摘要:

J O U R N A L THE CHEMICAL SOCIETY. Contmittee of 13. E. ARMSTROXG Pli.D. F.R.S. A. DUPR~ Ph.D. F.R.S. J. H. GILBERT Ph.D. F.R.S. C. GRAHAN D.Sc. F. R. JAPP M.A. Pl1.D. Hrao MULLER Pli.D. F.R.S. vitblicntion : IT. H. PERKIN F.R.S. W. J. RUSSELL Yh.D. F.R.S. J. MILLAR Tlioxsos. F.C.S. R. WARISGTON F.C.S. c'. R. A. WILIGIIT D.Sc. F.R.S. 6bitor : HEXRP WATrs B.A. F.R.S. VOl. XLI. 1883. TRANSACTIONS. L 0 N n 0 N : J. V A N VOORST 1 P A T E R N O S T E R ROW. 1882 LONDON : HARRISON BND SONS PRTNTERS Ih’ ORDINARY TO HEE MAJRATY ST. AfA.BTIN’S LANE C 0 N T E N T S. PAPERS READ BEFORE THE CHEMICAL SOCIETY :-I.-On the Volumetric Estimation of Bismuth in the Form of Oxalate. By M. M. PATTISON MUIR M.A. F.R.S.E. Fellow and Przelector in Chemistry and C.E. ROBBS B.A. B.Sc., Scholar of Gonville and Caius College Cambridge 11.-The Action of Water on Bismuthous Iodide a Lecture Experiment. By M. M. PATTISON MUIR . 111.-Aluminium Alcohols. Part 11. Their Products of Decom-position by Heat. By J. H. GLADSTONE P1i.D. F.R.S. and AJ~FRED TRIBE F.C.S , Lecturer on Chemistry in Dulwich 1V.-On the Action of Oxides on Salts. Part IV. Potassic Chlorate and Ferric Oxide. By EDMUND J. MILLS D.Sc., F.R.S. and GEORGE DONALD . V.-a- and P-Amylan Constituents of some Cereals. By C. O'SULLIVAN . . . VL-Note on the Action of Ethyl Chlorocarbonste on Benzene in presence of Aluminium Chloride. By EDWARD H. RENNIE M.A. (Sydney) D.Sc. (London) By EDWARD H. RENNIE M.A. (Sydney) D.Sc. (London) By EDMUNI) J. MIms D.Sc., F.R.S." Young" Professor of Technical Chemistry in Anderson's College Glasgow and J. PETTIGREW . 1X.-Researches on the Relation of the Molecular Structure of Carbon Compounds to their Absorption-spectra. By W. N. HARTLEY F.R.S.E. &c. Professor of Chemistry Royal Oollege of Science Dublin . X.-On Peppermint Camphor (Menthol) and some of its Deri-vatives. By Hi. W. ATKIESOP; B.Sc. and H. YOSHIDA . XI.-On some Higher Oxides of Manganese and their Hydrates. Part 11. By V. H. VELEY B.A. F.I.C. Christ Church Laboratory Oxford . By DAVD HOWARD and JOHN HODGKIN . . . . College . . . . VI1.-On Benzyl-phenol and its Derivatives. VII1.-On the Steeping of Barley. . . XI1.-On a New Alkalo'id from Cinchona Bark. PAUE 1 4 5 18 24 33 33 38 45 4 iv C,ONTESTS.XII1.-Contributions t o the Chemistry of Rare Ea.rth-1LIetaIs. By B. BRAUNER Ph.D. Fellow of the Owens College . X1V.-On the Composition of Pennant Grits in contact with and at a distance from Carbonaceous Deposits. By EDWARD WRTHERED F.C.S. F.G.S. . XV.-Note on Certain Photographs of the Ultra-Violet Spectra of Elementary Bodies. By W. N. HARTLEY F.R.S.E. &c., Professor of Chemistry Royal College of Science Dublin ( c o n t k u e d ) . XV1.-The Chemistry of Bast Fibres. By C. F. CROSS and E. J. BEVAN . XVI1.-A New Apparatus for the Determination of Melting Points. By C. F. CROSS and E. J. BEVAN . XVII1.-On the Reaction of Chromic Anhydride with Sulphuric Acid. By C. F. CROSS and A. HLGGJN . XIX.-On some Decompositions produced by the Action of Chloride of Aluminium.By C. FRIEDEL and J. M. CRAFTS XX.-Chemical Examination of the Buxton Thermal Water. By J. C. THRESH B.Sc. . XX1.-Dibenzoylaniline and its Isomerides. Byv A. HIGGIN . XXII. -Contributions to our Knowledge of the Composition of Alloys and Metal-work for the most part Ancient. By WALTER FLIGHT D.Sc. F.G.S. of the Department of Mineralogy British Museum ; Examiner in Chemistry and Physics Royal Military Academy . XXITI. -On the Action of Aldehydes on Phenanthraquinone in Presence of Ammonia. (Third Notice.) By &'RANCIS R. JAPP MA. Ph.D. Assistant Professor of Chemistry in the Normal School of Science South Kensington and FREDK. W. STREATFEILD . XX1V.-Application of the Aldehyde and Ammonia Reaction in Determining the Constitution of Quinones.By FRANCIS R. JAPP M.A. Ph.D. and FRRDK. W. STREATFEILD . XXV.-On the Action of Sodium Hydrate and Carbonate on Felspars and Wollastonite. By WAT,TER FLIGHT D.Sc., F.G. S. of the Department of Mineralogy British Museum XXV1.-On Pentsthionic Acid. (Part 11.) By WATSON SNITH aiid T. TAKAMATSU . XXVI1.-On Some Constituents of Resin Spirit. By G. HARRIS MORRIS F.C. S. Demonstrator in the Chemical Laboratories of the Mason Science College Birmingham XXVIIL-On the Preparation of Dietliylnaphthylamine. By XXIX.-On the Action of Sulphuric Acid upon Diethylnaph-thvlaniine at Hiph Temueratures. Bv BERNAKD E. SNITH . . BERNARD E. SMlTH . PAGE 68 79 84 90 111 113 115 117 13.2 134 146 157 150 162 167 180 18 CONTENTS.XXX.-On the Action of Carbon Oxydichloride (Phosgene Gas) upon Diethylnaphthylamine. XXX1.-Contributions to the Chemical History of the Aromatic Derivatives of Methane. XXXI1.-Contributions to the Chemistry of Cerium Compounds. By W. N. HARTLEY F.Rl.S.E. &c. Professor of Chemistry, Royal College of Science Dublin XXXII1.-The Analysis of Rhabdophane a New British Mineral. By W. N. HARTLEY F.R.S.E. &c. Professor of Chemistry Royal College of Science Dublin (Part TI.) By EDWARD H. RENNIE M.A. (Sydney) D.Sc. (London.) . By BERNARD E. SMTTH . By RAPHAEL MELDOLA . . . XXX1V.-On Benzyl-phenol and its Derivatives. Anniversary Meeting . . . . Appendix to Report of Anniversary Meeting . . . . XXXV.-On the Solubility of Glass in Certain Reagents.By R,TCEIARD COWPER A.R.S.M. Demonstrator of Chemistry a t the Royal Naval College . XXXV1.-Analysis of a Piece of Oxidiseci Iron from the Con-denser of H.M.S. “ Spartan.” B~RICHARD COWPER A.R.S.M., Demonstrator of Chemistry at the Royal Naval College . XXXVI1.-Note on a convenient Apparatus for the Liquefaction of Ammonia. By J. ENEBSON REYNOLDS M.D. F.R.S. Pro-fessor of Chemistry University of Dublin . XXXVII1.-Transformation of Urea into Cyanamide. By H. J. H. FENTON M.A. Demonstrator of Chemistry in the University of Cambridge . XXX1X.-On the Action of Halojid Acids upon Hydrocyanic Acid. By L. CLAISEN Ph.D. and F. E. MATTHEWS F.C.S XL.-On t.he Action of Acetyl Chloride on Fumnric Acid. By W. H. PERKIN F.R.S. XL1.-On the Action of Acetone on Phenanthraquinone both alone and in presence of Ammonia.By FRANCIS R. JAPP, M.A. Ph.D. Assistant Professor of Chemistry in the Normal School of Science South Kensington ; and FREDK. W. STRFATFEILD . XLI1.-A Study of some of the Earth-metals contained in Samarskite. By HENRY E. ROSCOE V.P.R.S. President of the Manchester Literary and Philosophical Society XLIIL-The Spectrum of Terbium. By H. E. ROSCOE and A. SCIIUSTER . XL1V.-On the Behaviour of Zinc Magnesium and Iron as Reducing Agents with Acidulated Solutions of Ferric Salts. By T. E. THORPE F.R.S. . SLV.-Note on the Action of the Oxychlnrides of Sulphur on Silver Nitrate. By T. E. THOBFE F.R.S. . . v PAGE 185 187 202 210 220 229 247 254 256 259 262 264 268 2 70 277 283 28 7 29 vi CONTENTS.XLT71.-On the Action of Thiophosphoryl Chloride upon Silver By T. E. THOBPE Ph.D. F.R.S. and SEPTIMUS XLVI1.-Experiments on the Action of Potassium-amalgam, Sulphuretted Hydrogen and Potassic Hydrate respectively, on Tetra- and Penta-thionate of Potassium. By VIVIAN LEWES Assistant in the Laboratories Royal Naval College. XLVII1.-On the Estimation of Retrograde Phosphates. By XL1X.-Action of Heat on Mercuric Chloride under Low Pres-sures. By THOS. CARNErmx D.Sc. Professor of Chemistry in Firth College Sheffield . By FRANCIS R. JAPP M.A. Ph.D. Assistant Professor of Chemistry in the Norma1 School of Science South Kensington and H. H. ROBINSON L1.-On Rotary Polarisation by Chemical Substances under Magnetic Influence.By W. H. PERKIN F.R.S. . LI1.-A Spectroscopic Study of Chlorophyll. By W. J. RUSSELL, Ph.D. F.R.S and W. LAPRAIK F.C.S. LII1.-On the Precipitation of the Alums by Sodic Carbonate. By EDNUND J. MILLS D.Sc. F.R.S. and R. L. BARR . LIV.-On the Determination Qf Nitric Acid as Nitric Oxide by means of its Reaction with Ferrous Salts. (Part 11.) By ROBERT WARINGTON . LV.-On the Determination of Nitric Acid in Soils. By ROBERT WARINUTON . LV1.-Communications from the Laboratory of the University of Tokio Japan. Metallic Componnds containing Bivalent Hydrocarbon Radicals. (Part 111.) By J. SAKURAI F.C.S. LV11.- Some Observations on the Luminous Incomplete Com-bustion of Ether and other Organic Bodies. By W. H. LVII1.-Contributions from the Dye-house of the Yorkshire College.On some New Compounds of Haematein and Braziie'in. By J. J. HUMMEL and A. G. PERKIN . L1X.-On the Crystallisation from Supersaturated Solutions of certain Compound Salts. By JOHN M. THOMSON and W. POPPLEWELL BLOXAM King's College London LX.-On Oxypropyltoluidine. By H. FORSTER MOBLEY M.A., Fellow of University College . LX1.-On some Halogen Compounds of Acetylene. By R. T. PLIMPTON Ph.D. LXI1.-On Dihydroxybenzoic Acids and Iodosalicylic Acids, By ALEX. K. MILLER Ph.D. Nitrate. DYSON Esq. . . . . FREDERICK JAMES LLOYD . L.-On the Constitution of Amarine and Lophine. . PERKIN F.R.S. . . . . , PAGE 297 300 306 31 7 323 330 334 341 345 351 360 363 367 379 38 7 391 39 CONTEKTS. yii PAGE LXII1.-Crystalline Molecular Compounds of Naphthalene and Benzene with Antimony Trichloride. By WATSON SMrTH and G. W. DAVIS . . 411 LX1V.-An Additional Evidence by Analysis of the Quinoline Molecule that this Base belongs to the Aromatic Series of Organic Substances. By WATSON SNITH and G. W. DAVIS . 412 LXV.- On Orcinol and some of the other Di hydroxytoluenes. By R. H. C. NEVILE and DR. WIXTHER . . 4.1

ISSN:0368-1645    

DOI:10.1039/CT88241FP001

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

11.- The Action o,f Water o n Bismwthous Iodide a Lecture Experiment. By M. M. PATTISON MUIR. THE action of water on bismuthous iodide affords a reaction well adapted for illustrating the influence of (u) time ; ( 6 ) temperature ; (c) mass on a chemical change. The experiment may be conducted in two ways the second of which is I think perhaps the best the meaning o€ the expressions " direct " and " reverse " action may also be well illustrated by this modification of the experiment. A quantity of aqueous hydriodic acid-about 1 part strong acid to 100 parts water-is divided into two equal parts ; one is heated to boiling, the other remains cold a small quantity of the cold solution is diluted with about three times its own bulk of water ; a little of this is again diluted with about three or four times its own bulk of water.The four liquids are placed in beakers standing on whike surfaces with white backgrounds and a few grains of solid bismuthous oxide are shakeu into each. I n the cold comparatively concentrated liquid, brown BiI is produced ; in the hot liquid red BiOI ; in the cold and moderately dilute BiOI ; and in the most dilut,e there is little or no action. The brown BiI slowly changes on standing to red BiOI. The experiment may be conducted more easily and with more striking effect by pouring R little of a solution of BiT in concentrated hydriodic acid into three beakers standing on white surfaces and with white backgrounds and containing (1) a little cold water (about 100 o.c.); (2) the same quantity of water at about 90-100"; (3) a large quantity (about 500 c.c.) of cold water. Brown BiI is precipi-tated in (1) ; red crystalline BiOI in (2) ; and red BiOI but in smaller quantity in (3). Here again the brown BiI is slowly changed to red BiOI on standing by pouring a little strong hydriodic acid inho this beaker after this change is nearly complete the reverse change-with reproduction of brown Bi13-is rendered very apparent

