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JOURNAL OF THE CHEMICAL SOCIETY. CONTAINING THE PAPERS READ BEFORE THE SOCIETY AND ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN OTHER JOURNALS. F. A. ABEL,F.R.S. W. MARCET,M.D. F.R.S. Ph.D. F.R.S. N. STORY-MASKELYNE, H. E. ARMSTRONG F.R.S. Ph.D. E. J. MILLS,D.Sc. F.R.S. E. ATKINSON F.C.S. HUGO M~LLER C. L. BLOXAN Ph.D. F.R.B. H. DEBUS,Ph.D. F.R.S. H. M. NOAD Ph.D. F.R.S. B.A. F.R.S. W. ODLING M.B. F.R.S. G. C. FOSTER MI~HAEL M.D. F.R.S. W. H. PERKIN, FOSTER F.R.S. E. FRANKLAND Ph.D. F.R.S. D.C.L. F.R.S. H. E. ROSCOE Ph.D. F.R.S. J. H. GILBERT,Ph.D. F.R.S. W. J. RUSSELL Ph.D. F.R.S. A. VOELCKER, J. H. GLADSTONE Ph.D. F.X.S. HARCOURT Ph.D. F.R.S. A. VERNON M.A . F.R.S. A. W. WILLTANSON @;bitar HENRYWATTS,B.A. F.R.S.2JbsfrLIctars G. T. ATKINSOS. E. W. PRh'OST Ph.D. Ph.D. E. C. BABER. W. RAMSAY ROBINSON. D. BENDIX. JOHN D.Sc. R. ROUTLEDGE F. D. BROWN B.Sc. D,Sc. c. SCHORLEMMER F.R.8. C.A. BURGHARDT FRANK D.Sc. H. H. B. SHEPHERD. CLOWES c. L. FIELD. WATSON SMITH. THOMSON. C. E. GROVES. J. MILLAR F. J. LLOYD. WILLIAMVALENTIN. lif. kf.PATTISOX 31UIR. ROBERTWARINGTON. E. NEISON. c. w. WATTS. WATTS D.SC. C. €1. PIESSE. JOHN W. 1%.PIKE,Ph.D. c. R. A. \\71tIGHT n.8~. LONDOX J. VAN VOORST 1 PATERNOSTER ROW. 1877. LONDON JIARRISON AND SCNS PRINTERS IX OllDXMANT TO HEB MAJESTY 8T. NARTIX’S LANE. CONTENTS. PAPERS READ BEFORE THE CHEMICAL SOCIETY :-PAGZ I.-Study of Hydrogen Dioxide and certain Peroxides including Experiments to Determine the Heat of Formation of the Oxygen-molecule.By T. Fairley F.R.S.E. . .I 11.-On certain Bismuth Compounds. By M. M. Pattison Bl'uir F.R.S.E. . 24 ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS :-General and Physical Chemistry. Annaheim (J.). The Absolute Weight of Atonis. . . . . . Marignac (C.). Specific €hat of Saline Solutions ..... Mendele,jeff (R.) and N. Kajnncler. Coeflicieiit of Expansion of Gases . IIemili~21i Mendele j eff and Bogusky. Coinprcssion of Gases by Low Prcssiires . . . . . . . . . . . . . Troost (L.) and F. Hautcfcuille. The Laws of Coiiipressibility and the CoeEcirnt of Dilatation of ccrtaiii Vapours ...... Bellemy (F.). The Migration of Gases ....... Troost (L.) and P. Haut ef cuille.Determination of Vapour-densities . Hof man n (A. W.). Determination of Vapour-densities in the Torricellian Vacnu1ll . . . . . . . . . . . . . 31 e y e r. (,V.).A Method of Determining the Vapour-clensitics of Substances Roiling at lIigli Teniperatui*es ......... Ducleus (33.). The Separation of Mixed Liquids. . . . . . Guthrie (F.). Salt-solutions and Attached Water. ..... P isati (G.). Elasticity of illetals at various Temperatu~es . . . . Pi sat i (G.). Elasticity of Torsion . . . . . . . . . 