium, zinc, uranium, copper, and iron, which give the following salts :- Mg(NO,),.SH,O 2[Mn(N0,),].5H20 (UOz)(N03)z.3H20 Mg (NO,) 2. 2H,O Mn(NO,),.H,O Cu(N0,),.3H20 2 [ Zn .3H20 A123 ( IYO3)2.4H2O Pe,3 ( NO,) 2. 6Hz0. Of these, the nitrates of manganese, aluminium, and iron leave a residue of oxide when heated ; the others yield basic nitrates.Secondly, there exists a class of nitrates which are insoluble, or only sparingly soluble in nitric acid, to which belong the nitrates ofIN ORGANIC CHEMISTRY. 155 sodium, lithium, calcium, strontinm, barium, nickel, cobalt, bismuth, cadmium, mercury, and silver. Contributions to our Knowledge of Clays and Earthenware Goods. (Dingl. polyt. J., 234, 465--473).-Bischof mentions a new source of bauxite at Kleinsteinheim, in the Offenbach district. The following is the composition :- L. T. 0’s. Al20,. SiO,. Fe,O,. Loss on ignition. 56-02 10.9 7 6-19 26-42 = 99.60 Leger gives the following analyses (p. 156) of clay substances used for the preparation of fine white goods. A and B are French goods, C and D are Belgian goods, the former being used for fine goods, the latter for ordinary ; and E is German.Lindhorst states that, besides lime and the flue gases, the alumina and alkalis contained in clay also influence the coloration of clay; whereas gypsum is inactive. Experiments were made with various oxides, the colour prcduced being red with iron, green with chromium, grey with copper, white with zinc, yellowish-grey with nickel, brown with manganese, pink to violet with gold, and greyish-white with platinnm. Mixtures of these substances produce intermediate shades. The black-burning of Indian goods is explained by Sarnow as follows : -When earthenware goods are polished by rubbing them, the surface of the clay is rendered more compact ; by subsequently placing the clay in a sooty atmosphere, and exposing it t o a temperature high enough t o expel the combined water, the pores produced are filled wlth coal.The latter cannot ignite in a reducing atmosphere, and becomes fixed in the pores as the clay shrinks. A shining mass is produced, which is so dense that it resists even the penetration of water. D. B. Ultramarine. By KNAPP (D;Y@. pdyt. J., 234, 47%--486) .-In the first part of his investigation of this subject (&id., 229, 69, 173), the author considered mainly the changes taking place during the formation of ultramarine, and its subsequent conversion into blue. The object of the present paper is to consider the cases, which, although not strictly connected with ultramarine, represent properties common to the same.These are well known, and the author merely mentions a few instances, which have not yet been noticed. Dressel found that nosean assumed a pure blue colour, when heated with coal. (Nosean is a mixture of haiiyne and sodalite.) During the fusion of borax with sodium sulphide, i.e., the yellow colouring of glass, it was noticed that after the addition of boracic acid to the fused mass, a black product was formed, which on continued heating assumed a blue colour. The same colour was produced when potassium thiocya- nate was fused, and also when sulphur was introduced into potassium cyanide and the mixture heated. The formation of blue with fused borax led to the following important deductions :-1. Silicic acid can be replaced by boracic acid, in order t o produce the blue.2. The borate gives a blue as stable in properties as the silicate. 3. The blue of the borate is not altered by fusion, its melting point being highConstituents. SiO, ................ A120,. ............... Fe,03 ............... CaO ................ MgO ................ K,O ................. RTa,O.. .............. co, ................ H,0 orgapic substance, Clay substance.. ...... Quartz .............. Pelepnr .............. Calcium carbonate .... 1.6.39 100 .o: 53.61 - 3 G * t i G - 9.73 - 0 - - ri i;l s 65.92 23 -32 0.69 trace 0 2.2 1 -4% 0.60 0 7 *24 99 37 - - - - - p- 46'13 64.25 38-17 21-46 0.89 0'54 0.94 2.38 0 36 trace } 2.16 { i::: 0 1.99 1 1 9 7 6-12 100.42 99.74 ~~ - - -- -INORGANIC CHEMISTRY. 157 enough to avoid the destruction of colour.4. Alumina is not abso- lutely requisite for developing the blue colour. Silica without alumina, and alumina without silica form the blue colour. Besides these, other bodies gave similar results, e.g., aluminium borate, calckm phosphate, and stannic oxide produce the blue colour. D. B. Erbium. By P. T. C L ~ E (Conzpt. rend., 89, 708-709).-This is an acknowledgment of Soret's claims to priority in the discovery pub- lished by the author (ibid., 15th September, 1879). He poiiits out that the substance called by him Iiolmiztrn is the same as that called z by Soret. L. T. 0's. Tungsten Bronze, By J. PHILIPF and P. SCHWEBEL (Be?-., 12, 2234-2236) .-Although tungsten bronze (the golden-yello w com- pound obtained by fusing acid sodium tungstate in a current of hydrogen) resists the action of acids and of alkalis, it is readily de- composed by an ammoniacal solution of silver nitrate.. By making use of this fact in analping the substance, the authors find that its composition is NaWO.?, instead of Na,WO, + W205, as stated by TN. c. FIT. Malaguti ( A m . Chin&. Yhys,, 60, 284). New Easic Salts of Mercuric Sulphide. By W. SPRING (Annalen, 199,116-12G).-The yellow amorphous substance, which is precipitated on the addition of mercurous nitrate to an aqueous solution of totrathionic acid (Wachenroder, AnualeN, 60, 190), has, after drying and treatment with carbon bisulphide, the composition Hg4S404. Its foTmation is due to the following reactions :- H,S40s + Hg,(N03), = HgsSaOs + 2HN0, 2116.,8,0, + 3H2O = Hg;PS,0* + 2H2SO4 + H,SOa + S.When perfectly free from te tratbionic acid, this substance undergoes no change on exposure to the light or to a temperature of 120". The amount of heat evolved on treating this body with sodium sulphide shows that it is not a mixture of mercuric sulphide and sulphate, but a definite compound, viz., tritlLiobasic wercuric sulphate. The salt is insoluble in water and in most acids. It is soluble in rcqucc regia and in a mixture of hydrochloric acid and bromine, and it is converted by the action of warm nitric acid into a white insoluble salt, mortothiobasic trim ercur ic suZp hate, HgS (Hg SO,) 3. Trithiobasic mercuric sulphate is decomposed by alkaline solutions, forming black mercuric sulphide. On boiling with barium nitrate, mercuric sulphide and barium sulphate are obtained.When the salt is boiled in water, sulphuric acid passes into solution and a dark yellow product remains, which has the composition (HgS),HgO. Trithio- basic mercriric oxide turns black, and evolves sulphuretted hydrogen when brought in contact with dilute hydrochloric acid. It is suggested that, for the purpose of classification, the basic mer- curic sulphates may be considered to be derived from the following types, in which the 0 or S is replaced by the group SO,.158 ABSTRACTS OF CHEMICAL PAPERS. Thiobasic. 0 xybasic. w. c. w. Oxidation of Gold by Galvanic Action. By BERTHELOT (Coin@. rend., 89, 6b3--684).-Grotthuss (An7b. Chim.. Phys., 58, 60) observed that a gold wire is dissolved when employed as the positive terminal of a circuit in sulphuric acid.The author confirms these results, and shows that under similar circumstances nitric acid also dissolves gold. This is due neither to ozone nor, as suggested by Chevreul, to persulphuric acid, for neither of them has any action on gold. L. T. (3’5.INORGANIC CHEMISTRY. 153Inorganic Chemist rg.Silicon Nitride. By P. SGH~~ZENBERGER (Compt. rend., 89, 644-646) .-The composition of the silicon nitrides discovered by Sainte-Claire Deville and Wohler, not having been experimentally determined,the author has sought to prove the existence of two compounds by thefollowing experiments :-By heating crystnllised silica with gas carbm in a blast furnace forsome time, a mass is obtained consisting of unaltered silica, a whitesubstance soluble in cold concentrated hydrofluoric acid without evolu-tion of gas, and a green substance which is insoluble in hydrofluoricacidand caustic alkalis, and, after successive treatment with hydrofluoricacid and dilute potash, is obtained as a green infusible powder : this isriot attacked by water or by solution of caustic alkalis, but i s dissolvedby potash a t a red heat with formation of potassium silicate andevolution of hydrogen and ammonia.The analyses agree with theformula (SiN),.The white substance soluble in hydroflnoric acid cannot be obtaineclin the pure state, but most probably it has the formula Si3N4 ; this isrendered probable by the fact that 011 heating (SiN), in a current of'chlorine, it loses 22 per cent.of its weight of silicon, and a white sub-stance, soluble in hydrofluoric acid, is, left, The equation, (SiN)4 +ClA = SiC1, + Si3N4, represents the loss of 22.4 per cent. of silicon.By passing ammonia gas into a flask containing silicon tetrachloride,a very light white powder is obtained soluble in water with separationof Si(H0)4; when heated in a current of hydrogen, amramium chlo-ride sublimes. The results of analyses compare fairly with thoserequired by the formula Si,N,,Cl,H. Its formation may be expressedthus: 8SiCl4 + 10NH8 = Si,N,,Cl,H + 29HC1, and its decomposi-tion by water, thus: Si8NloCl3H + 16H20 = 8Si02 + +3HC1. When heated to bright redness in a current of ammonia, awhite powder is obtained which, is not attacked by water, and onlyslightly soluble in alkalis; its formuTa is Si2N3H..These experimentsshow the existence of two silicon nitrides, one (SiN), correspondingto CN, the other probably of the formula SiJV,. L. T. 0'3.Action of Metallic Nitrates on Nitric Acid. By A. Dmm(Con2pi. rend., 89, 576-579) .-Ammonium nitrate dissolves readil2in fuming nitric acid, forming a, liquid which does not solidify at 5" ;below this temperature crystallisation takes place, when the ther-mometer immediately rises to 18". The crystals melt regularly a t 18",but generally exhibit the phenomenon of surfusion, in which canditioi154 ABSTRACTS OF CHEMICAL PAPERS.a crystal of ammonium nitrate will not determine solidification. Thecomposition of the salt is NH4N0,.2HN0, ; when melted the liquidclosely resembles nitric acid, but does not fume in the air ; it is capableof dissolving a large quantity of ammonium nitrate to form the saltNH4N03.HN03, melting at 9" ; this latter remains liquid at 4", and acrystal of the di-acid salt does not induce crystallisation. The samecompounds are produced when dry ammonium nitrate is placed in anatmosphere containing nitric acid vapour.Potassium nitrate, in like manner, produces the salt KN03.2HN0,,melting at -3" ; when carefully cooled the whole will remain liquidat -lo", bnt the temperature rises to -3" its soon as crystallisationsets in.The monacid salt, KNO,.HNO,, could not be prepared.Thallium and rubidium nitrates also combine with nitric acid to formthe salts T1N O3.3HNO3 and RbN0,.5MN03 respectively ; theirmelting points are not given, but in general properties they resemblet lie potassium and ammonium salts previously described.J. W.Action of Metallic Nitrates on Nitric Acid. By A. DITTE(Cowpt. rend., 89, 641--643).-The author has shown (see previousabstract) that aertain metallic nitrates combine with nitric acid toform acid salts. There are, however, other salts which behave dif-ferently. Magnesium nitrate, M,q(NO,),GH,O, for example, whichcontains 6 mols. of water of crystallisation, melts and begins todecompose when heated ; under certain circumstances, however, whenheated, it yields a syrnpy mass, which suddenly solidifies, evolving alarge amount of heat; it consists of Mg(N03)23H20. It is decom-posed by heat, leaving a residue, from which is separated by water anitrate having the composition MgO.Mg(NO,), ; this decomposeswithout me1 ting, leaving magnesia.I f the decomposition of the neutra'l nitrate be stopped the momentnitric oxide begins to be evolved, a deliqaescent mass is obtained,which dissolves in nitric acid, and on cooling deposits transparentprisms, consisting of Mg(N03)2.2Hz0.The basic nitrate, when treated with nitric acid,. yields the neutralsalt, but owing to the quantity of water set free it is impossible toobtain acid salts ; the aukhor therefore proposes to saturate a solutionof the neutral salt with nitric anhydride, which will combine with thewater, and thus a solution of the anhydrous salt in nitric acid will beobtained.To this group besides magnesium nitrate belong the nitrates ofmanganese, aluminium, zinc, uranium, copper, and iron, which givethe following salts :-Mg(NO,),.SH,O 2[Mn(N0,),].5H20 (UOz)(N03)z.3H20Mg (NO,) 2.2H,O Mn(NO,),.H,O Cu(N0,),.3H202 [ Zn .3H20 A123 ( IYO3)2.4H2O Pe,3 ( NO,) 2. 6Hz0.Of these, the nitrates of manganese, aluminium, and iron leave aresidue of oxide when heated ; the others yield basic nitrates.Secondly, there exists a class of nitrates which are insoluble, oronly sparingly soluble in nitric acid, to which belong the nitrates oIN ORGANIC CHEMISTRY. 155sodium, lithium, calcium, strontinm, barium, nickel, cobalt, bismuth,cadmium, mercury, and silver.Contributions to our Knowledge of Clays and EarthenwareGoods. (Dingl. polyt.J., 234, 465--473).-Bischof mentions a newsource of bauxite at Kleinsteinheim, in the Offenbach district. Thefollowing is the composition :-L. T. 0’s.Al20,. SiO,. Fe,O,. Loss on ignition.56-02 10.9 7 6-19 26-42 = 99.60Leger gives the following analyses (p. 156) of clay substances usedfor the preparation of fine white goods. A and B are French goods,C and D are Belgian goods, the former being used for fine goods, thelatter for ordinary ; and E is German.Lindhorst states that, besides lime and the flue gases, the aluminaand alkalis contained in clay also influence the coloration of clay;whereas gypsum is inactive. Experiments were made with variousoxides, the colour prcduced being red with iron, green with chromium,grey with copper, white with zinc, yellowish-grey with nickel, brownwith manganese, pink to violet with gold, and greyish-white withplatinnm.Mixtures of these substances produce intermediate shades.The black-burning of Indian goods is explained by Sarnow as follows :-When earthenware goods are polished by rubbing them, the surfaceof the clay is rendered more compact ; by subsequently placing theclay in a sooty atmosphere, and exposing it t o a temperature highenough t o expel the combined water, the pores produced are filled wlthcoal. The latter cannot ignite in a reducing atmosphere, and becomesfixed in the pores as the clay shrinks. A shining mass is produced,which is so dense that it resists even the penetration of water.D. B.Ultramarine. By KNAPP (D;Y@.pdyt. J., 234, 47%--486) .-Inthe first part of his investigation of this subject (&id., 229, 69, 173),the author considered mainly the changes taking place during theformation of ultramarine, and its subsequent conversion into blue.The object of the present paper is to consider the cases, which, althoughnot strictly connected with ultramarine, represent properties commonto the same. These are well known, and the author merely mentionsa few instances, which have not yet been noticed.Dressel found that nosean assumed a pure blue colour, when heatedwith coal. (Nosean is a mixture of haiiyne and sodalite.) During thefusion of borax with sodium sulphide, i.e., the yellow colouring of glass,it was noticed that after the addition of boracic acid to the fused mass,a black product was formed, which on continued heating assumed ablue colour.The same colour was produced when potassium thiocya-nate was fused, and also when sulphur was introduced into potassiumcyanide and the mixture heated. The formation of blue with fusedborax led to the following important deductions :-1. Silicic acid canbe replaced by boracic acid, in order t o produce the blue. 2. Theborate gives a blue as stable in properties as the silicate. 3. The blueof the borate is not altered by fusion, its melting point being higConstituents.SiO, ................A120,. ...............Fe,03 ...............CaO ................MgO ................K,O .................RTa,O.. ..............co, ................H,0 orgapic substance,Clay substance........Quartz ..............Pelepnr ..............Calcium carbonate ....1.6.39 100 .o:53.61 -3 G * t i G -9.73 -0 --rii;l s65.9223 -320.69trace0 2.21 -4%0.6007 *2499 37 ---- INORGANIC CHEMISTRY. 157enough to avoid the destruction of colour. 4. Alumina is not abso-lutely requisite for developing the blue colour. Silica without alumina,and alumina without silica form the blue colour. Besides these, otherbodies gave similar results, e.g., aluminium borate, calckm phosphate,and stannic oxide produce the blue colour. D. B.Erbium. By P. T. C L ~ E (Conzpt. rend., 89, 708-709).-This isan acknowledgment of Soret's claims to priority in the discovery pub-lished by the author (ibid., 15th September, 1879).He poiiits outthat the substance called by him Iiolmiztrn is the same as that called zby Soret. L. T. 0's.Tungsten Bronze, By J. PHILIPF and P. SCHWEBEL (Be?-., 12,2234-2236) .-Although tungsten bronze (the golden-yello w com-pound obtained by fusing acid sodium tungstate in a current ofhydrogen) resists the action of acids and of alkalis, it is readily de-composed by an ammoniacal solution of silver nitrate. . By makinguse of this fact in analping the substance, the authors find that itscomposition is NaWO.?, instead of Na,WO, + W205, as stated byTN. c. FIT. Malaguti ( A m . Chin&. Yhys,, 60, 284).New Easic Salts of Mercuric Sulphide. By W. SPRING(Annalen, 199,116-12G).-The yellow amorphous substance, whichis precipitated on the addition of mercurous nitrate to an aqueoussolution of totrathionic acid (Wachenroder, AnualeN, 60, 190), has,after drying and treatment with carbon bisulphide, the compositionHg4S404.Its foTmation is due to the following reactions :-H,S40s + Hg,(N03), = HgsSaOs + 2HN0,2116.,8,0, + 3H2O = Hg;PS,0* + 2H2SO4 + H,SOa + S.When perfectly free from te tratbionic acid, this substance undergoesno change on exposure to the light or to a temperature of 120". Theamount of heat evolved on treating this body with sodium sulphideshows that it is not a mixture of mercuric sulphide and sulphate, buta definite compound, viz., tritlLiobasic wercuric sulphate. The salt isinsoluble in water and in most acids. It is soluble in rcqucc regia andin a mixture of hydrochloric acid and bromine, and it is converted bythe action of warm nitric acid into a white insoluble salt, mortothiobasictrim ercur ic suZp hate, HgS (Hg SO,) 3.Trithiobasic mercuric sulphate is decomposed by alkaline solutions,forming black mercuric sulphide. On boiling with barium nitrate,mercuric sulphide and barium sulphate are obtained. When the saltis boiled in water, sulphuric acid passes into solution and a dark yellowproduct remains, which has the composition (HgS),HgO. Trithio-basic mercriric oxide turns black, and evolves sulphuretted hydrogenwhen brought in contact with dilute hydrochloric acid.It is suggested that, for the purpose of classification, the basic mer-curic sulphates may be considered to be derived from the followingtypes, in which the 0 or S is replaced by the group SO,158 ABSTRACTS OF CHEMICAL PAPERS.Thiobasic. 0 xybasic.w. c. w.Oxidation of Gold by Galvanic Action. By BERTHELOT(Coin@. rend., 89, 6b3--684).-Grotthuss (An7b. Chim.. Phys., 58, 60)observed that a gold wire is dissolved when employed as the positiveterminal of a circuit in sulphuric acid. The author confirms theseresults, and shows that under similar circumstances nitric acid alsodissolves gold. This is due neither to ozone nor, as suggested byChevreul, to persulphuric acid, for neither of them has any action ongold. L. T. (3’5