ISSN:0368-1645    

DOI:10.1039/CT8824100004

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

5 111.-Aluminium Alcohols. Part 11. Their Proclucfs of Decomposition by Heat. By J. H. GLADSTONE Ph.D. F.R.S. and ALFRED TRIBE F.C.S., Lecturer on Chemistry in Dulwich College. WE lately described some alcohols in which the basic hydrogen is replaced by aluminium (Clzern. Xoc. J. 1876 p. 158; 1881 p. 1 ; Proc. Roy. Soc. 1880 p. 546). We have also observed (Proc. Roy. Xoc., 1880 p. 548) that these compounds are decomposed by heat and that in two ways they may split up into alumina and the alcohol and olefine or into alumina and the ether. The further investigation of this matter forms the subject of the present paper. Ethyl Series. The effect of heat on the aluminic ethylate has already been par-tially described. Although the compound may be distilled in vucuo it is almost wholly broken up near its boiling point under the ordinary pressure of the atmosphere.A little ether is formed bat the decom-position takes place almost entirely into ethene alcohol and alumina, thus :-(CzH,0)6Al = 8 1 2 0 3 + 3C2H4 + 3czH60. In the case of the amylate a similar decomposition occurs but the yield of amylic ether is somewhat greater. Pheny 1 Series. If similar reactions take place with the aluminic alcohols of the phenyl series we should obtain the simple ethers (CaH2B-7)20 only one of which has been described together with the hydrocarbons, CsH and C7H6 and their homologues. We therefore studied more completely the action of heat upon the aluminium derivatives of certain of the phenyl alcohols. Aluminium Pheny late. 469 grams of this compound were heated in a flask fitted with B wide bent tube about 16 inches long.The substance quickly melted, and after a little free phenol had passed over a somewhat viscid yellowish-brown liquid distilled. 'l'he residue consisted of charcoal, tarry matter and alumina. The distillate weighed 268 grams and after redistillation to remove a small quantity of aluminium phenjlat 6 GLADSTONE AND TRIBE ALUMIXIUM ALCOHOLS. which was carried over there remained 252 grams. rated by fractionation into three portions :-This was sepa-u. b. 160 grams from 200-280". e. 34 grams above 280'. 52 grams from abont 80-200". Fraction a.-The greater part of this portion distilled between 178" nud 184" a small quantity of a very mobile liquid of the odonr of benzene passing over a t about 80".By repeated distillation of this higher boiling point product and rejecting small portions above 180", a considerable part of it was obtained boiling between 178" and 180". This liquid was colourless; it was soluble in a solution of potash, .e:*ystallised on csoling in long needles; gave hydrogen with the aluminium-iodine reaction and on combustion with oxide of copper, yielded 76-57 per cent of carbon and 6.79 of hydrogen. The prin-cipal part of this fraction consisted therefore of phenol. Fraction b.-This portion was shaken repeatedly with three or four times its volume of boiling water to remove any phenyl alcohol nut separated by distillation. The residual oily liquid was dried over calcium chloride and subsequently distilled several times each time rejecting whatever failed to pass over below 300".The distillate was now quite colourless and nearly the whole of it boiled constantly This substance was not miscible with water or aqueous potash and did not yield hydrogen by the aluminium-iodiiie reaction. It separated from an alcoholic solution on cooling to a low temperature in colour-less prisms. Its specific gravity was 1.0904. iJt 249". Burnt with oxygen and copper oxide-I. 0.3658 gram gave 1-1320 gram CO and 0.1955 HLO ; 11. 04241 , , 1.3175 gram COz and 0.2279 H,O ; results which appear from the following comparison to agree with the formula CI2H,,O which is that of plLenyZ e t h e r described by Hoff meister in 1871 ( B e r . 3 747). I. IT. C12 144 8470 84.40 8 4 i 2 H, I G 5-88 5.93 5.97 0 16 9.42 170 100.00 - I -I t s index of refraction for A was 1.5675 at 25" and the length of the spectrum from A to H was 0.0583 Two determinations gave 90.05 and 90-22 as the refraction equivalent.for A which accords with theory GLADSTONE AND TRIBE ALUNINIUM ALCOHOLS. 7 Portions of this compound were found to solidify to a mass of colourless prismatic crystals while other portions apparently identical remained liquid. A few experiments were made in the hope of elucidating this anomaly. A quantity of the freshly distilled com-pound was well shaken in a stoppered bottle. No solidification occurred. A crystal of' the substance was now introduced and imme-diately beautiful star-shaped crystals formed on several parts of the introduced crystal others forming on these and the whole liquid speedily passed to the crystalline condition.This change was accom-panied by a rise in temperature of 8". Another portion of the substance remained liquid a t 2" for hours but quickly solidified on the vessel containing it being immersed in a freezing mixture. Iimction c.-This portion consisted of a viscid brown liquid con-taining grains of' a yellow solid. It was distilled a number of times, rejecting each time a small quantity of a non-volatile tarry substance. The distillate was now less viscid and much lighter in colour. On slowly distilling it an almost colourless liquid passed over a t about 280" which condensed to a nearly white solid ; and this was followed at a higher temperature by a comparatively small quantity of a non-crystallisable thick orange-coloured liquid.The solid was purified by repeated solution in and crystallisation from alcohol of sp. gr. 0.880. It was white in colour soluble in absolute :tlcohol and more so in ether. It melted a t 97" and sublimed slowly a little below this temperature. On combustion with oxygen and copper oxide after drying a t 100" : I. 0.1275 gram gave 0.4018 CO and 0.0654 H,O 11. 0,1268 , ,) 0.3387 , ,) 0.0646 H,O 111. 0.1933 , , 0.6099 ) , 0.10U5 H,O. The third portion (111) analysed had undergone sublimation. The results expressed in parts per 100 give-I. 11. 111. C 85-94 85.75 86.03 H . . 5-70 5.66 5.77 On the determination of its vapour-density by the method of Victor Meyer-0.0978 gram gave vapour = in volume 12.04 C.C.(corr.) 0.0836 $ 7 ? 3 10.19 ,, These data give 181.4 and 183.0 respectively for the molecular weight of tlhe substance. Its most probable molecular formula is therefore C13H,o0 8 GLADSTONE AND TRIBE ALUMINIUM ALCOHOLS. Calc. for 100 pts. Found (mean). Cis 156 85.71 85.91 HI0 10 5-30 5.71 0 - 16 8.79 182 100*00 Three compounds of this formula have been described-fluorene alcohol and diphenyl ketone and its isomer. Our body does not accord in physical properties with the description of any one of these com-pounds. We are inclined however fro= the mode of its formation to regard it as a phenyl ketone. I- -It would appear then from these results :-1st. That about half of the phenylate was resolved by heat into phenyl ether and alumina thus-(C6H50)6A12 = A1d-A + 3(CsH5)20, which action gives a simple method of preparing this ether.latively small quantity. solved very probably in accordance with the equation -2nd. That a compound of the formula C13Hlo0 was formed in re-3rd. That about one-quarter of the aluminium compound was re-(CsH,O)6AI2 = A1203 + 3C16H60 + 3CsH2. No evidence was found of the existence of the hydrocarbon C6H4, shown in this scheme but it is not improbable that it existed in admix-ture in that portion of the distillate above 300" which was richer in carbon than any of the bodies separated ; in fact it contained 87.5 per cent. and its specific refraction and dispersion were very high. Aluminium Para-cresylate. 760 grams of aluminium para-cresylate were heated as in the case of the phenylate.The distillate was almost solid when cold yellowish-brown in colour and weighed 463 grams. This product was boiled with 6 lit'res of alcohol sp. gr. 0.805 and filtered from alumina by a calico strainer supported in a hot water funnel. On cooling a yellow crystalline substance separated which after washing with 9 litres of alcohol weighed when dry 71 grams. This body wm dis-solved in alcohol and crystallised therefrom until the menstruum was free from yellow colour. After drying at loo" the body was burnt with oxygen and copper oxide. I. 0.1622 gram gave 0.5097 gram CO and 0.0956 gram H,O. This substance was however still yellow and when melted exhi-It was slowly distilled when nearly the bited a blue fluorescence GLADSTONE AXD TRIBE ALUMIXIUM ALCOHOLS.9 whole passed over at 307". The distilInte was of the colour of pale hock free from the blue fluorescence and solidified on cooling t o a cream-coloured crystalline mass. This was dissolved in boiling alcohol from which solution the substance separated on cooling in very thin plates white in colour and of a pearly lustre. On combustion-11. 0.1619 gram gave 0.5081 gram CO and 0.0989 H,O. Tbe substance permitted of sublimation and by the following method was obtained in long whitle lustrous plates. The compound in the condition of the white plates was melted and poured into a porce-lain boat and placed in the forepart of a glass tube about 12j inch in diameter through which a current of hydrogen was passing. The part of the tube in proximity to the loaded boat was heated and the boat and the flame slowly moved backwards as the compound sub-limed.On combustion-111. 0.1205 gram gave 0.3774 gram CO and 0.0717 gram H20. These results expressed in parts per 100 give-I. 11. 111. C . . 85.70 85.59 85.70 H 6-54 6-78 (5.52 On the determination of its vapour- density-0.1186 gram gave vapour = in volume 12.64 C.C. (corr.) 0.1179 , , , 12.60 9 , These determinations were made in hydrogen,and give 2094 and 208.8 respectively for the molecular weight of the substance. The most probable molecular formula of the compound is therefore Cl5HI40. Calc. for 100 pts. Found (mean). C15 180 85-71 85.66 HI4 14 6-66 6-61 0 16 7-63 210 10u~00 It melted at 168" and dissolved but slightly in alcohol giving 2.5 per cent.at the boiling temperature and 0.4 per cent. at 20". The alcoholic liquids obtained in the operations just described were distilled. About 10 grams of the solid compound Reparated and after the alcohol had passed over the residual liquid began boiling at 190°, gradually rising beyond the limits of the thermometer. The greater part however (120 grams) distilled between 190" and 300". This --10 GLADSTOYE AND TRIBE ALUMINIUX ALCOHOLS. fraction was digested with successive portions of aqueous potash and the alkaline liquid subsequently neutralised with hydrochloric acid. 36 grams of an oily brown liquid separated which after washing with a little water and drying with calcium chloride boiied for the most part between 199" and 202".This distillate was colourless and had the composition refraction and other physical and chemical qualities of para-cresol. The portion of the fraction not soluble in aqueous potash was of a dark yellowish-brown colour. It was washed with water and digested with calcium chloride. It was now distilled about thirty times each time rejecting small portions above 300" and below points gradually rising from 220-270". The distillate was colourless a t this stage, and on cooling to a low temperature formed a semi-fluid mass con-taining colourless prismatic crystals. This product was dissolved in about twice its volume of warm alcobol from which solation on cool-ing to a low temperature the substance separated in prisms. It was dried a t lOO" and burnt with copper oxide.I. 0.1070 gram gave 0.3324 CO and 0.0710 H,O. 11. 0.094'2 , , 0.2928 , , 0.0597 ,, 111. 0-1541 , , 0.4793 , , 0.0972 ,, These results expressed in parts per 100 give-I. 11. 111. C . . 84.72 85.30 84.82 H 7.37 7-04! 7-00 On the determination of its vapour-density-0.1077 gram gave vapour = in volume 12-13 C.C. (corr.). 0.1040 , 7 7 , 11.75 9 7 These numbers give 198.1 and 197.6 respectively for the molecular Its most probable molecular formula is weight of the substance. therefore C14HlhO-Calculated. Found (mean). C14 168 84.84 84-94 H14 14 7-07 7.13 0 16 8.09 -which would be that of cresyl ether and from the general analogy between it properties and mode of preparation and that of phenyl ether little doubt can exist as to the compound being the second ether of the phenyl series.As it was obtained through the aluminium derivative of para-cresylate we name tile compound para-cresy I ether GLADSTOSE ASD TRIBE ALCMINIUJI ALCOHOL?. 11 This compound melts a t 50" C. is very soluble in ether and in benzol, moderately so in alcohol and has an odour resembling that of phenyl ether but fainter. The action of heat on aluminium cresylate as was to be expected, presents a general similarity to the action of the same agent on the analogous phenyl compound. The points of difference in the two cases are to be found in the variations in the amount of the corre-sponding compounds produced. The aluminium phenylate for example yields A relatively large quantity of phenyl ether while the cresyl-aluminium alcohol gives only a relatively small quantity of the corresponding compound.Again the phen y l compound yields only a small quantity of the ClsHl,O body while the cresyl compound yields a relatively large quantity of the homologue Cl5H,,0. The hypo-thetical hydrocarbon CiH6 has not been found. Aluminizm Thymlate. 1000 grams of this compound were heated as in the cases of the analogous phenyl and cresyl compounds. A little free thymol a t first passed over then an orange viscid liquid which partially solidified on cooling. As soon as the thymolate became fluid by heat it was noticed to be in violent commotion evidently from the passage through it of gas. The nature of this gas and the meaning of its evolution were determined. 45 grams of thymolate were heated until gas evolution practically ceased.The gas for the first 3240 C.C. was a pure olefine after which i t consisted of a mixture of the olefine and probably marsh-gas, the latter compound being evolved in an increasing ratio towards the completion of the action. The total gas collected (corr.) measured 5856 c.c. of which 3032 C.C. combined with bromine. I n another experiment employing 230 grams of thymolate 196 grams of an olefine bromide were obtained. The greater part of this compound boiled on rectification between 136" and 133". Its sp. gr. at 4" was 1.913 and when dissolved in alcohol and treated with zinc it gave zinc bromide and a gas burning with very luminous flame. The gas set free on heating the fluid thymolate is therefore propylene.The distillate from the 1000 grams of thjmolate weighed 470 grams. It was divided by distillation into two portions:-a which passed over below 280" and b above that temperature. Fraction a .-This portion was liquid of a brownish-yellow colour, and weighed 207 grams. It was treated with successive quantities of a warm solution of potash in which it partially dissolved. The alkaline solutions obtained were neutralised with hydrochloric acid when 12 GLADSTOSE AND TRIBE ALUNINIUM ALCOHOLS. brownish oily liquid separated which was dried over calcium chloride and distilled. The distillate was redistilled some five or six times, each time rejecting the portion not passing over below 205". The distillate at this stage was colourless and nearly the whole of it dis-tilled between 196-2052".On combustion with copper oxide and oxygen-0.1820 gram gave 0.5164 gram ( 1 0 2 and 0.1208 gram H,O. The substance gave hydrogen with the aluminium reaction and readily dissolved in aqueous potash. Its refractive index for A was 1.5316 at 23' C. These qualities jointly with its composition ex-hibited in the foIlowing comparison show the compound to be creso1:-Calculated. Found. Ci 77.77 7 7.38 H 7-40 7.37 0 14.83 15.25 (by diff .) 100~00 Moreover as this substance did not solidify a t a temperature of -17" C. we concluded that it is meta-cresol. Hitherto this modifi-cation had not. been seen in the solid condition but on stirring the product just described with a iherrnometer it underwent solidification at -14" C.Fraction b.-This portion consisted apparently of a yellow crystal-line body in admixture with a brownish viscid liquid. It weighed 231 grams. After the addition to it of the high boiling portion of fraction a the product was mixed with about twice its volume of ether and the mixture heated for a few niinutes in hot water. On cooling in a freezing mixture the brown liquid remained in solution, while the solid was apparently unaffected. The solid was now washed on a filter with cooled ether. It quickly became white and was then found to weigh 15 grams and to consist of small shining scales. This body was next dissolved in boiling alcohol sp. gr. 0.805 from which solution on cooling it separated in large white plates having a pure pearly lustre. It was dried and 'burnt with copper oxide and oxygen with the following results :-I.0-1917 gram gave 0.6017 gram CO and 0.1142 gram H,O. 11. 0.2035 , 0.6383 7 0.1218 ,, These data expressed in parts per 100 give-I. 11. C . . 85.60 83.54 H 6-61 )3 6.t GLADSTONE AND TRIBE ALUMINIUJI ALCOHOLS. 13 On the determination of its vapour-density-0.1279 gram gave vapour = in volume to 13.66 C.C. (corr.). 0.1219 ,! 3 ? 13.04 7 ? These numbers give 209 and 208.6 respectively for the molecular weight of the compound. Its molecular formula is therefore CI5Hl4O-Calc. for 100 pts. Found (mean). C15 180 85.71 85-57 Hid 14 6.66 6.63 0 7.63 - 16 -210 100*00 This compound permits of sublimation by the method used for the compound of the same molecular formula from para-cresol.It sublimes however much more readily and forms larger crystals than that substance. The ethereal liquids obtained in the operation described were dis-tilled. The residuum after the ether had separated commenced dis-tilling at about 250° from which temperature to 300" an almost colourless liquid passed over. The portion above 300" after distil-lation was treated with about twice its volume of ether. On stand-ing more of the ClaH,40 compound separated and by distilling the ethereal solution itself another quantity of liquid was obtained, boiling between 250" and 300". These operations were performed on the residue boiling above 300" until no more of the solid com-pound separated. All the liquid obtained between 250" and 300" was now treated with a hot solution of potash then washed with water dried over calcium chloride and distilled.The liquid commenced boiling at about 270". It was distilled some 40 times each time rejecting small quantities boiling above 300". The liquid had now a faint yellow tinge and boiled for the most part between 284" and 288' C. Its index of refraction for a was 1.5576 at 16' C. Burnt with oxygen and copper oxide-I. 0.1500 gram gave 0.4676 gram COz and 0.0963 gram H,O. 11. 0.1765 , 0.5488 9 9 0.1136 ,, These results expressed in parts per 100 give-I. IT. C 85.01 84.80 H . . 7.13 7.1 5 0.0929 gram gave vapour = in volume t,o 10.68 C.O. (corr.). On the determination of its vapour-density-0.11 76 , 7 9 ? 9 13.56 9 14 GLADSTOYE AYD TRIBE ALU?IIINIUM ALCOHOLS.These numbers give 19416 and 193.58 respectively for the mole-Its most probable molecular formula i s cular weight of the substance. the ref ore C 14H,40 -Calc. for 100 pts. Found (mean). CI4 168 84.84 84.91 H,4 14 7.0 7 7.1 4 0 16 8-09 7-95 (by diff.) .-198 100*00 100~00 which is that of cresyl-ether. The physical properties of this sub-stance however differ materially from those of the cresyl-ether discovered among the products of the aluminium para-cresylate. For example it does not solidify even in a freezing mixture or crys-tallise from alcohol. We are disposed therefore to regard it as iso-meric wit.h the ether of para-cresol and from the mode of its formaftion to name it meta-cresyl-ether. It appears then that heat readily resolves aluminium thymolate into aluminium meta-cresylate and propylene thus-and further that the same agent splits up the aluminium compounct so produced into alumina meta-cresol meta-cresyl-ether and the pearly compound Cl6Hl4O which judging from the want of agreement between the physical properties of this substance and the one of the same molecular formula from the para-cresylate would appear to be isomeric with this latter compound.The points of difference referred to are set out in the table below :-Solubility in abs. alcohol Solubility Melting r y - 7 in benzol C,5H140 from para-cresylate 168" 2.5 p. C. 0.4 p. c. 3.3 p. c. C,5H,40 from meta-cresylate (thymo-point. Boiling. 20" c. 21° c. late). . 200 1.0 , 0-17 , 0-93 ,, Both of these substances are alike in one special particular that of giving out a bluish-white light when shaken or rubbed, Two substances of the formula C15H1,0 have already been de-scribed viz.para-ditolyl and di-benzyl ketones. Our compounds do not accord in physical properties witlh either of these bodies From the composition and mode of formation we are however inclined to regard them as ketones and provisionally as para- and meta-cresyl ketones respectively GLADSTONE ASD TRIBE ALUXISIUN ALCOHOLS. 15 A1 umimiuw @-Nap ht h y 1 ate. 150 grams of 6-naphthol were heated with 10 grams of aluminium until the evolution of hydrogen nearly ceased. Some of the metal yemained in the free condition which is doubtless to be attributed to the infusible character of the resulting iiaphthylate preventing the completion of the action.On distilling the mixture of naphthol and naphthylate a reddish-brown viscous liquid was obtained which solidi6ed on cooling. It was divided by distillation into two portions :-a which passed over below 300° and b above this temperature. Fraction a weighed 40 grams and consisted of naphthalene and naphthol in about equal proportions. Fraction b.-This portion was solid and dark yellowish-brown in colour. It was dissolved in boiling alcohol and the yellow crystalline substance which separated as the solution cooled again and again crystallised from the same liquid. This product was next dried and twice distilled which it did at a temperature above the limit's of the thermometer. On cooling the distillate formed a crystalline mass pale yellow in colour.It was crystallised from boiling alcohol untril the menstruum was free from colour. The sixbstanca now separated from alcohol in thin pearly white rhomboidal plates. It melted a t 104" C. and on combustion-I. 0.2713 gram gave 0.8837 CO and 0.1268 gram H,O. 11 0.2874 , 0.9359 , 0.1354 ,, These results expressed in parts per 100 give-I. 11. C 88.83 88.81 H . . . . . . . . . . . . . . . . . . 5-19 5-23 On the determination of its vapour-density-0.1219 gram gave vapour = in volume 10.16 C.C. 0-1341 , 7 9 Y 11.02 77 0.1399 , 7 7 7 11.64 7 7 These numbers give 267.8 271.4 and 268.7 respectively for the I t s most probable molecular for- molecular weight of the substance. mula is therefore C2,,H140-Calculated. Found (mean).C?o 240 88.84 88.82 HI 1 4 5.18 5.21 o . . . . . . . . . . . . . . 16 5-98 5.97 (by diff.) - -2 70 100. 1 t; GLADSTONE AND TRIBE A1,UJIINIUM ALCOHOLS. which would be that of a naphthyl ether. As the body was formed by the decomposition of the P-naphthylate we name it provisionally p-nuphthyl ether. The alcoholic liquids obtained in the operations just described were distilled. After the alcohol had passed over the residuum com-menced boiling at 290° but quickly rose beyond the limits of the thermometer. A dark-brown viscous liquid distilled. This dissolved readily in alcohol and the resulting solution very slowly deposited a quantity of the solid body just described. When this body had ceased separating a comparatively small quantity of a very viscous substance was obtained on distillat'ion containing 89.5 per cent carbon and 5.3 per cent.hydrogen. It freely dissolved in alcohol the solution exhibiting a blue fluorescence. On distilling the several highest boiling point portions collected in the above operations a semi-solid distillate was obtained which on heatment with boiling alcohol left a dark-yellow crystalline substance. This separated from benzene in square dark golden-yellow shining plates. It dissolved very slightly in alcohol to which it mere trace imparted a powerful blue fluorescence. The quantity obtained was too small to determine its molecular formula b u t combustion showed it to be a very highly carbonaceous hydrocarbon probably contami-nated with u small quantity of an oxygenated body.For future reference we propose from its double colour the temporary name of chryseudiene. The principal product of the decomposition by heat of ,&aluminium naphthylate is P-naphthyl ether thus :-Aluminium- a- Nup h t h y 1 ate . I n order for aluminium to replace the basic hydrogen in a-naphthol the usual quantity of iodine must be employed. This difference between the a- and P-modification serves to discriminate the two naphthols. 520 grams of a-naphthylate were prepared in the manner ordinarily used for the aluminium-derivatives of the other alcohols. This com-pmnd underwent decomposition on heating but the temperature re-quired was much higher than in the case of the analogous @compound. A bmwnish-yellow viscous liquid distilled which solidified on cooling, and weighed 319 grams.This product was separated by distillation into two portions a which passed over below 310" and b above this temperature. Fractiolz a weighed 90 grams and mainly consisted of naphthalene GLADSTONE Axil TRIBE ALUMISIUJI ALCOHOLS. 17 Fraction b.-This was melted and poured into about twice its volume of boiling alcohol. A quantity of a yellow substance remained undissolved and a little more separated on the cooling of the alcoholic liquid. These operations were repeated four times on the yellow body successively obtained. The substance was now dis-tilled and on cooling the distillate solidified to a yellow crystalline mass. This was crystallised some four times from benzene in which it dissolved more readily than in alcohol.It now separated in large shining rhombic plates of the colour of uranium glass. Burnt with copper oxide-I. 0.2694 gram gave 0.9302 gram CO and 0.1342 gram H20. 11. 0.2816 , 0.9741 0.1498 ,, These results expressed in parts per 100 give-,, I. 11. C 94.17 94.34 H 5.53 5.55 On the determination of its vapour-density-0.1026 gram gave vapour = in volume to 9.06 C.C. 0.1029 , 9 9 9.06 ,, These numbers give 253.0 and 253.4 respectively for the molecular weight of the substance. Its most probable molecular formula is therefore C20H,4. Calculated. Found (mean). C, 240 94.43 94.26 HI4 14 5.57 5.54 254 100.00 99.80 - -Three compounds of this formula are known viz. ax- a& PB-di. naphthyls. The substance described resembles in physical properties the pp-dinaphthyl of Mr.Watson Smith. It dissolves in hot oil of vitriol forming a light green and subsequently a blue colour and melts a t 189". The residue left after distilling off the benzene from the liquids ob-tained in ihe purification of the hydrocarbon just described was boiled with alcohol in which the greater part dissolved. On cooling a sub-stance separated which after many crystallisations formed long flat buff-coloured needles. When burnt with copper oxide it gave as the mean of two determinations 90.8 per cent. carbon and 5 per cent. of hydrogen. And two determinations of its vapour-density gave for mean 132.6. It would appear from these results that the substance is not a single couipound. We are inclined to regard it in fact as VOL.XLI. 18 NILLS AND DONALD ON THE consisting of a C,,H,,O or C21H140 body in admixture with di-naphthy 1. After the alcohol had passed over a brown viscous substance distilled containing 90.38 per cent. oE carbon and 5.21 per cent. of hydrogen. It dissolved readily i n alcohol the solution exhibiting a blue fluorescence. The action of heat on the two aluminium naphthylates is seen to be very different. The @-compound splits up a t a lower temperature than does the a and yields as the ‘principal product naphthol-ether, while it is douhtlul whether an ether is formed a t all in the case of the a-compound. Though these aluminium alcohols are more or less distillisable at reduced pressures the7 are alike decomposed by heat a t the ordinary pressure of the almosphere. The products of the decomposition of the series CaHZn+ ,OH CxH2x-,0H. and C7,B2,,-,-OHl appear however, to be somewhat different. The first series yields the corresponding ethers alcohols and olefines ; the second. the correspondivg ethers and alcohols (with the exception of the thyrnolaie which suffers re-duction to cresylale in the fiist stage of the aciion) together with Crystalline bodies hitherto undescri bed and probably consisting of ketones. The third series gives in one case the corresponding ether and p~obably alcohol together with hydrocarbons of a class differing from the olefines. The alcoholic liquids from fraction b were distilled