1; un g e (G.). Rctnrclation of Chemical Reactions by Indifferent Substances Mitscherlich (A). The Point of Combustion . . . . . . Heumann (Karl). Contributions to the Theory of Luminous Flames. Part 11. ............. Inorganic Chemistry.Bellacci {G.) Production of Ozone by the Pulrerisation of Water .. Geriiez (D.). Prismatic and Octoheclml Sulphur . . . . . . Petterssoiz (0.). The Atomic Weight of Seleiiiuni ..... D i tt e (A). Action of Halogen-acids on Selenions Oxide .... Dittc (-4.).Action of Halo*cn-acids on Telliirous Oxide . . . . Bert helot (M.). Tlicriilic %ormation of IIydrosylaiiiine or Oxyanimonis . T h or p e (T. E.).Phosphorus Pentafluoride . . . . . . . Lissenko (K.). Formation of Phosphonium Iodide ..... 11 CONTENTS. PA GB Rchacherl (G.). Action of Hydrochloric Acid on Potassium Chloirtte . . 47 Debray (H.) The Dissociation of Calomel-vapoui-. . . . . 47 Lecoq cle Eoisbaudran. New Process for the Extraction of Galliuiii. . 48 Lecoq dc Boisbaudran.On the Physical Properties of Gnllium . . 4.8 Nilson (L. F.). The Quantivalence of the Rare Earth-metals . . . 40 Hillebrand (W. P.). T'he Specific IIeats and Atoniic Weights of Cerium Lanthanum and Didyniium . . . . . ... 50 Carnot (A). New Salts of Bismuth and their Use in tile Detection of Potash . . . . . . . . . . . . . 50 Troost (L.) and P. Hantefeuille. Researelies on tde Solution of Gascs in Iron Steel and Manganese . . . . . . . . . 51 Fremy (E.). Salts of Maiiganese Dioxide . . . . . . . 53 lllinera1ogical Chemistry. v. Las aul x (A). Mineralogical and Crptallographical Contributions (con- tinuation). . . . . . . . . . . . . 53 Hatchings. Analrsis of Clirpsocolla and Copper Pitchblende . . . 55 €€awes (G. 17.). 9 Lithia-bearing Variety of Biotite .. . . . 56 Field (F.). Kote on a Kew Cornish Mineral. . . . . . . 56 Yi sa n i (F.). A S~ilpliantimonideof Lead found at Amsberg Westphalia . 56 Levy (A. M.). Origin of Crystalline Rocks . . . . . . . 57 Meunier (Stanislas). Experiments and Observations on Vitreous Rocks . 57 Organic Chemistry. Pnn lorn (D.). Formation of Tertiary Alcohols . . . . . . 5'7 DjaBonow (D.). Conversion of Acid Chlorides into Alcohols . . . 55 Walitzhg (TV. E.,). Cholcsterin . . . . . . . . . 58 ~ Nevolb (11.). Actioii of Water in Gljcdu . . -.. . 55 Lrrnient of€ (J.). Preparation of 'I'riinetli~lcne Bromide . . . . 59 lt'ailach (0.). Preparation of Diclilorarctic il<.itl . . . . . . 59 C;~rj!arolli-'lliuriilali(I<.). Action of 1'ot:isli on Triclilorobutyric Acid .59 Pittig (It.). Siiiiple BLetlioil of Prepariiig GlJmllic Acicl . . . . 59 Wallacli (0.). Action of Chloral and B~oninlon Osjacicls . . . . 59 Prscliibitesk (S,). Synthesis of a-Oxybut>ricAcid . . . . . 60 Patcynb (E.) mid P. Spica. Action of Alljl Iodide and Zinc on Ethyl Ornlatc . . . . . . . -. . . . . . G c) li'ittig (K,.).. On so-called Non-satnmtcd Coinpoimds . . . . . 61 Mnr1,o~nihoff (JV.). On the Isomeric P~rotar'nriciicitls. . . . 61 31arLon.nihoff (W.). Norinal OsyPyrota'tai.ic,Icicl (Glutanic Acid) and its AJ:ILI tliiclcs ........... 6.3 I3i t t iq (12.). Conrcrsioti of Citraconic Aiili-ydride into Sci*onic Aii1i~dricle . 64 Chit t en tlcn (R. 11.). Product of the Oaiclation of Gljcogaii \\it11 Uroimiie Silver Oxide and Water .. . . . . . . . . t14 Leclderhose (G.). Glj cosaminc Hydrochloride . . . . . . cid Fittig (R.). Sew Deriratives of Xucic Acitl . . . . . . 