ISSN:0368-1769    

DOI:10.1039/CA8803800153

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

158 ABSTRACTS OF CHEMICAL PAPERS. Organic Chemistry. Normal Paraffins. By C. SCHORLEMMER (Annulen, 199, 139- 144) .-By chlorinating pure hexane (fiwm secondary hexyl iodide prepared by the action of hydriodic acid on mannitol), a mixture of monochlorides is obtained (b. p. 121-134"), which yields hexylene and ethyl-hexyl ethers on decomposition with alcoholic potash. The olefine combines with hydrochloric acid at the ordinary temperature, forming a chloride which boils at 1 2 4 O without decomposition ; whilst, alecording to Morgan (Allen., 161, 275), the corresponding chloride from petroleum boils a t 116' with decomposition. The acetate from t'he chloride yields an alcohol boiling a t 130-135" and another at 135-140", which split up on oxidation into acetic and butyric acids ; propionic acid could not be detected.The fact that the paraffins from petroleum have a higher specific gravity than those from other sources, and that the specific gravity diminishes when a portion of the hydrocarbon is oxidised by nitric acid, indicates that the normal paraffins from petroleum probably con- sist of a comphated mixture of homologous and isomeric hydro- carbons. w. c. w. Constitution of Dibrom-ethylene. By E. DEMOLE (Ber., 12, 2245--2247).-3y the action of aluminium chloride on a solution of dibromethylene in benzene, zLnsymmetlricd d@henylethyZene, CH, CPh,, b. p. 174-176", and a liquid boiling above 350", are formed. The production of the former hydrocarbon &ows that dibromethylene is also unsymmetrical, Br,C CH2. This result agreea with the con- elusions arrived a t by Anschiita (Ber., 12, 2073).w. c. w. Glucose. By PRANCHIMONT (Con@. rend., 89, 713-714).-1n "pplying Liebermann's method for the preparation of the acetyl deri- vatives of the phenols to the carbohydrates, the author obtained withORGANIC CHEMISTRY. 159 glucose a crystalline acetyl compound soluble in benzene, alcohol, acetic anhydride, and acetic acid; sparingly soluble in ether and in petroleum spirit, and insoluble in water. It is octo-acetyl diglucose, C~zHl103(CzH302)8, (m. p. 100’). It has a bitter taste, is dextrorota- tory, and unlike glucose it is oxidised only with great difficulty; boiling chromic mixture does not attack it, and phosphorus pentn- chloride acts on it but slowly. L. T. 0’s. Cellulose. By FRANCHIMONT (Compt. rend., 89, 711-712) .--Not being able to obtain any reaction between cellulose, acetic anhydride, and sodium acetate, the author substiOuted concentrated sulphuric acid for the last substance, when a violent reaction set in, and the cellu- lose was dissolved, the solution becoming coloured.On adding water to the solution, a white precipitate is formed, which is filtered and washed with cold alcohol until the washings are no longer coloured. The residue is then dissolved in hot alcohol, arid from the solution microscopic needles or plates separate out (m. p. Zl2O). These are soluble in benzene, sparingly soluble in cold alcohol, and insoluble in ether. It has the empirical formula C40H54027, and appears to be a derivative of triglucose, containing the acetj-1-group eleven times.An acetyl-derivative is also obtained by substituting zinc chloride for sul- phuric acid. This corresponds with a triacetyl-compound, but it is more probable that it is ;I saturated acetyl-derivative of n-molecules of glucose -(n-l)OH?. It has not yet been identified with Schutzen- berger’s triacetyl-cellulose. The author has applied the same reaction to other carbohydrates. L. T. 0’s. Commercial Trimethylamine. By 131. DUVILLIER and A. BUI- SINE (Compt. rend., 89, 709--711).-To detect the presence of ethyl- amine in commercial trimethylanline, which escaped tlhe authors’ notice in their previous research (this Journal, Abst,., 1879, 912 j, from being present only in very small quantity (2 per cent.) ; the mother-liquors from the purification of the oxamides are decomposed with potash and the bases converted into sulphates ; these are treated with absolute alcohol, which dissolves, all with the exception of mouomethylamine sulphate.The soluble sulphates are distilled with potash, the bases collected over absolute alcohol, and the solutions treated with oxalic ether. The oxamic ethers are decomposed with lime, when crystals of calcium monethyloxamate separate out. This is the sixth base found in commercial trimethylamine. The authors also reply to Vincent’s remarks (this Journal, Abst., 1879, 913) on their previous publication. L. T. 0’s. Ethylamine. By H. KOHLEE (Ber., 12, 2208--221l).-When a solution of mercuric chloride is boiled with ethylanline and the hot inixture filtered, the filtrate deposits on cooling white pearly scales, which have the composition C1.HgNHEt.The insoluble precipitate which is formed at the same time is converted by boiling with water into yellow oxymercurethglamine chloride, C1Hg.O.HgNHEt. Hence it appears that the action of ethylamine on mercuric chloride160 ABSTRACTS OF CHEMICAL PAPERS. is analogous to that of ammonia ; the product, however, is much more readily oxidisable than is the case with white precipitate. w. c. w. Action of Potassiam Dichromate o n Acetic Acid and Potassium Acetate. By I;. DANESI (Gazzetta, 9, 4120-421).-The author finds that, when acetic acid is boiled with a solution of potas- sium dichromate, the acid is oxidised at the expense of the chromic acid, and carbonic anhydride is produced.In one experiment, the author employed equal weights of potassium. dichrornate and acetic acid ; the latter diluted with. water, but how much is. not skated. The dichromate acts on potassinm acetate in a similar manner, the chromic acid liberating ace& acid, which is subsequemtly onidised. C. E. G. Action of Hypochlorous Acid on Acrylic. Acid. By P. MEL~KOFF (Be,.., 12, 222 7-2228),-The monochlorolactic acid ob- tained by the action of hypochlorous acid 00 a dilute aqueous solution of acrylic acid and the acid formed by treating glyceric acid with hydrochloric acid (Be?-., 12, 178, this Journal, Abst., 1879, 521) are shown to be identical, by a comparison of their amido-derivatives and of their barium and tin salts (both of which are amorphous). The amido-acid, which is produced by heating ethyl chlorolactate and ammonia a t 120", crptallises in long, thin prisms, and also in four- sided plates.It resembles serine in most of its properties, but is somewhat less soluble in water. ?V. c. w. Acetylenedicarboxylic Acid. By E. BANDROWSKI (Rer., 12, 2212-22l6) .--Copper acetylenedicarboxylate, CuC404 + 3H20, forms glistening blue scales, which are sparingly soluble in cold water, and are decomposed by hob water. This salt slowly undergoes decom- position at the ordinary temperature. The silver salt dissolves in strong nitric acid, but the solution rapidly becomes turbid, owing to the deposition of silver cyanide. Acetylenedicarboxylic acid is converted into succinic acid by the action of nascent hydrogen, When heated with water, it splits up according to the equation C4H,0a = GO2 + C,H,O,.The new acid melts at 145", and is soluble in water, alcohol, and ether. It is crys- talline, and forms well crystallised salts. When bromine is added to an aqueous solution of acetylenedicar- boxy lic acid, the dibromo-acid, C4H,Br2O4, is formed, together with small quantities of bromoform, and a crystalline compound of unknown composition. DibromacetyZ~edicarboxylic acid is deposited from its aqueous solution in transparent crystals, which dissolve freely in ether and in alcohol. The silver salt, C4Br204Ae + iH,O, crystallises in small needles, whi'ch explode when heated. The lead salt, C4Br204Pb, also forms needles which are soluble in water. The acid begins to blacken ttt 217", and melts with decomposition at 220".On distillation it yields hydrobromic acid and KekulB's dibroniomaleic acid (m. p. 108") (AnnaZen, 130, 3), hence it may be regarded as dibromofumaric acid.ORGANIC CHEMISTRY. 161 Attempts to prepare tetrabromosuccinic acid by the action of bro- Carbamido-palladions Chloride, or Palladoso-uramonium Chloride, By E. DRECHSEL (% pr. Chem., 20, 469--475).--This substance is obtained by mixing solutions of palladious chloride an2 urea. It forms a brownish crystalline powder, sparingly soluble in water, and has the formula PdCI2.2CN2H,O = fd[NH,(CO.NH,)Cl]?. As it is nearly insolable in water, attempts were made to found a method of estimating urea and palladium by its formation, but with no success in the former, and unsatisfactory results in the latter case.When boiled with water, it undergoes the following decomposition :- mine on acetylenedicarboxylic acid were unsnccessful. w. c. w. PdC1*.2NH,(CO.NH,) + 2HZO = PdC12.2NHS + 2NH3 + 2C0,. When evaporated with excess of pall.adious chloride, the urea appears Some to be paztially decomposed with formation of free cyanic acid. urea combining with the cyanic acid, biuret is produced :- NH2.CONHz + HCNO = (NH,.CO)ZNH. An attempt was made to prepare hydantoic acid by evaporat,ing glycocine with carbamido-palladious chloride, but wilthout success. Besides small quantities of biuret, urea hydrochloride, and palla- dium bases, palladious amidoaaetate was formod. No hydantoic acid could be detected. W. R. Relative Displaceabili ty of Bromine in the Monobromo- benzyl Bromides.By C. L. JACKSON (Ber., 12, 2243-2245).- When sodium acetate acts on the ortho-, meta-, and para-monobromo- benzyl bromides under bimilar conditions, t'he bromine replaced in these compounds in a given time is in the r d i o .52 : 7/ : 100. w . c. w. Tolylphenol. By G. MAZZARB (Qazzetta, 9, 421-423) .-The xylene employed for the preparation of the tolyl chloride is obtained from commercial xylene by fractional distillation, and agitating the portion boiling at 136-139" with concentyated sulphuric acid. On redistilling the undissolved hydrocarbon, it yields a fraction boiling at 137-139", which is treated with chlorine while boiling to convert it into tolyl chloride (b. p. 290-195"). When equal parts of tolyl chloride and phenol are heated with zinc filings, a violent reaction takes place, with evolution of hydrochloric acid and formation of tolyl- phenol, OH.CsH4.CliH4.CHzMe, which may be separated from the pro- duct by fractional distillation.It is a, colourless liquid of feeble odour, boiling a t 250-255" under a pressure of 8-10 mm. It is in- soluble in water, but dissolves in alcohol, ether, chloroform, and alkaline Bolutions. It gives no coloration with ferric salts. When tolylphenol is treated with acetic chloride, i t yields an acetate, BcO. C,H,. C6H4. CH2Me. This is a colourless liquid, boiling at 2-50" under a, pressure of 8 mm., and decomposingon exposure t o moist air, with formation of tolyl- phenol and acetic acid. C. E. G.162 ABSTRACTS OF CHEMICAL PAPERS. Action of Nitrosodimethylaniline on Phenols which do not contain the Methyl Group.By R. MELDOLA (Ber., 12, 2065- 2066) .-When nitrosodimethylaniline hydrochloride (1 mol.) is slowly added to a solution of &naphthol (1 mol.) in glacial acetic acid at 110", a blue mass is produced. This is washed with water, dissolved in hot alcohol, and mixed with hydrochloric acid. On cooling, bronze- coloured needles are deposited, which dissolve in alcohol and in water, forming a bluish-violet solution. Similar compounds are obtained by the action of nitrosodimethyl- Action of Ferric Chloride on Orthodiamidobensene. By C. RUDOLPH (BRT., 12, 2211-221 2).-By the action of ferric chloride on orthodiamidobenzene, a hydrochloride is formed which has the com- position C,1H,8N60.2HC1.511~0. The base combines with snlphuric acid, yielding several different salts.The formula of the neutral sul- aniline on resorcinol and on a-naphthol. w. c. w. phate is C,4H18N,0.HZS0,.3H,0. w. c. w. Tolylenedimines. By R. NIETZKI (Bm., 12, 2236-2238) .- Paradiamidotoluene (m. p. 64") from nitrosrthotoluidine (m. p. 130") is identical with the tolylenediamine from amidoazotoIuene. The para-diarnines can be distinguished from the ortho- and mets-diamines by their forming quinones on oxidation with ferric chloride, whilst the ortho-compounds yield a coloured crystslline precipitate having a metallic lustre. When treatedwith nitrous acid, para-diarnines form diazo-compounds, whilst the meta-derivatives yield colouring matters analogous to phenylene brown, and the ortho-diamines g i n colourless stable com- w.C. w. Occurrence of Paraleucaniline in the Manufacture of Rosaniline. By C. GRAEBE ( B e r . , 12, 2241-2242) .-Considerable quantities of paraleucaniline are found in the rosaniline manufacture in the mother liquors from which the chrysaniline has been precipi- tated. Whether lencaniline is the first product of the reaction of arsenic acid on a mixture of aniline and tohidine (the cnlouring matters being afterwards formed by oxidation), or whether it owes its origin to the reduction of pararosaniline is uneertain, but the author w. c. w. Dirnethylphenyl Glycocine or Phenylbetayne. By J. ZIMRIER- pounds containing nitrogen. considers the first hypothesis the more probable. MANN (Rer., 12, 2206-2207) .-Plienylbetaine hydrochloride, formed by digesting an ethereal solution of dimethylaniline (2 mols.) with monochloracetic acid (1 mol.) can be obtained in white needles by adding ether t o the concentrated aqueous solution of the compound.The platinochloride forms beautiful dark red crystals. C J3I,OJT.H C1, CH2\ PhenyZbetaBne ethylchloride, I )N. (Me),PhEtCl, is deposited in coz hygroscopic crrstals when a mixture of ethyl monochloracetate andORGANIC CHEMISTRY. 163 dimethylaniline is heated at 100" for four hours. On treatment with silver oxide, the chlorine is eliminated from this substance, and a powerful base is produced, which is very deliquescent, and does not Hydroxyazobenzene and Paramethylhydroxyazobenzene. By G. MAZZARA (Gazzetta, 9, 424-425) .-Zydroxyazobe?izene or phend- diazobenzene, C12H,,N20, has already been obtained by Griess (Annalen, 137, 841, and by Kekulb and Higed (Ber., 4, 233). The author finds that the most convenient mode of preparation is to dissolve 3 parts of potassium nitrite in 400 of water, and pour in a solution of 2 parts of aniline nitrite and 2 of pbenol in 200 of water.The solution soon becomes turbid and deposits the azo-compound, which should be collected after 24 hours, dissolved in dilute ammonia to separate resin, and the filtered solution precipitated with hydrochloric acid. After recrystallisation from boiling dilute alcohol the substance melts at 148-154'. appear to form crystalline salts. w. c. w. Paramethy lhydyoxybenzene or Paracyesoldiazobenzene, CsH,.N : W.C6H3Me.0H, may be prepared in a similar manner, substituting pure paracresol for phenol. The product is purified from an oily substance by repeated crystallisation from boiling alcohol.It forms lustrous red crystals (m. p. 108-109") which are but little soluble in cold and only mode- rately soluble in hot alcohol. I t is soluble in ether, in alcohol, and in alkaline solutions. C. E. G. Cymenecarboxylic Acid. By E. PATERNZ) and P. SPICA (Gaz- zetta, 9, 400).-1t has been shown (Gaz., 5, 30) that when sodium cymenesulphate is distilled with potassium cyanide, an oil is produced which may be converted into the amide C6H,Me(C3H7).CONI'I, (m. p. 138-139') by the action of alcoholic potash. Although this com- pound resists the action of alcoholic potash in a remarkable degree, i t splits up when fused with potash, yielding an acid of the formula C6H,Me(C3H,) .COOH, crystallising in slender needles (m.p. 63") and isomeric with Rossi's homocuminic acid (m. p. 52"). The amide is converted into the acid much more readily by heating it with concen- trated hydrochloric acid at 180" than by fusion with potash. The authors have endeavoured to prepare cymenecarboxylic acid by other methods, such as fusing the cymenesulphate with sodium formate, and by the action of sodium and carbonic anhydride on bromocymene, but without any satisfactory result. By G. MAZZARA (Gaxzetta, 9, 425- 428) .-The metanitrocinnamic acid from which the amido-acid was obtained was prepared according to Schiff's method by heating nitro- benzoic aldehyde with acetic aldehyde and sodium acetate. On re- ducing the nitro-group in the acid by boiling it with tin and hydro- chloric acid, and subsequently removing the tin by means of hydrogen sulphide, the metamidocinnnmic ucid hydrochloride, C.E. G. Metamidocinnamic Acid. HCl.NHz.C,H,.CH : CH.COOH,164 ABSTRACTS OF CHEMICAL PAPERS. was obtaineii in thin plates, permanent in the air and soluble in hot alcohol, from which it crystallises in needles. The amido-acid sepa- rated from the copper salt by hydrogen sulphide was very unstable. Attempts were made to oxidise the amido-acid with nitrous acid, so as to obtain the corresponding metahydroxycinnamic acid, which with cumaric and paracumaric acids would complete the series of the three possible hydroxycinnamic acids. It was found, however, that the action went much further, metahydroxybenzoic acid, C6H,(OH).COOH (m.p. 196-197") being produced. By A. OGLIALORO (Gazzetta, 9, 428--432).-0n heating 20 parts of salicylaldehyde with 28 of dry sodium alphatoluate and '70 of acetic anhydride a t 150" for 8 hours, a red-brown crystalline mass is obtained which is boiled with water for some time and then allowed to cool. The insoluble portion, when treated with a hot solution of sodium carbonate, partly dissolves, and on acidifping the liquid, acety lpheity lcoumnric acid, C1,H140i, is preci- pitated in the crystalline state. The portion remaining undissolved, which is the chief product of the reaction, is impure phenylcou- marin. Acetyl phenylcoumaric acid, when purified by crystallisation from boiling water, in which it is moderately soluble, forms long, white, very slender needles.It is soluble in alcohol and in ether, but, only sparingly so in cold water. When heated, it begins to soften and give off gas a t 170", but a t 180" it fuses to a transparent liquid; if after being allowed to cool it is again heated, it melts at 130". From this the author is inclined to believe that when the acid is heated, it loses acetic acid and is converted into phenylcoumarin. The silver met& pheny Zcoum nrate, CliHIY04Ag, obtained by precipitating the sodium salt with silver nitrate, crystallises from boilicg water in tufts of slender, colourless needles, which become yellowish-red on keeping. The pheny Zcournarin, C,,HI,O2, after purification by crystallisation from boiling alcohol, with addifion of animal charcoal, forms large transparent colourless prisms (m.p. 139-140"), soluble in ether. It is odourless. Like coumsrin, it dissolves when boiled with potash solution, and is precipitated unchanged on adding an acid. When treated with sodium-amalgam in dilute alcoholic solution, phenyl- coumarin is converted into a new acid, which may be isolated by acidulating the solution and agitating it with ether. It crystallises in prisms (m. p. l'LO"), and is, perhaps, phenylmelilotic acid, but has not as yet been further examined. From its mode of formation the author- believes that acetylphenyl- coumaric acid has the rational formula AcO.C,HL.CB: C'Ph.COOH. C. E. G. Synthesis of Phenylcuumarin. whilst phenylcoumarin, if regarded as t'he anhydride of phenylcournaric /Ce,H4.CH C.E. G. acid, would be 0 II \co . C P i Pittical and Eupittonic Acid. By A. W. HOFMAR" (Bet-. 12, 2216--2222).--The formation of eupittonic acid is analogous to that of pararosaniline, as is shown by the following equations :-ORGANIC: CHEMISTRY. 165 2CJC7N + C7H9N = CigHi,Ns + H, 2C8HioO3 + CgHi?O, = C25H2609 + HZ Dirnethyl- Dimethyl- Eupittonic pyrogallate. methylpyro- acid. gallate. The sodium and barium salts of this acid have the composition Cz5H,,Na?O9 and C,,H,,Ra09 respectively. The diacetyl derivative, C25H2PA~209, is best prepared by the action of acetic anhydride on an alcoholic solution of sodium eupittonate ; it crystallises in yellow needles, which melt a t 265" and decompose with evolution of violet vapours. The crystals are soluble in alcohol and are decomposed by alkalis and by acids.The yellow amorphous substance (Ber.,.12,1371) obtained as a bye- product in the preparation of diacetyleupittonic acid by heating a mixture of acetic anhydride and eupittonic acid is insoluble in water, but dissolves freely in alcohol, ether, and acetic acid. It is also dis- solved by alkalis and by strong sulphuric acid ; on neutralising the alkaline, or diluting the acid solutions, the original substance is repre- cipitated. Dibenzoyleupittonic acid, Cz5Hz4Bz2O9, remains as a yellow powder when a mixture of benzoic anhydride and sodium eupittonate is fused and the product extracted with alcohol. The compound dissolves in chloroform, and may be obtained in golden needles (m. p. 232") by adding alcohol to the chloroform solution.By the action of benzoic chloride on eupittonic acid, a white crystalline powder is obtained. MetliyZ eupittonate prepared by the action of methyl iodide on sodium eupittonate is deposited from alcohol in golden needles (m. p. 242"). The ethyl salt (m. p. 202") resembles tbe preceding compound in its mode of preparation and in its properties. When a concentrated alcoholic solution of iodine is added to a cold' acetic acid solution of eupittonic acid, brown glistening prisms are deposited which have the composition C25H:26091p. This compound is decomposed by heat. By the action of strong alkalis and acids, eupit- tonic acid is regenerated. On treating an alcoholic solution of the iodine-compound with sulphurous acid, hydriodic, sulphuric, and eupit- tonic acids are formed, but on heating the liquid, the original su bstnnce is again formed, since the sulphurous acid decomposes the hydriodic mid with formation of iodine, which a t once combines with the eupit- tonic acid.Eupittonic acid is decomposed by the action of water at 270°, with formation of dimethyl pyrogallate and a crystalline body w.hich is soluble in alcohol, ammonia, and soda. The dimethyl ether of methyl pyrogallol is not produced by this reaction. Eupittonic triamine undergoes no change on boiling with aniline. When heated at 250" with water, it splits up into ammonia and eupittonic acid. Hydroxylation by Direct Oxidation. w. c . w. By R. MEYER and A. BAUR (Bey., 12, 2238-2241) .-The following experiments support the hypothesis that it is only atoms of hydrogen occupying a ter- tiary position which are capable of uudergoiug direct oxidation to hydroxy1:- VOL.XXXVIII. 12166 ABSTRACTS OF CHEMICAL PAPERS. Normal propylhenzenesulphonic acid is oxidised to carbonic anhy- dride and potassium sulphate by the action of potassium permanga- nate in an aniline solution, whilst, under similar conditions, cumene- sulphonic acid is converted into hydroxypropylbenzenesulphonic acid, By treating the product of the action of phosphorus pentachloride CsHa(S0,H) C3Hs.OH. on this acid with ammonia, propenylbenzenesulphamide, C,H,(SO,.NH,)C,H,, is'formed. bromine. w. c. w. This sulphamide melts at 152", and combines readily with Cumenesulphonic Acids and a New Cumol. By P. SPICA (Gazzetta, 9, 433-444).-&1 observers who have hitherto studied the action of sulphuric acid on cumene are agreed that only one sul- phonic acid is formed; although there is great discrepancy in the description of the salts which this acid forms, and especially with regard to the amount oi' water of crystallisation they contain.As, how- ever, it has been show by Patemi, and Spica (Guz., 7, 21, and this Journal, 1877,1, 707) that normal propylbenzene forms two sulphonic acids, and analogous results have been obtained with butylbenzene, &c., it seemed highly improbable that cumene (isopropylbenzene) should give such a different result, especially as the author had observed, in the preparation of cumol from the crude cumenesulphate, that a small portion of the product passed over below 220°, and that this did not completely solidify a t a low temperature.The cumene employed in the research was prepared by distilling cumic acid with lime and iron filings and rectifying over sodium. The pure cumene, boiling at 150-155", was roiiverted into the sul- phonic acid by agitating it with twice its weight of a mixture of equal parts of ordinary and of fuming sulphuric acid, the action being com- pleted by heating it a t 100" for a few minutes. The sulphonic acid was diluted, neutralised with pure barium carbonate, and the product submitted to a careful fractional cry stallisation. By this means the author succeeded in isolating two barium cumenesulphates ; the one which is formed in larger quantity crystallises in micaceous scales, somewhat unctuous to the touch, and containing 1 mol- H,O, thus confirming the observations of Fittig, Schaeffer, and Koenig ; the other, formed only in small quantity, remains in the mother-liquors from the crystallisation of the first salt, being much more soluble.It crystal- lises in microscopic nodules, and contains 3H20 or 3&H20, which can- not be driven off completely without decomposing the salt. The cor- responding lead salts are very similar, containing 1 mol. HzO and 3 mols. H,O respectively. By treating the sodium salts with phos- phorus pentachloride and converting the chlorides thus formed into the amides by the action of alcoholic ammonia, two sulphamides are obtained corresponding with the two barium cumenesulphates. The one from the less soluble barium salt is a solid substance which, by crystallisation from dilute alcohol, may be separated into two aefinite compounds, both containing sulphur and nitrogen, and having the for- mula C6H4(C3H7).S0& Elz.The less soluble compound which occursOROANIC CHEMISTRY. 167 in largest quant'ity forms white micaceous scales (m. p. l07"), very soluble in alcohol, soluble also in boiling sodium carbonate solution without altzration ; t b more soluble compound obtained from the mother-liquors of t h e firsb is relatively small in quantity and crys- tallises in white scales (m. p. 96"). The sulphamide corresponding with the barium salt with 3E20 is a brown oily liquid which could not be purified, but the author believes it to be identical with the crys- talline sulphamide mentioned above as melting at 96".The aulpha- mide (m. p. 107"), when oxidised by fusion with potash, appears to yield a mixture of salicylic and parahydroxybenzoic acids, whilst the oily sulphamid'e gives a small quantity of a very impure acid, melting between 150" and 170". CumoZ, C6H4(CsH7).OH. -The crystallisable cum01 (m. p. 61') ob- tained from the cumenesulphonic acid formed in largest quantity has already been described by Patelm6 and the author. The small quan- tity of the sodium salt of the second sulphonic acid at the author's disposal yielded about 5 grams of a new phenol by fasion with potash in the ordinary way. This new cumol is an almost colourless liquid, and boils at 218.5" (cor.) under a pressure of 756.18 mm. It does not solidify when cooled with ice and salt.It is slighhly soluble in water, and the solution is coloured violet by ferric salts. In order to ascertain the constitution of the two cumols, they were converted into bhe corresponding ethyl ethers in Ohe usual way and then oxidised with chromic mixture. The ethylcwnzol, CgH,,.OE t, from the solid cumol (m. p. 61") is a colourless, mobile liquid (b. p. 220' cor. a t 757 mm.) and sp. gr. a t 0" = 0.943T7, at 100" = 086369. By oxidation it yields paraethoxybenzoic acid (m. p. 194-195"). The ethylcumol from the liquid ciimol boils at 213" (uncor.), and on oxidation gives an oily acid soluble in alcohol and in ether, besides a small quantity of an acid melting R t 194". Ethysalicylic acid melts at 19.5" C.. From these results it would seem that the solid cumol is yaraisopropylplienoE, arid the liquid cum01 orthoisopro~)2J~henoZ. It is evident also that the perfect separation of the isomeric barium cumene- sulphonates cannot; be effected without great difficulty.(2. E. G. Empirical Formula of Skatole. By M. NENCEI (J. pr. Chern., 20, 466-469) .-This product is the result of long putrefaction of animal matter, and its formation is subsequent to that of indole and phenol. The author prepared it by the putrefaction of pancreas and muscle for five months. The putrefied niass was acidified with acetic acid and distilled, and the skatole, which volatilised with water-vapour, was separated from the distillate by acidifying it with hydrochloric acid and adding picric acid. On analysis, it gave numbers agreeing with the formula CgHgN, and its picric derivative has the formula CgH,N.C6H2(N0,),0H. The author throws out the suggestion that skatole is methylindole. W. R. Action of Chlo.rine on Naphthalene-a-sulphonic Chloride : .,-Trichloronaphthalene. By 0. WIDMANN (Ber 12, 2228--CL231 j .- The tetrachloride of the a-suZphmic chloride, (C~~H,Cl,SO,Cl)CI,, formed rL 9168 ABSTRACTS OF CHEMICAL PAPERS. when chlorine (2 mols.) is passed into a solution of naphthalene- a-sulphonic chloride in carbon bisulphide : it is an oily liquid, freely soluble in the usual solvents: it has not yet been solidified. The potassium dichlorosnlphonate, which is obtained by the action of alco- holic potash on the tetrachloride, yields on treatment with phosphorus pentachloride, dichlorona~hthalene-a-sul~honic chloride, Cl0H2Cl2.SO2C1.After recrystallisation from boiling glacial acetic acid and from ben- zene, the chloride is deposited in glistening needles or scales (m. p. 145"). Heated in sealed tubes with water, it yields dichloronaphtha- Iene-a-sulphonic acid. y-TrichZoronni,hthclZene, CI0H5Cl3, previously de- scribed by Atterberg (Ber., 9, 316), is formed when the sulphonic chloride is distilled with phosphorus pentachloride. This derivative j-ields dinitrodichlorophthalic acid on nitration, which indicates that the y t richloronaphthalene contains two chlorine atoms in one benzene iiucleus and one chlorine atom in the other. Hence it is probable that the only difference in the constitution between the 7 and y compounds is that the isolated chloyine atom occupies the a position in the one compound and the p position in the other.w. c. w. Dichloronaphthalene-a-sulphonic Acid. By 0. WIDMANN (L'er., 12, 2231-2233) .