ISSN:0368-1645    

DOI:10.1039/CT8824100005

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

18 NILLS AND DONALD ON THE IV.-On the Action of Oxides on Salts. .Part IV.* Potassic Chlwate and Ferric Oxide. By EDMUND J. MILLS D.Sc. F.R.S. and GEORGE DONALD. 33. THE work accomplished in previous parts naturally led us to con-sider the decomposition of potassic chlorate by oxides a reaction which during the 50 years since Dohereinert first ohserved it has been and still continnes a problem in theoretical chemistry. There are several oxides which are known to facilitate the evolution * For Part I11 see Journal 1881 1 533. + Ann. Pharm. 1 236. Dobereiner thus states the problem :-" Welche Rolle spielt nun dcr Braunstein in diesem Processe ? wirkt er blos als guter Wfirmeleiter oder als Electromotor ? oder ist es endlich noch ein Minimum yon inharirendem Wasser welches die totale Zerzetzung des Salzes bedingt und die Bildung des oxy-chlorsauren Kslis verhindert ? BCTION OF OXIDES ON SALTS.19 of oxygen from potassic clilorate and to prevent perhaps entirely the formation of perchlorate. Of these manganic dioxide is t'he most strik-ing example. One of us acc )rdingly in association with Mr. John Stevenson M.A. made iiumerous experiments with this substance ; but trhe investigation was eventually abdndoned partly because we were unable to prepare* a srable anhydrous dioxide and partly on account of the irregulai.ity and comparative violence of the reaction. We shall again refer to tbese results in a supplementary note. 34. The chlorate employed in our experiments consisted of a fair commercial sample which was purified by repeated crystal lisation and filtration.J t was powdered sified dried a t loo" and kept in dry air. The ferric oxide was prepared lrorn a sample of piire ferrous sulphate by oxidation with hydric ni hate precipitation hy ammonia complete washing solution in hydric chloride and reprecipitation with ammonia. Washing was again proceeded with until the washings were free from chloride or sulphate. The hydrate was then dried over the water-bath and ignited irl successive small quantities in a porcelain crucible. I n order to preclude thP gas flame which surrounded the crucible from attacking the oxide the crucible was cemented into a circular apertme cut centrally i n a plate of iron about 2 feet square. All the ignitions were as far as possible carefully executed in the same manner.The residual preparations of oxide were all mixed together powdered and sifted thr0uF.h fine muslin. Renewed absorp-tion of water was prevented by heating to loo" alid preservation in B desiccator. 35. The apparatus which was used for the reaction consisted of a shallow iron pot inside which a low stage of porous tile was con-structed ; upon this stage lay the horse-shoe-shaped horizontal bulb of a Schlosing's rqydator and within the bulb was placed the porcelain crucible containing the mixture of oxide and chlorate. The crucible was covered with a lid ;md the bulb of a mercurial thermometer was placed very near to it. The iron cover of the pot protected the whole arrangement. As a source of heat we employed a Fletcher's burner, and the entire a,pparatus was as far as could conveniently be managed, screened on all sides from draught.36. The actual course of an experiment will siiggest itself to the reader. All we need remark is (1) that the air-bath was heated for half-an-hour before each operation; (2) that the insertion of the crucible was an almost momentary act. Thus the time consumed in heating up the mixture of chlorate and oxide must hare bezn very short ; and the disturbance introduced into our work by this condition -especially when it is remembered that the duration of heating was always four hours-we regard as inappreciable. At the end of our * Comp. Picbering Chem. fieus 43 226. c 20 MILLS AXD DONALD ON THE experiment the crucible was instantly removed placed in a desiccator, and weighed the next morning.37. Our trial series of experiments was performed with pure sub-stances prepared by Mr. Pratt (Part II) in 1878. The constant weight of potassic chlorate was 5 grams ; the weight of oxide ranged from 0.5 to 3.0 grams and the meantemperature" was 189.8". Under these conditions the loss of oxygen amounted to 0.0083 gram to 0.0311 gram. We found however on repeating some of our work, that we could not obtain constant results neither were these of suffi-cient magnitude to serve as a basis for accurate determinations of a " factor of chemical effect." This factor had values extending from 0.11200 to 0.35742 and amounted on the average to 0.20750. It was evidently necessary t o obtain a larger evolution of oxygen. We therefore (now taking substances of our own preparation and the same constant weight of chlorate) raised the temperature to about 19.5".39. I n the course of our calculations we have had occasion to use the following numbers viz. :-KC103 = 122.47 Fe,O = 159.92 0 = 15.96. Actual weights appropriately divided by these figures, map be considered as expressed in " chemical units." The temperatures reported below are very good means of quarter-hourly observations. If the action of ferric oxide upon potassic chlorate be similar to that of an ordinary oxide on an ordinary salt the numerical results should admit of represefltation under some form of the general equation-In this E is the chemical effect on oxygen expelled a and y are respectively the masses of oxide and chlorate ; xr yo are the residues of these masses after action ; and a is a " factor of chemical effect," depending upon the particular conditions of chemical change.In our calculations we have taken a = zr since the oxide remains constant in each experiment ; and chemical units have been employed throughout. The necessary details will be found in the following Table -* All our temperatures are corrected for zero error and exposure. For the expo-sitre correction the ordinary formula and the factor 0.00013 were employed Experiment . -. I I1 111 IV v ,, PI VII VIII IX x XI XI1 XI11 XIV xv * . . Oxide taken . grams . 0 - l G 0.15 0 *20 0 *25 0 '50 0 -75 1 -00 2 -00 3 -00 5 -00 8.00 8 '00 8 *oo 10 *00 10 .00 .-ACTION OF OXIDES ON SALTS . TABLE XI . X . -.-0 *00062532 0 *00093797 0 *0012506 0 4015632 0 * 0031 266 0 *0046898 0 *0068532 0 *0125064 0 *0187596 0 -0312660 0 *050026 0 *OS'i532 9 ) 3 ) Oxygen expelled . gram . 0 -0213 0 -0312 0 *0230 0.0833 0 *0435 0 *0591 0 -0629 0 '0993 0 -1246 U -1563 0 *1900 0 *1103 0.1158 0 -1320 0 * 1228 E . 0 '0013346 0.0019559 0 9014411 0 *0014599 0.0027250 0 * 0037230 0 *0039411 0.0062218 0 *0078070 0 -0097932 0 *011915 0 *0069110 0 '0072556 0 -0082707 0 -0076942 a . 2 *1437 2 *0998 1 '1769 0 *95862 0.91900 0.65643 0 -70656 0 *6246S 0 *68086 0 '52806 0 50688 0 -29964 0 -31416 0 -32591 0 *30377 21 .!emp . C . 195* 6 O 195 * 1 . 195 *1 194 *7 194 *7 195 -6 194.9 194 -7 194 *7 194 -7 195 * 1 195 '2 194 *7 195 '1 194 *7 39 . I t is evident from the above results that the chemical effect of the oxide increases rapidly a t first. and afterwards a t a diminishing rate ; and the numbers suggest that the values of a are inversely pro-portional to the ralues of o . In order to test this hypothesis. we took all the values of a excepting IX and X (the mean of the value8 a t 8 grams* and 10 grams oxide respectively being assumed. instead of the single quantities there). and calculated t. he following equation :-( a - 0.27420) (Z + 0*00095942) = 0.0029056. A comparison between theory and experiment is given in the Table below -TABLE XI1 .Experiment . I I1 . . . . . . . . . . . . . . I11 IV v VI VI I VIII IX x x r-XI 1 I XIV. xv a calculated . 210770 1.80560 1.58890 1.42600 0.98532 0.78854 0.67706 0.48998 0.364367 0.331191 0-319965 0.42 1 5 *5 a found . 2.14370 2.09980 1.1 7690 0.95862 0.9 1900 0.85643 0-70656 0.62468 0.58086 0.52806 0.31484 0.37356 * I n Experiment X it is probable that the temperature accidentally rose WIIC t. he thermometer was not under observation. but as we are not certain of t. Ilia explanation we have retained the result 23 MILLS Ah9 DONALD Ulu’ THE Probable error of a single comparison 0.15215 ; of 12 comparisons, -043921. Sum 02 the errors 0.0231 6:;. The hypothesis therefore, with regard to a may be accepted as fairly correct’.40. Some of the relations between the acting quantities are worthy of special consideiqation. The factor a of chemical effect is the number of chemical units of oxygen expelled per unit of oxide. Now since-it follows that when o is very small a = 3.3028. Hence within the Limits of experimental error FeLO expels 0.:.3 or 3Fe20 expels Ole, when the weight of oxide is very small ; and a unit of the oxide then acts on rather more than a unit of the dhlorste. On the other hand, when o is very large a = 0.27240. Heuce 0.2 7240ay E = _____ x + y r ’ an expression which on the understanding stated reduces to-E = 0*27240 y = 27240 x 0.040826 = 0.01112 unit = 0.1775 gram. Assuming then 1 he qiicznt,i ty of oxide to be indefinitely great the 5 grams of xchlorate would not under the conditions of our experiments, have lost more than 0.1775 gram oxygen.This amount has not in fact been exceeded except in Experiment IX which we believe to be of an accidental character. Another inference which may be drawn from our work is very obvious. As the mass of oxide increases so does its efficiency decrease; it stands so to speak in ihs own way. Large quantities of oxide present little real advantage over medium quantities such for instance, as an equal weight. There can be no doubt if we compare our first with our second series of experiments that bhe value of 01 rises with the temperature. The constant X seems to depend on the physical condition of the oxide. 41. In Part ZI (23) of these researches i t was shown that the action of ferric oxide on -5 grams potassic carbonate leads to the expulsion of carbonic dioxide in three stages and that in the first of these (ie., from 2.4 grams oxide downwards) the factor of chemical effect is inversely proportional to the mass of the oxide.Thus the entire course of the action of ferric oxide upon potassic chlorate is strictly analogous to the first stage of the action of the same oxide on potassi ACTIOS OF OXlDES OX SALTS. 23 carbonate ; and both actions are particular ca8ses of the general effect of an oxide on a salt represented by the equation-any :c'r j- yr* E = -It is obvious then that the case of chemical change which me have had under consideration presents nothing abnormal or peculiar in its features.From the carbonate an oxide of carbon is the matter expelled ; from the chlorate an oxide of oxygen. The law of action is the same in both instances. The name catalysis therefore which was applied by Berzelius to this case of chemical change ceases to have any reason for its existence. SUPPLEMENTARY NOTE. Jlanganic Dioxide and Potassic Chlomte. By EDXUSD J. MILLS D.Sc. F.E.S. and JOHN STEVENSOF M.A. 42. As stated in (33) Ke performed a number of experiments with manganic dioxide. The particular mode of preparation which we eventually selected was that of Beilstein and Jawein (Ber. 1879 p. IS%) which leads t o a body really consisting of manganic dioxide in a hydrated condition. Our hydrate contained 331 per cent. of water. With this preparation we uniformly obtained a very violelit action at 210'.As previous trials with this and another sample of hydrous dioxide had convinced us that evolution of oxygen begins at about 160", we selected an intermediate temperature (180°) the time being four hours and the weight of chlorate 5 grams. With quantit,ies of oxide less than 0.05 gram we obtained only very irregular results ; hut with that quantir;y and higher f act0 ry . [MnO. = 86-92.] -weights the values of z were fairly satis-TABLE XIII. Anhydrous oxide. 0 '0483 0 -0967 0.4835 0 -9669 1.9338 4 *8345 9 . a 9 0 X . -1 2 10 20 40 100 200 The above calculation Oxygen expelled. 0 *4361 0 *6087 0'7731 0.7643 0 '7798 0.7416 0 '6-188 -u found.38 838 24.567 6.451 3 937 2.517 1 .ti57 1 *239 a calculated. 39 '1'75 24 '034 6.486 3 %9 2 -386 1.528 1 '239 has been simplified b j taking proportiona 24 O’SULLIVAN x - AND P-AMYLAN. values for x. The ‘( anhydrous oxide” is calculated from a determina-tion of water lost at 280-300° and the ‘‘ oxygen expelled” by deduct-ing the loss of water by the hydrate at 180” from t’he total loss. The equation is-(Z - 0.94800) (X + 0.32577) = 58.310. Probable error of a single comparison of theory with experiment, 0.18123 ; of seven comparisons 0*068499. 43. The relation which we have indicated between a and x rests upon a certain supposition. The percentage of water present in the hydrate was 3.31 a t the beginning and 0.144 a t the close of the reaction ; and this amount might very possibly have been sufficient, in accordance with Dobereiner’s snggestion to furnish an incentive for the powerful effects in the 0.0483-9.6690 gram experiments. On the other hand it might have produced no such effect but may have had influence merely in retarding the evolution of oxygen in the <O.O4SS gram experiment,s as seems to have been the case. What we can my with considerable confidence is that in either event the effect upon the form of the relation 01 to x of the presence of this quantity of water in the oxide is not traceable ; the action of manganic dioxide upon potassic chlorate resembles the ordinary behaviour of an oxide towards a salt