-This acid, CloH5C12. S03H, is deposited in colourless needles when dichloronaphthalene-a-sulphonic chloride is heated with water at 140". They lose a portion of their water of crystallisatiori at the ordinary temperature, but, to remove the whole, they must be heated nearly to 200". C,oH,C12.S03K + 2H20 forms needle-shaped crystals. The anhydrous salt dissolves in 115 parts of water at 15". C,oH5CI,.S0,Na + H20 crystallises in prisms, and CloH,C1,.SO,Ag + 2H20 in silky needles. The barium salt also forms needles which require 1650 parts of water for complete solution. The lead salt (needles) dissolves in 700 parts of water. ( CloHjClz.SO3),Ca + 4H,O crystallises in quadratic plates, 1 part of the salt dried at 100" dissolves in 1270 parts of water at 14", and in 145 at 100". The zinc salt forms pearly scales containing 7 lnols.of H,O. The amide, CloH,C1,.SO,NH,, forms feathery crystals soluble in water and alcohol, which melt and blacken at 250". Jts salts are crystalline and spariugly soluble in water. w. c. w. Phenylnaphthylcarbazol. By C. GBAEBE and W. KNECHT (Bey., 12, 2242-2243) .-The carbazol, CIGH1lN, discovered by Brunck (Ber., 12, 341) in crude anthracene, is formed synthetically when P-phenyl- naphthylamine is passed through a red-hot tube. w. c. w. Balsamum Antarthriticum Indicum. By B. HIRSCH ( A d . Phnrm. [ 31 , 15, 27-47) .-Three specimens, labelled Balsamuam amntnr- t7u-itLcicnL Indicum, Wapa balsam, and oil of Wapa, together with a block of wood of the same sort as that from which the above were prepared, Eperna falcata, came under the author's observat,ions.He concludes from careful comparison that the balsams and oil closely resemble one another in their chemical and physical properties, butORGANIC CHEMISTRY. 169 that the wood in its present state (being without bark or centre) could not, without the addition of other materials produce the balsam. E. W. P. Coca. By G. W. KENNEDY (Pharrn. J. Trans. [3], 10, 65).-The physiological action of coca in small doses is to. produce excitement, of trhe functions, to relieve or prevent muscular fatigue, and, t o some extent, to take the place of food; large and frequent doses producc effects similar to those of opium.Attempts have been made t o isolate the narcotic principle which produces these effects. Nenmann dis- covered an alkalojid named cocaine ; a volatile alkalojid, hygrirze, has also been scparated, and an essential oil which imparts the peculiar odour to the leaves. Cocaine or erythroxyline appears to be the active principle; it is soluble in 704 parts of water, more soluble in cold alcohol, and quite soluble in hot alcohol and ether. The author gives proportions and directions for the preparation of a fluid alcoholic extract, and an elixir. Berberine Salts. By J. U. LLOYD (Pharnz. J. T ~ w . [3], 10, 125-127) .-The finely powdered roots of Hydrastis cmadetrsis are extracted with alcohol by percolation; the extract is cooled by ice, and mixed with excess of mlphuric acid ; and after it has been kept cool for about twelve hours the precipitate is separated by filtration and stirred up with cold alcohol; and the impure berberine sulphate is separated and dried by exposure to the air.SuZphate of beyberine in the pure state is obtained. by adding thc above impure product to 16 parts of water, dropping in ammonia in digkt excess, with constant stirring, and allowing the liquid to stand in a cool place for twelve to twenty-four hours. The liquid is then filtered, cooled by ice, and exactly neutralised with snlphuric aLid : the crystals can be strained off in a few hours. The sulphate is orange- red, soluble in about 100 parts of water at 21" C. ; it is readily decom- posed by alkalis, yielding free berberine. i t is unaffected by exposure to the air, but becomes moist if extractive matter or sulphuric acid is present.From 18 to 20 ounces are obtained from 100 pounds of liydrastis. The author prepares pure berherine from the sulphate by treating it with slight excess of ammonia, dissolving in alcohol, and precipitation with ether. Berberine is soluble in about 44 parts of water a t 21", nioderately soluble in alcohol, and insoluble in ether and chloroform. It readily yields salts with acids : the pyrophosphate is very soluble, the picrate insoluble in water. The phosphate, hypophosphite, and chloride are readily prepared by adding the respective acids in slight excess to an aqueous solution of berberine.The ortho-phos- phate is soluble in 280, and the hypophosphite in about 60 parts OP water. Berberhie hydrochloride, prepared by Precipitation, is soluble in about 500 parts of water ; almost insoluble in cold alcohol, ether, and chloro- form. Berberine nitrate is greenish-yellow, it is made in a similar way to the chloride, and resembles it closely in solubility. Remarks.-The alcoholic extract of IEydrastLs canaclensis contains, F. C.1 TO ABSTRACTS OF CHEMICAL PAPERS. besides berberine, a greenish fixed oil, an acrid resin, a white alkalo'id, a vegetable acid, yellow colouriiig matter, and small amounts of other hubstances. These substances are protmbly combined in the root, but 011 adding an acid, the alkalwids are converted into snlphates, with separation of the vegetable acid, the resinous matters and the colouring matter.I n the process given above for preparing berberine, the impure berberine sulphate is decclmposed by ammonia, a slight ex- cess of which precipitakes the white alkalo'id hydrastine, together with the resin and oil. 'The berberine sulphate made from the filtrate by cooling and adding sulphuric acid, contains some ammonium sul- phnte and foreign matters ; it may be purified by dissolving in hot alco h ol and re crystal 1 iking . The volatile oil is obtained by distilling the root with water. When the mother-liqaor of the berberine sulphate crystals is mked with its own bulk of water, and the alcohol removed by evaporation, the green fixed oil rises to the surface, and the resinous substances settle to the bottom : the water contains the hgdrastine as sulphate.Hydrastine is separated from this solution of ,its asulphate by adding ammonia in excess in the cold ; it is purified by converting it once more into sul- phate, reprecipittating .with ammonia, and crystallising from boiling alcohol. The crystals are coloured yellow by admirct.ure with a yellow substance ; they are not bitter, but amid ; hydrastine is almost insoluble in water, somewhat soluble in cold alcohol, and freely soluble in boil- ing alcoholand in chloroform : it forms salts with aczids, which are, as By C. BULLOCK (Phnrm. J. Trans. [3], 10, 186).-The powdered rhizome and rootlets of t h i s plaE t wereexhausted with alcohol, and after evaporation, the residue was freed from alcohol by a continued moderate heat: the =sin which separated from the soft extract was removed and allowed to drain for several weeks during warm weather.The Soft .E'xtrccct.--86 per cent. was soluble in water ; 43 per cent. of fatty mat'ter was removed by light petrole.um. Tlhe aqueous extract was concentrafed and made alkaline with sodium carbonate : after filtering OR the precipitated alkala'ids, the solution was heated to Go C. and a little soda added ; the additional precipitate was then filtered off while ,he liquid was warm : the precipitated alkaloids from 1 pound of root amounted to 19:3 grains, about me-ninth of which was precipi- tated by warming after addition .of soda. Colauring matter was yemoved by dissolving in acetic acid and reprecipikating from the warm solution : and the united mother-liquors, after being acidified and evaporated, were made alkaline, treated with ether, the ether product dissolved in acetic acid, $filtered, and precipitated as before.The total weight of mixed alkalo'ids obtained was 1 2 4 grains, of which 1.7 grains had been separated from the mother-liquors. The jervine was precipitatd as nitrat'e from an acetic acid solution containing 3 grains in each fluid ounce, by addition of an equal volume of eatura ted potassium nitmke solukion. The precipitate was filtered off after six hours, washed with potassium nitrate solution, pressed hetween bibulous paper, and dried : its weight was 7.9 grains, and the a rule, very soluble and d r i f i u l t to crystallise. F. c. V e r a t m viride.ORQANIC CHEMISTRY.171 weight of alkalo'ids precipitated from the concentrated filtrate by warming with soda was 3.2 grains. The aqueous solution, after removal of the alkalo'ids, was treated with subacetate of lead, the excess of lead separated, and the free acid iientralised with barium carbonate ; the filtered solution was then evaporated to a syrup, and thrown into alcohol. The filtered alcohol solution, evaporated and dried at loo", yielded a product with sweet and somewhat bitter taste, energetically reducing copper and silver salts, and apparently consisting almost entirely of glucose : its weight amounted to 8.5 per cent. of the total aqueous extract. The alkalojids were then removed from the resin, both that from the soft extract and also the hard resin. Fatty matter was first dissolved away by light petroleum, then the powdered resin was made into a smooth paste with water, and dissolved in a solution of sodium car- bonate containing soda. The alkaline solution was twice agitated with ether, and the ether extract dissolved in acetic acid, filtered, and the alkalo'ids Precipitated as above ; the alkaloids were also extracted from the mother-liquor, and the jervine separated from the alkaloi'ds as nitrate.A further minute quantity of alkalbi'ds was obtained from the alkaline solution of the resin. The total amount of alka€oids obtained from the extract representing 1 pound of root was 46.6 grains, and from this, 31-2 grains of nitrate of jervine and 11 grains of other alkalo'ids were obtained, the loss of 10 per cent.representing loss and removal of foreign matter. About one-quarter of the total weight of nitrake of jervizle was obtained fmm the soft extract and frsm the re'sin from the soft extract, the hard resin yielding about one-half of the total weight. Wright obtained only 0.80 gram of alkalo'ids per kilogramme of the root employed ; the author obtains 6.612 grams: the excess being due probably Lo the alkalo'id separated from the resin by (the author. The alkaloids, after separation of the jervine and crystallimtion from alcohol, showed under the microscope crystdline forms differing from jervine, the substance probably being Wright's pseadojervine : when purified, it amounted to 5 per cent. of lthe mixed alkalojids. Saponijicatio?b of the Hard Resin by Lime.-From L pomd of the hard resin the fatty matter was removed by light petroleum ; it was then rubbed into a smooth paste with 2 pounds of slaked lime, water added, and the mixture boiled for a few minutes.Aftel. evaporation and drying on the steam-bath, the powdered mass was exhausted with 3 gallons of hot alcohol. The alkalo'ids obtained from the alcoholic extract, when purified by sepreeipitation, amounted to more than 485 grains, a quantity 20 per cent. greater than that yielded by the ether process, and corresponding to 4.21 grams per kilogram of the root. F. C. - On Casein, and the Action of Rennet. By 0. HAMMARSTEN (Bied. Ceiiti.., 1879, 147).-Pure casein may be prepared by preci- pitating with acetic acid, care being taken t.0 avoid excess of acid, dis- solving the washed precipitate in alkali, so that the solution remains slightly acid, filtering from separahed fats, reprecipitating several times by acetic acid, and washing with alcohol and ether.The casein thus172 ABSTRACTS OF CHEMICAL PAPERS. prepared appears t o be a weak acid, dissolving calcium and barium carbonates, and calcium phospha,te. Salts appear to keep casein i n solution, and tlhis accounts for the fact, that, in the precipitation of case'in by acids, the amount obtained is not equivalent to the wid em- ployed. Rennet, when i t precipitates caqejin, appears to break it up into two albumino'ids, one which is greatest in quantity is combined with calcium phosphate, and appears as cheese ; the other (a peptone) remaining dissolved in the whey. For complete precipitation, the presence of calcium phosphate is necessary, acd this accounts for the fact that dilute milk cannot be coagulated. The presence of calcium chloride also partly aids curdling, and one part of rennet ferment is capable of curdling 800,000 parts of casein.E. W. P. Fibrinogen. By 0. HAMMARSTEN (P'iigel.'s Arch. f. Phys.; 19, 563--622).--The author's researches have led him to regard para- globulin and fibrinogen as entirely distinct snhstances, each charac- terised by well-marked properties. In the present cornrnunication, he describes his method for preparing fibrinogen from venous blood, and claims €or the substance so prepared that it is perfectly free from hemoglobin, serum, albumin, and paraglobulin, that it is in no way altered by the process of preparation, and that it is the true parent body whence fibrin is derived.To prepare fibrinogen, the author mixes 3 vols. of blood with 1 vol. of a saturated solution of magnesium sulphate, filters, and precipitates by addition of an equal volume of a saturated solution of sodium chloride. After continued shaking, t,he precipitated fibrinogen is removed, broken in very small pieces. and shaken up with a half- saturated sodium chloride solution. This process of washing with sodium chloride solution is repeated five or six times, care being taken that no lumps are allowed to form in t'he fibrinogen. The fibrinogen is finally collected on filters, strongly pressed, dissolved in water, and the solution is filtered. Slight modifications of this method are described, and the process is compared, a t great length, with those of Gautier and A.Schmidt. The properties of pure fibrinogen are scarcely mentioned in the present paper, but are reserved for a further communication. The author states that a solution of fibrinogen is altered by long-continued dialysis; that it may be frozen without inducing any turbidity, but that if a trace of altered fibrinogen is present, small solid particles separate when the mass is melted ; that fibrinogen readily undergoes fermentative changes ; and that when precipitated by sodium chloride and allowed to remain in contact with the supernatant liquid, its solu- bility diminishes. M. M. P. M.> Note on Hyraceum. By W. H. GREENE and A. J. PARKER (Phwm. J. Trans. [3], 10, 188).-Hyraceum is believed t o be the inspissated urine of the Cape Hyrax (H?paa capensis), the urine col- lecting in hollows of rocks and gradually evaporating ; its medicinal effect is reported to be the same as that of castoreurn.It is a dark- brown, brittle, resinous substance, with aromatic odonr and bitter taste. About 56 per cent. of it is soluble in water, and nearly one-PHYSIOLOGICAL CHEMISTRY. 173 thkd of the residue (14 per cent.) in alcohol, ether, and chloroform ; of the 30 per cent. of insoluble matter, 14 is woody fibre and inso- luble organic material, and 16 consists of sand and other inorganic substances. On ignition, hyraceum leaves 34 per cent. of ash, con- sisting of chlorides, snlphates, phosphates, and carbonates of sodium, potsssium, calcium, and magnesium. Sma,ll quantities of nitrates are also present.When the organic matter in the aqueous extract was precipitated by lead acetate, and the precipitate was decomposed by snlphnric acid, a hard, horny, resinous, brown, transparent substance, emitting a faecal odonr, was obtained. Hyraceum eonsisBs of various salts and organic substances ; the latter constitute about one-half, and contain urea in small quantity, besides uric, hippuric, and benzoic acids ; yobably also glycocol, derived from the breaking up of the hippuric acid. Hyraceum is, therefore, undoubtedly derived from a urine ; but the large amount of calcium salts in proportion to the other salts, and the character of the organic matter, indicate the presence also of faecal matter. F. c.158 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Normal Paraffins.By C. SCHORLEMMER (Annulen, 199, 139-144) .-By chlorinating pure hexane (fiwm secondary hexyl iodideprepared by the action of hydriodic acid on mannitol), a mixture ofmonochlorides is obtained (b. p. 121-134"), which yields hexyleneand ethyl-hexyl ethers on decomposition with alcoholic potash. Theolefine combines with hydrochloric acid at the ordinary temperature,forming a chloride which boils at 1 2 4 O without decomposition ; whilst,alecording to Morgan (Allen., 161, 275), the corresponding chloridefrom petroleum boils a t 116' with decomposition. The acetate fromt'he chloride yields an alcohol boiling a t 130-135" and another at135-140", which split up on oxidation into acetic and butyric acids ;propionic acid could not be detected.The fact that the paraffins from petroleum have a higher specificgravity than those from other sources, and that the specific gravitydiminishes when a portion of the hydrocarbon is oxidised by nitricacid, indicates that the normal paraffins from petroleum probably con-sist of a comphated mixture of homologous and isomeric hydro-carbons. w.c. w.Constitution of Dibrom-ethylene. By E. DEMOLE (Ber., 12,2245--2247).-3y the action of aluminium chloride on a solution ofdibromethylene in benzene, zLnsymmetlricd d@henylethyZene, CH, CPh,,b. p. 174-176", and a liquid boiling above 350", are formed. Theproduction of the former hydrocarbon &ows that dibromethylene isalso unsymmetrical, Br,C CH2.This result agreea with the con-elusions arrived a t by Anschiita (Ber., 12, 2073). w. c. w.Glucose. By PRANCHIMONT (Con@. rend., 89, 713-714).-1n"pplying Liebermann's method for the preparation of the acetyl deri-vatives of the phenols to the carbohydrates, the author obtained witORGANIC CHEMISTRY. 159glucose a crystalline acetyl compound soluble in benzene, alcohol,acetic anhydride, and acetic acid; sparingly soluble in ether and inpetroleum spirit, and insoluble in water. It is octo-acetyl diglucose,C~zHl103(CzH302)8, (m. p. 100’). It has a bitter taste, is dextrorota-tory, and unlike glucose it is oxidised only with great difficulty;boiling chromic mixture does not attack it, and phosphorus pentn-chloride acts on it but slowly.L. T. 0’s.Cellulose. By FRANCHIMONT (Compt. rend., 89, 711-712) .--Notbeing able to obtain any reaction between cellulose, acetic anhydride,and sodium acetate, the author substiOuted concentrated sulphuric acidfor the last substance, when a violent reaction set in, and the cellu-lose was dissolved, the solution becoming coloured. On adding waterto the solution, a white precipitate is formed, which is filtered andwashed with cold alcohol until the washings are no longer coloured.The residue is then dissolved in hot alcohol, arid from the solutionmicroscopic needles or plates separate out (m. p. Zl2O). These aresoluble in benzene, sparingly soluble in cold alcohol, and insoluble inether. It has the empirical formula C40H54027, and appears to be aderivative of triglucose, containing the acetj-1-group eleven times.Anacetyl-derivative is also obtained by substituting zinc chloride for sul-phuric acid. This corresponds with a triacetyl-compound, but it ismore probable that it is ;I saturated acetyl-derivative of n-molecules ofglucose -(n-l)OH?. It has not yet been identified with Schutzen-berger’s triacetyl-cellulose. The author has applied the same reactionto other carbohydrates. L. T. 0’s.Commercial Trimethylamine. By 131. DUVILLIER and A. BUI-SINE (Compt. rend., 89, 709--711).-To detect the presence of ethyl-amine in commercial trimethylanline, which escaped tlhe authors’ noticein their previous research (this Journal, Abst,., 1879, 912 j, from beingpresent only in very small quantity (2 per cent.) ; the mother-liquorsfrom the purification of the oxamides are decomposed with potash andthe bases converted into sulphates ; these are treated with absolutealcohol, which dissolves, all with the exception of mouomethylaminesulphate.The soluble sulphates are distilled with potash, the basescollected over absolute alcohol, and the solutions treated with oxalicether. The oxamic ethers are decomposed with lime, when crystalsof calcium monethyloxamate separate out. This is the sixth basefound in commercial trimethylamine. The authors also reply toVincent’s remarks (this Journal, Abst., 1879, 913) on their previouspublication. L. T. 0’s.Ethylamine. By H. KOHLEE (Ber., 12, 2208--221l).-When asolution of mercuric chloride is boiled with ethylanline and the hotinixture filtered, the filtrate deposits on cooling white pearly scales,which have the composition C1.HgNHEt.The insoluble precipitatewhich is formed at the same time is converted by boiling with waterinto yellow oxymercurethglamine chloride, C1Hg.O.HgNHEt.Hence it appears that the action of ethylamine on mercuric chlorid160 ABSTRACTS OF CHEMICAL PAPERS.is analogous to that of ammonia ; the product, however, is much morereadily oxidisable than is the case with white precipitate. w. c. w.Action of Potassiam Dichromate o n Acetic Acid andPotassium Acetate. By I;. DANESI (Gazzetta, 9, 4120-421).-Theauthor finds that, when acetic acid is boiled with a solution of potas-sium dichromate, the acid is oxidised at the expense of the chromicacid, and carbonic anhydride is produced.In one experiment, theauthor employed equal weights of potassium. dichrornate and aceticacid ; the latter diluted with. water, but how much is. not skated. Thedichromate acts on potassinm acetate in a similar manner, the chromicacid liberating ace& acid, which is subsequemtly onidised.C. E. G.Action of Hypochlorous Acid on Acrylic. Acid. By P.MEL~KOFF (Be,.., 12, 222 7-2228),-The monochlorolactic acid ob-tained by the action of hypochlorous acid 00 a dilute aqueous solutionof acrylic acid and the acid formed by treating glyceric acid withhydrochloric acid (Be?-., 12, 178, this Journal, Abst., 1879, 521) areshown to be identical, by a comparison of their amido-derivatives andof their barium and tin salts (both of which are amorphous). Theamido-acid, which is produced by heating ethyl chlorolactate andammonia a t 120", crptallises in long, thin prisms, and also in four-sided plates. It resembles serine in most of its properties, but issomewhat less soluble in water.?V. c. w.Acetylenedicarboxylic Acid. By E. BANDROWSKI (Rer., 12,2212-22l6) .--Copper acetylenedicarboxylate, CuC404 + 3H20, formsglistening blue scales, which are sparingly soluble in cold water, andare decomposed by hob water. This salt slowly undergoes decom-position at the ordinary temperature. The silver salt dissolves instrong nitric acid, but the solution rapidly becomes turbid, owing tothe deposition of silver cyanide.Acetylenedicarboxylic acid is converted into succinic acid by theaction of nascent hydrogen, When heated with water, it splits upaccording to the equation C4H,0a = GO2 + C,H,O,.The new acidmelts at 145", and is soluble in water, alcohol, and ether. It is crys-talline, and forms well crystallised salts.When bromine is added to an aqueous solution of acetylenedicar-boxy lic acid, the dibromo-acid, C4H,Br2O4, is formed, together withsmall quantities of bromoform, and a crystalline compound of unknowncomposition.DibromacetyZ~edicarboxylic acid is deposited from its aqueous solutionin transparent crystals, which dissolve freely in ether and in alcohol.The silver salt, C4Br204Ae + iH,O, crystallises in small needles,whi'ch explode when heated. The lead salt, C4Br204Pb, also formsneedles which are soluble in water.The acid begins to blacken ttt217", and melts with decomposition at 220". On distillation it yieldshydrobromic acid and KekulB's dibroniomaleic acid (m. p. 108")(AnnaZen, 130, 3), hence it may be regarded as dibromofumaricacidORGANIC CHEMISTRY. 161Attempts to prepare tetrabromosuccinic acid by the action of bro-Carbamido-palladions Chloride, or Palladoso-uramoniumChloride, By E. DRECHSEL (% pr. Chem., 20, 469--475).--Thissubstance is obtained by mixing solutions of palladious chloride an2urea. It forms a brownish crystalline powder, sparingly soluble inwater, and has the formula PdCI2.2CN2H,O = fd[NH,(CO.NH,)Cl]?.As it is nearly insolable in water, attempts were made to found amethod of estimating urea and palladium by its formation, but withno success in the former, and unsatisfactory results in the latter case.When boiled with water, it undergoes the following decomposition :-mine on acetylenedicarboxylic acid were unsnccessful.w. c. w.PdC1*.2NH,(CO.NH,) + 2HZO = PdC12.2NHS + 2NH3 + 2C0,.When evaporated with excess of pall.adious chloride, the urea appearsSome to be paztially decomposed with formation of free cyanic acid.urea combining with the cyanic acid, biuret is produced :-NH2.CONHz + HCNO = (NH,.CO)ZNH.An attempt was made to prepare hydantoic acid by evaporat,ingglycocine with carbamido-palladious chloride, but wilthout success.Besides small quantities of biuret, urea hydrochloride, and palla-dium bases, palladious amidoaaetate was formod.No hydantoic acidcould be detected. W. R.Relative Displaceabili ty of Bromine in the Monobromo-benzyl Bromides. By C. L. JACKSON (Ber., 12, 2243-2245).-When sodium acetate acts on the ortho-, meta-, and para-monobromo-benzyl bromides under bimilar conditions, t'he bromine replaced inthese compounds in a given time is in the r d i o .52 : 7/ : 100.w . c. w.Tolylphenol. By G. MAZZARB (Qazzetta, 9, 421-423) .-Thexylene employed for the preparation of the tolyl chloride is obtainedfrom commercial xylene by fractional distillation, and agitating theportion boiling at 136-139" with concentyated sulphuric acid. Onredistilling the undissolved hydrocarbon, it yields a fraction boiling at137-139", which is treated with chlorine while boiling to convert itinto tolyl chloride (b.p. 290-195"). When equal parts of tolylchloride and phenol are heated with zinc filings, a violent reaction takesplace, with evolution of hydrochloric acid and formation of tolyl-phenol, OH.CsH4.CliH4.CHzMe, which may be separated from the pro-duct by fractional distillation. It is a, colourless liquid of feebleodour, boiling a t 250-255" under a pressure of 8-10 mm. It is in-soluble in water, but dissolves in alcohol, ether, chloroform, and alkalineBolutions. It gives no coloration with ferric salts. When tolylphenolis treated with acetic chloride, i t yields an acetate,BcO. C,H,. C6H4. CH2Me.This is a colourless liquid, boiling at 2-50" under a, pressure of 8 mm.,and decomposingon exposure t o moist air, with formation of tolyl-phenol and acetic acid.C. E. G162 ABSTRACTS OF CHEMICAL PAPERS.Action of Nitrosodimethylaniline on Phenols which do notcontain the Methyl Group. By R. MELDOLA (Ber., 12, 2065-2066) .-When nitrosodimethylaniline hydrochloride (1 mol.) is slowlyadded to a solution of &naphthol (1 mol.) in glacial acetic acid at110", a blue mass is produced. This is washed with water, dissolvedin hot alcohol, and mixed with hydrochloric acid. On cooling, bronze-coloured needles are deposited, which dissolve in alcohol and in water,forming a bluish-violet solution.Similar compounds are obtained by the action of nitrosodimethyl-Action of Ferric Chloride on Orthodiamidobensene. ByC. RUDOLPH (BRT., 12, 2211-221 2).-By the action of ferric chlorideon orthodiamidobenzene, a hydrochloride is formed which has the com-position C,1H,8N60.2HC1.511~0.The base combines with snlphuricacid, yielding several different salts. The formula of the neutral sul-aniline on resorcinol and on a-naphthol. w. c. w.phate is C,4H18N,0.HZS0,.3H,0. w. c. w.Tolylenedimines. By R. NIETZKI (Bm., 12, 2236-2238) .-Paradiamidotoluene (m. p. 64") from nitrosrthotoluidine (m. p. 130")is identical with the tolylenediamine from amidoazotoIuene. Thepara-diarnines can be distinguished from the ortho- and mets-diaminesby their forming quinones on oxidation with ferric chloride, whilst theortho-compounds yield a coloured crystslline precipitate having ametallic lustre.When treatedwith nitrous acid, para-diarnines form diazo-compounds,whilst the meta-derivatives yield colouring matters analogous tophenylene brown, and the ortho-diamines g i n colourless stable com- w.C. w.Occurrence of Paraleucaniline in the Manufacture ofRosaniline. By C. GRAEBE ( B e r . , 12, 2241-2242) .-Considerablequantities of paraleucaniline are found in the rosaniline manufacturein the mother liquors from which the chrysaniline has been precipi-tated. Whether lencaniline is the first product of the reaction ofarsenic acid on a mixture of aniline and tohidine (the cnlouringmatters being afterwards formed by oxidation), or whether it owes itsorigin to the reduction of pararosaniline is uneertain, but the author w. c. w.Dirnethylphenyl Glycocine or Phenylbetayne.By J. ZIMRIER-pounds containing nitrogen.considers the first hypothesis the more probable.MANN (Rer., 12, 2206-2207) .-Plienylbetaine hydrochloride,formed by digesting an ethereal solution of dimethylaniline (2 mols.)with monochloracetic acid (1 mol.) can be obtained in white needlesby adding ether t o the concentrated aqueous solution of the compound.The platinochloride forms beautiful dark red crystals.C J3I,OJT.H C1,CH2\PhenyZbetaBne ethylchloride, I )N. (Me),PhEtCl, is deposited in cozhygroscopic crrstals when a mixture of ethyl monochloracetate anORGANIC CHEMISTRY. 163dimethylaniline is heated at 100" for four hours. On treatment withsilver oxide, the chlorine is eliminated from this substance, and apowerful base is produced, which is very deliquescent, and does notHydroxyazobenzene and Paramethylhydroxyazobenzene.ByG. MAZZARA (Gazzetta, 9, 424-425) .-Zydroxyazobe?izene or phend-diazobenzene, C12H,,N20, has already been obtained by Griess (Annalen,137, 841, and by Kekulb and Higed (Ber., 4, 233). The author findsthat the most convenient mode of preparation is to dissolve 3 parts ofpotassium nitrite in 400 of water, and pour in a solution of 2 parts ofaniline nitrite and 2 of pbenol in 200 of water. The solution soonbecomes turbid and deposits the azo-compound, which should becollected after 24 hours, dissolved in dilute ammonia to separateresin, and the filtered solution precipitated with hydrochloric acid.After recrystallisation from boiling dilute alcohol the substance meltsat 148-154'.appear to form crystalline salts.w. c. w.Paramethy lhydyoxybenzene or Paracyesoldiazobenzene,CsH,.N : W.C6H3Me.0H,may be prepared in a similar manner, substituting pure paracresol forphenol. The product is purified from an oily substance by repeatedcrystallisation from boiling alcohol. It forms lustrous red crystals(m. p. 108-109") which are but little soluble in cold and only mode-rately soluble in hot alcohol. I t is soluble in ether, in alcohol, and inalkaline solutions. C. E. G.Cymenecarboxylic Acid. By E. PATERNZ) and P. SPICA (Gaz-zetta, 9, 400).-1t has been shown (Gaz., 5, 30) that when sodiumcymenesulphate is distilled with potassium cyanide, an oil is producedwhich may be converted into the amide C6H,Me(C3H7).CONI'I, (m.p.138-139') by the action of alcoholic potash. Although this com-pound resists the action of alcoholic potash in a remarkable degree, i tsplits up when fused with potash, yielding an acid of the formulaC6H,Me(C3H,) .COOH, crystallising in slender needles (m. p. 63") andisomeric with Rossi's homocuminic acid (m. p. 52"). The amide isconverted into the acid much more readily by heating it with concen-trated hydrochloric acid at 180" than by fusion with potash. Theauthors have endeavoured to prepare cymenecarboxylic acid by othermethods, such as fusing the cymenesulphate with sodium formate,and by the action of sodium and carbonic anhydride on bromocymene,but without any satisfactory result.By G.MAZZARA (Gaxzetta, 9, 425-428) .-The metanitrocinnamic acid from which the amido-acid wasobtained was prepared according to Schiff's method by heating nitro-benzoic aldehyde with acetic aldehyde and sodium acetate. On re-ducing the nitro-group in the acid by boiling it with tin and hydro-chloric acid, and subsequently removing the tin by means of hydrogensulphide, the metamidocinnnmic ucid hydrochloride,C. E. G.Metamidocinnamic Acid.HCl.NHz.C,H,.CH : CH.COOH164 ABSTRACTS OF CHEMICAL PAPERS.was obtaineii in thin plates, permanent in the air and soluble in hotalcohol, from which it crystallises in needles. The amido-acid sepa-rated from the copper salt by hydrogen sulphide was very unstable.Attempts were made to oxidise the amido-acid with nitrous acid, soas to obtain the corresponding metahydroxycinnamic acid, whichwith cumaric and paracumaric acids would complete the series ofthe three possible hydroxycinnamic acids.It was found, however,that the action went much further, metahydroxybenzoic acid,C6H,(OH).COOH (m. p. 196-197") being produced.By A. OGLIALORO (Gazzetta, 9,428--432).-0n heating 20 parts of salicylaldehyde with 28 of drysodium alphatoluate and '70 of acetic anhydride a t 150" for 8 hours,a red-brown crystalline mass is obtained which is boiled with waterfor some time and then allowed to cool. The insoluble portion, whentreated with a hot solution of sodium carbonate, partly dissolves, andon acidifping the liquid, acety lpheity lcoumnric acid, C1,H140i, is preci-pitated in the crystalline state.The portion remaining undissolved,which is the chief product of the reaction, is impure phenylcou-marin.Acetyl phenylcoumaric acid, when purified by crystallisation fromboiling water, in which it is moderately soluble, forms long, white,very slender needles. It is soluble in alcohol and in ether, but, onlysparingly so in cold water. When heated, it begins to soften and giveoff gas a t 170", but a t 180" it fuses to a transparent liquid; if afterbeing allowed to cool it is again heated, it melts at 130". From thisthe author is inclined to believe that when the acid is heated, it losesacetic acid and is converted into phenylcoumarin. The silver met&pheny Zcoum nrate, CliHIY04Ag, obtained by precipitating the sodiumsalt with silver nitrate, crystallises from boilicg water in tufts ofslender, colourless needles, which become yellowish-red on keeping.The pheny Zcournarin, C,,HI,O2, after purification by crystallisationfrom boiling alcohol, with addifion of animal charcoal, forms largetransparent colourless prisms (m.p. 139-140"), soluble in ether. Itis odourless. Like coumsrin, it dissolves when boiled with potashsolution, and is precipitated unchanged on adding an acid. Whentreated with sodium-amalgam in dilute alcoholic solution, phenyl-coumarin is converted into a new acid, which may be isolated byacidulating the solution and agitating it with ether. It crystallisesin prisms (m. p. l'LO"), and is, perhaps, phenylmelilotic acid, but hasnot as yet been further examined.From its mode of formation the author- believes that acetylphenyl-coumaric acid has the rational formula AcO.C,HL.CB: C'Ph.COOH.C.E. G.Synthesis of Phenylcuumarin.whilst phenylcoumarin, if regarded as t'he anhydride of phenylcournaric/Ce,H4.CHC. E. G.acid, would be 0 II \co . C P iPittical and Eupittonic Acid. By A. W. HOFMAR" (Bet-. 12,2216--2222).--The formation of eupittonic acid is analogous to thatof pararosaniline, as is shown by the following equations :ORGANIC: CHEMISTRY. 1652CJC7N + C7H9N = CigHi,Ns + H,2C8HioO3 + CgHi?O, = C25H2609 + HZDirnethyl- Dimethyl- Eupittonicpyrogallate. methylpyro- acid.gallate.The sodium and barium salts of this acid have the compositionCz5H,,Na?O9 and C,,H,,Ra09 respectively.The diacetyl derivative,C25H2PA~209, is best prepared by the action of acetic anhydride on analcoholic solution of sodium eupittonate ; it crystallises in yellowneedles, which melt a t 265" and decompose with evolution of violetvapours. The crystals are soluble in alcohol and are decomposed byalkalis and by acids.The yellow amorphous substance (Ber.,.12,1371) obtained as a bye-product in the preparation of diacetyleupittonic acid by heating amixture of acetic anhydride and eupittonic acid is insoluble in water,but dissolves freely in alcohol, ether, and acetic acid. It is also dis-solved by alkalis and by strong sulphuric acid ; on neutralising thealkaline, or diluting the acid solutions, the original substance is repre-cipitated.Dibenzoyleupittonic acid, Cz5Hz4Bz2O9, remains as a yellow powderwhen a mixture of benzoic anhydride and sodium eupittonate is fusedand the product extracted with alcohol. The compound dissolves inchloroform, and may be obtained in golden needles (m.p. 232") byadding alcohol to the chloroform solution. By the action of benzoicchloride on eupittonic acid, a white crystalline powder is obtained.MetliyZ eupittonate prepared by the action of methyl iodide on sodiumeupittonate is deposited from alcohol in golden needles (m. p. 242").The ethyl salt (m. p. 202") resembles tbe preceding compound in itsmode of preparation and in its properties.When a concentrated alcoholic solution of iodine is added to a cold'acetic acid solution of eupittonic acid, brown glistening prisms aredeposited which have the composition C25H:26091p.This compound isdecomposed by heat. By the action of strong alkalis and acids, eupit-tonic acid is regenerated. On treating an alcoholic solution of theiodine-compound with sulphurous acid, hydriodic, sulphuric, and eupit-tonic acids are formed, but on heating the liquid, the original su bstnnceis again formed, since the sulphurous acid decomposes the hydriodicmid with formation of iodine, which a t once combines with the eupit-tonic acid.Eupittonic acid is decomposed by the action of water at 270°, withformation of dimethyl pyrogallate and a crystalline body w.hich issoluble in alcohol, ammonia, and soda. The dimethyl ether of methylpyrogallol is not produced by this reaction.Eupittonic triamineundergoes no change on boiling with aniline. When heated at 250"with water, it splits up into ammonia and eupittonic acid.Hydroxylation by Direct Oxidation.w. c . w.By R. MEYER and A.BAUR (Bey., 12, 2238-2241) .-The following experiments supportthe hypothesis that it is only atoms of hydrogen occupying a ter-tiary position which are capable of uudergoiug direct oxidation tohydroxy1:-VOL. XXXVIII. 1166 ABSTRACTS OF CHEMICAL PAPERS.Normal propylhenzenesulphonic acid is oxidised to carbonic anhy-dride and potassium sulphate by the action of potassium permanga-nate in an aniline solution, whilst, under similar conditions, cumene-sulphonic acid is converted into hydroxypropylbenzenesulphonic acid,By treating the product of the action of phosphorus pentachlorideCsHa(S0,H) C3Hs.OH.on this acid with ammonia, propenylbenzenesulphamide,C,H,(SO,.NH,)C,H,,is'formed.bromine. w.c. w. This sulphamide melts at 152", and combines readily withCumenesulphonic Acids and a New Cumol. By P. SPICA(Gazzetta, 9, 433-444).-&1 observers who have hitherto studiedthe action of sulphuric acid on cumene are agreed that only one sul-phonic acid is formed; although there is great discrepancy in thedescription of the salts which this acid forms, and especially with regardto the amount oi' water of crystallisation they contain. As, how-ever, it has been show by Patemi, and Spica (Guz., 7, 21, and thisJournal, 1877,1, 707) that normal propylbenzene forms two sulphonicacids, and analogous results have been obtained with butylbenzene,&c., it seemed highly improbable that cumene (isopropylbenzene)should give such a different result, especially as the author hadobserved, in the preparation of cumol from the crude cumenesulphate,that a small portion of the product passed over below 220°, and thatthis did not completely solidify a t a low temperature.The cumene employed in the research was prepared by distillingcumic acid with lime and iron filings and rectifying over sodium.The pure cumene, boiling at 150-155", was roiiverted into the sul-phonic acid by agitating it with twice its weight of a mixture of equalparts of ordinary and of fuming sulphuric acid, the action being com-pleted by heating it a t 100" for a few minutes.The sulphonic acidwas diluted, neutralised with pure barium carbonate, and the productsubmitted to a careful fractional cry stallisation. By this means theauthor succeeded in isolating two barium cumenesulphates ; the onewhich is formed in larger quantity crystallises in micaceous scales,somewhat unctuous to the touch, and containing 1 mol- H,O, thusconfirming the observations of Fittig, Schaeffer, and Koenig ; the other,formed only in small quantity, remains in the mother-liquors from thecrystallisation of the first salt, being much more soluble. It crystal-lises in microscopic nodules, and contains 3H20 or 3&H20, which can-not be driven off completely without decomposing the salt. The cor-responding lead salts are very similar, containing 1 mol.HzO and3 mols. H,O respectively. By treating the sodium salts with phos-phorus pentachloride and converting the chlorides thus formed intothe amides by the action of alcoholic ammonia, two sulphamides areobtained corresponding with the two barium cumenesulphates. Theone from the less soluble barium salt is a solid substance which, bycrystallisation from dilute alcohol, may be separated into two aefinitecompounds, both containing sulphur and nitrogen, and having the for-mula C6H4(C3H7).S0& Elz. The less soluble compound which occurOROANIC CHEMISTRY. 167in largest quant'ity forms white micaceous scales (m. p. l07"), verysoluble in alcohol, soluble also in boiling sodium carbonate solutionwithout altzration ; t b more soluble compound obtained from themother-liquors of t h e firsb is relatively small in quantity and crys-tallises in white scales (m.p. 96"). The sulphamide correspondingwith the barium salt with 3E20 is a brown oily liquid which couldnot be purified, but the author believes it to be identical with the crys-talline sulphamide mentioned above as melting at 96". The aulpha-mide (m. p. 107"), when oxidised by fusion with potash, appears toyield a mixture of salicylic and parahydroxybenzoic acids, whilst theoily sulphamid'e gives a small quantity of a very impure acid, meltingbetween 150" and 170".CumoZ, C6H4(CsH7).OH. -The crystallisable cum01 (m. p. 61') ob-tained from the cumenesulphonic acid formed in largest quantity hasalready been described by Patelm6 and the author.The small quan-tity of the sodium salt of the second sulphonic acid at the author'sdisposal yielded about 5 grams of a new phenol by fasion with potashin the ordinary way. This new cumol is an almost colourless liquid,and boils at 218.5" (cor.) under a pressure of 756.18 mm. It does notsolidify when cooled with ice and salt. It is slighhly soluble in water,and the solution is coloured violet by ferric salts.In order to ascertain the constitution of the two cumols, they wereconverted into bhe corresponding ethyl ethers in Ohe usual way andthen oxidised with chromic mixture. The ethylcwnzol, CgH,,.OE t, fromthe solid cumol (m. p. 61") is a colourless, mobile liquid (b.p. 220'cor. a t 757 mm.) and sp. gr. a t 0" = 0.943T7, at 100" = 086369.By oxidation it yields paraethoxybenzoic acid (m. p. 194-195").The ethylcumol from the liquid ciimol boils at 213" (uncor.), and onoxidation gives an oily acid soluble in alcohol and in ether, besides asmall quantity of an acid melting R t 194". Ethysalicylic acid melts at19.5" C.. From these results it would seem that the solid cumol isyaraisopropylplienoE, arid the liquid cum01 orthoisopro~)2J~henoZ. It isevident also that the perfect separation of the isomeric barium cumene-sulphonates cannot; be effected without great difficulty.(2. E. G.Empirical Formula of Skatole. By M. NENCEI (J. pr. Chern., 20,466-469) .-This product is the result of long putrefaction of animalmatter, and its formation is subsequent to that of indole and phenol.The author prepared it by the putrefaction of pancreas and muscle forfive months.The putrefied niass was acidified with acetic acid anddistilled, and the skatole, which volatilised with water-vapour, wasseparated from the distillate by acidifying it with hydrochloric acidand adding picric acid. On analysis, it gave numbers agreeing withthe formula CgHgN, and its picric derivative has the formulaCgH,N. C6H2(N0,),0H. The author throws out the suggestion thatskatole is methylindole. W. R.Action of Chlo.rine on Naphthalene-a-sulphonic Chloride :.,-Trichloronaphthalene. By 0. WIDMANN (Ber 12, 2228--CL231 j .-The tetrachloride of the a-suZphmic chloride, (C~~H,Cl,SO,Cl)CI,, formedrL 168 ABSTRACTS OF CHEMICAL PAPERS.when chlorine (2 mols.) is passed into a solution of naphthalene-a-sulphonic chloride in carbon bisulphide : it is an oily liquid, freelysoluble in the usual solvents: it has not yet been solidified.Thepotassium dichlorosnlphonate, which is obtained by the action of alco-holic potash on the tetrachloride, yields on treatment with phosphoruspentachloride, dichlorona~hthalene-a-sul~honic chloride, Cl0H2Cl2.SO2C1.After recrystallisation from boiling glacial acetic acid and from ben-zene, the chloride is deposited in glistening needles or scales (m. p.145"). Heated in sealed tubes with water, it yields dichloronaphtha-Iene-a-sulphonic acid. y-TrichZoronni,hthclZene, CI0H5Cl3, previously de-scribed by Atterberg (Ber., 9, 316), is formed when the sulphonicchloride is distilled with phosphorus pentachloride.This derivativej-ields dinitrodichlorophthalic acid on nitration, which indicates thatthe y t richloronaphthalene contains two chlorine atoms in one benzeneiiucleus and one chlorine atom in the other. Hence it is probable thatthe only difference in the constitution between the 7 and y compoundsis that the isolated chloyine atom occupies the a position in the onecompound and the p position in the other. w. c. w.Dichloronaphthalene-a-sulphonic Acid. By 0. WIDMANN(L'er., 12, 2231-2233) .-This acid, CloH5C12. S03H, is deposited incolourless needles when dichloronaphthalene-a-sulphonic chloride isheated with water at 140".They lose aportion of their water of crystallisatiori at the ordinary temperature,but, to remove the whole, they must be heated nearly to 200".C,oH,C12.S03K + 2H20 forms needle-shaped crystals.The anhydroussalt dissolves in 115 parts of water at 15". C,oH5CI,.S0,Na + H20crystallises in prisms, and CloH,C1,.SO,Ag + 2H20 in silky needles.The barium salt also forms needles which require 1650 parts of waterfor complete solution. The lead salt (needles) dissolves in 700 partsof water. ( CloHjClz.SO3),Ca + 4H,O crystallises in quadratic plates,1 part of the salt dried at 100" dissolves in 1270 parts of water at 14",and in 145 at 100". The zinc salt forms pearly scales containing 7lnols. of H,O.The amide, CloH,C1,.SO,NH,, forms feathery crystals soluble inwater and alcohol, which melt and blacken at 250".Jts salts are crystalline and spariugly soluble in water.w.c. w.Phenylnaphthylcarbazol. By C. GBAEBE and W. KNECHT (Bey.,12, 2242-2243) .-The carbazol, CIGH1lN, discovered by Brunck (Ber.,12, 341) in crude anthracene, is formed synthetically when P-phenyl-naphthylamine is passed through a red-hot tube. w. c. w.Balsamum Antarthriticum Indicum. By B. HIRSCH ( A d .Phnrm. [ 31 , 15, 27-47) .-Three specimens, labelled Balsamuam amntnr-t7u-itLcicnL Indicum, Wapa balsam, and oil of Wapa, together with ablock of wood of the same sort as that from which the above wereprepared, Eperna falcata, came under the author's observat,ions. Heconcludes from careful comparison that the balsams and oil closelyresemble one another in their chemical and physical properties, buORGANIC CHEMISTRY.169that the wood in its present state (being without bark or centre) couldnot, without the addition of other materials produce the balsam.E. W. P.Coca. By G. W. KENNEDY (Pharrn. J. Trans. [3], 10, 65).-Thephysiological action of coca in small doses is to. produce excitement,of trhe functions, to relieve or prevent muscular fatigue, and, t o someextent, to take the place of food; large and frequent doses producceffects similar to those of opium. Attempts have been made t o isolatethe narcotic principle which produces these effects. Nenmann dis-covered an alkalojid named cocaine ; a volatile alkalojid, hygrirze, hasalso been scparated, and an essential oil which imparts the peculiarodour to the leaves.Cocaine or erythroxyline appears to be the activeprinciple; it is soluble in 704 parts of water, more soluble in coldalcohol, and quite soluble in hot alcohol and ether. The author givesproportions and directions for the preparation of a fluid alcoholicextract, and an elixir.Berberine Salts. By J. U. LLOYD (Pharnz. J. T ~ w . [3], 10,125-127) .-The finely powdered roots of Hydrastis cmadetrsis areextracted with alcohol by percolation; the extract is cooled by ice, andmixed with excess of mlphuric acid ; and after it has been kept coolfor about twelve hours the precipitate is separated by filtration andstirred up with cold alcohol; and the impure berberine sulphate isseparated and dried by exposure to the air.SuZphate of beyberine in the pure state is obtained.by adding thcabove impure product to 16 parts of water, dropping in ammonia indigkt excess, with constant stirring, and allowing the liquid to standin a cool place for twelve to twenty-four hours. The liquid is thenfiltered, cooled by ice, and exactly neutralised with snlphuric aLid :the crystals can be strained off in a few hours. The sulphate is orange-red, soluble in about 100 parts of water at 21" C. ; it is readily decom-posed by alkalis, yielding free berberine. i t is unaffected by exposureto the air, but becomes moist if extractive matter or sulphuric acid ispresent. From 18 to 20 ounces are obtained from 100 pounds ofliydrastis.The author prepares pure berherine from the sulphate by treating itwith slight excess of ammonia, dissolving in alcohol, and precipitationwith ether.Berberine is soluble in about 44 parts of water a t 21",nioderately soluble in alcohol, and insoluble in ether and chloroform.It readily yields salts with acids : the pyrophosphate is very soluble,the picrate insoluble in water. The phosphate, hypophosphite, andchloride are readily prepared by adding the respective acids inslight excess to an aqueous solution of berberine. The ortho-phos-phate is soluble in 280, and the hypophosphite in about 60 parts OPwater.Berberhie hydrochloride, prepared by Precipitation, is soluble in about500 parts of water ; almost insoluble in cold alcohol, ether, and chloro-form.Berberine nitrate is greenish-yellow, it is made in a similar way tothe chloride, and resembles it closely in solubility.Remarks.-The alcoholic extract of IEydrastLs canaclensis contains,F. C1 TO ABSTRACTS OF CHEMICAL PAPERS.besides berberine, a greenish fixed oil, an acrid resin, a white alkalo'id,a vegetable acid, yellow colouriiig matter, and small amounts of otherhubstances.These substances are protmbly combined in the root, but011 adding an acid, the alkalwids are converted into snlphates, withseparation of the vegetable acid, the resinous matters and the colouringmatter. I n the process given above for preparing berberine, theimpure berberine sulphate is decclmposed by ammonia, a slight ex-cess of which precipitakes the white alkalo'id hydrastine, togetherwith the resin and oil.'The berberine sulphate made from the filtrateby cooling and adding sulphuric acid, contains some ammonium sul-phnte and foreign matters ; it may be purified by dissolving in hotalco h ol and re crystal 1 iking .The volatile oil is obtained by distilling the root with water. Whenthe mother-liqaor of the berberine sulphate crystals is mked with itsown bulk of water, and the alcohol removed by evaporation, the greenfixed oil rises to the surface, and the resinous substances settle to thebottom : the water contains the hgdrastine as sulphate. Hydrastine isseparated from this solution of ,its asulphate by adding ammonia inexcess in the cold ; it is purified by converting it once more into sul-phate, reprecipittating .with ammonia, and crystallising from boilingalcohol.The crystals are coloured yellow by admirct.ure with a yellowsubstance ; they are not bitter, but amid ; hydrastine is almost insolublein water, somewhat soluble in cold alcohol, and freely soluble in boil-ing alcoholand in chloroform : it forms salts with aczids, which are, asBy C. BULLOCK (Phnrm. J. Trans. [3], 10,186).-The powdered rhizome and rootlets of t h i s plaE t wereexhaustedwith alcohol, and after evaporation, the residue was freed from alcoholby a continued moderate heat: the =sin which separated from thesoft extract was removed and allowed to drain for several weeks duringwarm weather.The Soft .E'xtrccct.--86 per cent. was soluble in water ; 43 per cent. offatty mat'ter was removed by light petrole.um.Tlhe aqueous extractwas concentrafed and made alkaline with sodium carbonate : afterfiltering OR the precipitated alkala'ids, the solution was heated to Go C.and a little soda added ; the additional precipitate was then filtered offwhile ,he liquid was warm : the precipitated alkaloids from 1 pound ofroot amounted to 19:3 grains, about me-ninth of which was precipi-tated by warming after addition .of soda. Colauring matter wasyemoved by dissolving in acetic acid and reprecipikating from the warmsolution : and the united mother-liquors, after being acidified andevaporated, were made alkaline, treated with ether, the ether productdissolved in acetic acid, $filtered, and precipitated as before. The totalweight of mixed alkalo'ids obtained was 1 2 4 grains, of which 1.7grains had been separated from the mother-liquors.The jervine was precipitatd as nitrat'e from an acetic acid solutioncontaining 3 grains in each fluid ounce, by addition of an equal volumeof eatura ted potassium nitmke solukion.The precipitate was filteredoff after six hours, washed with potassium nitrate solution, pressedhetween bibulous paper, and dried : its weight was 7.9 grains, and thea rule, very soluble and d r i f i u l t to crystallise. F. c.V e r a t m virideORQANIC CHEMISTRY. 171weight of alkalo'ids precipitated from the concentrated filtrate bywarming with soda was 3.2 grains.The aqueous solution, after removal of the alkalo'ids, was treatedwith subacetate of lead, the excess of lead separated, and the free acidiientralised with barium carbonate ; the filtered solution was thenevaporated to a syrup, and thrown into alcohol.The filtered alcoholsolution, evaporated and dried at loo", yielded a product with sweetand somewhat bitter taste, energetically reducing copper and silversalts, and apparently consisting almost entirely of glucose : its weightamounted to 8.5 per cent. of the total aqueous extract.The alkalojids were then removed from the resin, both that from thesoft extract and also the hard resin. Fatty matter was first dissolvedaway by light petroleum, then the powdered resin was made into asmooth paste with water, and dissolved in a solution of sodium car-bonate containing soda. The alkaline solution was twice agitated withether, and the ether extract dissolved in acetic acid, filtered, and thealkalo'ids Precipitated as above ; the alkaloids were also extracted fromthe mother-liquor, and the jervine separated from the alkaloi'ds asnitrate.A further minute quantity of alkalbi'ds was obtained fromthe alkaline solution of the resin.The total amount of alka€oids obtained from the extract representing1 pound of root was 46.6 grains, and from this, 31-2 grains of nitrate ofjervine and 11 grains of other alkalo'ids were obtained, the loss of10 per cent. representing loss and removal of foreign matter. Aboutone-quarter of the total weight of nitrake of jervizle was obtained fmmthe soft extract and frsm the re'sin from the soft extract, the hardresin yielding about one-half of the total weight.Wright obtainedonly 0.80 gram of alkalo'ids per kilogramme of the root employed ;the author obtains 6.612 grams: the excess being due probably Lo thealkalo'id separated from the resin by (the author.The alkaloids, after separation of the jervine and crystallimtionfrom alcohol, showed under the microscope crystdline forms differingfrom jervine, the substance probably being Wright's pseadojervine :when purified, it amounted to 5 per cent. of lthe mixed alkalojids.Saponijicatio?b of the Hard Resin by Lime.-From L pomd of thehard resin the fatty matter was removed by light petroleum ; it wasthen rubbed into a smooth paste with 2 pounds of slaked lime, wateradded, and the mixture boiled for a few minutes.Aftel. evaporationand drying on the steam-bath, the powdered mass was exhausted with3 gallons of hot alcohol. The alkalo'ids obtained from the alcoholicextract, when purified by sepreeipitation, amounted to more than 485grains, a quantity 20 per cent. greater than that yielded by the etherprocess, and corresponding to 4.21 grams per kilogram of the root.F. C.-On Casein, and the Action of Rennet. By 0. HAMMARSTEN(Bied. Ceiiti.., 1879, 147).-Pure casein may be prepared by preci-pitating with acetic acid, care being taken t.0 avoid excess of acid, dis-solving the washed precipitate in alkali, so that the solution remainsslightly acid, filtering from separahed fats, reprecipitating several timesby acetic acid, and washing with alcohol and ether.The casein thu172 ABSTRACTS OF CHEMICAL PAPERS.prepared appears t o be a weak acid, dissolving calcium and bariumcarbonates, and calcium phospha,te. Salts appear to keep casein i nsolution, and tlhis accounts for the fact, that, in the precipitation ofcase'in by acids, the amount obtained is not equivalent to the wid em-ployed. Rennet, when i t precipitates caqejin, appears to break it upinto two albumino'ids, one which is greatest in quantity is combinedwith calcium phosphate, and appears as cheese ; the other (a peptone)remaining dissolved in the whey. For complete precipitation, thepresence of calcium phosphate is necessary, acd this accounts for thefact that dilute milk cannot be coagulated. The presence of calciumchloride also partly aids curdling, and one part of rennet ferment iscapable of curdling 800,000 parts of casein. E. W. P.Fibrinogen. By 0. HAMMARSTEN (P'iigel.'s Arch. f. Phys.; 19,563--622).--The author's researches have led him to regard para-globulin and fibrinogen as entirely distinct snhstances, each charac-terised by well-marked properties. In the present cornrnunication, hedescribes his method for preparing fibrinogen from venous blood, andclaims €or the substance so prepared that it is perfectly free fromhemoglobin, serum, albumin, and paraglobulin, that it is in no wayaltered by the process of preparation, and that it is the true parentbody whence fibrin is derived.To prepare fibrinogen, the author mixes 3 vols. of blood with 1 vol.of a saturated solution of magnesium sulphate, filters, and precipitatesby addition of an equal volume of a saturated solution of sodiumchloride. After continued shaking, t,he precipitated fibrinogen isremoved, broken in very small pieces. and shaken up with a half-saturated sodium chloride solution. This process of washing withsodium chloride solution is repeated five or six times, care being takenthat no lumps are allowed to form in t'he fibrinogen. The fibrinogenis finally collected on filters, strongly pressed, dissolved in water, andthe solution is filtered.Slight modifications of this method are described, and the processis compared, a t great length, with those of Gautier and A. Schmidt.The properties of pure fibrinogen are scarcely mentioned in thepresent paper, but are reserved for a further communication. Theauthor states that a solution of fibrinogen is altered by long-continueddialysis; that it may be frozen without inducing any turbidity, butthat if a trace of altered fibrinogen is present, small solid particlesseparate when the mass is melted ; that fibrinogen readily undergoesfermentative changes ; and that when precipitated by sodium chlorideand allowed to remain in contact with the supernatant liquid, its solu-bility diminishes. M. M. P. M.>Note on Hyraceum. By W. H. GREENE and A. J. PARKER(Phwm. J. Trans. [3], 10, 188).-Hyraceum is believed t o be theinspissated urine of the Cape Hyrax (H?paa capensis), the urine col-lecting in hollows of rocks and gradually evaporating ; its medicinaleffect is reported to be the same as that of castoreurn. It is a dark-brown, brittle, resinous substance, with aromatic odonr and bittertaste. About 56 per cent. of it is soluble in water, and nearly onePHYSIOLOGICAL CHEMISTRY. 173thkd of the residue (14 per cent.) in alcohol, ether, and chloroform ;of the 30 per cent. of insoluble matter, 14 is woody fibre and inso-luble organic material, and 16 consists of sand and other inorganicsubstances. On ignition, hyraceum leaves 34 per cent. of ash, con-sisting of chlorides, snlphates, phosphates, and carbonates of sodium,potsssium, calcium, and magnesium. Sma,ll quantities of nitrates arealso present.When the organic matter in the aqueous extract was precipitated bylead acetate, and the precipitate was decomposed by snlphnric acid, ahard, horny, resinous, brown, transparent substance, emitting a faecalodonr, was obtained.Hyraceum eonsisBs of various salts and organic substances ; thelatter constitute about one-half, and contain urea in small quantity,besides uric, hippuric, and benzoic acids ; yobably also glycocol, derivedfrom the breaking up of the hippuric acid. Hyraceum is, therefore,undoubtedly derived from a urine ; but the large amount of calciumsalts in proportion to the other salts, and the character of the organicmatter, indicate the presence also of faecal matter. F. c