ISSN:0368-1645    

DOI:10.1039/CT8824100018

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

26 O'SULLIVAN x - AND P-AXYLAN. V.-a- and P-Amylalz Cowtituents of some Cereals. By C. O'SULLIVAN. FROM amongst the constituents of a few cereals I have succeeded in isolating two bodies which possess some points of interest in con-sequence of the relation they appear to hold to t h e starch group of carbohydrates. This interest is considerably increased when the position which the bodies dextran (Scheibler Zeitschrift f u r Rubenzucker In-dustrie 1874 309) and l ~ v u l a n (Lippeniann Ber. 14 1509) seem to occupy to the cane-sugar group is taken into consideration, The method employed in the preparation of the bodies from barley, skinless barley wheat and rye may be described as follows :-The finely-ground grain was treated with alcohol (sp. gr. 90) at 40" as long as anything was dissolved.Certain albumino'ids sugars (cane-sugar laevulose a,nd dextrose) &c. were thereby removed. The residue pressed as free as possible from alcohol was t,reated with a large bulk of water (10 or 12 times the weight of the cereal em O'SULLIVAN u- AXD 6-AMYLAN. 25 ployed) and the temperature of the mixture maintained a t 35" to 38" for several hours with continual stirring. The insoluble portion was allowed to settle the fairly clear supernatant liquid was decanted off, more water at 40' added and the process repeated as long as anything was dissolved. It was difficnlt to obtain the solution absolutely clear, but a few filtrations through moderately good filtering cloth freed i t from starch. The solution thus freed was submitted to evaporation, whereupon a white gummy skin began to form on the surface the removal of which facilitated the process.As soon as the solution became fairly thick the removed gummy matter was stirred into it and the liquid allowed to cool. Alcohol (sp. gr. 0-83-0.84") was then added as long as a precipitate formed. This precipitate was fairly white aqd stringy ; it soon settled to a tough woolly mass. It was washed several times with .dilute (0*88) then with st,rong (0*82) and finally allowed to stand for a few hours under absolute alcohol. The alcohol was then drained off the residue pressed and placed over sulphuric acid in a desiccator. In a short time it dried to an almost white friable mass, becoming electric on being powdered in an agate mortar. This appa-rently dry body lost a t 100" in dry air 13 to 15 per cent.of its weight, aud was found to contain 14 to 15 per cent. of ash consisting of phosphoric acid potash magnesia and lime. The ash from the body yielded by skinless barley gave the following percentage com-position :-p2a = 38.15 G O = 34.26 MgO = 15-91 CaO = 10.02 LOSS &c. = 1.66 100~00 The constituents of the ash of the bodies obtained from the ot,her cereals were not estimated. These bodies are no doubt the so-called vegetable mucilage in a rather pure state. The raw product was treated with cold water as long as anything was dissolved ; of that from barley mid skinless barley a large por-tion remained insoluble in the form of a crumby mass. For the pre-sent we shall neglect the solution.The crumby insoluble portion was treated with cold dilute hydrochloric acid (5 per cent.) for some days and afterwards washed free from the acid by repeated treatment with cold water. It was then dissolved in boiling water, in which it a t first melted and filtered from a little flocculent matter. This operation by the way is long and tedious in the extreme, unless the solution be dilute and even then it is far from what could be called a rapid process. The filtrate was concentrated an 26 O'SULLIVAN a- AND P-ASIYLAZ;. alcohol (0.83) containing 3 or 4 per cent. hydrochloric acid added. The precipitate was white and fibrous; it was washed free from hydrmhloric acid with alcohol (0*86) and a3fter being pressed was placed under absolute alcohol for a few hours.Again pressed as free as possible from the liqnid and placed over sulphuric acid in a desiccator, it soon dried to a perfectly white easily friable mass becoming strongly electric when powdered in an agate mortar. In order further to purify this body i t was again treated with cold water and acid washed free from acid dissolved in hot water preci-pitated with alcohol and dried. A few repetitions of this treatment yielded a snow-white bodp containing not more than 0.3 per cent. of ash. The substance as will be seen from the mode of preparation is almost insoluble in cold water; it mclts or prcbably gelatinises, in hot water and if the solution contains anything like 2 grams of dry substance in 100 c.c. forms a clear jelly-like fluid. A solution containing L gram of dry substarlce (dried in dry air at 100" and afterwards at 120" in an air-bath) in 100 C.C.at 15*5" gave a specific gravity = 1.00396 and in a 200 mm. tube (Soleil-Scheibler) an optical activity a t 15*5O* = - 1.3 divisions or thereabouts ; this gives [alj = - 25" for the body. Numbers varying between -22" and -26" were obtained for varioiis preparations and I should say -24 &2 contains the t r u t h ; but in consequence of the low solubility and low opticity it is difficult to determine the factor with any degree of accuracy. The number however with the other characters is sufficient to establish the identity of the body. A portion of the substance was dissolved in hot water and alcohol added until a precipitate began to form. This was allowed to settle, and the supernatant liquid decanted off.The precipitate was dried as described above. To the decanted liquid more strong alcohol was added and a further precipitate obtained. This was also dried. When the original body was so far purified as to give an optical activity [a]j = - 24 the first and second precipitates yielded also the same opticity. Hence the body in this state was a simple substance and could be submitted to analysis. When dried it yielded on combustion in oxygen-(4 (b.1 C = 44.39 per cent. H = 6-26 , 6.35 ,, 44.22 per cent. The formula C6HlU05 requires-C = 44.44 per cent. H = 6.17 ,, * All the opt,ical observations mentioned in this paper were made at l5*5*-16" O'SIJLLIVAN CC- AND S-AXYLAN. 27 The body (a) was prepared from skinless barley and ( b ) from ordi-nary barley.I must not omit to skate that oxygen had to be used to burn these bodies as well as those hereinafter to be described because I found that with cupric oxide alone the carbon came out 1 to 1.5, and sometimes 2 per cent. too low altliongh the hydrogen seldom exceeded 6*% per cent. The substance is therefore a carbohydrate of the same percentage composition as starch. I t does not reduce alkaline copper solution. Treated with a 5 per cent. sulphuric acid and boiled for n short time, it is converted into dextrose; but if a 2 per cent. acid be employed, the time required -for conversion is considerably increased yet even then it is very much less than that required to convert starch or any of its transformation products into dextrose.It was nevertheless, desirable to determine whether any of the bodies between starch aud dextrose were produced in the process of conversion. For this pur-pose the strength oE the acid was so regulated that a t the end of 30 minutes the acid being separated with pure baryta-water and the filtered solution evaporated until i t contailled 4 grams substance in 100 c.c. the body in solution was fouud to have the following characters :-I( (cupric oxide reducing power) = [alj ,. = + 46.79'. 88.3 The opticity of a mixture containing 88.3 per cent. of dextrose and 11.7 of the unaltered body is-[%$ = + 47-41". A portion of the solution in which the acid mas not neutralised was digested for 15 minutes longer and in a part of it the acid separated as beibre.The solid matter then in solution yielded the factors-JC = 94.1 , [a]j = + 51.6". A mixture containing 94.1 per cent. dextrose and 5.9 of the nn-changed body yields an optical activity-[a$ = + 52.2". The portion of the solution which was not neutralised was digested for 15 minutes longer ; the solid matter was then found to have the following properties :-I( = 98'5 [alj = + 56.2,". The solution at this stage freed from acid mas evaporated to a syrup which on standing a few days yielded a crop of warty crystals ; when the syrup was too concentrated i t solidified on standing. Th 28 O'SULLKAN U- AND 6-AMYLAN. crystals yielded the leading factors of ordinary dextrose. Carefully dried a t 100" in dry air the temperature being gradually arrived at, they gave-K = 100 to 102.5 [a]j = + 57" to 58".The body is therefore converted directly into dextrose withont yielding any of the intermediate products furnished by starch. Although lfevo-rotatory and possessing many properties in common with Lippmann's laxulan it is altogether distinct from that substance (lsvulan yields l~vulose when acted upon with sulphuric acid and has an opticity [a]= = -221) and inasmuch as it yields like starch and the ti-ansformation products thereof (the amylan group) dextrose by the action of dilute sulphuric acid I propose to call it an~ylan; and in consequence of what I have to describe below it would be best to designate it as a-amylnn. When the body is dried without previous treatment with absolute or very strong alcohol it is a white semi-transparent horny mass resisting all efforts to pulverise it.I have now to turn to the cold water solution neglected in the preparation of ~-awiyZaiz from barley and skinless barley. It was evaporated to a small bulk and allowed to cool. An excess of hydro-cliloric acid was added and the mixture well shaken. The addition of alcohol (.84) yielded a bulky precipitate the alcohol being added as long as anything fell out. This precipitate was washed with alcohol containing hydrochloric acid and afterwards with pure alcohol until the washings ceased to give a cloud with silver nitrate. It was then dried in the usual way by treating with absolute alcohol, pressing that liquid out and placing the pressed mass over sulphnric acid.On submitting the dried body to the action of cold water only a small portion remained insoluble ; the great bulk gelatinised and dissolved. The insoluble portion was found from opticity &c. to be a-amylan. The solution was evaporated until a trial portion became a jelly on cooling ; the whole was then gradually mixed with alcohol, care being taken that as much of the substance as possible was retained in the form of a WUG by the alcohol. I use the term " milk," because I can find no other word to express the appearance; the alcohol becomes a white opalescent liquid with very minute suspended particles which do not fall out on standing. If the aqueous solution were free from a-amylan nearly the whole of the substance would be retained by the alcohol in this milky form.The addition of a few drops of hydrochloric acid with a little stirring produced it white bulky flocculent precipitate. This soon settled and was washed and dried by treatment with alcohol as described in the case of a-amylan. A few resolutions and reprecipitations in this way yielded a body free, or nearly so from ash. Dried in dry air at loo" and afterwards i O'SULLIVAX tc- AND &AMYLAS. 29 an air-bath at 120" the substance thus purified gave the following factors. A solution containing 1 gram in 100 C.C. a t 15.5" ha? a sp. gr. = 1.00392 to 1.00396 and an optical activity calculated on the dry body [ a ] j = -72 to -74. Submitted to combustion it yielded-C = 44.35 per cent. H = 6.28 ,, the percentage composition of starch.own weight of a sugar having the same opticity and K viz. :-Digested with dilute sulphuric acid i t gave a little more than its [a]j = + 55.5" to + 57" K = 100.5 to 101 as ordinary dextrose. This solution when concentrated to a syrup, did not however yield crystals on long standing. I n order to determine whether it was a simple body or a mixture I proceeded in the same way as 1 had done in the case of a-amglan. I t melts (gelatinises) readily and dissolves in cold water a solution con-taining more than 1 gram in 100 C.C. being a quite thick fluid. I divided a portion into two parts by mixing with alcohol and partial precipitation and found upon the first attempt a t separation that the portion first precipitated gave upon examination a much increased optical activity ; but the second precipitate retained the original opticity.I felt at first inclined to think that I had at least two bodies to deal with. Further attempts at separation yielded a body gradually increasing in optical activity, until I obtained a product yielding, This result was rather puzzling. [.]j = - 141 to 148". This I could not further increase but I was able to separate it into two parts each of which had the same opticity. The body worked with in this case was obtained from barley. Skinless barley yielded the same results. I t seemed then probable that this soluble portion consisted of two bodies one having optical activity [ a ] j = - 144 to - 148" and another much less ; but as the opticity of the original body was [ajj = - 72" and as I could not obtain a less active sub-stance from it it was fairly obvious that the process of purification was effecting some change in the material.While these separations were being performed I had a preparation of the same character in my hands obtained from rye. The raw product from this cereal that is, the precipitate from the aqueous solution everything soluble in alcohol sp. gr. 90 having been previously remored was found t o contain but very little not more than 3 or 4 per cent. of tlie insoluble (in cold water) crumby botly a-amylau the remaining 96 to 97 per cent 30 O'SULLIVAY tl- AND P-AMYLAN. being soluble after at first gelztinising. It was difficult to obtain portions of this substance capable of yielding solutions sufficiently bright for opt,ical observation yet a t the earliest stages of the attempts to purify specimens were obtained the opticity of which I was able to satisfy myself was below [ a ] j = - 80".These bodies yielded more than their own weight of sugar the K of which was 98 to loo" and the [a]j = + 57 to 58" (determined in solutions containing from S to 6 grams in 100 c.c.) and therefore so far agreeing with the €actors of ordinary dextrose. I n order if possible to remove the cause of the opalescence of solutions of the body I boiled some of them for a time with lime filtered evaporated the bright filtrate to a thick liquid, ailowed to cool added excess of hydrochloric acid and precipitated with alcohol. The precipitate was washed free from hydrochloric acid with alcohol dried with absolute alcohol pressed and placed over sulphuric acid.The body thus prepared is almost exactly the same in general appearance as a-amplan but on being submitted to the action of cold water it gelatinises to a transparent gum and gradually dissolves yielding a thick fluid solution which when it contains little more than 1 gram in 100 c.c. flows very slowly. The aqueous solution containing 1 gram substance (dried in dry air a t 100") in 100 C.C. at 15*5" was found to have a sp. gr. = 1.00394 to 1.00396. Determinations of the optical activity of the body in solutions containing from 0.6 to 1.3 grams in 100 c.c. gave numbers varying between [a]j = -144" and - 148". I may state that the low solubility together with the short length of tube-200 mm.-at my disposal did not admit of highly accurate observations ; they were however sufficiently accurate for the purpose.When the body so purified was divided into two or three portions by partial precipitation each fraction was found to retain the opticity of the original body. It could therefore be looked upon as a simple substance. Dried in dry air at loo" and afterwards at 120" in an air-bath it gave on combustion-C = 44.49 per cent. H = 6.24 ,, These numbers agree closely with those required by the formula C,H,,O,. Digested in a water-bath a t 100" with a 5 per cent. solution of sulphuric acid for 30 to 35 minutes the acid being separated with pure baryta-water i t yielded more than its own weight of solid matter having the K = 100.9 and [ z ] j = 57.5" ; the factors of ordinary dextrose.The. solution evaporated to a syrup O'SULLNAS U- AYD P-ANTLAN. 31 did not however even after standing six months yield sufficient crystals for exam inat ion. The substance is therefore ',he same as that described above as having been oblained from barley and skinless barley. Treatment with lime obviously convei.ted it into a bi-rotntlory modification. It was sufficiently easy to piit t,his t80 the test with the barley body. A weighed portion of that body ( [ a ] j = - 72") was dissolved in water, and boiled with lime for a few hours. The solution after filtration, was evaporated to a thick fluid excess of hydrochloric acid added, and then alcohol as long as a przcipitaie formed. The precipitate when dried was within two or three per cent.(a loss to be easily accounted for) of the amount of substance empioyed. The optical activity of this body was found to be [ a ] j = - 144" ; exactly double that of the body taken. That no othcr change took place will be obvious from the following :-Dried as usual it gave-C = 44.45 per cent. H = 6.13 ,, All these bodies left a slight ash in the platinum boat but so slight was i t from the 0.3 to 0.4 gram taken that it was not indicated on a balance turning to half a milligram. On digestion with sulphuric acid it gave a body the factors of which were found to be-i K = 101 and [ a ] j = + 57.6" ii K = 700.5 , .]j = + 56.4" These solutions too when evaporated t o a syrup did not cr-ptallise satisfactorily. I have not as get determined whether intermediate bodies are formed but I have satisfied myself that neither maltose nor dex trin are produced.Wheat treatfed after the manner described above yielded the same body but I did not succeed in isolating the body a-amylan with any degree of satisfaction. Dried as usual it gave on combustion-C = 44.56 per cent. H = 6.21 ,, and an opticity gradually increasing to-[ a ] j = - 144" (1.2 gram in 100 c.c.) Treated with sulphuric acid it gave a body with-K = 99.23 [.]j = + 54" to + 55". This solution too on being concentrated to a syrup did not yiel 32 O’SULLIVAN 01- AND P-AMYLAN. sufficient crystals for examination on standing for some months. In fact while the sugar from a-amylan crystallised immediately on its solutions being evaporated to a syrup that from the soluble body, whether prepared from the mono- or bi-rotatory modification showed, under the same conditions little tendency to crystallise.This substance whether i t be prepared from barley rye or wheat, is like a-amylan and starch a C6Hlo05 body but it differs from the former in being soluble in cold water in having an opticity three times as great in yielding a bi-rotatory modification and in giving, by the action of sulpharic acid a dextrose possessing the same cupric oxide reducing power and opticity as ordinary dextrose but showing less tendency to crystallise. This body may be conveniently known as p-antyla<n. a- and 6-amylan are interesting not only for the light they throw upon the constitution of the mucilage of barley wheat and rye but more particularly for the relation they appear to hold to the starch (amylum ) group.When a mixture consisting of equal proportions of Scheibler’s dextran and Lippmann’s laevulan bodies existing in beet in which cane-sugar is stored up is submitted to the action of sul-phuric acid invert sugar is obtained having the same opticity and K as that derived from cane-sugar. In the same way a mixture containing a- and P-amylan (constituents of the cereals in which starch is stored up) in equal proportions yields a product having the same opticity and K as that yielded by starch or maltose ; hence the name arnylan from the amyluru group. Barley contains about 2 per cent. of a-amylan and of P-amylan not more than 0.3 per cent. ; indeed the @-body is isolated with great difficulty from some barleys. Wheat and rye contain from 2 to 2.5 per cent. of 6-amylan and the a-body is not present to a greater extent than 0.1 to 0.05 per cent. In conclusion I may state that I have not given all the analytical data but I believe I have given sufficient for the purpose of the work, to characterise the bodies described. Malted barley does not contain a-amylan ; a body like P-amylan, but apparently much more solnble can be isolated from i t ; of this I hope to have more to say on a future occasion