ISSN:0368-1769    

DOI:10.1039/CA8803800158

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y si 01 o gi cal Chemistry. 173 Assimilation of Ordinary Horse Fodder. By E. V. WOLFF and Others (Bied. C'entr., 1879, 663-667).-After a series of experiments given in detail, it WRS found that, generally speaking, the various componeni parts of ordinary fodder: were digested as well by horses as by sheep. J. K. C. Fattening of Animals. By E. v. WOLFF (Bied. C'entr., 1879,661- 663).-'l'he author makes some observations on the results given in a paper by Henneberg arid others on the fattening of sheep (this Journal, 36, S l l ) , showing hy a comparison of the food given and the resulting increase of fat, that at least one-third of this arose from the absorption and assimilation of the carbohydrates contained in the fodder used. J. I(. C. Source of Hippuric Acid in the Urine of Herbivora.By 0. LOEW ( J . pr. Chew, 20, 4?6--479).-The author discovered an acid in meadow hay closely resembling quinic acid, but was not success- ful in demonstratiiig the identity of the two. On repeating his expe- riments, he found it impossible to effect a satisfactory separation from a substance resembling peptone ; but tlhe impure substance resembles quinic acid by giving hy droqninone with lead peroxide, and proto- catechuic acid with bromine. Researches by several chemists have shown that hippuric acid is not increased in the urine of an animal by giving it quinic acid in its food; and hay, after treatment with soda, is still a source of hippuric acid in urine. But after treatment with sulphuric acid, the source of hippuric acid is removed from hay.174 ABSTRACTS OF CHEMICAL PAPERS.The only definite compound which the author was able to isolate from an extract of hay made with dilute sulphuric acid was some acid resembling quinic acid. It has been suggested by Weiske that the real source of hippuric acid may be the meadow plants with which hay is mixed. The author, therefore, investigated the officinal extract of dandelion, and again found the acid resembling quinic acid along with some succinic acid, and an acid oil, heavier than water, which gradually became resinous. W. R. Analysis of a Calculus from a Horse. By P. PETERS and K. M ~ ~ L L E R (Bied. Centr., 1879, 714).-A calculus formed in con- centric layers and weighing 84 kilos.-was analysed by the authors with the following results :- Magnesium Soda and Organic amrnsnium Ferric Calcium potash Water. matter.phosphate. phosphate. phosphate. Silica. salts. 4.22 6-20 87.37 0.29 0.11 1.36 0.45 J. K. C. Physiological Inflaence of Adulterated Wine. By A. SCHMITZ ( R i d . Centr., 1879, 712-713) .--The unfermentable residues of grape- sugar, which are used. for the adulteration ~ l f wine, were subjected to experiment with reference to their physiological action. Sn b- cutaneous injection in $he case of dogs was found to produce vomiting and general derangement. The author is of the opinion that these residues contain a poison similar to that in fuse1 oil. Chemical Cause of the Toxicslogical Action of Arsenic. By C. BINZ and H. SCHULZ (BeT., 12, 2199--2202).--The authors are of opinion that arsenic owes its poisonous nature to the alternate oxidation of arsenious to arsenic oxide and reduction of arsenic to arsenious oxide, which produces a rapid oscillation of the atonis of oxygen in the molecules of albumin, causing their complete destruc- tion.Arsenic acts as a carrier of oxygen, resembling nitric oxide in this respect. Phosphorus and the ether members of the nitrogen group appear to act in a similar manner. The authors base their opinion on the following observations :-(1.) That in cases of arse- nical poisoning, i t is those portions of the system which have the power of taking up oxygen from the blood which suffer most severely; (2) and that egg albumin, blood fibrin, and brain reduce arsenic oxide to arsenious at a blood heat', and that the salivary glands and liver not only reduce arsenic to arsenious oxide, but also oxidise arsenious to arsenic oxide, whereas blood, hamoglobin, and fat have no action on the oxides of arsenic.w. c. w. J. R. C. Presence of Alcohd in Amtrnal Tissues during Life and after Death. By J. B~CHAN'P (Compt. rend., 89, 573--574).-1n order to verify the truth of the statement that flesh mperficially coagu- lated would rapidly putrefy under conditions in which well-cooked flesh would remain sound for many weeks, some horseflesh was coagu- lated by immersion for ten minutes in boiling water, then wrapped inVEGETABLE PBYSIOLOGY AND AGRICULTURE. 175 a closely woven cloth, and placed aside for eight days. At the expira- tion of that time, the meat was found in an advanced state of decom- position, and the muscular striation had disappeared, although the air had not penetrated to the interior of the substance, whilst bacteria and vibrios abounded. By methods described in the original memoir, the author isolated and characterised about 0.8 gram of alcohol and 10 grams of sodium sa.lts formed by acetic, butyric, and other acids.The alcohol was converted into aldehyde, and oxidised to acetic acid, so that its identity was established beyond doubt ; within certain limits the quantity obtained was larger, the further the extent of the decom- position. It would seem, therefme, t,hat the phenomena accompanying putre- faction are very closely allied to those belonging to fermentation properly so called, perhaps more directly with those of the butyric fermentation. By the same process alcohol was obtained from the jresh tissues.The brain of sheep gave a larger quantity tJhan the liver, but the largest quadity was,obtained from the brain of an ox, which furnished sufficient alcohol (to measure with the hydrometer. It may be argued, therefore, that in medico-legal cases, the detection or separation of alcohol from putrid or healthy tissues, is not suflicien t evidence to show that alcohol has been administered a t all: still less that this liquid has been the cause of death. J. W.PHYSIOLOGICAL CHEMISTRY.P h y si 01 o gi cal Chemistry.173Assimilation of Ordinary Horse Fodder. By E. V. WOLFF andOthers (Bied. C'entr., 1879, 663-667).-After a series of experimentsgiven in detail, it WRS found that, generally speaking, the variouscomponeni parts of ordinary fodder: were digested as well by horsesas by sheep.J. K. C.Fattening of Animals. By E. v. WOLFF (Bied. C'entr., 1879,661-663).-'l'he author makes some observations on the results given ina paper by Henneberg arid others on the fattening of sheep (thisJournal, 36, S l l ) , showing hy a comparison of the food given and theresulting increase of fat, that at least one-third of this arose from theabsorption and assimilation of the carbohydrates contained in thefodder used. J. I(. C.Source of Hippuric Acid in the Urine of Herbivora. By0. LOEW ( J . pr. Chew, 20, 4?6--479).-The author discovered anacid in meadow hay closely resembling quinic acid, but was not success-ful in demonstratiiig the identity of the two. On repeating his expe-riments, he found it impossible to effect a satisfactory separation froma substance resembling peptone ; but tlhe impure substance resemblesquinic acid by giving hy droqninone with lead peroxide, and proto-catechuic acid with bromine.Researches by several chemists haveshown that hippuric acid is not increased in the urine of an animalby giving it quinic acid in its food; and hay, after treatment withsoda, is still a source of hippuric acid in urine. But after treatmentwith sulphuric acid, the source of hippuric acid is removed from hay174 ABSTRACTS OF CHEMICAL PAPERS.The only definite compound which the author was able to isolatefrom an extract of hay made with dilute sulphuric acid was some acidresembling quinic acid.It has been suggested by Weiske that the real source of hippuricacid may be the meadow plants with which hay is mixed.The author,therefore, investigated the officinal extract of dandelion, and againfound the acid resembling quinic acid along with some succinic acid,and an acid oil, heavier than water, which gradually became resinous.W. R.Analysis of a Calculus from a Horse. By P. PETERS andK. M ~ ~ L L E R (Bied. Centr., 1879, 714).-A calculus formed in con-centric layers and weighing 84 kilos.-was analysed by the authorswith the following results :-Magnesium Soda andOrganic amrnsnium Ferric Calcium potashWater. matter. phosphate. phosphate. phosphate. Silica. salts.4.22 6-20 87.37 0.29 0.11 1.36 0.45J.K. C.Physiological Inflaence of Adulterated Wine. By A. SCHMITZ( R i d . Centr., 1879, 712-713) .--The unfermentable residues of grape-sugar, which are used. for the adulteration ~ l f wine, were subjected toexperiment with reference to their physiological action. Sn b-cutaneous injection in $he case of dogs was found to produce vomitingand general derangement. The author is of the opinion that theseresidues contain a poison similar to that in fuse1 oil.Chemical Cause of the Toxicslogical Action of Arsenic.By C. BINZ and H. SCHULZ (BeT., 12, 2199--2202).--The authors areof opinion that arsenic owes its poisonous nature to the alternateoxidation of arsenious to arsenic oxide and reduction of arsenic toarsenious oxide, which produces a rapid oscillation of the atonis ofoxygen in the molecules of albumin, causing their complete destruc-tion.Arsenic acts as a carrier of oxygen, resembling nitric oxide inthis respect. Phosphorus and the ether members of the nitrogengroup appear to act in a similar manner. The authors base theiropinion on the following observations :-(1.) That in cases of arse-nical poisoning, i t is those portions of the system which have thepower of taking up oxygen from the blood which suffer mostseverely; (2) and that egg albumin, blood fibrin, and brain reducearsenic oxide to arsenious at a blood heat', and that the salivary glandsand liver not only reduce arsenic to arsenious oxide, but also oxidisearsenious to arsenic oxide, whereas blood, hamoglobin, and fat haveno action on the oxides of arsenic.w. c. w.J. R. C.Presence of Alcohd in Amtrnal Tissues during Life andafter Death. By J. B~CHAN'P (Compt. rend., 89, 573--574).-1norder to verify the truth of the statement that flesh mperficially coagu-lated would rapidly putrefy under conditions in which well-cookedflesh would remain sound for many weeks, some horseflesh was coagu-lated by immersion for ten minutes in boiling water, then wrapped iVEGETABLE PBYSIOLOGY AND AGRICULTURE. 175a closely woven cloth, and placed aside for eight days. At the expira-tion of that time, the meat was found in an advanced state of decom-position, and the muscular striation had disappeared, although the airhad not penetrated to the interior of the substance, whilst bacteria andvibrios abounded. By methods described in the original memoir, theauthor isolated and characterised about 0.8 gram of alcohol and10 grams of sodium sa.lts formed by acetic, butyric, and other acids.The alcohol was converted into aldehyde, and oxidised to acetic acid, sothat its identity was established beyond doubt ; within certain limitsthe quantity obtained was larger, the further the extent of the decom-position.It would seem, therefme, t,hat the phenomena accompanying putre-faction are very closely allied to those belonging to fermentationproperly so called, perhaps more directly with those of the butyricfermentation. By the same process alcohol was obtained from thejresh tissues. The brain of sheep gave a larger quantity tJhan theliver, but the largest quadity was,obtained from the brain of an ox,which furnished sufficient alcohol (to measure with the hydrometer.It may be argued, therefore, that in medico-legal cases, the detectionor separation of alcohol from putrid or healthy tissues, is not suflicien tevidence to show that alcohol has been administered a t all: still lessthat this liquid has been the cause of death. J. W

ISSN:0368-1769    

DOI:10.1039/CA8803800173

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

VEGETABLE PBYSIOLOGY AND AGRICULTURE. 175 Chemistry of Vegetable Physiology and Agriculture. Unorganised Ferments in Plants. By C. KRAUCH (Bied. Centr., 1879, 120-122) .-The ferments from various plants were obtained by t,he method of Wittich, or by that proposed by Erlenmeyer. For the detection of diastatic ikrrnenkation, the decomposition of starch into sugar and dextrin was employed. Tho ahion of the ferments on nlbu- minoids could be studied only when free acids (2 : 1000) were present ; to detect and recognise the ferments which act on fatJs, the decompo- sition (1) of an emulsion of gum arabic water ; ( 2 ) of oil with free mid and glycerol; (3) of oil in the state of an emulsion, were taken advan- tage of. The substances which came under examination mere buds and twigs of horse chesiiiit, which were separated into wood and bark : the same also of the birch ; the young and old bark a d wood of oak, the leaves of hawthorn ; bulbs and tubers ; starchy grains, as barley and maize, the endosperm and embryo being in the last grain examined separately ; oily seeds, as pumpkin. I n no case could albuminous or fatty ferments be detected.A strong diastatic ferment is found in the horse chesnut a t all periods of growth. Slight fermenting action in the leaves of oak and hawthorn, whilst the birch is free of ferment. In onions and potatoes, a weak ferment is present, but during the period when there is EO growth, the onion alone possesses a ferment. Diastase is present in unsprouted barley, but the action is weaker than that of malt176 ABSTRACTS OF CHEMICAL PAPERS.diastase; in unsprouted maize diastase is found only in the embryo and hilum. It would seem, therefore, that in all starch-containing plants, diastase is present more or less, the quantity being dependent on the amount of starch present ; but the change of starch into glucose does not necessitate the presence of diastase : for example, the birch contains no diastase at any time. Further experiments were directed towards determining the action of the ferment of the above plants on gum nrabic and quince em~ulsion ; in all cases sugar was formed. The ferment of oak and hawthorn leaves, d t and pumpkin seeds, affected salicin, but the action wats most energetic in the case of the pumpkin seeds ; only oak leaf ferment had any action on amygdalin, and that only after 48 houvs' contact.. The composition of diastase is given as C, 45.68 ; H, 690 ; N, 4.57 ; ash, 6.08 ; 0, 36.77 parts per. hundred ; sulphur is also present in wall quantities. E. w. P. Chemical Composition of Bacteria in Putrefying Liquids. By M. NENCKl and 3'. SCHAFFER (J. pr. Chem., 20, 443-465).-The authors have found t h a t on adding a few drops of acid (sulphuric, hydrochloric, or acetic) t o a liquid containing bacteria, and boiling it for a few minutes, the bacteria shrivel up, and settle ; the liquid may then be filtered, and the bacteria separated in a " chemically pure " condition. Of course the fluid must contain no substances precipi- table by boiling, such as albumin. Ordinary gelatin was therefore chosen as a suitable medium for propagating the growth of bacteria.The dried mass of bacteria was first exhausted with alcohol, and the alcoholic extract then treated with ether. A slight brownish residue of a substance resembling peptone was left. The ethereal extract contained the fat, the elementary composition of which -72.54 per cent. C., and 11.73 per cent. H-corresponds fairly with that of vegetable and animal fats, but contains 1.5 per cent. too little carbon. I n order to ascertain whether any change in the composition of bacteria occurs in the course of their development, analyses were made of undeveloped granules, of a mixture of granules and rod-like bodies, and of the rod-like bodies after f u l l growth. The results are as follows :- Uranular mass Pure granular with partially mass developed Perfect (Zooglcea).bacteria. bacteria. Water ............ 84.81 84.26 83.42 Fat (contained in dry substance) ......- 7.89 6-41 6-04 Ash (in substance de- prived of fat) .... 4.56 3-25 5.03 - 53.07 53.82 H - 7.09 7.76 N 14-34 13-82 14-02 a. 14.60 0. 13.82 Elementary com- position of the substances de- prived of fat An estimation was made of the albumino'id substance cont,ained inVEGETABLE PHYSIOLOGY AND AGRICULTURE. 177 the bacteria, by exhausting the mass wifh very dilute alkali, separating the soluble from the insoluble portion by filtration, neutralisation with hydrochloric acid, and precipitation by addition of crystals of salt. The precipitate consists of a new albumino'id, soluble in excess of acetic acid, and has been named by the authors mycoprotezn. It contains 52.32 per cent.C. ; 7.55 per cent, H., and 14.75 per cent N., and corre- sponds well with the formula C25H4,N60,. I t was proved that neither sulphur nor phosphorus were present. Freshly precipitated myco- protein is easily soluble in water, alkalis, and acids, but after being dried a t 110", it is no longer perfectly soluble in water. It exhibits the usual properties of an albumin, and is laworotatory, [a] = -79. Acids convert it into peptones. The authors believe that this simple form of albumin is obtained from a simple organism ; a general law may be deduced, the more complex the organism, the more complex its proximate chemical mastituente. The residue left insoluble on treating the bacteria wit,h dilute alkali, consists of cell-membrane, and amounts to about 5 per cent.of their weight ; it contains a little nitrogen. This may point to some albumin not removed, for Loew analysed similar cell-membranes, and found them to contain a mere trace, or no nitrogen. W. R. Germinating Power of Beetroot Seeds. By A. PETERMANS (Bied. Centr., 697--699).-The author is of opinion that beetroot seeds of good quality should have a germinating power of not less than 85 per cent. ; he also observes that this depends very largely on the ripeness of the seeds st the time of gathering. Influence of Smoke on the Development of Blossoms. By E. DA CANTO (Bied. Centr., 1879, 715).-It is found in the Azores that the eritrance of smoke into the conservatories causes a rapid develop- ment of the buds in the case of roses, ananas, &c., and this fact is now made use of in hastening the blooming.Causes of the Change in the Form of Etiolated Plants. By E. GODLERSKI (Bied. Cerhtr., 1879, 715-716).-The author shows that want of light stops the growth of the cotyledons, and favours that of the stems; hence the changes of form observed. J. K. C. J. K. C. J. K. C. Notes on Cinchona Bark. By D. HOWARD (Phurm. J. Truns. [3], 10, 181).--The author has been enabled to compare the proportion of quinine and other alkalo'ids contained in the " natural '' bark and in that formed by " renewing," L e , , growing after the artificial removal of the bark. This renewed bark is termed " mossed bark," because the tree, after being stripped of its bark, is usually protected by acovering of moss, whilst fresh bark is being formed. The natural bark was found to be generally inferior to the mossed bark, since it had been collected either from the upper stem, or from inferior old trees, whereas the mossed bark represents the product of the main stems of the oldest trees.As far as the effect of age was concerned, it was found that both the quinine and total crystallisable alkaloid steadily increased in quantity with the age of the trees ; this is probably due to178 ABSTRACTS OF CHEMICAL PAPERS. the greater maturity of the trees. The trees from which the bark was taken were specimensof Cinchona qficinalis. The author, on the other hand, confirms from recent experience an opinion previously expressed, that the bark of szccciruhra deteriorates in quality when the tree has passed a certain age. Root bark shows a marked tendency to develope the dextrogyrate alkaloids.A sample of renewed bark, which had been formed without " mssing," or any kind of protection, was also examined, and was found equal in quality to the best mossed bark; hence it appears that the only advantage of mossing is to enable the tree to form bark again with a minimum injury to its hcvdth; the process does not appear to improve the quality of badk formed. The author also compares the proportions of alkaloids contained in outer and inner bark ; the outer bark not only contains a larger quantity of alkalo'ids, but these contain a larger proportion of quinine ; hence it has been suggestled to shave off only the outer layers, without cutting quite through the bark.Relation of Yield of Beet to Rain and Sunshihe. By J. HANAMANN (Bied. Centr., 1879, 694--697).--The author has made observahions in Bohemia, on the relation. of beetroot produce to the weather during the last twelve years, and arrives a t trhe following conclusions. A mean temperature of from 14 to 18" C., from May to October inclusive, and a warm and wet spring, together with a not too dry sumlmer, are the best conditions under which beet can be grown. Researches on the Ripening of Grapes and F9uits. By C. PORTELE (Bied. Centr., 1879, 123--131).-The composition of apples, pears, and other- fruits was determined a t various periods of their growth. The results are as follows.:-The absolute weight of pears and apples increases, whilst that of grapes increases only up to the time when colour appears, and then begins to decrease.The per- centage of d r r matter in the pear a t first increases and then diminishes, whereas with apples the decrease is sudden and then remains constant. I n the same way alteration of the amount of insoluble residue occurs. The percentage o€ ash constantly sinks, which with the apple is twice as great as with the pear. The amount of free acid is greatest in the young pear, gradually sinking, but again slightly increasing a t the end of ripening ; this last does not occur in the app'le. Grapes differ from kernel fruit, in that with them there is not only a change in the rela- tive percentage of the various acids present, but also a decided decrease in the total free acid.Pears appear to contain a t first only tan& acid, which gives place to mnlic acid as growth proceeds, whilst the apple appears to contain both, and these diminish regularly. Sugar increases as apples, pears, and grapes ripen, but with grapes it is the dextrose which increases most, whilst lavulose increases in greatest proportion in other fruits. Comparing the constitution of the leaves with the frnit, we find that the acid in the leaf is present in greatest quantity when that in the fruit is lowest. Sugar increases in the leaf and then decreases, and there is more present in the leaf a t first than in the fruit ; lsevu- lose and dextrose are present in equal quantities. F. C. J. K. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 179 Other specimens of fruit were examined which had been plucked and put aside to ripen, and it8 was found that the loss in weight was less, the riper the fruit was when plucked. Fibre, &c., and acid de- crease, but sugar increases, and dextrose is converted into laevulose.Various other fruits, as strawberries, peaches, &c., were also examined, and with similar results. lil w. P. Depreciation of Barley by Overgrowth. By LAUENSTEIN (Bied. Centr., 1879, 676-681).-The difference betweeri barley gathered at the right time and barley which has been allowed to lie out on the field for some time after it was ripe is not clearly shown by direct chemical analysis. An examination of the separate con- stituents is necessary in order to ascertain the changes which have taken place.I n carrying out this plan the autrhor turned his attention first to the starch present in the seed. Ordinary barley contains 64 per cent.; in the overgrown corn was found, however, only 58 per cent., the remainder having been converted into dextrin and sugar : a loss of 10 per cent., therefore, on the total quantity of starch was dis- covered. The change whish the starch .had undergone would of course not affect the nutrit$ve value of the barley ; this, however, was not the case with t h e albumin, nearly one-fourth of which was found t o be converted into amido-compounds, which are of very little nutritive value. The worth of barley for the preparahion of malt depends to a very large extent on its powers of germinating. This was found to have suffered a loss of 53 per cent.in the overgrown corn. J. K. C. On the Quantities of Acid and Srrgar in Grapes cut at Various Stages of their Growth. By P. WAGNER and W. ROHX (Bied. Centr., 1879, 681--686).-These researches have been so far only of a tentative character, the objecb being to discover if possible a practicable method of examining various sorts of grapes a t different stages of their growth, and chiefly at the ripening stages. The authors carried out their researches at six different places, with vines of various kinds. The grapes were cut four times during the last month of ripening, and the relative quantities of sugar and acid determined in the Rap. In some cases the relation improved, in others it remained constant for some weeks. The authors hope, by repeating these obser- vations for some time to come, to arrive at results of great practical value.J. I(. C. Ripening of AppIes after Gathering. By F. TSCHAPLOWITZ (Bied. Cen,tr., 1879, 686-689).-The author finds that the loss of weight undergone by apples on keeping is dependent on the position i n which they are left and the dryness of the surrounding air. It may be almost, entirely considered as loss of moisture, the amount of car- bonic anhydride which is given off being but very small. It is notice- able that smaller apples lose more in weiqht than those of a larger description. The temperature of the fruit is also the same as that of the air. The results of various analyses show that the quantity of sugar in180 ABSTRACTS OF CHEMICAL PAPERS. the apples increases during the ripening process a t the expense of the pectin and acid.Decomposition of Albuminoi'ds in Pumpkin Sprouts. By E. SCHULZE and J. BARRIERI (J. pr. Chem., 20, 383-418).-The seeds of plants contain albumino'ids, staich, and oil, by which the sprouts, which are not able to decompose carbonic anhydride and water, are nourished. During germination the starch and fat decrease, whilst sugar, dextrin, and cellulose are formed, and carbonic anhydride and water are eliminated. From more recent observations, it has also been discovered that the albumino'ids become soluble, and that in many plants, especially in Papilionace=, nsparagine is produced. As that body decomposes on boiling with hydrochloric acid into aspartic acid and ammonia, its amount may be determined by estimating the ammonia.Gorup-Besanez afterwards found leucine amongst the de- composition-products of albuminoids. In pumpkin sprouts, which contain no asparagine, Sabania and Laskowski supposed that another amide existed; this was shown to be correct by the authors and by Ulrich. I n the beetroot this amide has been shown to be glutamine, and the object of the present paper is to show thak it is also present in germinating pumpkin sprouts, along with asparagine, leucine, and tyrosine. The albuminoids and fatty oil form 86-88 per cent. of the weight of dry pumpkin seeds, the former being present as protein granules. When the crushed seeds are treated with ether, the fat dissolves and the prote'in substances sink to the bottom of t'he vessel. They are in- soluble in water, but dissolve in a 10 per cent. solution of salt.On addition of solid salt, a small quantity of vegetable myosine separates, and on dilution with water, vegetable vitelline is deposited. Non- albuminoid principles containing nitrogen are present in very small amount in pumpkin seeds. The sprouts after germination were dried, boiled with alcohol, and the evaporated extract was treated with lead acetate. The filtrate from the lead precipitate was boiled for several hours with hydro- chloric acid, and again mixed with lead acetate to remove hydrochloric acid. The filtrate from the lead chloride after evaporation was mixed with alcohol, and the precipitated lead salts were decomposed with sulphuretted hydrogen. The soiution filtered from the lead- sulphide and treated with silver oxide to remove traces of hydrochloric acid was evaporated, when glutaminic acid, C5H9N04, separated in the crystalline state.It was shown that this acid was not present as such in the sprouts, but was formed by.the action of hydrochloric acid on glutamine, a body bearing the same relation to glutaminic acid as asparagine does to aspartic acid. From sprouts which had germi- nated for eight days, 100 grams gave only a few decigrams, but 16 days' growth increased the amount, to 1.75 gram of acid, representing 1.74 gram of glutamine. The ammonia produced by the action of hydrochloric acid on glutamine corresponds to twice that amount, and to account for it a seal-ch was made for substances which would nndergo a similar decomposition with hydrochloric acid.Aspart- ate of copper, amounting to 0.5 gram in 400 grams, was separated J. I(. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 181 from the mother-liquors of the glutamic acid, and leucine and tyro- sine were isolated by boiling the juice from sprouts 2-3 weeks old ; and after precipitating with alcohol and evaporating the filtrate, wart- like crystals were deposited, consisting of tyrosine. From 1,000 grams of fresh sprouts (60 grams when dried), 0.15 gram of tyrosine was obtained, and leucine was isolated from the mother-liquor of the tyro- sine, but in much smaller quantity. The nature of the decomposition products is thus the same as when the albuniino'id is heated with baryta-water or hydrochloric acid ; but the proportion of each product differs greatly.On decomposing the albuminoi'ds from pumpkin seeds with hydrochloric acid and stannous chloride, 120 grams yielded leucine, 24 grams ; tyrosine, 2.5 grams ; aspartic acid, 3 grams ; glutamic acid, 4 grams; and an uncrys- tallisable residue of 40 grams, the sum being 75 grams. The differ- ence between 120 and 75 = 45 grams, was lost. If these amounts represent even approximately the proportions in which the nitrogenous materials are present in the mixture, i t is seen that they differ greatly from the proportions produced by the deconiposition of the albuniino'ids during germination. The author's explanation is that in a growing plant albumino'ids are being formed as well as decomposed, any one of the decomposition products serving as material for their formation.The co-existing decomposition products of albumino'ids may, however, not be equally used in the formation of new albumino'ids, and those which resist the process of regenerating albumin longest accumulate in largest quantity. Thus leucine, which is produced in large quan- tity by the artificial decomposition of albumin, is probably one which lends itself best to the natural formation of albumin, and is therefore present in germinating plants in small amount, whilst such substances as asparagine and glutamine are comparatively stable, and resist ab- sorption to form new albumino'ids. I n conclusion, the authors remark that as ferments are capable only of changing albuminoi'de into peptones, soma other reason must be sought for to account for their decomposition into much more simple products, and quotes a sentence of v.Nageli, in which such changes are ascribed to the molecular force of living tissue. The Most Advantageous Method of Sowing Corn. By F. HABERLANDT (Bied. Centr., 1879, 689-694) .-The author has made several experiments with wheat, rye, and barley, with a view of ascer- taining the number of seeds per square meter which will give the best yield. His results have necessarily only a special value for the soil and climate in which the experiments were carried out. He was able to obtain a yield twice as great as that usually obtained, and thinks that this might be effected in most cases where the proper conditions are observed. It was noticed that the latest development occurred where the seed was most sparsely sown.Proper Thickness and Depth to Sow Corn. By SCHENK- BAUHOF (Bied. Centr., 1879, 717). Amount of Carbonic Anhydride in Shingle. By G. WOLFF- H ~ G E L (Bied. Centr., 1879, 709) .-The author brings forward tables W. R. J. I(. C. VOL. XXXVIII. 0182 ABSTRACTS OF CHEMICAL PAPERS. Contraction and expansion. already published in defence of his view that the amount of carbonic anhydride in the ground air is a measure of the degree of impregns- tion of the soil with organic matter and of the progress of its decom- position. J. K. C. ~- ~ Capillary saturation capacity. Saturated with capil- lary water. Peaty Soils. By A. v. SCHWARZ (Bied. Centr., 1879, 84--93).-- The analyses of 26 Austrian peaty soils are given, in which the ash varies from 2.30 to 76-08 per cent.To one soil the author has paid special attention, and he has determined the physical properties (which are here appended) of soil from the moorland of Kirchberg a. W. He also finds that this soil when treated with artificial manures yields average crops. The physical properties of the soil were compared with those of alluvial sand from Rotz, loam, and clay, and are as follows :- 100 c*e* '::i:$* saturated when satu- after dry- rated in ing in C.C. C.C. Soil. -- Peaty . . . . Sand , . . . . Loam . . . . Clay . . . . . -___ ____ 100 c.c. 100 grme. contain contain of of water water Weight of 100 C.C. in grams. 39 *8 100.0 83.9 70.2 Air dry. 28 -7 .57 -9 .55 * 2 -40 '1 - - 82 '0 77 .G 100 0 34.9 18 -3 119.2 43 .2 22 -6 142.1 51 -5 28 *6 Satu- rated.LO5 - 6 190 -6 t92 9 179 -8 - ~ Equal weights specific heat. Saturated 1 Dried at m-it11 1 Dried at 1000. capillary 1 1000. ' - SP. !2T* water at 17.5 = 1 -00. Equal volunies setumted with capilltwy water. 1 %70 2 '569 2 -729 2 914 I I----I-- -- In the determination of cohesion by Haberlandt's process, clay was found to stand highest and loam lowest, sand naturally possessing none. In the case of adhesion by Schiibler's method, clay st,ands first, then loam, peat, sand. Masses of soil 10 cm. deep, m d exposing a surface of 10 square cm., allowed the passage in 24 hours of 1 C.C. water in the case of pest, Soil. IIygroscopicit,? 100 grams dry soil absorb of water Peaty . . . . . . Sand . . . . . . . bani . . . . . . Clay . . . - . . . 21 43 1.1 3.7 9 -2 0 -960 0 %'75 0 '762 0 *8@kVEGETABLE PHYSIOLOGY AND AGRICULTURE.183 5,760 in the case of sand, 1,674 in the case of loam, and 0.7 in the case of clay. Conductivity for heat was determined (1) by the increase of tem- perature of the unheated soils, and (‘2) by the loss of temperature experienced .in cooling. In this the soils were experimented on when dry, and when moist, or saturated with capillary water, the source of heat was 60°, and the original temperature 16*3-16*7”. From the results, it would appear that under direct action of solar radiation peaty soil when dry assumes a higher temperature than either of the others, but the case is reversed if the soils be moist. As regards the rising of water in columns of sand, loam, and clay, it is found that in 100 days water had risen to the height of 408 mm.in sand, to 1,627 in loam, and to 770 in clay. E. w. P. Composition of Maize. By L. GRAKPEAU (Biecl. Cencr., 1879, 149) .-Analyses of various specimens of maize used as feeding stuffs are given. The best appear to be the Hungarian (nutrient ratio, 1 : 8*8), then American (nutrient ratio = 1 : 8*6), but the AmePican is very hard to crush. E, W. P. New Plant for Fodder. By J. DEIWINGER ( B i d . Cewtr., 1879, 700--702).-Seeds of a plant known in India as “gram,” a variety of chick-pea, were planted in various kinds of soil in Hungary. The plant thrived exceedingly well, especially in sandy soils, which m-ere worthless for other purposes, and proved very productive. The following analysis of the seeds show that they are sery valuable as fodder :- Nitrogen- free Water. Protein.Fat. extract. Fibre. Ash. First year . . . . 10.72 12.88 4-39 58.02 10.20 3.i9 Second year . . 9.80 17.68 3.77 54.32 10.89 3.54 J. K. C. Analysis Of Materials used for Fodder. By P. WITmLsHiimIt ( B i d Centr., 1879, 713).-Analyses were made of soured cabbage leaves, dried sprigs of broom, concentrated residues from a starch manufactory, and potato pulp. The first two proved to be excellent, for fodder, but the last was too poor in nutritive matter t o be used alone. J. K. C. Feeding Value of some Manufacturers’ Waste. By 3 . MOSER (Bied. Oentr., 1879, 3_14-117). - The analyses of seveml feeding-stuffs, which however do not appear in large quantities in the market, are given, and are as follows :- 0 2184 ABSTRACTS OF CHEMICAL PAPERS.Fennel seed cake.. Sunfiower cake : (1.) As powdery mass. . . . . . . . . (2.) As coherent cake . . . . . . . . . Pumpkin seed cake Loosely coherent mass. . . . . . . . . Decorticated.. . . Tobacco seed cake, containing no ni- cotine. . . . . . . . . . Wine lees cake.. Dried brewers' grains : Mixed with meal and dried.. . . Fresh and un- dried . . . . . . . . Brandy manufac- turers' waste*, pressed and dried Boiled and press- ed. . , . . . . . . . . Same not pressed Suet grieves : - Ilbum. 9 '23 :LO -62 8.07 11 *25 11 *01 10 '69 54 -04 12 *94 79 -22 12 -42 4 9 7 58 -29 - - Water. -- 15 *28 38 -00 37 -69 32 -56 38 -74 25 *60 2 *54 18 *69 4.92 24 *50 48.06 11 '75 - - Fat. 12 .o 6 *44 23 -73 25 *57 23 *55 14.6C 8-54 ci -3c 1 '35 11 -87 41 -1C 24 -2C ~~ ~ Non- nitrog.extract. -- 33 *12 28 *11 19 *29 9 -13 10 -75 15 *08 7 -41 38 -00 9 *36 39 -30 - - Fibre. 20 -15 10'4F 6 '05 15 -6E 10 -33 22 -43 11 *1C 16 *95 3 -44 c Ash. 8 -14 4.96 5 '10 4 '79 5 -39 5.31 1 '74 4'31 0 *89 1 5 2 4 -88 - E. m - Sand. 1 -93 1 *39 0 -62 1 -02 0 *23 6 *29 9 -20 2 *81 0 -52 1.61 0 '41 - - P. Certain Sorts of Pumpkin. By C. 0. HARZ (Bied. Centr., 1879, 717) .-The author recommends Cucurhita rnaxinza Brasilierisis and C. m. eZZiptica as the best kinds to grow, because the fruit does not putrefy and can be kept many years. Analysis of the dried fruit gave the following results :- Nitrogen- free Protein. Fat. extract. Fibre. Ash. 10.87 1-64 72-75 9-39 5-35 J. K. C. Influence of Fodder on the Quantity and Qualityof Milk Fat.By H. WEISRE, M. SCHRODT, and B. DEHMEL ( B i d Centr., 1879, llO-l13).-The present opinions concerning the influence of Eodder on milk produced are, that dry food produces more solid gly- cerides in butter than the green feeding of summer, and that a hard hntter is produced when the feeding has been scanty, or poor in albu- minoid matter. The analyses of the milk of a cow which had been li; Note by Abstractor.-There is evidently a printer's error here, as t,he above malysis is said to be that of a substance undried, whereas the analysis of the same inaterial which is called " dry," shows a percentage of 61.41 water.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 185 fed a t different periods with various kinds of food, show that a high melting point of butter is not dependent on scanty feeding; the melting point, and also the quantity of the butter fats, and of the fatty acids, show no regularity, even when the feeding remains the same.Highly albuminous fodder produces the highest yield of milk ; addition of albuminoid matter to fodder increases the amount of fat in milk, but addition of oil and of stearic acid causes a much greater amount of fat and dry substance to be formed. Comparing morning and evening milk, no difference in the amount of solid matter or fat could be detected; and the melting points of the fats were the same on the same days, the melting point of the cream fat being 2" lower than that of the fat of the skimmed milk. The amount of fatty acid insoluble in water varied very considerably, varying from 84-889 per cent.E. W. P. Four-yearly Rotation of Crops. By A. VOELCKER (R*ietb. Centr., 1879, 658--661).--These experiments mere conducted a t Woburn on behalf of the English Agricultural Society; .the plan of rotation was the following:-1st year, clover; 2nd year, wheat; 3rd year, roots (turnips, &c.) ; 4th year, barley. The results obtained in 1878 were mostly of a normal chractw. The author has found that manure obtained after a fodder of cotton seeds is of more value to the land than if the animals had been fed on maize; and that the mate- rials for plant nutriment have a better effect when applied directly to the land than when they have been mixed with fodder and allowed to pass into dnng. J. I(. C. Manuring of Oats on Fen Lands. By H. .J. CARSTEN (Bled. Centr., 1879, 97-99).-Oats were found to be most prolific on moor land when manured with stable manure.Comparing the two methods of cultivation, " Veen" and '' Damm kultur," it was found thai the " Damm" method (covering the moor with a layer of sand), in all cases when the manuring with artificial manures was employed, gave better results than the " Teen'' method (where the surface to a depth of 10-12 cm. is mixed with sand). Effect of Gypsum ow the Quantity and Quality of Clover Crops. By A. PASQUALM (Bied. Ceizta-., 1879, 99).--Clover manured with gypsum is not affected as regards its feeding qualities, although the total yield is increased. E. W. P. E. W. P. Manuring of Sugar Beet. By. J. MOSER (Bied. Centr., 1879, 100--106).-This paper contains an account of the manures used (salts of potash, soda, and magnesia), the yield of mots, tops, and sugar obtained in experiments made in the years 1876-77; but no conclusions are drawn, as the experiments are still being carried on.The manures were employed in quantities equal to one-eighth of the capacity of the soil for potash. Manuring of Beet. By H. BRTEM (Bied. Centr., 1879, 656-658). -Two kinds of lime manure are used in this investigation, the object E. W. P.186 ABSTRACTS OF CHEMICAL PAPERS. --- 105 122 210 of which was to compare their action. One of these was the ordinary lime-scum from sugar works, and the other a mixture of lime-dust with the residues from a beet and molasses disti1ler.y : the latter con- taining about 43 per cent., and the former 30 per cent.of lime: t,hey were applied to a soil very poor in lime, containing about 4 parts per thousand, the experiments being carried out in two successive years : the mean results are as follow : - 335 384 736 Manure used. 3 . 2 5 3.23 4.44 -- iY.,ue Lime from eugar works. . . . . . . . . Lime with distil- lery residues. . . . . . . . . . , . . - - 82.8 0.80 84.7 0.91 I Weigkt of the beet in grams, Total. Leaves. Root. 1 1 440 506 946 Polarisation of 1 Percentage sap. I Of Degrees. 14 -2 15 0 14 *1 Sugar. 10 -95 11 -67 9 -66 - sugar. The difference in the effects produced by the two manures is very marked: the distillery residues produced a wonderful effect in in- creasing the <total weight of the yield, at the same time, however, deteriorating greatly the quality of the juice obtained, as is observed on comparing the ratio of the quantities of sugar and non-saccharine matter present in tbe juice : this relation cis of the greatest importance to the manufacturer, as a juice containing such a quantity of extra- neous matter would be found very difficult to work.J. I(. C. Influence of Soluble and Insoluble Phosphates as Manure for Turnips. By T. JAMsEsoN ( B e d . Cewh-., 1879, 659--656).--Thcse investigations were carried out near Aberdeen., with a view of com- paring the effect of phosphoric acid in the soluble and imoluble form applied as manure to turnips. Five fields, lying at considerable dis- tances from one another, were selected, and each made the subject of eighteen experiments, each of which was carried out on two separate plots.The experiments were conducted in the years 1876 and 1877, the latter proving a bad year for turnip crops. No difference was observed between the effect of animal and mineral phosphates. Froni the results obtained, the author shows that the effect of insoluble phos- phates varied little from that produced by soluble phosphates :- Yield per acre in kilos. after tieatinent with Insoluble Soluble phosphate. phosphate. F \ 1876. Mean of 30 experiments a t 35 places.. 17,270 18,290 7, 6 :7 1 place . . 18,290 17,260 1877. ,, 4 . ,, ,, . . 8,430 9,860VEGETABLE PHYSIOLOGY AND AGRICULTURE. 187 Addition of nitrogenous manures to the phosphates yielded the following results in 1876 :- Sulphate of ammonia Chili saltpetre with with 7 f----- I Soluble Insoluble Soluble Insoluble bone-ash. bone-ash.bone-ash. bone-ash. Mean of 10 experiments . . 20,720 20,720 21,130 18,699 7, 2 7 9 . . 24,380 24,380 23,350 22,350 The increase in the yield produced by the addition of nitrogenous manures is, however, onlyan apparent one, as it arises merely from an increase of the percentage of water in the product. The same inorease in the yield ma<y be obtained when the phosphate is very finely powdered. The author also finds that the highest percentage of nitrogenous rnatker and the smallest quantity of sugar was the result of manuring with soluble phosphate, whilst insoluble phosphate produced the exactly opposite effect, and a medium result was obtained when nitrogen had been added to either. Those plots which were manured in 1876 were left unrnanured in 1877 in order to observe the after-effects of the various materials used.It was observed that those fields which gave the best yields in the former year were the least productive in the latter, and vice versG. Animal phosphate also appeared to have a better after effect than Ijhosphates of mineral origin. The highest produce as a total of both rears was obtained by using raw dried bone-ash, which is more effec- tive when applied in spring than in autumn. The results obt,ained by the use of this manure show that it is the best that can be applied in the case of turnips. J. K. C. Action of Different Manures on the Yield of Potatoes. By W. PAULSEN (Bied. Ceiztr., 1879, 106--108].