ISSN:0368-1645    

DOI:10.1039/CT8824100024

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

33 VII.-On Bemyl-pheiaol and its Derivatives. By EDWARD H. RENNIE M.A. (Sydney) B.Sc. (London.) BENZYL-PHENOL was first prepared a few years ago by Paternb (Guzxetta, 2 l) and further investigated by Paternb and Fileti (ibid. 3 121-251). These chemists state that by treatment with nitric acid a nitro-compound may be obtained and by treatment with bromine dis-solved in carbon disulphide a solid bromo-compound is produced ; but these substances do not appear to have been very thoroughly examined. By the action of excess of sulphuric acid for about an hour a t loo" they obtained an uncrystallisable disulplionic acid which yielded only uncrystallisable salts. The following experiments were undertaken with the view of obtaining if possible more definite information regarding the deriva-VOL.XLI. tives of this body. The benzyl-phenol used in the operations to be described was prepared by the method given by Paternh viz. by the action of benzyl chloride 011 phenol in presence of zinc. It was found advantageous to cool the mixture otherwise the reaction becomes very violent some of the liquid being often projected from the mouth of the flask. The crude product obtained by distillation was well pressed and crystallised from alcohol and then melted at 84" the melting point given by Paternb. When concentrated pure sulphuric acid slightly in excess of the quantity required theoretically for the formation of a monosulphonic acid is added to some benzyl-phenol and the mixture warmed on the water-bath for a few minutes the whole dissolves to a clear liquid, which on cooling and standing for a short time solidifies to a crystal-line mass.On dissolving this in water adding ammonia shaking up with ether to remove any unattacked phenol (which is moderately soluble in water) and then concentrating an ammonium salt crystal-lises out in fine needles as the liqnid cools. After recrystallisation it yielded on aiialysis the following numbers :-0.5535 gram of the air-dried salt lost a t 100" 0.033C; gram = 6-07 p.c. Theory for C7Hi.C,H,(OH)SOJYEI~ + H20 = 6.02 per cent. 0.2423 gram burnt with oxide of copper by Dumas' method gave 10.409 C.C. of nitrogen at 0" and 760 mm. equal to 0*013011Z gram = 5.37 per cent. If potassium carbonate be used instead of the ammonium salt proceeding otherwise as above, :I potassium salt separates in groups of feathery crystals.On annlgsis it proved to be anhydrous and gave the f'ollowing results :-Tlieo~y = 5.00 per cent. 0.6203 gram gnve 0.1813 gram K,SOI = 0.08127 gram K = 13.10 p.c. Theory for C7H7.C,HJ(OH)S0,K = 12.91 per cent. On adding barium chloride to a solution of either of the above salts a barium salt separates out which after filtering off may be clissolved in boiling wat'er. On slow cooling i t separates out in moss-like crystals. After drying in air they yielded on analysis the following results :-0.501 gram lost at 100" 0.0132 gram = 2.63 per cent. Theory for [C5H,.CeH,(OH)SOJ],Ba + H,O = 2.64 per cent. 0.5454 gram gave 0.189 gram BaSOd = 0.1107 gram Ba = 20.41 p.c. Theory 20.66 psr ceilt. If t,his barium salt be dissolved in hot water and barium hydrate, or barium chloride and ammonia be added an almost insoluble basic salt separates in minute glistening crystals.A single analysis gav ASD ITS DERIVATI\'ES. 35 36.5 per cent. of barium instead of 34.4 per cent. reqnired for a basic salt of the composition-- 0-Ba-0 - C7H,*C6H3<S0 Ba-$o >.CBH3*C7H7. 3-The great difficulty of preventing the formation of barium carbonate in preparing this salt will easily account for the high percentage of barium obtained on analysis. All the salts of the acid which have been examined are but sparingly soluble in water the mono-barium salt being much less soluble than the alkaline salts and the di-barium salt almost insoluble. In order to isolate the acid some of the pure potassium salt was dissolved in water and acetate of lead added.A very insoluble lead salt waa thereby precipitated which was well washed suspended in pure water, and decomposed by sulphuretted hydrogen. The cleay filtrate was evaporated to a small bulk in a platinum dish and then placed orer sulphuric acid. The quantity hitherto obtained however is insufficient for a detailed examination. A further description will follow in a subsequent paper. The acid and its salts give a splendid violet coloration with ferric chloride. In a few hours it solidified to a crystalline mass. Potassium ATit ro- Z cgi xy 1 -p h eii 01 -s dpph onafe. If potassium benzyl-phenol-sul phonate be added in fine powder to dilute nitric acid (equal volumes of ordinary concentrated acid and water) keeping the liquid constantly stirred a sparingly soluble crys-talline yellow salt separates out.After recrystallisation and drying at loo" it gave on analysis the following numbers :-0.283 gram gave 0*0704 gram KzSOa = 0.03156 gram K = 11.15 p.c. Theory for C,H,.C,H,.(OH)(NO,)SOsR = 11.24 per cent. 0.224 gram by Dumas' method gave 7.36 C.C. of nitrogen at 0" and 760 mm. = 0.0092 gram = 4.10 per cent. Theory 403 per cent. This salt is therefore a mononitro-benzyl-phenol-sulphonate. On boiling with potassium carbonate it yields an orange-coloured di-potassium salt. Potnssium B.1.on2o-beiizlli-~phe~l~l-~~l~~h~ilate. When one molecular proportion of bromine is added drop by drop to a solution of potassium benzyl-phenol-sulphonate keeping the liquid in constant agitation n white salt separatev out which on recrystal 36 RENNIE ON BENZPL-PHENOL lisation from hot water separates iu beautiful glistening scales.On analysing the anhydrous salt the following numbers were ohtnined :-0.224 gram gave 0.05 gram K2S04 = 0.0224 gram K = 10.00 p.c. Theory for C,H,.C,H2.(OH)Br.S03K = 10.23 per cent. 0.2108 gram gave 0.1036 gram AgBr = 0.44085 gram Br = 20.91 p.c. Theory 20.99 per cent. The salt is therefore a monobromo-henzyl-phenol-sulphonate. Triwitrobenzyl-p henol. If potassium or ammonium benzyl-phenyl-sulphonate in fine powder be added with constant agitation to an excess of ordinary concentrated nitric acid the salt dissolves easily with scarcely any evolution of red fumes forming a deep red liquid.If this liquid be exposed to the air in a shallow dish for several hours it becomes semi-solid from separa-tion of a yellow crystalline substance. On diluting more of the yellow substance is precipitated. When well washed with water and recrystallised two or three times from boiling alcohol the body separates in fine silky needles of a pale yellow colour. It is very sparingly soluble in cold alcohol and only moderately soluble in the boiling liquid. A specimen crystallised three times melted at 148", and after a fourth crystallisation the melting point was the same. The following are the results of analysis :-0.052 burnt in a vacuum with copper oxide gave 0.0067088 gram nitrogen 12.90 per cent. N. (The details of a combustion hare been lost the results only by some oversight having been entered in the note-book.) Found.7- 7 Theory for I. 11. C13H8 (NO,) 30H. C 48.86 - 48.90 H . . . . . . 3.73 - 2.82 N - 12.90 13.16 These numbers point clearly to a tri-~itro-derivative. The per-centage of hydrogen is very high but this was found to be due to the condensation of nitrous fumes in the drying tube. It was found extremely di5cult t o prevent their formation. In order to confirm the above numbers some of the substance was boiled up with a dilute solution of pure potassic carbonate. It dis-solved to a deep red liquid which on cooling deposited small orange AXD ITS DERIVATIVES. 37 red needles of the potassium-derivative. when heated. Thc dry substance explodes On analysis it yielded the following numbers :-I.0.069 gram gave 0.0164 gram K2S0 = 0.00735 gram I(. 11. 0.1066 , 0.0258 , K,SO = 0.011565 ,, These correspond to the following percentages :-Required for Required for I. 11. dinitro-derivative. tri-derivative. 10-65 10.85 12-50 10.92 Constitution of the foregoing Bodies. From the mode of formation of benzyl-phenol from its properties, and from what is known of laws of substitution in phenol there can be little doubt t,hat it is a para-derivative. No direct proof of this has however been given. With the view of solving if possible this question the methyl ether was prepared by digesting the phenol with the theoretical quantity of potassium hydrate and a slight excess of methyl iodide mixed with some methyl alcohol in a flask attached to a reversed condenser.The action was complete in an hour or two. On distilling the product after thorough washing the greater part came over from 305-315'. On redistilling this product the greater part came over between 304" and 308". The boiling point of this substance as given by Paternh who prepared it by the action of benzyl chloride on anisol in presence of zinc is about 305" and the product obtained as above agrees in all particulars with that previously de-scribed. On oxidation with chromic liquor the ether yielded only benzoic acid (melting at 121°) but no anisic acid. This result evi-dently throws no light on its constitution. On oxidation with alkaline potassic permanganate neither benzoic nor anisic acid is obtained but a white crystalline substance easily soluble in alcohol and ether and crystallising from the latter in fine prisms.This body is probably formed by the oxi.dation of the methylene (CH,) group and is in all likelihood a ketone having the formula CsH5.C0.CsH4.0.CH3. It is undergoing further investigation. Oxidation with fused potash remains to be tried but for want of material I have been compelled to leave it for the present. Should it fail to yield anisic acid I hope to establish the constitution of benzyl-phenol by another method. The great resemblance which benzyl-phenol shows to paracresol O n treatment first with sulphuric acid and then with nitric acid and bro-mine affords strong evidence in favour of the view that it is really a para-derivative. Armstrong and Field have shown that when paracresol is treated 1) 38 MILLS ASD PETTIGREW ON THE with sulphuric acid an ortho-sulphonic acid is produced and that when the salts of this acid are treated with dilute nitric acid or bro-mine the other ortho-position (withregard to the OH group) is taken by the nitro-group or the bromine.The following formulz therefore represent in all probability the constitution of the potassium salts above described :-When potassium paracresol-sulphonate is treated with concentrated nitric acid a diorthonitroparacresol is formed whereas the correspond-ing potassium benzyl-phenol-sulphonate yields a trilzitro-derivative. This is easily explained when it is remembered how easily the benzyl-group is nitrated. This trinitro-body very probably has the con-stitution :-NO, NO2 Should this be so it would probably yield paranitrobenzoic acid on oxidation. Experiments to decide this point if possible are in progress and I hope soon to be in a position to lay before the Society the results of a further investigation of the whole subject