-Sheep’s dung produces a yield 50 per cent.higher than that produced by various other artificial manures, and 60 per cent. higher than if no dung be applied. Extra supplies of ammoniacal superphosphate produce no increase, and ‘ * compost” does not appear to be capable of producing larger yields than unmanured land. But, on the other hand, manures increase the amount of starch. The number of diseased potatoes was highest in the plots which were unmanured, and more especially high in the crops of “ Furstenwalder ;” amongst the “ snow flake ” potatoes there \yere also many diseased. Of the seven sorts grown, “ Ayrora ” seems t o have been the most satisfactory. E. W. P.VEGETABLE PBYSIOLOGY AND AGRICULTURE. 175Chemistry of Vegetable Physiology and Agriculture.Unorganised Ferments in Plants. By C.KRAUCH (Bied. Centr.,1879, 120-122) .-The ferments from various plants were obtained byt,he method of Wittich, or by that proposed by Erlenmeyer. For thedetection of diastatic ikrrnenkation, the decomposition of starch intosugar and dextrin was employed. Tho ahion of the ferments on nlbu-minoids could be studied only when free acids (2 : 1000) were present ;to detect and recognise the ferments which act on fatJs, the decompo-sition (1) of an emulsion of gum arabic water ; ( 2 ) of oil with free midand glycerol; (3) of oil in the state of an emulsion, were taken advan-tage of.The substances which came under examination mere buds and twigsof horse chesiiiit, which were separated into wood and bark : the samealso of the birch ; the young and old bark a d wood of oak, the leavesof hawthorn ; bulbs and tubers ; starchy grains, as barley and maize, theendosperm and embryo being in the last grain examined separately ;oily seeds, as pumpkin.I n no case could albuminous or fatty fermentsbe detected. A strong diastatic ferment is found in the horse chesnuta t all periods of growth. Slight fermenting action in the leaves ofoak and hawthorn, whilst the birch is free of ferment. In onions andpotatoes, a weak ferment is present, but during the period when thereis EO growth, the onion alone possesses a ferment. Diastase is presentin unsprouted barley, but the action is weaker than that of mal176 ABSTRACTS OF CHEMICAL PAPERS.diastase; in unsprouted maize diastase is found only in the embryoand hilum.It would seem, therefore, that in all starch-containingplants, diastase is present more or less, the quantity being dependenton the amount of starch present ; but the change of starch into glucosedoes not necessitate the presence of diastase : for example, the birchcontains no diastase at any time. Further experiments were directedtowards determining the action of the ferment of the above plants ongum nrabic and quince em~ulsion ; in all cases sugar was formed. Theferment of oak and hawthorn leaves, d t and pumpkin seeds, affectedsalicin, but the action wats most energetic in the case of the pumpkinseeds ; only oak leaf ferment had any action on amygdalin, and thatonly after 48 houvs' contact. . The composition of diastase is given asC, 45.68 ; H, 690 ; N, 4.57 ; ash, 6.08 ; 0, 36.77 parts per.hundred ;sulphur is also present in wall quantities. E. w. P.Chemical Composition of Bacteria in Putrefying Liquids.By M. NENCKl and 3'. SCHAFFER (J. pr. Chem., 20, 443-465).-Theauthors have found t h a t on adding a few drops of acid (sulphuric,hydrochloric, or acetic) t o a liquid containing bacteria, and boiling itfor a few minutes, the bacteria shrivel up, and settle ; the liquid maythen be filtered, and the bacteria separated in a " chemically pure "condition. Of course the fluid must contain no substances precipi-table by boiling, such as albumin. Ordinary gelatin was thereforechosen as a suitable medium for propagating the growth of bacteria.The dried mass of bacteria was first exhausted with alcohol, andthe alcoholic extract then treated with ether.A slight brownishresidue of a substance resembling peptone was left. The etherealextract contained the fat, the elementary composition of which-72.54 per cent. C., and 11.73 per cent. H-corresponds fairly withthat of vegetable and animal fats, but contains 1.5 per cent. too littlecarbon.I n order to ascertain whether any change in the composition ofbacteria occurs in the course of their development, analyses were madeof undeveloped granules, of a mixture of granules and rod-like bodies,and of the rod-like bodies after f u l l growth. The results are asfollows :-Uranular massPure granular with partiallymass developed Perfect(Zooglcea). bacteria. bacteria.Water ............ 84.81 84.26 83.42Fat (contained in drysubstance) ......- 7.89 6-41 6-04Ash (in substance de-prived of fat) ....4.56 3-25 5.03- 53.07 53.82H - 7.09 7.76N 14-34 13-82 14-02a. 14.60 0. 13.82Elementary com-position of thesubstances de-prived of fatAn estimation was made of the albumino'id substance cont,ained iVEGETABLE PHYSIOLOGY AND AGRICULTURE. 177the bacteria, by exhausting the mass wifh very dilute alkali, separatingthe soluble from the insoluble portion by filtration, neutralisation withhydrochloric acid, and precipitation by addition of crystals of salt.The precipitate consists of a new albumino'id, soluble in excess of aceticacid, and has been named by the authors mycoprotezn. It contains52.32 per cent.C. ; 7.55 per cent, H., and 14.75 per cent N., and corre-sponds well with the formula C25H4,N60,. I t was proved that neithersulphur nor phosphorus were present. Freshly precipitated myco-protein is easily soluble in water, alkalis, and acids, but after beingdried a t 110", it is no longer perfectly soluble in water. It exhibitsthe usual properties of an albumin, and is laworotatory, [a] = -79.Acids convert it into peptones. The authors believe that this simpleform of albumin is obtained from a simple organism ; a general lawmay be deduced, the more complex the organism, the more complex itsproximate chemical mastituente.The residue left insoluble on treating the bacteria wit,h dilute alkali,consists of cell-membrane, and amounts to about 5 per cent.of theirweight ; it contains a little nitrogen. This may point to some albuminnot removed, for Loew analysed similar cell-membranes, and foundthem to contain a mere trace, or no nitrogen. W. R.Germinating Power of Beetroot Seeds. By A. PETERMANS(Bied. Centr., 697--699).-The author is of opinion that beetroot seedsof good quality should have a germinating power of not less than85 per cent. ; he also observes that this depends very largely on theripeness of the seeds st the time of gathering.Influence of Smoke on the Development of Blossoms. ByE. DA CANTO (Bied. Centr., 1879, 715).-It is found in the Azores thatthe eritrance of smoke into the conservatories causes a rapid develop-ment of the buds in the case of roses, ananas, &c., and this fact is nowmade use of in hastening the blooming.Causes of the Change in the Form of Etiolated Plants.ByE. GODLERSKI (Bied. Cerhtr., 1879, 715-716).-The author shows thatwant of light stops the growth of the cotyledons, and favours that ofthe stems; hence the changes of form observed.J. K. C.J. K. C.J. K. C.Notes on Cinchona Bark. By D. HOWARD (Phurm. J. Truns.[3], 10, 181).--The author has been enabled to compare the proportionof quinine and other alkalo'ids contained in the " natural '' bark andin that formed by " renewing," L e , , growing after the artificial removalof the bark. This renewed bark is termed " mossed bark," because thetree, after being stripped of its bark, is usually protected by acoveringof moss, whilst fresh bark is being formed.The natural bark wasfound to be generally inferior to the mossed bark, since it had beencollected either from the upper stem, or from inferior old trees,whereas the mossed bark represents the product of the main stems ofthe oldest trees. As far as the effect of age was concerned, it wasfound that both the quinine and total crystallisable alkaloid steadilyincreased in quantity with the age of the trees ; this is probably due t178 ABSTRACTS OF CHEMICAL PAPERS.the greater maturity of the trees. The trees from which the bark wastaken were specimensof Cinchona qficinalis. The author, on the otherhand, confirms from recent experience an opinion previously expressed,that the bark of szccciruhra deteriorates in quality when the tree haspassed a certain age.Root bark shows a marked tendency to developethe dextrogyrate alkaloids. A sample of renewed bark, which hadbeen formed without " mssing," or any kind of protection, was alsoexamined, and was found equal in quality to the best mossed bark;hence it appears that the only advantage of mossing is to enable thetree to form bark again with a minimum injury to its hcvdth; theprocess does not appear to improve the quality of badk formed. Theauthor also compares the proportions of alkaloids contained in outerand inner bark ; the outer bark not only contains a larger quantity ofalkalo'ids, but these contain a larger proportion of quinine ; hence ithas been suggestled to shave off only the outer layers, without cuttingquite through the bark.Relation of Yield of Beet to Rain and Sunshihe.By J.HANAMANN (Bied. Centr., 1879, 694--697).--The author has madeobservahions in Bohemia, on the relation. of beetroot produce to theweather during the last twelve years, and arrives a t trhe followingconclusions. A mean temperature of from 14 to 18" C., from May toOctober inclusive, and a warm and wet spring, together with a not toodry sumlmer, are the best conditions under which beet can be grown.Researches on the Ripening of Grapes and F9uits. ByC. PORTELE (Bied. Centr., 1879, 123--131).-The composition ofapples, pears, and other- fruits was determined a t various periods oftheir growth. The results are as follows.:-The absolute weight ofpears and apples increases, whilst that of grapes increases only up tothe time when colour appears, and then begins to decrease.The per-centage of d r r matter in the pear a t first increases and then diminishes,whereas with apples the decrease is sudden and then remains constant.I n the same way alteration of the amount of insoluble residue occurs.The percentage o€ ash constantly sinks, which with the apple is twiceas great as with the pear. The amount of free acid is greatest in theyoung pear, gradually sinking, but again slightly increasing a t the endof ripening ; this last does not occur in the app'le. Grapes differ fromkernel fruit, in that with them there is not only a change in the rela-tive percentage of the various acids present, but also a decided decreasein the total free acid.Pears appear to contain a t first only tan&acid, which gives place to mnlic acid as growth proceeds, whilst theapple appears to contain both, and these diminish regularly. Sugarincreases as apples, pears, and grapes ripen, but with grapes it is thedextrose which increases most, whilst lavulose increases in greatestproportion in other fruits.Comparing the constitution of the leaves with the frnit, we findthat the acid in the leaf is present in greatest quantity when that inthe fruit is lowest. Sugar increases in the leaf and then decreases,and there is more present in the leaf a t first than in the fruit ; lsevu-lose and dextrose are present in equal quantities.F. C.J. K. CVEGETABLE PHYSIOLOGY AND AGRICULTURE.179Other specimens of fruit were examined which had been pluckedand put aside to ripen, and it8 was found that the loss in weight wasless, the riper the fruit was when plucked. Fibre, &c., and acid de-crease, but sugar increases, and dextrose is converted into laevulose.Various other fruits, as strawberries, peaches, &c., were alsoexamined, and with similar results. lil w. P.Depreciation of Barley by Overgrowth. By LAUENSTEIN(Bied. Centr., 1879, 676-681).-The difference betweeri barleygathered at the right time and barley which has been allowed to lieout on the field for some time after it was ripe is not clearly shownby direct chemical analysis. An examination of the separate con-stituents is necessary in order to ascertain the changes which havetaken place.I n carrying out this plan the autrhor turned his attentionfirst to the starch present in the seed. Ordinary barley contains 64per cent.; in the overgrown corn was found, however, only 58 percent., the remainder having been converted into dextrin and sugar : aloss of 10 per cent., therefore, on the total quantity of starch was dis-covered. The change whish the starch .had undergone would of coursenot affect the nutrit$ve value of the barley ; this, however, was not thecase with t h e albumin, nearly one-fourth of which was found t o beconverted into amido-compounds, which are of very little nutritivevalue. The worth of barley for the preparahion of malt depends to avery large extent on its powers of germinating.This was found tohave suffered a loss of 53 per cent. in the overgrown corn.J. K. C.On the Quantities of Acid and Srrgar in Grapes cut atVarious Stages of their Growth. By P. WAGNER and W. ROHX(Bied. Centr., 1879, 681--686).-These researches have been so faronly of a tentative character, the objecb being to discover if possible apracticable method of examining various sorts of grapes a t differentstages of their growth, and chiefly at the ripening stages. The authorscarried out their researches at six different places, with vines ofvarious kinds. The grapes were cut four times during the last monthof ripening, and the relative quantities of sugar and acid determinedin the Rap. In some cases the relation improved, in others it remainedconstant for some weeks.The authors hope, by repeating these obser-vations for some time to come, to arrive at results of great practicalvalue. J. I(. C.Ripening of AppIes after Gathering. By F. TSCHAPLOWITZ(Bied. Cen,tr., 1879, 686-689).-The author finds that the loss ofweight undergone by apples on keeping is dependent on the positioni n which they are left and the dryness of the surrounding air. It maybe almost, entirely considered as loss of moisture, the amount of car-bonic anhydride which is given off being but very small. It is notice-able that smaller apples lose more in weiqht than those of a largerdescription. The temperature of the fruit is also the same as that ofthe air.The results of various analyses show that the quantity of sugar i180 ABSTRACTS OF CHEMICAL PAPERS.the apples increases during the ripening process a t the expense of thepectin and acid.Decomposition of Albuminoi'ds in Pumpkin Sprouts.ByE. SCHULZE and J. BARRIERI (J. pr. Chem., 20, 383-418).-The seedsof plants contain albumino'ids, staich, and oil, by which the sprouts,which are not able to decompose carbonic anhydride and water, arenourished. During germination the starch and fat decrease, whilstsugar, dextrin, and cellulose are formed, and carbonic anhydride andwater are eliminated. From more recent observations, it has also beendiscovered that the albumino'ids become soluble, and that in manyplants, especially in Papilionace=, nsparagine is produced. As thatbody decomposes on boiling with hydrochloric acid into asparticacid and ammonia, its amount may be determined by estimating theammonia. Gorup-Besanez afterwards found leucine amongst the de-composition-products of albuminoids.In pumpkin sprouts, whichcontain no asparagine, Sabania and Laskowski supposed that anotheramide existed; this was shown to be correct by the authors and byUlrich. I n the beetroot this amide has been shown to be glutamine,and the object of the present paper is to show thak it is also present ingerminating pumpkin sprouts, along with asparagine, leucine, andtyrosine.The albuminoids and fatty oil form 86-88 per cent. of the weightof dry pumpkin seeds, the former being present as protein granules.When the crushed seeds are treated with ether, the fat dissolves andthe prote'in substances sink to the bottom of t'he vessel.They are in-soluble in water, but dissolve in a 10 per cent. solution of salt. Onaddition of solid salt, a small quantity of vegetable myosine separates,and on dilution with water, vegetable vitelline is deposited. Non-albuminoid principles containing nitrogen are present in very smallamount in pumpkin seeds.The sprouts after germination were dried, boiled with alcohol, andthe evaporated extract was treated with lead acetate. The filtratefrom the lead precipitate was boiled for several hours with hydro-chloric acid, and again mixed with lead acetate to remove hydrochloricacid. The filtrate from the lead chloride after evaporation was mixedwith alcohol, and the precipitated lead salts were decomposed withsulphuretted hydrogen.The soiution filtered from the lead- sulphideand treated with silver oxide to remove traces of hydrochloric acidwas evaporated, when glutaminic acid, C5H9N04, separated in thecrystalline state. It was shown that this acid was not present as suchin the sprouts, but was formed by.the action of hydrochloric acid onglutamine, a body bearing the same relation to glutaminic acid asasparagine does to aspartic acid. From sprouts which had germi-nated for eight days, 100 grams gave only a few decigrams, but 16days' growth increased the amount, to 1.75 gram of acid, representing1.74 gram of glutamine. The ammonia produced by the action ofhydrochloric acid on glutamine corresponds to twice that amount, andto account for it a seal-ch was made for substances which wouldnndergo a similar decomposition with hydrochloric acid.Aspart-ate of copper, amounting to 0.5 gram in 400 grams, was separatedJ. I(. CVEGETABLE PHYSIOLOGY AND AGRICULTURE. 181from the mother-liquors of the glutamic acid, and leucine and tyro-sine were isolated by boiling the juice from sprouts 2-3 weeks old ;and after precipitating with alcohol and evaporating the filtrate, wart-like crystals were deposited, consisting of tyrosine. From 1,000 gramsof fresh sprouts (60 grams when dried), 0.15 gram of tyrosine wasobtained, and leucine was isolated from the mother-liquor of the tyro-sine, but in much smaller quantity.The nature of the decomposition products is thus the same as whenthe albuniino'id is heated with baryta-water or hydrochloric acid ; butthe proportion of each product differs greatly.On decomposing thealbuminoi'ds from pumpkin seeds with hydrochloric acid and stannouschloride, 120 grams yielded leucine, 24 grams ; tyrosine, 2.5 grams ;aspartic acid, 3 grams ; glutamic acid, 4 grams; and an uncrys-tallisable residue of 40 grams, the sum being 75 grams. The differ-ence between 120 and 75 = 45 grams, was lost. If these amountsrepresent even approximately the proportions in which the nitrogenousmaterials are present in the mixture, i t is seen that they differ greatlyfrom the proportions produced by the deconiposition of the albuniino'idsduring germination. The author's explanation is that in a growingplant albumino'ids are being formed as well as decomposed, any one ofthe decomposition products serving as material for their formation.The co-existing decomposition products of albumino'ids may, however,not be equally used in the formation of new albumino'ids, and thosewhich resist the process of regenerating albumin longest accumulatein largest quantity.Thus leucine, which is produced in large quan-tity by the artificial decomposition of albumin, is probably one whichlends itself best to the natural formation of albumin, and is thereforepresent in germinating plants in small amount, whilst such substancesas asparagine and glutamine are comparatively stable, and resist ab-sorption to form new albumino'ids.I n conclusion, the authors remark that as ferments are capable onlyof changing albuminoi'de into peptones, soma other reason must besought for to account for their decomposition into much more simpleproducts, and quotes a sentence of v. Nageli, in which such changesare ascribed to the molecular force of living tissue.The Most Advantageous Method of Sowing Corn.By F.HABERLANDT (Bied. Centr., 1879, 689-694) .-The author has madeseveral experiments with wheat, rye, and barley, with a view of ascer-taining the number of seeds per square meter which will give the bestyield. His results have necessarily only a special value for the soiland climate in which the experiments were carried out. He was ableto obtain a yield twice as great as that usually obtained, and thinksthat this might be effected in most cases where the proper conditionsare observed.It was noticed that the latest development occurredwhere the seed was most sparsely sown.Proper Thickness and Depth to Sow Corn. By SCHENK-BAUHOF (Bied. Centr., 1879, 717).Amount of Carbonic Anhydride in Shingle. By G. WOLFF-H ~ G E L (Bied. Centr., 1879, 709) .-The author brings forward tablesW. R.J. I(. C.VOL. XXXVIII. 182 ABSTRACTS OF CHEMICAL PAPERS.Contraction andexpansion.already published in defence of his view that the amount of carbonicanhydride in the ground air is a measure of the degree of impregns-tion of the soil with organic matter and of the progress of its decom-position. J. K. C.~- ~Capillary saturationcapacity.Saturated with capil-lary water.Peaty Soils.By A. v. SCHWARZ (Bied. Centr., 1879, 84--93).--The analyses of 26 Austrian peaty soils are given, in whichthe ash varies from 2.30 to 76-08 per cent. To one soil the author haspaid special attention, and he has determined the physical properties(which are here appended) of soil from the moorland of Kirchberg a. W.He also finds that this soil when treated with artificial manures yieldsaverage crops. The physical properties of the soil were comparedwith those of alluvial sand from Rotz, loam, and clay, and are asfollows :-100 c*e* '::i:$*saturated when satu-after dry- rated ining in C.C.C.C.Soil.--Peaty . . . .Sand , . . . .Loam . . . .Clay . . . . .-___ ____100 c.c. 100 grme.contain contain ofof water waterWeight of100 C.C.ingrams.39 *8100.083.970.2Airdry.28 -7.57 -9.55 * 2-40 '1 -- 82 '0 77 .G100 0 34.9 18 -3119.2 43 .2 22 -6142.1 51 -5 28 *6Satu-rated.LO5 - 6190 -6t92 9179 -8 -~Equal weights specific heat.Saturated 1Dried at m-it11 1 Dried at1000. capillary 1 1000.'-SP. !2T*waterat 17.5= 1 -00.Equal voluniessetumtedwithcapilltwywater.1 %702 '5692 -7292 914I I----I-- --In the determination of cohesion by Haberlandt's process, claywas found to stand highest and loam lowest, sand naturally possessingnone. In the case of adhesion by Schiibler's method, clay st,ands first,then loam, peat, sand.Masses of soil 10 cm. deep, m d exposing a surface of 10 square cm.,allowed the passage in 24 hours of 1 C.C.water in the case of pest,Soil.IIygroscopicit,?100 gramsdry soilabsorb ofwaterPeaty . . . . . .Sand . . . . . . .bani . . . . . .Clay . . . - . . .21 431.13.79 -20 -9600 %'750 '7620 *8@VEGETABLE PHYSIOLOGY AND AGRICULTURE. 1835,760 in the case of sand, 1,674 in the case of loam, and 0.7 in the caseof clay.Conductivity for heat was determined (1) by the increase of tem-perature of the unheated soils, and (‘2) by the loss of temperatureexperienced .in cooling. In this the soils were experimented on whendry, and when moist, or saturated with capillary water, the source ofheat was 60°, and the original temperature 16*3-16*7”.From the results, it would appear that under direct action of solarradiation peaty soil when dry assumes a higher temperature thaneither of the others, but the case is reversed if the soils be moist.Asregards the rising of water in columns of sand, loam, and clay, it isfound that in 100 days water had risen to the height of 408 mm. insand, to 1,627 in loam, and to 770 in clay. E. w. P.Composition of Maize. By L. GRAKPEAU (Biecl. Cencr., 1879,149) .-Analyses of various specimens of maize used as feeding stuffsare given. The best appear to be the Hungarian (nutrient ratio,1 : 8*8), then American (nutrient ratio = 1 : 8*6), but the AmePicanis very hard to crush. E, W. P.New Plant for Fodder. By J. DEIWINGER ( B i d . Cewtr., 1879,700--702).-Seeds of a plant known in India as “gram,” a variety ofchick-pea, were planted in various kinds of soil in Hungary.Theplant thrived exceedingly well, especially in sandy soils, which m-ereworthless for other purposes, and proved very productive. Thefollowing analysis of the seeds show that they are sery valuable asfodder :-Nitrogen- freeWater. Protein. Fat. extract. Fibre. Ash.First year . . . . 10.72 12.88 4-39 58.02 10.20 3.i9Second year . . 9.80 17.68 3.77 54.32 10.89 3.54J. K. C.Analysis Of Materials used for Fodder. By P. WITmLsHiimIt( B i d Centr., 1879, 713).-Analyses were made of soured cabbageleaves, dried sprigs of broom, concentrated residues from a starchmanufactory, and potato pulp. The first two proved to be excellent,for fodder, but the last was too poor in nutritive matter t o be usedalone.J. K. C.Feeding Value of some Manufacturers’ Waste. By 3 .MOSER (Bied. Oentr., 1879, 3_14-117). - The analyses of sevemlfeeding-stuffs, which however do not appear in large quantities in themarket, are given, and are as follows :-0 184 ABSTRACTS OF CHEMICAL PAPERS.Fennel seed cake..Sunfiower cake :(1.) As powderymass. . . . . . . . .(2.) As coherentcake . . . . . . . . .Pumpkin seed cakeLoosely coherentmass. . . . . . . . .Decorticated.. . .Tobacco seed cake,containing no ni-cotine. . . . . . . . . .Wine lees cake..Dried brewers'grains :Mixed with mealand dried.. . .Fresh and un-dried . . . . . . . .Brandy manufac-turers' waste*,pressed and driedBoiled and press-ed.. , . . . . . . . .Same not pressedSuet grieves :-Ilbum.9 '23:LO -628.0711 *2511 *0110 '6954 -0412 *9479 -2212 -424 9 758 -29 --Water.--15 *2838 -0037 -6932 -5638 -7425 *602 *5418 *694.9224 *5048.0611 '75 --Fat.12 .o6 *4423 -7325 *5723 *5514.6C8-54ci -3c1 '3511 -8741 -1C24 -2C~~ ~Non-nitrog.extract.--33 *1228 *1119 *299 -1310 -7515 *087 -4138 -009 *3639 -30--Fibre.20 -1510'4F6 '0515 -6E10 -3322 -4311 *1C16 *953 -44cAsh.8 -144.965 '104 '795 -395.311 '744'310 *891 5 24 -88-E. m-Sand.1 -931 *390 -621 -020 *236 *299 -202 *810 -521.610 '41- -P.Certain Sorts of Pumpkin.By C. 0. HARZ (Bied. Centr., 1879,717) .-The author recommends Cucurhita rnaxinza Brasilierisis andC. m. eZZiptica as the best kinds to grow, because the fruit does notputrefy and can be kept many years. Analysis of the dried fruit gavethe following results :-Nitrogen- freeProtein. Fat. extract. Fibre. Ash.10.87 1-64 72-75 9-39 5-35J. K. C.Influence of Fodder on the Quantity and Qualityof MilkFat. By H. WEISRE, M. SCHRODT, and B. DEHMEL ( B i d Centr.,1879, llO-l13).-The present opinions concerning the influence ofEodder on milk produced are, that dry food produces more solid gly-cerides in butter than the green feeding of summer, and that a hardhntter is produced when the feeding has been scanty, or poor in albu-minoid matter.The analyses of the milk of a cow which had beenli; Note by Abstractor.-There is evidently a printer's error here, as t,he abovemalysis is said to be that of a substance undried, whereas the analysis of the sameinaterial which is called " dry," shows a percentage of 61.41 waterVEGETABLE PHYSIOLOGY AND AGRICULTURE. 185fed a t different periods with various kinds of food, show that a highmelting point of butter is not dependent on scanty feeding; themelting point, and also the quantity of the butter fats, and of thefatty acids, show no regularity, even when the feeding remains thesame. Highly albuminous fodder produces the highest yield of milk ;addition of albuminoid matter to fodder increases the amount of fatin milk, but addition of oil and of stearic acid causes a much greateramount of fat and dry substance to be formed.Comparing morningand evening milk, no difference in the amount of solid matter or fatcould be detected; and the melting points of the fats were the sameon the same days, the melting point of the cream fat being 2" lowerthan that of the fat of the skimmed milk. The amount of fatty acidinsoluble in water varied very considerably, varying from 84-889per cent. E. W. P.Four-yearly Rotation of Crops. By A. VOELCKER (R*ietb. Centr.,1879, 658--661).--These experiments mere conducted a t Woburn onbehalf of the English Agricultural Society; .the plan of rotationwas the following:-1st year, clover; 2nd year, wheat; 3rd year,roots (turnips, &c.) ; 4th year, barley.The results obtained in 1878were mostly of a normal chractw. The author has found thatmanure obtained after a fodder of cotton seeds is of more value to theland than if the animals had been fed on maize; and that the mate-rials for plant nutriment have a better effect when applied directly tothe land than when they have been mixed with fodder and allowed topass into dnng. J. I(. C.Manuring of Oats on Fen Lands. By H. .J. CARSTEN (Bled.Centr., 1879, 97-99).-Oats were found to be most prolific on moorland when manured with stable manure.Comparing the two methods of cultivation, " Veen" and '' Dammkultur," it was found thai the " Damm" method (covering the moorwith a layer of sand), in all cases when the manuring with artificialmanures was employed, gave better results than the " Teen'' method(where the surface to a depth of 10-12 cm.is mixed with sand).Effect of Gypsum ow the Quantity and Quality of CloverCrops. By A. PASQUALM (Bied. Ceizta-., 1879, 99).--Clover manuredwith gypsum is not affected as regards its feeding qualities, althoughthe total yield is increased.E. W. P.E. W. P.Manuring of Sugar Beet. By. J. MOSER (Bied. Centr., 1879,100--106).-This paper contains an account of the manures used(salts of potash, soda, and magnesia), the yield of mots, tops, andsugar obtained in experiments made in the years 1876-77; but noconclusions are drawn, as the experiments are still being carried on.The manures were employed in quantities equal to one-eighth of thecapacity of the soil for potash.Manuring of Beet.By H. BRTEM (Bied. Centr., 1879, 656-658).-Two kinds of lime manure are used in this investigation, the objectE. W. P186 ABSTRACTS OF CHEMICAL PAPERS.---105122210of which was to compare their action. One of these was the ordinarylime-scum from sugar works, and the other a mixture of lime-dustwith the residues from a beet and molasses disti1ler.y : the latter con-taining about 43 per cent., and the former 30 per cent. of lime: t,heywere applied to a soil very poor in lime, containing about 4 parts perthousand, the experiments being carried out in two successive years :the mean results are as follow : -335384736Manure used.3 . 2 53.234.44--iY.,ueLime from eugarworks.. . . . . . . .Lime with distil-lery residues. . .. . . . . . . , . . - -82.8 0.8084.7 0.91IWeigkt of the beetin grams,Total. Leaves. Root. 1 1440506946Polarisation of 1 Percentagesap. I OfDegrees.14 -215 014 *1Sugar.10 -9511 -679 -66 -sugar.The difference in the effects produced by the two manures is verymarked: the distillery residues produced a wonderful effect in in-creasing the <total weight of the yield, at the same time, however,deteriorating greatly the quality of the juice obtained, as is observedon comparing the ratio of the quantities of sugar and non-saccharinematter present in tbe juice : this relation cis of the greatest importanceto the manufacturer, as a juice containing such a quantity of extra-neous matter would be found very difficult to work.J. I(. C.Influence of Soluble and Insoluble Phosphates as Manurefor Turnips. By T. JAMsEsoN ( B e d . Cewh-., 1879, 659--656).--Thcseinvestigations were carried out near Aberdeen., with a view of com-paring the effect of phosphoric acid in the soluble and imoluble formapplied as manure to turnips. Five fields, lying at considerable dis-tances from one another, were selected, and each made the subject ofeighteen experiments, each of which was carried out on two separateplots. The experiments were conducted in the years 1876 and 1877,the latter proving a bad year for turnip crops. No difference wasobserved between the effect of animal and mineral phosphates. Fronithe results obtained, the author shows that the effect of insoluble phos-phates varied little from that produced by soluble phosphates :-Yield per acre in kilos. aftertieatinent withInsoluble Solublephosphate. phosphate.F \1876. Mean of 30 experiments a t 35 places.. 17,270 18,2907, 6 :7 1 place . . 18,290 17,2601877. ,, 4 . ,, ,, . . 8,430 9,86VEGETABLE PHYSIOLOGY AND AGRICULTURE. 187Addition of nitrogenous manures to the phosphates yielded thefollowing results in 1876 :-Sulphate of ammonia Chili saltpetrewith with7 f----- ISoluble Insoluble Soluble Insolublebone-ash. bone-ash. bone-ash. bone-ash.Mean of 10 experiments . . 20,720 20,720 21,130 18,6997, 2 7 9 . . 24,380 24,380 23,350 22,350The increase in the yield produced by the addition of nitrogenousmanures is, however, onlyan apparent one, as it arises merely from anincrease of the percentage of water in the product. The same inoreasein the yield ma<y be obtained when the phosphate is very finelypowdered.The author also finds that the highest percentage of nitrogenousrnatker and the smallest quantity of sugar was the result of manuringwith soluble phosphate, whilst insoluble phosphate produced the exactlyopposite effect, and a medium result was obtained when nitrogen hadbeen added to either.Those plots which were manured in 1876 were left unrnanured in1877 in order to observe the after-effects of the various materials used.It was observed that those fields which gave the best yields in theformer year were the least productive in the latter, and vice versG.Animal phosphate also appeared to have a better after effect thanIjhosphates of mineral origin. The highest produce as a total of bothrears was obtained by using raw dried bone-ash, which is more effec-tive when applied in spring than in autumn. The results obt,ained bythe use of this manure show that it is the best that can be applied inthe case of turnips. J. K. C.Action of Different Manures on the Yield of Potatoes. ByW. PAULSEN (Bied. Ceiztr., 1879, 106--108].-Sheep’s dung produces ayield 50 per cent. higher than that produced by various other artificialmanures, and 60 per cent. higher than if no dung be applied. Extrasupplies of ammoniacal superphosphate produce no increase, and‘ * compost” does not appear to be capable of producing larger yieldsthan unmanured land. But, on the other hand, manures increase theamount of starch. The number of diseased potatoes was highest inthe plots which were unmanured, and more especially high in thecrops of “ Furstenwalder ;” amongst the “ snow flake ” potatoes there\yere also many diseased. Of the seven sorts grown, “ Ayrora ” seemst o have been the most satisfactory. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8803800175

出版商:RSC    

年代:1880

数据来源: RSC

摘要:

188 ABSTRACTS OF CHEMICAL PAPERS. A n a l y t i c a l Chemistry. Method for the Continuous Measurement of the Intensity of Daylight, and of its Application to Physiological and Botanical Researches. By M. KREUPLER (Bied. Centr., 1879, 117--120).-1n the first portion of this article an instrument is described whereby the intensity of daylight can be estimated for any hour ; it consists of a hollow drum in which is cut a slit parallel to the terrestrial axis; behind this slit is a strip of sensitised paper, across whose surface the slit is cansed to pass by means of clockwork. To be able to compare the shades of colour, several tints are produced also on sensitised paper, by causing thc direct rays of the sun to fall on the paper a t various angles for twenty seconds, this being the length of exposure for each past of the registering paper.An inclination of 60" (cos. 0.5) produces half-tint, &c., the tints being numbered 1, 2, 3-10 ; 10 re- presenting full sunshine. I n the second portion, the author states that brightness of light is accompanied by increased assimilation on the part of the plant; but this regularity of increase continues only up to the point when the intensity of light is one-eighth that of the full sunshine, and after that assimilation goes on less rapidly, not keeping pace with the in- creased intensity. Now, as increased intensity of light is accompanied by increased chemical intensity, the former may be used as an indi- cator of the latter, as regards plant physiology, as it was found that assimilation increased as chemical intensity increased , at first rapidly, but afterwards in a less degree.Sub-aquatic plants are not of value in determining assimilation, as they are not sensitive enough to small changes of light ; an apparatus has therefore been devised in which it is possible to expose whole plants to the light, and is on the principle of an aspirator. Estimation of Chromium. By T. WILLM ( B e y . , 12, 2223--2226). -When chromium is estimated as sesquioxide by precipitation with ammonia, boiling off the excess of alkali, and ignition of the precipi- tated hydrate, the results obtained are invariably too high if the precipitation is carried on in a glass vessel. The small quantity of lime which is taken up by the ammonia from the glass enables the chromium sesquioxide, during ignition, to combine with the oxygen of the air to form chromic acid. Calcium chromate can be dissolved out E.W. P. cf thc ignited residue by treatment with hot water. w. c. w. Separation of the Heavy Metals of the Ammonium Sulphide Group. By c. ZIMMEBMANN (Anntllert, 199, 1--16).-Zin,c from the other MetnZs.-The sohition is made as nearly neutral as possible (this is absolutely essential) with sodium bicarbonate, and mixed with a not too dilute solution of ammonium thiocyanate. After being heated to 60' to 70°, a gentle stream of sulphuretted hydrogen is passed into the liquid a t intervals until it smells distinctly of the gns. I t is thenANALYTICAL CHEMISTRY. 189 left to stand for some hours a t a gentle heat, when the whole of the zinc is found to be depvsited as snlphide, and perfectly free from the other metals of the group. An excellent method of est'imating the zinc is to convert the sulphide into the chloride, and to heat the latter wit)h mercuric oxide, by which means the zinc is converted into oxide and may be weighed as such.Iron from Nickel and Cobalt.-The solution is mixed with excess of ammonium thiocyanate, and sodium bicarbonate is added until the red colour disappears. The iron is thus completely precipitated as ferrous hydrate, and is free from nickel and cobalt. The nickel and cobalt are then separated by Liebig's mercuric oxide method. Iron from Umn,ium.-The boiling hot solution is mixed with excess of ammonium thiocyanate, and sodium bicarbonate is added until the red colour disappears.The iron is precipitated entirely as hydrate, and is free from uranium. Precipita,tion of Uraniwn Oxide by Anaw onia.-Addition of ammonia in presence of ammonium chloride causes precipitat'ion of uranium oxide in solution so dilute that the former reagent alone produces no effect. G. T. A. New Method of Estimating the Air Space in Seeds and Fruits. By J. AUAMEC and E. KLOSE (Bied. Cent,-., 1879, 15O).-The volume of the sample is calculated from its specific gravity ; the volume of the several constituents is calculated from their specific gravity ; these added together give the volume of the solid, and, subtracting this from the original volume, the air enclosed is calculated. Composition of Bohemian Beer-wort, determined by Chemico-optical Processes.By T. HANAMANN (Bied. Centr., 1879, 138).-The author in this paper comes to the conclusion that by the early processes of determination, tlie amount of dextrin present in wort was too high ; by the modern process, the amount is too low ; the true quantity is to be found between, and can be closely determined by the polariscope. E. W. P. E. W. P. Determination of the Acid in Sugar of Lead and in Lead Vinegar. By F. SALOMON (Dingl. polyt. J., 234, 222-226) .-What the author claims as novelty in this paper is (1) that as standard acid a solution of acetic acid should be used, which contains exactly 50 grams of acetic anhydride in 1 liter ; (2) that the solution of potash used should be equivalent to the acetic acid solution. The following are the details of the method :-I0 C.C.of the solution to be examined are treated with an excess of the standard potash in a 100 C.C. flask, and the mixture is made up to 100 C.C. with distilled water. The portion of the lead which is dissolved by the excess of potash used is separated from the hydrate by filtration, and 50 C.C. of the filtrate titrated with standard acetic acid, using phenolphthaleh as indicator. I n the case of the solution containing sugar of lead, the total acid may be estimated a t once, providing the salt is neutral ; if acid, it is best to estimate the quantity of free acid with standard alkali, using litmus as indicator in this case. To apply the method to determinations of190 ABSTRACTS OF CHEMICAL PAPERS. acid in lead vinegar, it is necessary to neutralise the basic solution vith the titrated acetic acid solution.D. B. Analysis of Cinchona Barks. (Chem. News, 40, 209-210.)- 1. .Ether process.- 1,000 grains of very finely-powdered bark are mixed with suficient alcohol t o form a paste, and when the fibres are thoroughly saturated with the liquid, it is intimately mixed with 500 grains of calcium hydrate, and heated to drive off the alcohol. The dried rnass is exhnust,ed successively with ether, the ethereal solution evaporated, and the residue fused a t 125°C. The mass is weighed and dissolved in absolnte alcohol, and the solution neutralised with stzndard sulphwic acid (I00 C.C. = 10 grams crystalline quinine sulphate). The alcoholic solution of basic quinine sulpliate is eva- porated to dryness and treated with a quaritity of standard acid equal to that, previously used; water is added.and the salt com- pletely dissolved by boiling. Animal charcoal to the amount of 15 per cent. of the original weight of bark is then added ; the whole digested for 10 minutes, filtered, and washed with acidulated water. The fil- trate containing acid quinine sulphate is concentrated, nearly neu- trnlised with dilute ammonia ( 3 per cent. j , and allowed to crystallise. The crystals of basic quinine sulphate are collected and weighed. Weight of air-dried crystals = amount of crystalline quinine sulphate in the bark. 2. Acid process.-l,OOO grains of finely-powdered bark are treated twice with boiling dilute sulphuric acid, and once with water; the extracts are evaporated to a small bulk, neutrnlised with milk of lime, and filtered.The residue is dried and boiled repeatedly with alcohol of 90 per cent,. ; the alcoholic solutions are evaporated to dryness, and the residues treated with acidulated water and filtered ; the filtrate is neutralised with caustic soda and shaken with chloroform ; the chloro- form solution is separated and evaporated in a tared capsule. The residue consisting of the total quantity of quinine, cinchonine, and quinidine is treated with ether .to extract the quinine, which is esti- mated by the ether process. The residue is dissolved in dilute acetic acid, and treated with a Concentrated solution of potassium iodide. The precipitate consists of quinidine iodide, of which 100 grams = 71-69 quinidine, or 94.5 quinidine sulphake.The quinidine and cin- chonirie may be separated by treating the residue with proof spirit, in which the quinidine is soluble, whilst cinchonine and cinchonidine remain undissolved. Owing to the rapidity with which the ether process may be worked, it can be used with greater advantage than the acid process. The object of the former is to extract that alkaloid only on which the yalue of the cinchona bark depends, and is achieved without pro- ducing amorphous quinine, which is so liable to be formed by pro- tmcted boiling, as in the acid proce.ss. Calisaya and red cinchona barks may be analysed by the ether pro- cess, but it is not applicable to the Loss or grey barks. Estimation of Albuminoid Nitrogen in Fodders. By F. SESTINI (Bied. Centr., 1879, 7ll).-The author recommends boiling the Dried a t loo", 8-5.5 = 100 crystals.L. T. 0's.ANALYTICAL CHEMISTRY. 191 finely powdered substance for one hour in water, to which a few drops of lactic acid have been added, treatment with lead acetate and filtration. The nitrogen is then estimated in the precipitate and the filtrate, the amount contained in the former representing the quantity of albumin present. J. K. C. Enumeration of the Fat Globules in Milk as a Test. By E. BOUCHUT (Bied. Centr., 1879, 145).-One drop of milk is diluted with 100 drops of water, and this placed in a cell 0.1 mm. deep is examined under the microscope; the globules i n a space 0.1 mm. square are counted, the number obtained multiplied by 100,000, and this then gives the number contained in 1 cm. of the original milk.In human milk from 2,200,000 to 5,000,000 ghbules have been observed, but the average number appears to be from 1,000,000 to 2,OOQ,OOO. With COW'S milk, the results were- 1,102,500 globules 1032 sp. gr. 24 grams butter. per liter 2,205,000 ,, 1032 ,, 37 Y, 2,400,000 ,, 1030 ,, 3 7 >, 3,700,000 ,, 1030 ,, 34 7 , As human milk varies considerably, it is advisable, in comparing specimens from different individuals, to take five samples on the same day. When 800,000-1,O00,000 globules are fomd in human milk per centimeter, the milk may be considered as good. E. W. P. Foreign Colouring Matters in Red Wine. By J. NESSLER (Bied. Cextr., 1879, 142--145).-The author comes to the conclusion that we are a t present not in a position to determine chemically the difference between the colouring mathers of madder, Eil berry, and grapes. A pure wine reacts differently with the same reagents, the diff'erence depending on bhe rlode 0f preparation, and the qudity of Adulteration of Wine.By F. LEPEL (Bied. Centr., 1879, 709).- Red beet is often used in conjunction with fuchsine to colour wine. The presence of the former tnay always be recognised by the author's copper reaction (Ber., 10, 1875). the grape it,self. E. w. P. J. K. C. Morphiometric Processes for Opium. By A. B. PRESCOTT (Phaym. J. Tmns. [ 3 ] , 10, 128-130, and 182--185).-The author submits the following assay process for opium ; it is essentially the Huqer- Jacobserb's, but it is modified by a preliminary washing of the opium with benzene, to remove impurities. The opium is dried at 100" C., until it ceases to lose weight; i t is then powdered, and 66.5 grams are placed in a paper filter of 10 cm.diameter in a funnel ; benzene is poured in until the powder is covered, and as soon as it begins to drop through, the funnel is stopped, and allowed to macerate for an hour; the benzene is then allowed to per- colate, more being supplied, until the whole volume used is 50 C.C. 'I'he filter and its contents are dried with gentle heat, until there is no iurther smell of benzene, and the contents are then transferred to a192 ABSTRACTS OF CHEMICAL PAPERS. weighed flask of 120 C.C. capacity, the filter paper being kept. 20 C.C. of water are added, together with 3 grams of slaked lime, which has been slaked with one-third its weight of water.The contents of the flask are agitated for several minutes, and then uniformly mixed by closing the flask and shaking it. Distilled water is added, until the contents of the flask weigh 74.5 grams, and the flask is heated with occasional agitation for an hour in nearly boiling water; it is then cooled, and the exact' weight (74.5 grams) made up again by the addi- tion of water. The solution is then filtered through the paper pre- viously used, into a vessel of about 80 c.c: capacity, marked for a volume of 50 C.C. As soon as exactly SO C.C. of filtrate are obtained, the contents of the filter being gently squeezed, if necessary, to yield the last few drops, it is mixed with 8 drops of benzene, and 3 C.C. of washed ether, the vessel closed, and the whole agitated ; 4.5 grams of powdered ammonium chloride are then added, and as soon as it is dissolved the liquid is once more agitated, and then set aside in a cool place for three and a, half hours.The crystalline deposit is filtered through a weighed and moistened filter, and washed several times with a few drops of water ; it is then dried at 50" C., washed with 3 C.C. of washed ether, dried again and weighed. The weight of morphine thus obtained may be considered as that contained in 5 grams of opium ; this allows for loss during filtration ; the percentage is there- fore obtained by multiplying the weight found by 20. The author also submitted different processes for estimating morphine to a comparative trial by analysing several samples by each of the methods ; then estimating by Mayer's volumetric method the purit'y of the morphine obtained, and also determining the morphine remaining uncrystallised in the mother-liquor by extraction with amyl alcohol and titration.Mayer's solution was prepared by dissolving 13.55 grams of dry merciiric chloride and 49.84 grams potassium iodide in water, and making up to a litre; 1 C.C. corresponds to 0.02 of morphine. The morphine precipitates were dissolved in water with acidulated sulphuric acid, and so far diluted that a t the end of the titration the solution should be 200 parts to 1 of morphine, this pre- caution being necessary because of the solubility of the precipitate in water. The author finds that the results obtained by Mayer's process are more accurate than those yielded gritvimetrically after purification of the crystals, but- they are probably somewhat low.The morphine remaining in the mother-liquor was partially separated by allowing a further time for crystallisstion, and the filtered liquid was then well shaken with amyl alcohol in successive portions of 15, 10, and 5 C.C. ; the alcohol was separated and evaporated, and the residue titrated by hlayer's solution. The conclusions arrived a t are that hot benzene, if used for the pre- liminary treatment, occasions a loss of morphine as compared with cold benzene ; the cold benzene, however, must be used in limited quantity, since it dissolves some morphine. The omission of the preliminary treatment with benzene leaves the opium-lime mixture loaded with opium wax, and renders the filtration more difficult, and the entire operation less satisfactory, but results after deduction of one-tenth (or one-thirtieth if ether-washed) are fairly in accordance with thoseANALYTICAL CHEMISTRY.193 obtained by the modified process of treating with benzene. The Procter-Staples’ process yielded unsatisfactory results, more especially in the estimation of morphine extracted from the mother-liquor by amyl alcohol. The author suspected that something besides the alkalo’id, which acted on Mayer’s solution, was taken up by aniyl alcohol. It was found more satisfactory to extract the mother-liquor obtained by Staples’ process, first with benzene, and afterwards with amyl alcohol. By Huger’s process the filtrate contains in solution 1.9 times as much as pure water, and by Staples’ process 2.45 times as much.Sc7mc7~trupp~s pmcess for estimating morphine and narcotine in opium (Zeits. Anal. Chew., 1868, 7, 509), was also submitted to examination ; the author pronounces it to be untrustworthy and inex- pedient ; the experiments made by this process, however, proved that benzene does not ext,ract the whole of the narcotine from opium, unless an alkali is present, and therefore the preliminary treatment with benzene does not dispense with purification of the morphine crystals by washing with ether freed from alcohol and acetic acid by recent agitation with water ; the impurities left in the morphine may then be considered as counterbalancing the morphine left in the mother-liquor, and removed by washing.Valuation of Tincture of Opium. By A. B. PRESCOTT (Pharm. J. TYU~ZS. [3], 10, 66).-The author determined the opium in twelve different samples of the tincture, employing two different processes for each sample, viz., Aager’s and Staples’. The modified Hager’s process was carried out as follows :-The specific gravity of the tincture was taken ; then 25 grams were evapo- rated nearly to dryness on the water-bath, triturated with 1 gram of freshly slaked lime, and after adding 24 C.C. of water, the mixture was heated on the water-bath for an hour. The whole was then transferred to a wetted filter, and the residue washed on the filter with warm water, until the washings were nearly colourless ; the filtrate, after being concentrated on the water-bath to 25 grams, was transferred with rinsings to a wide-mouthed bottle, and mixed while warm with 1 C.C.of ether and 3 drops of benzene ; 1.1 gram of ammonium chloride was then dissolved in the liquid, and it was set aside €or 24 hours. The liquid was now well shaken, to detach crystals from the sides of the bottle, and the crystals collected on a weighed.filter, washed wit!h about 8 C.C. of distilled water, dried at 50” C., and weighed. If Hager’s plan is followed of allowing only three hours for the crystallisation of the morphine, t,he author prefers to wash the crystals with ether, and weigh t,hem, the impurities present counterbalancing the morphine left in solution. According to Stuples’ method, after estimating the specific gravity, 25 grams were evaporated to half the bulk on the water-bath, and 24 hours allowed for the subsidence of the tarry matters ; the liquid was decanted through a filter into a wide-mouthed bottle, and the tarry residue washed with 4 C.C.of water, the washings being added to the filtrate. An equal volume of alcohol of sp. gr. 0.835, and 1.3 C.C. of ammonia solution of sp. gr. 0.96, mixed with 1.7 C.C. of alcohol, were then added, the bottle stoppered and well shaken, and set aside. F. C.194 ABSTRACTS OF CHEMICAL PAPERS. After about four days the morphine crystals were filtered off, ‘rinsed with 4 C.C. of diluted alcohol, dried at 50°, and weighed. The crystals were afterwards washed with 8 C.C. of ether, and weighed again ; the ether removed about one-tenth by weight of the crystals.The author concludes that SGapZes’ process yields the best crystals of morphine, but considers that it is little if ah all preferable to Hager’s method. F. c. Analytical Examination of Tinctures. By A. H. ALLEN (Pharm. J, Trans. [3], 9, 1035-1037).-Tinctures are made with spirits of two alcoholic strengths. For some, rectified spirits, con- taining 84 per cent. by weight of absolute alcohol, equivalent to 155.5 per cent. of proof spirit, is used; for others proof spirit, containing 49 per cent. by weight of absolute alcohol, i;r sufficiently strong. Alcohol being frequently. the most expensive item in 1 he preparation of tinctures, it is liable to be economised, and this will often lead to an insuacient quantity of the drug being dissolved. Hence the deter- mination of the proportion of alcohol present irr a tincture is often of importance.With many tinctures, the a1 coho1 can be readily separated by distillation and estimated by taking the specific gravity of the dis- tillate, volatile alkaline or acid substances being retained during distil- lation by previously making the tincture acid or dkaline respectively. Tinctures containing volatile essential oils cannot be examined by dis- tillation, but the oil can usually be precipitated hy a sufficient dilution with water, and if it remains suspended in the liquid it may then be separated by adding ai few drops of strong calcium chloride solution and some sodium phosphate arid stirring vigorously ; the precipitated calcium phosphate carries down the oil globules and clarifies the liquid, which is then run through B dry filter and distilled.I n some cases sodium carbonate is substituted for sodium phosphate when an acid is to be retained during the subsequent distillation. The per- centage of alcohol present is best stated in terms of proof spirit. The process was tested on tincture of myrrh, which had been pre- pared for the purpose. The alcohol found was about 6 per cent, too low, but this discrepancy was explained by the fact that myrrh causes a considerable expansion of the volume during solution in spirit, and after estimating and allowing for this expansion exact results were secured. A similar result was obtained with camphor. Experiment showed that, camphor dissolved in alcohol without sensible change of volume, the volume of the tincture being equal to the sum of the volumes of the spirit and the camphor.Hence it appears that the spirit causes the camphor to liquefy and mingle as a liquid with the spirit. I n consequence of t>his peculiarity, the proportion by volume of proof spirit contained in spirit of camphor will be 0.9 of that pre- sent in the alcohol used in its preparation, and there is no doubt that a similar correction onghtl to be applied in certain other cascs. The distillation method, when applied to spirit of camphor, is also rendered inexact by some of the camphor remaining unprecipitated, owing to its solubility in water. The author found a deficiency of alcohol in a sample of “ compound tincture of camphor,’’ and this led to a deficiency also of oil of anise,TECHNICAL CHEMISTRY.195 since the spirit was too weak to dissolve the full proportion of oil. This tincture was examined by diluting with water, clarifying with calcium chloride and sodium carbonate solutions, distilling the alcohol, and estimating benzoic acid in the residue by acidifying it and shaking several times with ether. On evaporating the ether, the benzoic acid was left in a pure state ; the opium was roughly estiniated colorime- trically by adding proof spirit and a few drops of ferric chloride, and comparing with a similarly treated standard opium solution. The per- centage of alcohol found in this tincture by the distillation process never exceeded by two degrees that deduced from the density of the original tincture. The proportion of oil of anise present may be roughly judged by the readiness with which the liquid is precipitated on dilution with water.With a proper proportion of oil, precipihtion occurs on very slight dilution. F. c.188 ABSTRACTS OF CHEMICAL PAPERS.A n a l y t i c a l Chemistry.Method for the Continuous Measurement of the Intensity ofDaylight, and of its Application to Physiological and BotanicalResearches. By M. KREUPLER (Bied. Centr., 1879, 117--120).-1nthe first portion of this article an instrument is described whereby theintensity of daylight can be estimated for any hour ; it consists of ahollow drum in which is cut a slit parallel to the terrestrial axis;behind this slit is a strip of sensitised paper, across whose surface theslit is cansed to pass by means of clockwork.To be able to comparethe shades of colour, several tints are produced also on sensitisedpaper, by causing thc direct rays of the sun to fall on the paper a tvarious angles for twenty seconds, this being the length of exposurefor each past of the registering paper. An inclination of 60" (cos. 0.5)produces half-tint, &c., the tints being numbered 1, 2, 3-10 ; 10 re-presenting full sunshine.I n the second portion, the author states that brightness of light isaccompanied by increased assimilation on the part of the plant; butthis regularity of increase continues only up to the point when theintensity of light is one-eighth that of the full sunshine, and afterthat assimilation goes on less rapidly, not keeping pace with the in-creased intensity.Now, as increased intensity of light is accompaniedby increased chemical intensity, the former may be used as an indi-cator of the latter, as regards plant physiology, as it was found thatassimilation increased as chemical intensity increased , at first rapidly,but afterwards in a less degree. Sub-aquatic plants are not of valuein determining assimilation, as they are not sensitive enough to smallchanges of light ; an apparatus has therefore been devised in which itis possible to expose whole plants to the light, and is on the principleof an aspirator.Estimation of Chromium. By T. WILLM ( B e y . , 12, 2223--2226).-When chromium is estimated as sesquioxide by precipitation withammonia, boiling off the excess of alkali, and ignition of the precipi-tated hydrate, the results obtained are invariably too high if theprecipitation is carried on in a glass vessel.The small quantity oflime which is taken up by the ammonia from the glass enables thechromium sesquioxide, during ignition, to combine with the oxygen ofthe air to form chromic acid. Calcium chromate can be dissolved outE. W. P.cf thc ignited residue by treatment with hot water. w. c. w.Separation of the Heavy Metals of the Ammonium SulphideGroup. By c. ZIMMEBMANN (Anntllert, 199, 1--16).-Zin,c from theother MetnZs.-The sohition is made as nearly neutral as possible (thisis absolutely essential) with sodium bicarbonate, and mixed with a nottoo dilute solution of ammonium thiocyanate. After being heated to60' to 70°, a gentle stream of sulphuretted hydrogen is passed intothe liquid a t intervals until it smells distinctly of the gns. I t is theANALYTICAL CHEMISTRY.189left to stand for some hours a t a gentle heat, when the whole of thezinc is found to be depvsited as snlphide, and perfectly free from theother metals of the group. An excellent method of est'imating thezinc is to convert the sulphide into the chloride, and to heat the latterwit)h mercuric oxide, by which means the zinc is converted into oxideand may be weighed as such.Iron from Nickel and Cobalt.-The solution is mixed with excess ofammonium thiocyanate, and sodium bicarbonate is added until thered colour disappears. The iron is thus completely precipitated asferrous hydrate, and is free from nickel and cobalt.The nickel andcobalt are then separated by Liebig's mercuric oxide method.Iron from Umn,ium.-The boiling hot solution is mixed with excessof ammonium thiocyanate, and sodium bicarbonate is added until thered colour disappears. The iron is precipitated entirely as hydrate, andis free from uranium.Precipita,tion of Uraniwn Oxide by Anaw onia.-Addition of ammoniain presence of ammonium chloride causes precipitat'ion of uraniumoxide in solution so dilute that the former reagent alone produces noeffect. G. T. A.New Method of Estimating the Air Space in Seeds andFruits. By J. AUAMEC and E. KLOSE (Bied. Cent,-., 1879, 15O).-Thevolume of the sample is calculated from its specific gravity ; the volumeof the several constituents is calculated from their specific gravity ;these added together give the volume of the solid, and, subtractingthis from the original volume, the air enclosed is calculated.Composition of Bohemian Beer-wort, determined byChemico-optical Processes.By T. HANAMANN (Bied. Centr., 1879,138).-The author in this paper comes to the conclusion that by theearly processes of determination, tlie amount of dextrin present inwort was too high ; by the modern process, the amount is too low ;the true quantity is to be found between, and can be closely determinedby the polariscope.E. W. P.E. W. P.Determination of the Acid in Sugar of Lead and in LeadVinegar. By F. SALOMON (Dingl. polyt. J., 234, 222-226) .-Whatthe author claims as novelty in this paper is (1) that as standard acida solution of acetic acid should be used, which contains exactly50 grams of acetic anhydride in 1 liter ; (2) that the solution of potashused should be equivalent to the acetic acid solution.The followingare the details of the method :-I0 C.C. of the solution to be examinedare treated with an excess of the standard potash in a 100 C.C. flask,and the mixture is made up to 100 C.C. with distilled water. Theportion of the lead which is dissolved by the excess of potash used isseparated from the hydrate by filtration, and 50 C.C. of the filtratetitrated with standard acetic acid, using phenolphthaleh as indicator.I n the case of the solution containing sugar of lead, the total acid maybe estimated a t once, providing the salt is neutral ; if acid, it is best toestimate the quantity of free acid with standard alkali, using litmusas indicator in this case. To apply the method to determinations o190 ABSTRACTS OF CHEMICAL PAPERS.acid in lead vinegar, it is necessary to neutralise the basic solutionvith the titrated acetic acid solution.D. B.Analysis of Cinchona Barks. (Chem. News, 40, 209-210.)-1. .Ether process.- 1,000 grains of very finely-powdered bark aremixed with suficient alcohol t o form a paste, and when the fibres arethoroughly saturated with the liquid, it is intimately mixed with500 grains of calcium hydrate, and heated to drive off the alcohol.The dried rnass is exhnust,ed successively with ether, the etherealsolution evaporated, and the residue fused a t 125°C.The mass isweighed and dissolved in absolnte alcohol, and the solution neutralisedwith stzndard sulphwic acid (I00 C.C. = 10 grams crystalline quininesulphate). The alcoholic solution of basic quinine sulpliate is eva-porated to dryness and treated with a quaritity of standard acidequal to that, previously used; water is added. and the salt com-pletely dissolved by boiling. Animal charcoal to the amount of 15 percent. of the original weight of bark is then added ; the whole digestedfor 10 minutes, filtered, and washed with acidulated water. The fil-trate containing acid quinine sulphate is concentrated, nearly neu-trnlised with dilute ammonia ( 3 per cent. j , and allowed to crystallise.The crystals of basic quinine sulphate are collected and weighed.Weight of air-dried crystals = amount of crystalline quinine sulphatein the bark.2.Acid process.-l,OOO grains of finely-powdered bark are treatedtwice with boiling dilute sulphuric acid, and once with water; theextracts are evaporated to a small bulk, neutrnlised with milk of lime,and filtered. The residue is dried and boiled repeatedly with alcoholof 90 per cent,. ; the alcoholic solutions are evaporated to dryness, andthe residues treated with acidulated water and filtered ; the filtrate isneutralised with caustic soda and shaken with chloroform ; the chloro-form solution is separated and evaporated in a tared capsule. Theresidue consisting of the total quantity of quinine, cinchonine, andquinidine is treated with ether .to extract the quinine, which is esti-mated by the ether process. The residue is dissolved in dilute aceticacid, and treated with a Concentrated solution of potassium iodide.The precipitate consists of quinidine iodide, of which 100 grams =71-69 quinidine, or 94.5 quinidine sulphake.The quinidine and cin-chonirie may be separated by treating the residue with proof spirit,in which the quinidine is soluble, whilst cinchonine and cinchonidineremain undissolved.Owing to the rapidity with which the ether process may be worked,it can be used with greater advantage than the acid process. Theobject of the former is to extract that alkaloid only on which theyalue of the cinchona bark depends, and is achieved without pro-ducing amorphous quinine, which is so liable to be formed by pro-tmcted boiling, as in the acid proce.ss.Calisaya and red cinchona barks may be analysed by the ether pro-cess, but it is not applicable to the Loss or grey barks.Estimation of Albuminoid Nitrogen in Fodders.By F.SESTINI (Bied. Centr., 1879, 7ll).-The author recommends boiling theDried a t loo", 8-5.5 = 100 crystals.L. T. 0'sANALYTICAL CHEMISTRY. 191finely powdered substance for one hour in water, to which a few drops oflactic acid have been added, treatment with lead acetate and filtration.The nitrogen is then estimated in the precipitate and the filtrate, theamount contained in the former representing the quantity of albuminpresent. J. K. C.Enumeration of the Fat Globules in Milk as a Test.By E.BOUCHUT (Bied. Centr., 1879, 145).-One drop of milk is diluted with100 drops of water, and this placed in a cell 0.1 mm. deep is examinedunder the microscope; the globules i n a space 0.1 mm. square arecounted, the number obtained multiplied by 100,000, and this thengives the number contained in 1 cm. of the original milk. In humanmilk from 2,200,000 to 5,000,000 ghbules have been observed, but theaverage number appears to be from 1,000,000 to 2,OOQ,OOO. With COW'Smilk, the results were-1,102,500 globules 1032 sp. gr. 24 grams butter. per liter2,205,000 ,, 1032 ,, 37 Y,2,400,000 ,, 1030 ,, 3 7 >,3,700,000 ,, 1030 ,, 34 7 ,As human milk varies considerably, it is advisable, in comparingspecimens from different individuals, to take five samples on the sameday.When 800,000-1,O00,000 globules are fomd in human milkper centimeter, the milk may be considered as good. E. W. P.Foreign Colouring Matters in Red Wine. By J. NESSLER(Bied. Cextr., 1879, 142--145).-The author comes to the conclusionthat we are a t present not in a position to determine chemically thedifference between the colouring mathers of madder, Eil berry, andgrapes. A pure wine reacts differently with the same reagents, thediff'erence depending on bhe rlode 0f preparation, and the qudity ofAdulteration of Wine. By F. LEPEL (Bied. Centr., 1879, 709).-Red beet is often used in conjunction with fuchsine to colour wine.The presence of the former tnay always be recognised by the author'scopper reaction (Ber., 10, 1875).the grape it,self.E. w. P.J. K. C.Morphiometric Processes for Opium. By A. B. PRESCOTT(Phaym. J. Tmns. [ 3 ] , 10, 128-130, and 182--185).-The authorsubmits the following assay process for opium ; it is essentially theHuqer- Jacobserb's, but it is modified by a preliminary washing of theopium with benzene, to remove impurities.The opium is dried at 100" C., until it ceases to lose weight; i t isthen powdered, and 66.5 grams are placed in a paper filter of 10 cm.diameter in a funnel ; benzene is poured in until the powder is covered,and as soon as it begins to drop through, the funnel is stopped, andallowed to macerate for an hour; the benzene is then allowed to per-colate, more being supplied, until the whole volume used is 50 C.C.'I'he filter and its contents are dried with gentle heat, until there is noiurther smell of benzene, and the contents are then transferred to 192 ABSTRACTS OF CHEMICAL PAPERS.weighed flask of 120 C.C.capacity, the filter paper being kept. 20 C.C.of water are added, together with 3 grams of slaked lime, which hasbeen slaked with one-third its weight of water. The contents of theflask are agitated for several minutes, and then uniformly mixed byclosing the flask and shaking it. Distilled water is added, until thecontents of the flask weigh 74.5 grams, and the flask is heated withoccasional agitation for an hour in nearly boiling water; it is thencooled, and the exact' weight (74.5 grams) made up again by the addi-tion of water.The solution is then filtered through the paper pre-viously used, into a vessel of about 80 c.c: capacity, marked for avolume of 50 C.C. As soon as exactly SO C.C. of filtrate are obtained,the contents of the filter being gently squeezed, if necessary, to yieldthe last few drops, it is mixed with 8 drops of benzene, and 3 C.C.of washed ether, the vessel closed, and the whole agitated ; 4.5 gramsof powdered ammonium chloride are then added, and as soon as it isdissolved the liquid is once more agitated, and then set aside in a coolplace for three and a, half hours. The crystalline deposit is filteredthrough a weighed and moistened filter, and washed several timeswith a few drops of water ; it is then dried at 50" C., washed with 3 C.C.of washed ether, dried again and weighed.The weight of morphinethus obtained may be considered as that contained in 5 grams ofopium ; this allows for loss during filtration ; the percentage is there-fore obtained by multiplying the weight found by 20.The author also submitted different processes for estimatingmorphine to a comparative trial by analysing several samples by eachof the methods ; then estimating by Mayer's volumetric method thepurit'y of the morphine obtained, and also determining the morphineremaining uncrystallised in the mother-liquor by extraction with amylalcohol and titration. Mayer's solution was prepared by dissolving13.55 grams of dry merciiric chloride and 49.84 grams potassium iodidein water, and making up to a litre; 1 C.C.corresponds to 0.02 ofmorphine. The morphine precipitates were dissolved in water withacidulated sulphuric acid, and so far diluted that a t the end of thetitration the solution should be 200 parts to 1 of morphine, this pre-caution being necessary because of the solubility of the precipitate inwater. The author finds that the results obtained by Mayer's processare more accurate than those yielded gritvimetrically after purificationof the crystals, but- they are probably somewhat low. The morphineremaining in the mother-liquor was partially separated by allowing afurther time for crystallisstion, and the filtered liquid was then wellshaken with amyl alcohol in successive portions of 15, 10, and 5 C.C. ;the alcohol was separated and evaporated, and the residue titrated byhlayer's solution.The conclusions arrived a t are that hot benzene, if used for the pre-liminary treatment, occasions a loss of morphine as compared with coldbenzene ; the cold benzene, however, must be used in limited quantity,since it dissolves some morphine. The omission of the preliminarytreatment with benzene leaves the opium-lime mixture loaded withopium wax, and renders the filtration more difficult, and the entireoperation less satisfactory, but results after deduction of one-tenth (orone-thirtieth if ether-washed) are fairly in accordance with thosANALYTICAL CHEMISTRY.193obtained by the modified process of treating with benzene. TheProcter-Staples’ process yielded unsatisfactory results, more especiallyin the estimation of morphine extracted from the mother-liquorby amyl alcohol.The author suspected that something besides thealkalo’id, which acted on Mayer’s solution, was taken up by aniylalcohol. It was found more satisfactory to extract the mother-liquorobtained by Staples’ process, first with benzene, and afterwards withamyl alcohol. By Huger’s process the filtrate contains in solution1.9 times as much as pure water, and by Staples’ process 2.45 times asmuch. Sc7mc7~trupp~s pmcess for estimating morphine and narcotine inopium (Zeits. Anal. Chew., 1868, 7, 509), was also submitted toexamination ; the author pronounces it to be untrustworthy and inex-pedient ; the experiments made by this process, however, proved thatbenzene does not ext,ract the whole of the narcotine from opium,unless an alkali is present, and therefore the preliminary treatmentwith benzene does not dispense with purification of the morphinecrystals by washing with ether freed from alcohol and acetic acid byrecent agitation with water ; the impurities left in the morphine maythen be considered as counterbalancing the morphine left in themother-liquor, and removed by washing.Valuation of Tincture of Opium. By A.B. PRESCOTT (Pharm.J. TYU~ZS. [3], 10, 66).-The author determined the opium in twelvedifferent samples of the tincture, employing two different processes foreach sample, viz., Aager’s and Staples’.The modified Hager’s process was carried out as follows :-Thespecific gravity of the tincture was taken ; then 25 grams were evapo-rated nearly to dryness on the water-bath, triturated with 1 gram offreshly slaked lime, and after adding 24 C.C.of water, the mixture washeated on the water-bath for an hour. The whole was then transferredto a wetted filter, and the residue washed on the filter with warmwater, until the washings were nearly colourless ; the filtrate, afterbeing concentrated on the water-bath to 25 grams, was transferredwith rinsings to a wide-mouthed bottle, and mixed while warm with1 C.C. of ether and 3 drops of benzene ; 1.1 gram of ammonium chloridewas then dissolved in the liquid, and it was set aside €or 24 hours.The liquid was now well shaken, to detach crystals from the sides ofthe bottle, and the crystals collected on a weighed.filter, washed wit!habout 8 C.C.of distilled water, dried at 50” C., and weighed. If Hager’splan is followed of allowing only three hours for the crystallisation ofthe morphine, t,he author prefers to wash the crystals with ether, andweigh t,hem, the impurities present counterbalancing the morphine leftin solution.According to Stuples’ method, after estimating the specific gravity,25 grams were evaporated to half the bulk on the water-bath, and24 hours allowed for the subsidence of the tarry matters ; the liquidwas decanted through a filter into a wide-mouthed bottle, and thetarry residue washed with 4 C.C. of water, the washings being added tothe filtrate. An equal volume of alcohol of sp.gr. 0.835, and 1.3 C.C.of ammonia solution of sp. gr. 0.96, mixed with 1.7 C.C. of alcohol,were then added, the bottle stoppered and well shaken, and set aside.F. C194 ABSTRACTS OF CHEMICAL PAPERS.After about four days the morphine crystals were filtered off, ‘rinsedwith 4 C.C. of diluted alcohol, dried at 50°, and weighed. Thecrystals were afterwards washed with 8 C.C. of ether, and weighedagain ; the ether removed about one-tenth by weight of the crystals.The author concludes that SGapZes’ process yields the best crystals ofmorphine, but considers that it is little if ah all preferable to Hager’smethod. F. c.Analytical Examination of Tinctures. By A. H. ALLEN(Pharm. J, Trans. [3], 9, 1035-1037).-Tinctures are made withspirits of two alcoholic strengths.For some, rectified spirits, con-taining 84 per cent. by weight of absolute alcohol, equivalent to 155.5per cent. of proof spirit, is used; for others proof spirit, containing49 per cent. by weight of absolute alcohol, i;r sufficiently strong.Alcohol being frequently. the most expensive item in 1 he preparationof tinctures, it is liable to be economised, and this will often lead toan insuacient quantity of the drug being dissolved. Hence the deter-mination of the proportion of alcohol present irr a tincture is often ofimportance. With many tinctures, the a1 coho1 can be readily separatedby distillation and estimated by taking the specific gravity of the dis-tillate, volatile alkaline or acid substances being retained during distil-lation by previously making the tincture acid or dkaline respectively.Tinctures containing volatile essential oils cannot be examined by dis-tillation, but the oil can usually be precipitated hy a sufficient dilutionwith water, and if it remains suspended in the liquid it may then beseparated by adding ai few drops of strong calcium chloride solutionand some sodium phosphate arid stirring vigorously ; the precipitatedcalcium phosphate carries down the oil globules and clarifies theliquid, which is then run through B dry filter and distilled.I n somecases sodium carbonate is substituted for sodium phosphate when anacid is to be retained during the subsequent distillation. The per-centage of alcohol present is best stated in terms of proof spirit.The process was tested on tincture of myrrh, which had been pre-pared for the purpose. The alcohol found was about 6 per cent, toolow, but this discrepancy was explained by the fact that myrrh causesa considerable expansion of the volume during solution in spirit, andafter estimating and allowing for this expansion exact results weresecured. A similar result was obtained with camphor. Experimentshowed that, camphor dissolved in alcohol without sensible change ofvolume, the volume of the tincture being equal to the sum of thevolumes of the spirit and the camphor. Hence it appears that thespirit causes the camphor to liquefy and mingle as a liquid with thespirit. I n consequence of t>his peculiarity, the proportion by volumeof proof spirit contained in spirit of camphor will be 0.9 of that pre-sent in the alcohol used in its preparation, and there is no doubt thata similar correction onghtl to be applied in certain other cascs. Thedistillation method, when applied to spirit of camphor, is also renderedinexact by some of the camphor remaining unprecipitated, owing to itssolubility in water.The author found a deficiency of alcohol in a sample of “ compoundtincture of camphor,’’ and this led to a deficiency also of oil of aniseTECHNICAL CHEMISTRY. 195since the spirit was too weak to dissolve the full proportion of oil.This tincture was examined by diluting with water, clarifying withcalcium chloride and sodium carbonate solutions, distilling the alcohol,and estimating benzoic acid in the residue by acidifying it and shakingseveral times with ether. On evaporating the ether, the benzoic acidwas left in a pure state ; the opium was roughly estiniated colorime-trically by adding proof spirit and a few drops of ferric chloride, andcomparing with a similarly treated standard opium solution. The per-centage of alcohol found in this tincture by the distillation processnever exceeded by two degrees that deduced from the density of theoriginal tincture. The proportion of oil of anise present may beroughly judged by the readiness with which the liquid is precipitatedon dilution with water. With a proper proportion of oil, precipihtionoccurs on very slight dilution. F. c

ISSN:0368-1769    

DOI:10.1039/CA8803800188

出版商:RSC    

年代:1880

数据来源: RSC