ISSN:0368-1645    

DOI:10.1039/CT882410033b

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

38 MILLS ASD PETTIGREW ON THE VIIL-On the Steeping of Barley. By EDMUKD J. MILLS D.Sc. F.R.S. “ Young ” Professor of Technica,l Chemistry in Anderson’s College Glasgow and J. PETTIGREW. 1. IN the course of the processes which have for their object the preparation of malt from barley the grain has to undergo a more or less prolonged immersion in water. Various kinds of natural water, some of them of scarcely compatible character are highly esteemed €or the purpose of this steeping. We have not however been able t STEEPIKG OF BARLEY. 3 9 find any published statements * of a detailed description as to the action of water upon barley ; and it appeared to us desirable to make an experimental outline a t least of this undoubtedly complicated phenomenon. Our results are contained in the following para-graphs.2. The barley we employed throughout our investigations was a fine sample of “ chevalier,” grown on limestone soil. Its analysis furnished the percentages recorded below-Moisture . . . . . . . . . . . . . . 13.95 Nitrogen. . 1.87 Ash 2-25 3. The apparatus we employed consisted of a series of glazed cylin-drical earthen pots which were placed on a platform in a tank of water kept constantly running and supplied from the main. Into each pot we introduced 300 grams of barley and 400 cc. of water or some aqueous solution under trial and the whole was covered with a glass plate. Each set of experiments hereafter referred to in the tables was made at one time and under the same conditions. Tem-peratures were taken at noon by direct observation and at midnight by an automatic recording thermometer ; the mean of these tempera-tures is stated in each case.4. It is obvious that in working with a numberof individual grains of barley there may have been some whose outer coatings were injured and which may have yielded extract with more than average rapidity; this is a source of error to which we are undoubtedly, though-as we believe from actual inspection of many of the grains-but very little exposed. Moreover to destroy other small errors we always employed 300 grams of barley-a by no means inconsider-able weight ; and for the sake of obtaining largerresults we prolonged the operation of steeping to 72 hours. I. Calcic Curbonate. ti. A solution of calcic carbonate was made by passing purified car-bonic dioxide through distilled water in which well washed calcic carbonate was suspended.The filtered (saturated) solution contained -0896 per cent. of carbonate. * Xessrs. Lawes and Gilbert in a Parliamentary Report (1866 Reprint 1868) “ On the Relative Values of Unmalted and Malted Barley,” drew attention to the loss in steeping of “ a certain amount of solid matter which consisted of saccharine, nitrogenous and mineral substances” (p. 22). They also found (p. 65) that the barley imparted 391.66 grains per gallon of solid matter (containing 8-62 grains of nitrogen) to the water they had occasion to employ. Our tlianks are due to Dr. Gilbert for a copy of this Report Average temperature 4.8" C. TABLE I. Extract in 100 C.C. 0 *1800 0*1800 0 *1756 0 *1688 0 *1475 Carbonate Residue from Ash from 2:;:- 1 in 100 c.c.1 100 c.c. 1 100 c.c. Nitrogen from 150 C.C. --0 '00546 0 *00742 0.00770 0 '00973 0 '00932 I ,. I1 . . . . 111 . . TV V ,. 0.0896 1 0.4817 0 -3017 0 '0672 0 *4670 0 *2870 0 '0448 0 -4582 0.2830 . O*OOOO* I 0.4015 0 *2540 0.0224 1 0.4440 0.2752 According to these numbers as we diminish :the amount of car-bonate in the water so the extract decreases. The nitrogenous con-stituents of the extract simultaneously increase up to Expt. I V ; but distilled water extracts distinctly less of them than the *0224 solution of calcic carbonate. I I1 IJI . . . . IV v . . . . . . 11. Calcic Xdphate. 6. This salt was prepared by bringing well washed chalk in contact with very dilute snlphuric acid stirring frequently during three weeks and filtering the neutral liquid.Average temperature 11.0". 0'2210 0 *7240 0 -4440 0.1657 0.7470 0 *4296 0-1105 0 *6000 0 -344.0 0.0552 0.5480 0 -3400 0 '0000 0 -5110 0 -2760 TABLE 11. s($$'$e Residue from Ash from Extract in Experi- ment. 1 in c.c. 1 100 C.C. 1 100 C.C. 1 100 C.C. I I--I-- - I- I 0 * 2800 0'3174 0 '2560 0 *2080 0 '2350 Nitrogen from 150 C.C. __I-0 -00546 0 '00616 0 00532 0 *00560 0 -00716 Here also we notice that the extract decreases pari passu with the calcic sulphate from Expt. I1 to Expt. IV. The nitrogen and extract results are greatest of all at Expt. 11. At Expt. V as in the case of the carbonate we get a disproportionate increase of nitrogen in the extract but in addition a greater total extract.The total extract or nitrogen per unit of calcic salts is much greater with calcic sulphate than with carbonate. * Distilled water alone wns hcre used STEEPING OF BARLEY. 41 Buyton Water. 7. Through the good offices of a friend we were able to procure some water which is much used and held in great esteem for steeping purposes in Burton. The water is actually drawn at Lichfield and our sample was turbid. In the following determinations we hare compared it with a water analysed by the Rivers Commission (Report, p. 105) and described as being derived from a deep well in the new red sandstone a t Lichfield. The numbers refer to parts per 100,000, excepting those relating to dissolved gases which represent volumes per cent.TABLE 111. Total solid matter Organic carbon Organic nitrogen Nitric nitrogen Magnesia (MgO) Sulphate (SO,). . Ammonia Silica Lime (CaO) Chlorine. . Hardness (temporary). . , (permanent). . , (total) 32.440 ---0.393 0.656 1.412 10.034 4.450 1-950 7.0 70 11.100 18-700 Dissolved Gases. Ca,rbonic dioxide 3,0211 Nitrogen 3.4747 Oxygen 5.1080 Rivers Commission. 32.060 0.163 0.038 0.003 0.489 ----2.200 9.300 9.000 18.300 The Rivers Commission considered their sample to have been pol-The measured .effects of steeping are as follows :-luted as was doubtless the case with our own. TABLE IV. Residue from Ash from Extract from Nitrogen 1 100 C.C.I 100 C . C . I 100 C.C. jftom 150 C.C. Experiment. I. Burton water 0 -4540 0 *2113 0 *00525 11. Half Burton water 1 0*4100 1 :':;:; 1 0.1893 I lost 111. Distilled water 0 *4132 0 -2230 0 *1902 0 90630 Mean temperature 4.7O 43 hlILLS AKD PETTIGREW OK THE 0'2372 1 0.2156 0.2350 0.2280 0.2274 I 0.2060 Here again the extract decreases as we approach to distilled water. 8. On account of the great importance of this particular water we prepared two waters bearing a partial resemblance to it arid tried with them some steeping experiments. We shall call these liquids '' Factitious Water A " aiid " Factitious Water B." 0*00488 O.OC600 0*00588 Factitious Water A. Assuming the whole of the sulphate in the Burton product to be calcic and all the chlorine to be sodic we compounded this Water A, which was a solution of sulphatc aiid chloride in distilled water in the same proportions as we had fonnd in the Burton supply.Mean temperature 6.9". TABLE V. Experinien t. Residue from Ash from Extract from Nitrogen I 100 C.C. I 100 C.C. 1 100 C.C. 1 from 150c.c. I. Water A ,. 1 0'4382 1 0'2430 1 0'1952 I 0'00448 11. Half water A . . 0.4734 0 *2450 0 -2284 0 *00651 111. Distilled water . . . . 0 -4.132 0 -8112 0 -2020 0 -00483 Thus Water A gives rise on the whole t o more extract and less Water A and distilled water have nitrogen than the Burton sample. about the same effect. * Fuctitiozis Water R. 9. Assuming the temporary hardness to be due to calcic carbonate. and the chlorine to be wholly sodic we prepared this water so as to be a solution in these respects of the same composition as our Burton sample.[The carbonate had been previously dissolved in carbonic water.] Mean temperature 8.0". TABLE VI. Residue from Experiment. 100 C.C. I. Water B . . . . . . . . . . 11. Half water B . . . . . . 111. Distilled water . . . . 0 *4334 1 0 -4528 0 *4630 Like Water A this water takes up most extract and most nitrogen at the half dilution and in nearly the same absolute amount. Water B takes up less nitrogen than distilled water STEEPJSG OF B-\RLEY. 43 Sicpplemeutary Experim elits. 10. We took occasion t o examine several of the liquids in which we had steeped barley. All the solutions and ashes contained phosphates. In the gypsum solution there was an alkaline sulphate.The carbonate solution was slightly acid and gave a precipitate on boiling; the filtrate was not acid and was free from phosphate. 11. The reaction of water in which barley has been steeped is slightly acid and its colour orange or deep orange-yellow. Such water gives a white precipitate with hydric metaphosphnteX in the cold and the filtrate yields a further precipitate on boiling. Water contaiuing calcic sulphate was found to have taken up less colouring water than distilled water and to be lighter when more calcic sulphate was present. One of the gypsum water extracts when heated to boiling gave far less precipitate than the aqueous extract. It furnished no precipitai$e in the cold with hydric metaphosphate.12. Although the amount of orgamic constituents extracted from barley is small seldom exceeding four-tenths per cent. we cannot consider it unimportant. In the chemistry of minute quantities we repeatedly find vast qualitative effects arising from the presence of small masses and depending sometimes for their very occurrence on the condition that the masses are small. May not the absence a t a critical time in the life of the sprouting plant of a little or all of its most soluble albumino'id materially affect the quality of the resulting malt ; when even so apparently indifferent a circumstance as the mode of supplying air to the plant produces a marked alteration of cha-racter ? Aferences and BemarJis. It is obvious from the experiments recorded in (11) that water in which barley has been steeped contains a t least two albuminoid bodies, one of which is thrown down by metaphosphate in the cold the other on boiling.The former of these can be wholly kept back within the grain by the action of a gypsum solution and probably but with rather less efficiency by a chalk solution. 13. The results given in the Tables show that one general effect of a calcic solution is to keep back nitrogenous matter within the grain ; * This reagent which has been for sereral gears employed by one of us as an extremely delicate reagent for albumin is prepared as follows. A quantity of sodic metaphosphate (Madclrell's) is covered with strongly acetified m-ater set aside and occasionally shaken. The clear liquid which must always be kept over the undis-solved sodic salt constitutes the reagent.The metaphosphate has the great advan-tage over the nitrate of not decomposing albumin when boiled clierewitli 44 MILLS AND PETTIGREW ON THE STEEPING OF BARLEY. but the strongest solutions ever likely to be employed in malting are far from entirely preventing the escape of nitrogenous matter. If we glance also a t the " nitrogen " as compared with the " extracts," we cannot fail to perceive that the greater part of the extracts is made up of non-albuminous bodies. I n most cases the stronger the steep-water is in saline constituents the greater is the amount of extract with-drawn acd the less the amount of albuminoid matter allowed to escape. 14. I n comparing Table VI with Table V it will be found that the mineral constituents in Water A probably counterbalance each other's effects so that on the whole Water A acts like distilled water.Water B very closely resembles Watcr A as to extract; but when compared with distilled water it is seen to take out less nitrogen. If we have regard to temperature it is probable that the Burton water takes out more nitrogen than and a t least as much extract as, either gypsum or chalk solution or waters resembling the Burton sample in (I) gypsum + common salt or (2) chalk + common salt. The special esteem in which the Burton sample is held may therefore be due to its nitrate which is well known to hare a highly stimulant action in the germinating of malt -a process which demands much oxygen. 15. The practical value of our experiments will depend very much upon the view taken by maltsters as to the propriety of locking up as far as possible both the non-albuminous and albuminous matters of the grain.Opinions as to the employment of hard or soft waters are at present very much divided. For our own part we lean to the belief that the healthy germination of the seed will be best promoted by keeping within it as much as possible of its natural constituents as is done in ordinary processes of agricultural growth. We have how-ever shown that the usually available reagents for this purpose if employed in the concentrated form take out more extract ; if in the diluted form more albumin. The proper compromise then will be to select a reagent of medium strength; and the best a t present known to us is a gypsum solution containing about one-tenth per cent. It would be easy and probably advantageous to add to this such a pro-portion of calcic nitrate as would correspond to a few tenths per 100,000 of nitric nitrogen. Finally the question naturally occu1's, Why not use sufficient water just to saturate the grain and no more? If this plan were adopted (and we are unaware of any practical difi-culties in the way) the softest natural water might be employed with success and not a trace of its constituents would be lost as in the ljest existing practice to the germinating grain

ISSN:0368-1645    

DOI:10.1039/CT8824100038

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

1X.-RESEARCHES ON THE RELATION OF THE MOLE-CULAR STRUCTURE OF CARBON COMPOUNDS TO THEIR ABSORPTION-SPECTRA. By W. N. HARTLEY F.R.S.E. &c. Professor of Chemistry Royal College of Science Dublin. Part VI. On the Comtitution of Pyriditie Picolhae Quinoliue ant1 Cyanuric A cia. WrmN an atom of carbon is united to an atom of nitrogen no absorp-tion-bands are seen in the ultra-violet spectra transmitted by such a combination. This conclusion may be drawn from the experiments of 31. Soret and of the late Dr. W. A. Miller who proved the photo-graphic transparency of hydrocyanic acid and the cyanides. I 11:tve considered i t necessary to make independent observations 0 3 1 account of the more delicate nature of the instrument and the photo-graphic process I employ and because it is necessary to take into consideration the quantity of substance in the various solutions examined.A strong solution of hydrocyanic acid was prepared by distilling potassic ferrocyanide in the usual way with dilute sulphuric acid ; this was redistilled and its strength determined with a volumetric silver solution. It contained 11.9 per cent. of HCN. The liquid was examined in the undiluted state in layers 30 mm. and 15 mm. in thickness and subsequently in various degrees of dilution. Hgdrocyanic acid is a remarkably diactinic substance and does not under any ordinsry circumstances exhibit absorption-bands. Hence we may draw the conclusion that-The simple union of cwbon to nitrogen does not cause selective absoiptioir o f the ultra-violet rays.It has been suggested and it is generally believed that pyridine and its homologues are compounds in which an atom of triad nitrogsn replaces an atom of carbon in a closed chain of six atoms. Koerner’s formula for quinoline represents it as naphthalene in which an atom of carbon in one of the benzene nuclei is replaced by triad nitrogen, and moreover the recent synthesis of quinoline by Baejer has cou-firmed this theory of its constitution (Bey. 12 1320). Without com-mitting ourselves to views as to the internal structure of the molecules, we may write the two substances thus :-VOL. XLI. 46 HARTLET RELATION VF TIIE JIOLECULAR STRUCTURE C c Py ridine. H Quinoline. As already shown if a molecule contains only two pairs of carbon-atoms doubly linked it will show no absorption-bands and it is coil-ceivable that if a carbon-atom be replaced by nitrogen as in thc formulae given above the nature of the absorption will not b ~ materially affected by this modification because tbe structure of tllt: nucleus of the compound is unaltered ; and although there is one atom of hydrogen less i n the molecule we know that the addition uf hydrogen-atoms provided they do not interfere with the structure of the nucleus has no effect on the absorption so that we may expect the witlidrawal of one atom to have as little influence.In fact we should expect to see a banded spectrum whatever element might bc introduced into the benzene nucleus if the atom were capable o€ vibrating in unison with the carbon-atom it has replaced.Likewise if we regard picoline arid the two pyridine-dicarboxylic acids as modifications of the pyridine nucleus drawn above an(! &anding in the same relation to it that toluene and the phthalic acids occupy with regard to benzene we should expect them also to exhibit absorption- bands. Quinine shows a remarkable banded spectrum which is probably due to the conjugation of four ppidine or two quinoline nuclei since Dobbie and Ramsay (Chem. SOC. J. 1878; 1879 p. 189) have obtained two pyridine-dicarboxylic acids and pyridine-tricarboxyliu acid by the oxidation of this alkaloid. Samples of the two formein substances were kindly given to me by Dr. Ramsay and also some di-pyridine and picoline. Particulars regarding the spectra of these substances are the following :-a-Pyrit7irLe-dic~rbux2/llc Acid.- The substance was dissolved in absolute alcohol and solutions containing m1G3 T;m m;T*, and m&m were examined. A strong band of' absorption tvas noticed, which was not extinguished even in the weakest of these solutions. The band is most strongly marked a t a dilution of 1 in 20,000 ; it lies between the lines 1 7 and 18 Cd wave-lengths 2743.4 and 2,5i4?, Diagram X. 6-Py7iditie-diccLrbo~i~Z~c Acid. - The solutions in absolute alcoho 8. PPRIDINE-DI-CARBOXYLTG ACID. Scale. 10,000 parts to half an inch. Emison & Sons. L i d . S’ Martins Lane.%? DIAQBAM X. a. PYRIDINE-I>I-CARBOXYLIC ACID. Numbers indicating the position of cadmium Lines of known wave length. Scale. 10,OOO parts to half an iuoh. Harrison & S.ons.Litll. S Martins Lane,W. DIAGRAM XI. P I C O L I N E . Numbers indicating the position of cadmium lines of known wave length. Ordinates = volumes of solution containing one volume of Picoline. Scale. 20,000 parts to half an inch OF CARUOS COJIPOUXDS TO THEIR ABSORPTIOS-SPECTRA. 4 7 examined contained i,&5 dG m+5G h6 & and of their weight of the substance. There was a considerable absorption, though not of great intensity in this last liquid the bands stretching from below 1 7 to 18 Cd. The band of transmitted rays did not extend as far as 22 Cd while in the previous case they went up to 23 Cd Diagram IS. PicoZine.-Solutims in absoliite alcohol containing y$m hTi, The solution containing shows a strong absorption-band lying beyond 1 7 Cd but a broad band of rays is faintly transmitted further on.Solutions containing m:35 show a strong absorption-band lying between 17 and 18 Cd and a band of transmitted rays which how-ever are faint between 18 and 25 Cd. The absorption-band is narrowed but not destroyed by dilution to ha and the transmitted rays are still faint. As this substance is a methyl-pyridine it affords us direct evidence of the fact that the substitution of N for carbon in the benzene nucleus does not interfere with the selective absorption, but only modifies it in some degree. The chief modification is seen in the greatly increased. intensity of the absorption. By comparing the Diagram XI with that representing the absorp-tion of methyl-benzene (Phil. Trans. 1879 PI. 25) a very close and striking resemblance is noticed but with the following differences :-the narrow band of transmitted rays which is a little more refrangible than 1 7 Cd> and appears to he characteristic of benzene hydrocarbons, is absent from the picoline spectrum and the broad and similar band of faintly transmitted rays which appears first in solutions containing 1 part of toluene in 2,000 of alcohol does not become visible until a dilution of 1 in 15,000 in the case of picoline.And whereas a dilhtion of 3,000 times extinguishes a distinct absorption-band in the case of toluene the similar band of picoline is continued to a dilution of 1 part of the substance in 100,000 of liquid. QmhoZine.-The pure substance was obtained by fractionating a specimen purchased from Messrs.Burgoyne and Burbidges ; the portion distilling between 233" and 240" was regarded as the purest. Its identity was established and its purity determined in the following manner. Hydrochloric acid gas was passed into a portion of tlic quinoline until it solidified on cooling into a hard crystalline mass. This hydrochloride was dissolved in water and a solution of platinic chloride was added. The platinoquinoline hydrochloride precipitated was washed by decantation separated by filtration and again washed until free from platinic chloride then dried a t first a t a tem-perature not exceeding 80",and finally heated for a short time to 100". A weighed portion of the compound was then ignited and tlzc residual platinum determined. ,,:,, ~ z o o o - ,,:,, and iB$om of the substance were examined.E 48 HARTLEY RELATION OF TEE MOLECULAR STRUCTURE ETC. Weight of substance. Weight of platinum. Per cent. Pt. gram. gram. I 0.7516 0.2192 29.1 G 11 0.8008 0.2326 29-04 The theoretical quantity of platinum in the salt is 29.44 per cent. Photographs were taken of solutions of the base in alcohol. The solutions contained -I- -I_- -1- -I- ~ ___ 1000 5000 10000) 1 5 0 0 0 7 2 0 0 0 0 9 S O A O 0 40A00, 3h and One narrow band of absorption is seen just a little beyond 12 Cd in solutions Containing lo&u8. Two narrow bands and a broad one are seen in solutions containing =fm and traces of absorption con-tinue until the dilution has reached It is interesting to compare the quinoline Diagram XII with the naphthalene Diagram 111 (Chem.SOC. J. 1881). Two of the four absorption-bands have bzcome fused and the remaining ones are much lowered in refrangibility; a t the same time the intensity of the absorption is decreased. Thus three strong bands are seen in solutions containing 1 part of substance in 100,000 of a solution of naphthalene, but with a dilution of 1 in 50,000 they have all disappeared in the case of quinoline. From the ease with which cyanic acid becomes converted into cyanuric acid evolving a considerable amount of heat during thc change and on account of the necessity for the absorption of a large amount of heat to effect its decomposition into the simpler molecule, it appears highly probable that the carbon and nitrogen-atoms con-stitute a closed chaio forming a compound which may graphically be represented thus :-0 I€ their weight of the substance.I I1 \ x / HOC COH Such an atomic grouping would probabIy be the cause of absorption-bands the hydroxyls in the molecule however being inactive in this respect as I have shown by previous observations (see No. 11 April, 1881 this Journal). I n order to gain some knowledge of the constitution of cyanuric acid a beautifully crystallised specimen was dissolved and the ultra-violet spectrum was submitted to its action. A solution of 1 part, by weight in 200 of water gave a strong absorption-band stretchin,g from wave-length 2687 to about 2630 an interval lying midway hetween 17 and 18 Cd. The band of rays beyond this which was b u t faintly transmitted does not extend t o 22 Cd.A solution con 30,000 .tu,oao 50,auo I a 0,mo Absorption bands traceable in solutions contailring ha of the substance. Ordinates =proportion of alcohol to one part by weight of Quinoliiia Thickness of layel- of liquid = 15 mm. DIAGRAN XIII. C Y A N U R I C A O I D . Numbers indicating the position of cadmium lines of known wave length C+ p43. c+ - 9 7011 ?Z 17 I6 0. 50 100 I 50 2 00 Oidinates = The propoiition of liquid contJainmg one part by weight of tlie sut,staiice. Scale. 100 p&ts to Iialf an inch. 1 in 2,000 transmits all rays. Harrison b Ssns.Lith. S'Martins L3ne.VJ. ATKINSON AND TOSHIDA ON PEPPERPIIINT CAPIIPHOR ETC. 49 taining 1 part of substance in 2,000 of water is quite diactinic. The presence of the absorption-band proves I think that there is a union between the 6 atoms of nitrogen and carbon similar to that suggested by the graphic formula given aboye because otherwise the carbons and nitrogens would stand to each other in the same relation that obtains in hydrocyanic acid which is a perfectly diactinic substance.Jud,aing from the evidence afforded by the study of carbon compouiids, the account of which has been given in my former papers it is not a t all likely that the carbon-atoms in cyanuric acid can be only singly linked ; a t the same time the union of the atoms cannot be of so intimate a nature as that occurring in benzene because its actinic absorption is so much less powerful. It appears therefore that this substance possesses a nucleus with a compactness of structure intermediate between that of benzene hexchloride and that of benzene. Now as the atoms of the nucleus in the first body are singly linked if we accept the justifiable conclusion that those in cyanuric acid are alternately doubly linked it would appear probable that in benzene each carbon-atom is united with other three carbons since this is the only manner in which a more compact atomic linking than that expressed in the formulz of benzene hexchloride and cyanuric acid can be made consistent with the perfect symmetry of the compound or in other words with the perfect equality of function of the six carbon-atoms

ISSN:0368-1645    

DOI:10.1039/CT8824100045

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

ATKINSON AND TOSHIDA ON PEPPERPIIINT CAPIIPHOR ETC. 49 X.-On Peppermint Camphor (Afenthol) a d some of its Derivat ires. By R. W. ATKTNSQN B.Sc. and H. YOSHIDA. PEPPERMINT camphor as found in commerce even when not expressly adulterated with magnesium sulphate is almost invariably contaminated with oilrmatter which accompanies i t in the plant and on account of the difficulty of removing this impurity most of the previous determina-tions of the melting point are too low. The specimens upon which we worked came from Dewa in the north of Japan and were found to melt a t about 35' C. and to boil at 210-211" (uncorr.). This menthol was purified by distillation the first and last portions being rejected, after which the cooled and solidified product was well pressed between filtering paper and exposed repeatedly in thin layers to the air.By several repetitions of this process the melting point was finally raised to 42*2" the solidifying point t o 40*3' and the boiling point t 50 ATKINYON AKD YOSHIDA OK 212' (corr.). These numbers agree most nearly with those of Beckett and Wright (Chem. SOC. J. 187t; 1 1). The melting points were (letermined by enclosing the capillary tube containing the menthol, together with a delicate thermometer in a test-tube immersed in water which was slowly heated a process originally described by Anschiitz and Schultz (Ber. 10 1800). MEWHONE CloH,,O. Jlr. Moriyn has shown (Chew,. SOC. J. 1881 Trans. 77) that when menthol is heated in sealed tubes with acid bichromate solution at 120" for about 10 hours an oil boiling a t 204-205" is ohtained, having a composition which agrees with the formula C,,H,,O.We have repeated this experiment preparing larger quantities and have iuade determinations of some of the principal physical properties of the compound believing that this knowledge will be of assistance in elucidnting the structure of the menthol derivatives. Weak chromic acid liquor has very little action upon menthol at 100". To prepare menthone about 30 grams of purified menthol were placed in a narrow-necked bottle together with 10 grains of potassic clichromate and about an equal weight of sulphuric acid ; on shaking the mixture much heat was liberated and the menthol was changed into a black spongy mass. Thc bottle was then heatred in a digester to a temperature of 1%" for about four hours.At the end of that time the light oily layer was separated from the solution of chromic sulphste and subjected several times to the same treatment with fresh oxidising mixtures. The optical activity of the oil was examined after each treatment arid it was observed that it gradually decreased from - 59" to 0" for the transition tint but did not stop there the rotation bccotning positive and increasing till it rose to [ a ] j = + 2 1 ". Purified by distillation rnenthone is a colourless mobile liquid, neutral to test-papers soluble i n almost all proportions in alcohol, c*hloroform benzene and carbon disulphide but insoluble in water. On combustion the following numbers were obtained :-(1.) 0.5918 gram gave 1.6884 gram CO? and 0.6296 gram H,O.(2.) 0-4362 ) 1.2415 , , 0.4625 ., (3.) 0.3472 , 0.9902 , 0.3659 ,, Theory Chbon . . . . . . 77.81 p.c. 77.62 p.c. 77-78 p.c. 77-73 77-92 Hydrogen . . 11.82 , 11 78 , 11.71 , 11.77 11.69 1. 2. 3. Mean. C,,,H,,O. X i . Morip's numbers (not published in his paper) were I'EPPERJIIST CAJIPHOR (?IIESTT-TOL) ETC. 3 1 Mean. Cmbon 77.59 per cent. Hydrogen 11.87 ,, Two dcterminations of the vapour-density of the compouncl gave the numbers 77.45 and 76-69 the number calculated for CloH180 being i 7.0. Menthone boils a t 206.3" (cnri-.) and smells like much diluted peppermint. It does not combine with acid sodium sulphite; con-centrated oil of vitriol has scaIcely any :&ion on i t in the cold. When menthone is repeatedly cohobated with zinc chloride a hydro-carbon is obtaincd which smells like that of the hydrocarbon t o bc :tl'teraards described obtained from menthol I-iy the action of hydric iodide with subsequent treatment with caustic soda and sodium.A 1mty somewhat opalescent mass is formed from which the oil is liberated by treatment with water. The amonnt of the hydrocarbon obtained was however too small t o permit of its identification; i t was probably a misture of several bodies. Tliat menthone stands to menthol in a similar relation to that in which camphor stands to borneol is shown by the fact that menthol can be reproduced from its ketone C,,Hl80 by a reaction quite similai. to that by which borneol is produced from camphor. When a solution of menthone in petroleum of somewhat high boiling point is heatetl with metallic sodium the latter is quicklj dissolved ; and on decom-posing the solution by carbonic acid shaking u p the product with water rapidly separating the water from the oily layer and setting i t aside it deposits minute crystals of peppermint camphor which can be obtained in a coherent mass best by distilling in a current of steam.When purified by the process adopted for the natural menthol, it was found to melt a t 42.2" solidfying a t 40*3" but to have a lest, energetic hvorotatory power than the natural product viz. - 39". It may be remembered that sjnthesised borneol differs in its specific rotatory power from the natural substance but the present instance is perhaps more remarkable seeing that the intermediate body possesses ;I rotation opposite both t o the natural and to the artificial rnenthol.Specilfic Boiatory Pozuer.-Not having at our command any other kind of polarimeter we were obliged to be content with the results given by :I Soleil-Ventzky saccharimeter although as is well known its indica-tions are not exact for other substances than sugar. Mr. Moriya (70c. cit.) stated that this body was inactive t o polariaecl light but a s his experiments were made upon solutions of the oil, which further was probably not completely freed from menthol the rotatory effect was imperceptible. We found that the pure oil in a decimeter tube gave an average rotation of 49.73 divisions from which the specitic rotatory power is calculated 52 ATKISSON AND TOSHIDA 0s Speczjic Grazdy and Rate of Expa&on.-The specific gravity ZVRS determined by the use of a carefully calibrated specific gravity bottle, and the weights reduced to a vacuum ; the numbers give the density at the temperature mentioned compared with that of water a t 4" C.Each number is the mean of five experiments. Temperature. 0" 10 20 40 GO 80 100 DC 4 0.9126 0.9048 0.8972 0.8819 0.8665 0.851 1 0-8355 Volume. 1~00000 1.00862 1.01 716 1.03481 1.05320 1.07226 1.09228 When combined these nuEbers lead to the formula for the expan-sion-Vt = 1 + 0.000850375 + 0~0000004156t2 + 0*0000000031415t3. Molecular R,efi-action.-The refractive index was determined with the aid of a delicate spectrometer belonging to the physical laboratory of the University of TSki6 and fully described by Prof.Mendenhall in the Eighth Nemoir of the Science Department of the IJniversity (" On t>he Wave-lengths of some of the Principal Fraunhofer Lines). The sources of light employed were the Ted and green lines of the hydrogen spectrum having the wave-lengths 6563 and 4682 respectively. The temperature of the air at the time of the observations was 8-9", and the specific gravity of the liquid a t 8.5" was 090602. The index of refraction for Ha = 1.452d3 9 ) 7 9 9 Hfi = 1.46094 Using Cauchy's formula for an infinite ware-length (Briihl Annolev, 200,139 we get-A = 1.442998 B = 0.425268 The molecular refaction is therefore, Using the values given by Briihl for carbon hydrogen aud oxygen, the calculated molecular refraction for Cl0HL-O the carbon-atoms no PEPPERJIIST CAXPHOR (JIESTIIOL) ETC.5 3 being doubly combined is 75.1 a result agreeing so well with the observed number that we may conclude that t,he carbon-atoms are all singly united. MEKTHENE C,,H,,. This substance was prepared by heating menthol with zinc chloride. The purified peppermint camphor was cohobated with about twice it3 weight of zinc chloride in a flask provided with a vertical condenser. After heating for about half a day the hydrocarbon was separated and then digested with sodium for some time a t a gentle heat The product was carefully fractionated several times and the main portion which passed over at 165-166" (uncorr.) was preserved for examination. It was found necessary to purify it from small quantities of poly-merised bodies and for this purpose the liquid was digested with clean pieces of sodium and occasionally separated by distillation from a reddish-brown precipitate.After about a month the production of the reddish precipitate ceased ; the liquid was again fractionated ; and that portion which distilled a t 167.4" (corr.) served for the following determinations :-The observed boiling point 167-4" is higher than that usually given for menthene but the greater part of ths product obtained distilled constantly at that temperature. Specific Rotnfony Power.-At 15" the liquid contained in a tube 1 decimeter long gave a rotation equal to 10-73' the specific gravity at the same temperature being 0.8102 and the specific rotatory power [ a ] j = + 13.25".This observation differs from that of previous observers who have regarded menthene as an optically inactive body. I n Mr. Moriya's case this was perhaps caused by the menthene used containing a little unaltered menthol as well as from the cir-cumstance that he used dilute alcoholic solutions whilst the above determinations were made with the undiluted liquid. Spec;fic Gravity aid Rate of EqaizsiorL.-The specific gravity at the various temperatures was determined as in the case of menthone, each number being the average of five experiments, Volume. 0" 0.8226 1~00000 10 0.8145 1.00994 20 0.8073 1.01899 40 0.7909 1,04008 60 0-7761 1-OG000 t 4 Temperature. D-These results lead to the formula for the volumes-Vt = 1 + 0.00099183t + 0.000000592t2 + 0~0000000055t3 Xolecular Befructioib.-The indices of rehaction were found t o be-for Ha = 1.448997 and for H = 1.459200.from which we find-13 = 0.534289 h = 1.43664 The specific gravity a t 8.5" is 0.8137 hence the molecular refrac-tion is-The number calculated for CloH18 from the values for carbon (in single unioi:) and hydrogen given by Briihl is 71.82. A closer agree-iiient is obtained by assuming the existence o f one pair of carbon-:itoms doubly united the rest being in single union viz.,-C''B + GI8 + HI = 73.82. Menthene is a colourless mobile liquid of an agreeable odour re-calling that of cymene ; moderately soluble in ethw or alcohol more so in benzene turpentine and petroleum. When heated with faming hjdrocliloric acid for some time i t yields Zlydrocliloride of menthene, C,oH,9CI an oil more or less coloured yellow which after washing with water and drying over potassic carbonate contained in two experiments 20.25 and 20.3 per cent.of chlorine the theoretical per-centage being 20.34. Heated with hydriodic acid a t the ordinary pressure of the air,men-thene takes up the elements of the acid forming an uustable brown oil having an odour resembling that of the iodide formed by the action of hydriodic acid on menthol. ACTION OF HYDRIODIC ACID ON 3 u l m n r o L . About 10 oz. of hydriodic acid solution of sp. gr. 1.7 were heated with about G 02. of menthol in a flask with an iuverted condenser ; the heating was continued for three days a t the end of which time the dark oily liquid was separated from the aqueous portion.The oil decomposes on distillation between 170" and 200". The distillate was lighter than water and had a pleasant odour; when it was boilod with caustic soda solution the dark colour which it assumed on standing by the decomposition of some iodo-compound was removed ; but again on standing the dark colour reappeared. Nothing dis-tilled below 160" hence no decane was present. Berthelot (Bull. SOC. Ckim. 11 102) states that a small quantity of amyl hydride and of clecyl hydride together with terpilene hpdride (C,,,€T,,) which forme PEPPERXIST CANPIIOR (JIEWROL) ETC. 55 three-fourths of the total liquid are produced in this reaction. The strength of the hydriodic acid used in his experiments was however, higher than in ours.When the above liquid is cohobated with canstic soda-solution then with sodium and distilled i t yields a clear colourless hydrocarbon of ail agreeable odour. It polymerises on heating and can only be purified by long digestion with sodium. The corrected boiling point was found to be 168.6". Combustion showed that it consisted mainly of a hIdro-carbon CIOHIB mixed with a small quantity of a more highly hydro-qnised body ClOHl8 or CloH,. (I.) 0,3642 gram gave 1.1714 gram GO2 and 0.3989 gram H,O. (2.) 0.4212 , 1.3517 , , 0.4769 ,, ( 3 . ) 0.4034 , 1.S024 . , 0.4400 ,, 1. 2. 3. Mean. Carbon . . . . 87.72 p.c. 87.53 p.c. 86-05 p.c. 87-76 Hydrogen . . 12.17 , 12.58 , 18.12 , 12.29 100.05 Calculated for f--- 7 Cl(,Hlti ClOHI, Carbon.. . . . 88.i35 86-96 Hydrogeii 11.765 13-04! 100~000 lo0.00 -Two determinations of the vaponr-densi ty made with Victor Meyer's apparntns gave the numbers 66.1 and 68.4; mean 67.25. The iiumber calculated f o r CLoHls is 68.0. S ~ E C $ C Rotatory Power.-As a mean of five observations the liquid contained in a decimeter tube was found to rotate the ray of polarisecl light through 4.23' hence density at 18" = 0.8137, 4.23 [ . ] j = - o.81;37 = + 5.2". Specific Gravity and Rate of Expansion.-The specific gravity was determined as before. Volume. 0" 0.8254 1~00000 10 0.31 78 1.00929 20 0.8111 1.01763 40 0*8001 1.03162 60 0.7924 1.04163 t 4 Temperature. D 36 VELEY ON SOME HIGHER OXIDES These numbers lead to the following equation expressing the volumes a t different temperatures :-Vt = 1 + 0.000976768t - 0~00000479t2 + 0~00000000133t". Molecular Befraction.-The indices of refraction were found to bc for H I 1.4481614 and for H = 1.457148 from which we find-A = 1.43723 and B = 0.47059 The specific gravity a t 18" being 0.8115 the molecular refraction - = 73.28. for CloE16 is R = 136 x 0.8115 The number calculated for CIOHl6 all the carbons being in single union is 69.24 b u t if we assume the presence of two pairs doubly united we get the number-c'6 + C"4 + HI = 73.24. This hydrocarbon is a clear colourless mobile liquid easily soluble in petroleum or benzene less so in ether and alcohol and insoluble in water. Its odour resembles that of cymene. Bromine acts strongly upon it. about two atoms being taken up with evolution of some hydrobromic acid ; the resulting bromo-compound is as unstable as the iodo - compound

ISSN:0368-1645    

DOI:10.1039/CT8824100049

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

36 VELEY ON SOME HIGHER OXIDES XI.-On some Higher Oxides of Maizgnnese and their Hydrates. Part 11. By V. H. VELEY B.A. F.I.C. Christ Church Laboratory Oxford. P~el iminary Discussion. IT seemed t o the author that a continuation of the investigations on the higher oxides of manganese and their hydrates (cf. this Journal, 1880 581-592) might throw some fnrhher light on the constitution of these compounds. Experiments have recently been published on the oxides of manganese b.y Wright associated with others (this Journal 1880 775-785) Moissan (Arm. Chim. Phys. [ 5 ] 21 199-255) and Pickering (Chem. News 43 189 et sep.) ; these researches will be alluded to in the course of the present communication. Purity of the Oxides. As considerable stress was laid in the formep communication on th O F JIhSGAXESE ASD THEIR HYDRATES.57 probable difference of behaviour of the higher oxides when pure and when contaminated with alkali a spectroscopic analysis was made of the samples used. The method of procedure was as follows :-A strong solution was prepared by dissolving 1.358 grams of the hydrated oxide in 20 C.C. concentrated hydrochloric acid. A drop of this solution introduced on a platinum wire into a Bunsen burner, and the flame viewed through a double prism spectroscope gave a spectrum in which the presence of no metals other than manganese and sodium was indicated. I n order to determine the maximum amount of impurity of potassium two flasks A and B were taken in the former of which were placed 10 C.C. concentrated hydrochloric acid (prepared from ammonium chloride and sulphuric acid) and in the latter the same volume of hydrochloric acid containing a known weight of the hydrated oxide in solution.To the former mas added a dilute solution of potassium chloride a cubic centimeter at a time, until a drop taken up on a platinum wire gave distinctly the red line Ka,. The experiment was then repeated with flask B and it was found to require exactly the same number of C.C. before the line Kaz became visible. Hence the amount of impurity of potassium is less than the amount contained in 1 C.C. of the dilute potassium chloride solution. By this process it was shown that the manganese chloride solution contained less than 1 part of 1,000 of potassium chloride. (Further corroborative evidence of the absence of potash was afforded by the readiness with which the oxides were reduced in hydrogen and the freedom from so-called spontaneous oxidation of the manganese monoxide formed,) The experiment described above was repeated a calcium chloride (from Iceland spar) being substituted for the potas-sium chloride solution.Owing to the close proximity of the red and green lines Ca and Cag with Mn and Mng observations were made with the yellow calcium lines on either side of the sodium line ; or on moistening the wire after the experiment with dilute hydrochloric acid the calcium spectrum could be obtained free from that of man-ganese. (This is probably due to the retention of the lime by the oxide of mangauese as calcium manganate which is less readily dis-solved by the hydrochloric acid and so is volatilised after the greater part of the manganese passed off.) By this i t was shown that tllc chloride of manganese contained less than 1 in 6,800 of calcium chloride.The apparatus and the methods of analysis employed have already been described (vide s z y m ) . Changes produced when the Higher Oxides are EeateJ i i ~ Xitroym. Nitrogen was chosen in order to study the dehydration of tho per-oxides a t increased tempcratnres in an atmosphere free from oxjgen 58 VELET ON som HLQHER OXIDES Mean of values obtained. I whereby the loss of water is not accompanied with or affected by. any secondary chemicai reaction. The nitrogen gas was prepared by aspiring over red-hot metallic copper air purified from carbonic acid, and mixed with ammonia by passing through a strong solution of the gas.By so regulating the air and ammonia current that only on(' part of the copper is oxidised while the other part is unaltered ti),. nitrogen is obtained free from oxygen and hydrogen with one or other of which it would be contaminated if the contents of the heated tube were completely oxidised or completely reduced. (This ready methocl of obtaining pure nitrogen is not described in any of the more recent text-books and was 5rst) adopted by Harcourt.) Before the gas entered the drying and purifying apparatus it was passed through a considerable length of red-hot combustion tubing filled with copper foil and cupric oxide and then through a washing bottle containing a1 kaline pyrogdlate.Before commencing the experiments fresh analyses were made OF t,he hydrated peroxide used in the former publication the method of preparation of which has already been described a t length. Values obtained in former experiments. Manganese monoxide Oxygen Water . 75 *34 75 *37 14-28 14 '06 10.40 10.54 160.02 99 -97 ___-___--These analyses are fairly accordant and agree with the hypothesis t,hat it is an oxide of formula Mn60, of not very definite hydration. A series of experiments were then made to ascertain whether the composition of the oxide when heated in nitrogen from 60-200°, remains unchanged so far as regards the relation of manganese mon-oxide to available oxygen or whether the loss in weight is solely attributable to the loss of water of hydration.Reinadcs ON Table I. I. The temperatures a t which stable hydrates seem to be formed arc' 90-95" and 170-180". 11. Throughout the experiments there is no marked diffei*enw between the loss in weight of the oxide and the water collected in the drying tube. This shows that the oxide when heated in nitrogen from 180-200" loses only water of hydration aiid not available oxygeli. (In the experiments marked $ there mas slightly more water collectct . . . . . . . . . . . . . i + -0 0 0 0 0 0 3 0 0 0 3 0 0 0 0 0 0 0 . . . . . . . . . . . . . 3 A 0 0 0 0 3 0 0 0 0 0 0 0 0 0 . . . . . . . . . . . . . . s E H m 8 c;l YELEP OX SOME HIGHER OXIDES . . 0s 0 3 03 0 0 0 0 0 A+ I m u+ d .r( 4.2 .- a 6 I . . . . . . ci H H w L: 4 m t-i H I I I I I 00% 0 O r 0 03 0 0 0 0 0 0 0 0 A .. . . . . . $ . . . t D . . & . 5 . 4 . o . $ . ? : .- - .+ . . % * . o * . s . c 3 d c 3 : .5 .z :.5 OF MASGANESE AljD THEIR HYDRATES. 61 Values obtained. -78 $7 6 *78 14 '60-14 '53 than loss in weight of oxide; these differences amounting to 0.0065 gram may be due either to the absorption of oxygen by the oxide when cooling before weighing or t o Graces of water not derived from the oxide passing into the drying tube. In order to confirm these experiments and to obviate the first-named source of error the oxide aas.al1owed to cool to the temperature of the room in the current of nitrogen before it was taken out of the apparatus. By adopting this precaution the gain in weight of tho drying tube and the loss of the oxide corresponded exactly one with the other.A third series were made in order to establish the constitution of the oxide when heated to 200" and to corroborate the results detailed in the two tables above (I 11). From analyses of the hydrated oxides which remained constant in weight wBen heated to 90-95" 160-18U0 and 200" C. in Tables I-111 confirmed by others their constitntion was determined. Mesn. 78 -67 6 '78 14.57 Analysis of Oxide wJhen Dried in Nitrogen at 90-95". 3langanese monoxide . Osygen (by titration). . Water - 1 100*02 78-58 14 *77 6 -65 loo '00 --Analysis of Oxide when Dried i i z Nitrogen at 160-180". Valucs obtained. Mean. I I Calculated for Mn60,1H20.Manganese monoxide Oxygen (by titration). . Water . 81.60-81 -18 81 *31 15.21 1 li5fi 3 *44-3 '46 81 *2S 15 '28 3 *44 VOL. XLI. 62 VELEY ON SOME HIGHER OXIDES Analysis of Oziitle when Dried in Nitrogen at 300'. Manganese monoxide I Oxygen 15.66 Water . 1.75 82 04.2-82.56 -Values obtained. M-ean. I I 82 *49 15-66 1 - 7 5 99.90 I--I- -Both +b,e latter partially dehydrated oxides readily took up oxygen iit 100" C. and slowly even a t 6OO.X Repetition of Experiments. I n order t o confirm the former experiments it was considered desirable to repeat the whole oi the research ab initio. A different sample of manganesg chloride was purified by the processes described before and the oxide precipitated from the acetate by a current of chlorine a t 52-54" and finally dried a t 60-80".The composition of the new sample? was found to be very nearly but not exactly the same as that of the former sample the one being expressible by a formula Mn,,O4,8H2O the other by a formula Mn24041.SH20. This slight difference may be due to a rather greater oxidation by a longer continued action of chlorine or t o an absorption of oxygen during a protracted heating of the oxide in the air-bath. It is here only neces-sary to state that on repetition the former observations were confirmed in every respect. The sample B when heated in air went through the same cycle of changes ; there were the same stopping points a t which the oxide neither gained oxygen nor lost water; the absorption of oxygen began at the same (temperature and took place within the same limits ; and the composition of the oxide ultimately obtained after heating to 200" was tlie same as that obtained by the same pro-cesses in the former experiments, * Pickering has observed (Zoc.cit. supra) a similar absorption of oxygen a t 100' C. in the case of oxides prepared by different processes. H e considers that the tem-perature at which absorption begins probably depends on the physical condition of the oxide the quantity of so-called available oxygen t l e water of hydration and the condition to which it is exposed when heated. t This sample will hereafter be designated sample B OF MAKGASESE AND THEIR HYDRATES. Analysis of Oxides Dried in A ~ T at 200". 63 Mean values of second sample.--Manganese monoxide,. - . . Oxygen Water . Mean values of Calculated first sample. for Mn,,O,,H,O. 81 *68 16.75 1.65 99 -88 - -I--/ 81 '48 81 '44 16 -79 16 *84 1 '69 1-72 99 *96 100 .oo ---Condit.ion. Action of laryhogen. The behaviour of the oxides of manganese when heated in a current of hydrogen has lately been made the subject of careful investigation by Wright associated with others (this Journal 1878 Trans. 512-527 ; 1880 799-781). The author's experiments would not here be adduced did they not offer an independent confirmation of Wright's researches though the original object in view was the possible prepa-ration of hydrated peroxides containing less so-called available oxygen than the oxide MnGOli. Time.TABLE IV.-Contiwous Series iu Hydrogen. Heated in a elow current of hydrogen. Ditto,. Ditto . . . . . . . . Ditto . . . . . . . . Ditto Ditto . . . . . . . . Ditto Ditto . . . . . . . . Ditto Ditto . . . . . . . . Ditto . . . . . . 2 hrs. . . . . . . . . . . . . . . . . . . . . . . . . I - -Temp. 100" 110 120 130 140 152 180 190 200 200 60-17( Weight )f oxide. Gram. -0 *4192 0 *4062 0 -4040 0 *4010 0 *3970 0.3970 0.3880 0 '3792 0 '3710 0,3530 0.3525 0 *3525 Loss. Gram. -0.0130 0 .oil22 0 '0030 0 '0040 nil 0.0090 0 '0038 0 -0082 0 .Olt30 0 *0005 nil 8 (Mn,C4) 3H20 Remarlis 012 the Table above. I. The reduction or loss of available oxygen begins at a temperature of 130" when there is a marked difference between the percentage loss in hydrogen and the corresponding loss at the same temperature in a i r ; but this change is more marked a t 150".F 64 VELEY ON SO3E HIGHER OXIDES Mean* 11. The oxide constant in weight at 200" has the characteristic colour of the red oxide ; the hue was peculiarly bright on first taking the oxide out of the heating apparatus but on exposure to the air the bright surface was immediately dimmed. This outward change is probably accompanied with a.n absorption of oxygen for the oxide on keeping gained weight and had a composition only approximate to Mn304. Cnlculated for 8(Mn20,)311,0. Analysis of Oxide when Heated to 200" in a Current of Hydroqen. Manganese monoxide . . .Oxygen . . . . . . . . . . . . . . . . Water (by difference) . . . . Values obtained. 89 -90-89 90 7 '23- 7 -10 -I-- I 89 -80 90 *35 '7.16 1 6 .78 3 .O& 2 -87 100 *oo I 100 *oo In the oxide obtained the ratio of oxygen to the monoxide is '*'* x 100 = 7.97 ; in Mn304 it is 15.96 = 7.52. 9 3 21228 The retention of a greater quantity of water (3.04 per cent.) by the oxide when heated in hydrogen to 200" as compared with that retained by the oxide when heated to the same temperature in air (1.69 per cent.) oxygen (1.77. per cent.) or nitrogen (1.75 per cent.) can be explained thus the oxide though exposed to a current of dry hydro-gen is perpetually surrounded by the vapour of water formed by the reducing action of hydrogen on the oxide. It follows that the oxide will be dehydrated oiily when the tension of vapour of water emitted by it is greater than that of the water in the hydrogen atmo-sphere.Although the oxide was constant in weight after a second heating at 200° yet this constant weight was attained by the removal of the oxygen absorbed by the necessary though brief exposure to air chiring the process of weighing ; the formation of a small quantity of water in the cooled part of the apparatus gave on reheating a further proof of such absorption of oxygen by Mn301 which has been pointed out by Dittmar Wright and others. S$eciJic Grnvitl:ea of the Hydrated Oxides. It seemed of interest to ascertain how far these hydrated peroxides of manganese differing slightly from one mother in the relative pro-portions of constituents differ in their physical properties as apecific gravity OF MANGANESE AND THEIR HYDRATES.65 Pure benzene was carefully dehydrated by keeping for some week$, and subsequently distilling over sodium ; the fraction which passed over between 80-81" (uncorr.) was reserved for the determina-tions. In order to obtain as correct a value as possible for the specific gravity of the benzene two bottles were taken and their weights com-pared when filled to the mark with benzene and with water a t the same temperature (16.5") and the specific gravity of benzene was subsequerit,ly reduced to terms of water at 4". Specific gravity of benzene by bottle A Specific gravity of benzene by bottle B compared with water a t 4' C. 0.8944 cornpared with water a t 4" C.0.8945 Mean 0.89445 The specific gravity of the oxides was ascertained by dropping about 1 gram of the oxide into a specific gravity bottle from a weighing tube which fitted closely to the neck of the bottle to avoid unnecessary exposure to the air. It was theu covered by a lsyer of benzene and warmed in a water-bath to expel air bubbles and allowed to cool iu water to the temperature 16.5". Spea9c Gravity of Sample B ( Mnz10458H:20). Twb determinations were made by the method described above. (1) Specific gravity compared with water a t 4" . . 4.671 > > Y9 4-681 Mean 4.675 - (2) Specific Gravity of the Hydrate constant i ? ~ Air at 200" ( M T ~ ~ O ~ ~ H ~ O ) . (1) Determination compared with water a t 4" (2) $7 >> Y 4,750 Mean 4.775 4-800 Specific gravity of manganese monoxide obtained by igniting the higher oxide for some days in a current of hydrogen:-(1) Specific gravity compared with water at 4" 5.010 Former observations by Rammelsberg 5.000 As several determinations have been published by Playfair aud Joule and by Rammelsberg (Monuisb.Ber. Akad. 1865 110) of' the sesquioxide and red oxide prepared by artificial processes it was thought superfluous to repeat them 66 HOWARD AND HODGKIN ON A Summary of Xesults. I. The higher oxides of manganese when heated in dry nitrogen a t temperatures ranging from 60-200" are simply dehydrated without loss of available oxygen the dehydrated oxide formed readily absorbs. oxygen. 11. The oxides when heated in dry hydrogen are simultaneously dehydrated and reduced ; a hydrate of the red oxide is formed which readily absorbs oxygen. 111. The quantity of' water retained by tho peroxides when heated to 200" in dry hydrogen is greater than that retained by the same oxide when heated to the same temperature in air oxygen or nitrogen. The higher oxides and their hydrates obtained in the course of the former and present research are tabulated below and in order to facilitate comparison and to show their mutual relation they are represented as oxidised produds of a protoxide of' molecular formula AIn2,0,4 :-In conclusion the author wishes to express his best thanks to Mr. Vernon Harcourt for kind assistance and advice during the course of this investigation

ISSN:0368-1645    

DOI:10.1039/CT8824100056

出版商:RSC    

年代:1882

数据来源: RSC