63 Bentc (I?.). On the Pml)ariitioli of Lcvuliiiic~ Acitl and on Camglieen-sugar 63 de Girard (.T ). Spontaneous L4~tu~ntlon of II~tlrocyanic Acid and a Sew C' ~ceof the Coiiil)lcte Transforination of that LcBitl . . . . . 65 Nand1 11 (I,) a?id F. cle 3lontholon. J~~coiirpo~ition of Pota-sium CSanide Ziitc CTnnidc and I'otassiuin Fornliltc in Carboiiic Acid Air and Pure IIyflrogcii. . . . . . . . . . . . . 6G Clnrts ( I). ~tructnreof Cymic and Cpniii-ir -hi& . . . . . 67 C(.cIi (C1. 0.). Clilornl Cr:tnido-cj;~iiate i111ct itu Ikrimtires . . . . 67 l'roolrauer (B.) niicl E. Sell. Action of Biwniinc on Yhcnyl Sulphoc?aiinte 67 S c 11iff (EL.).Action of Alcoholic Potash on the Xustarcl-oils (Thiocarbi- iiclei) . . . . . . . . . . . . . 65 Wnllach (0.). Action of PhosDhorus Peiitabromide on Amicles . . . 68 ... CONTENTS. 111 PAQ 5 Hodges (N. D. C.). On Salts of Hydroxyl-urea and Double Salts of other I€yclroxamates . . . . . . . . . . . 69 Medicus (L.). Decomposition of Uroxanic Acid . . . . . . 69 De Clermont (P.) and E. Wehrlin. Two Sew Thiocarbamides (sulphurens) 70 Barbicr (Pli.). Fluorene and Pjmgenic 1J)drocnrbons . . . . 70 Pat ern0 (E.) and I’. Spicn. Synthesis of PropSlisoprop~l-benzeiie . 77 Reimer (K.). Action of Carbon Tetrachloride on Phenol iii Alkaline Solu- tion . . ..... ..... 77 Baeyer (A).The Cornpoimds of Plitlinlic Acid with the Plie~iols. Part I . 78 TT-eselski (P.)and J. Schuler. Preparation of Hydrocluinonc . . . 78 de 3f ontgolfirr (J.). Isonieyism of the Rotntoyy l’oncr in tlie Cnnipliols . 78 Annalieim (?J.). Crptnlline Foi-n~,Specific Gravity aid .Moleculnr Volume of O\.i~ri1l’TiOhen7ic7o . . . . . . . . . . 79 Xoeriier (W.) and G. 3ionselisc. Two ~ccnze~~c(lisulp~ionic Acids aiici their Re1:itions . . . . . . . . . . . . so Ciillen (Tli.) :ind C. Riittingcr. S~~lpliop~~~clilorobenzoic Beid . . . 82 Acid . I?irttinger ((3.). Si11~~lio~~art~broinnbcii~oie . . . . . 52 Reinlei-(I<.) aiid I?. Ticmann. Actioii of Clilorof‘orm 011 iSromatic Cyanides in Alkaline Solution . . . . . . . . . . 83 Klobnkomski (W.).Rufig:illir Acid . . . . . . . . 54 At terberg (A.). Action of PhoFphorus Pentacliloride on Nitronaphtha-Ieiies . . . . . . . . . . . . . 83 Mullcr (0sw;zlcl.). An Isoniericle of Pibromantliracenc . . . . 86 Liebcrmaiiii(C.)iiiidTopf. Antlii*anol . . . . . . 86 Plath (If ). X:intlioplivl~iiriii . . . . . . . . . 87 TiCIYIi7?ilJ (F.) and 3.M e~i(1clsohn. Constitution of Compounds of the Con11eql aild Va12i11in S cries . . . . . . . . . 87 Xoeriier (G.). Constitiition of Veratric Acid nndVeratro1 . . . . 88 Pntcrnb (E.). Vsnic Arid . . . . . . . . . b9 Sestiiii (F.).Ethyl Snntunatc . . . . . . . . . 90 €I ofin :I 11n (AZ.W.). Oxidation of ilrolnatic Arctarnines by Potassinm Per-111:I 11I$ii11 :it e . . . . . . . . . . . . 90 TTiIlp ero tl t.Bction of ct-ninitvoclilorohc~~~er~e on Arnido-compounds . !)O Nietzhi (R,). Anilinc-black . . . . . . . . . 91 Wallach (0.). Action of PltoyAiorus Pcntnch1or;de on Acetotoluiclide. . 91 l’fofiiiann (A. W.). Xylidincs . . . . . . . . . 92 Scliner (E.).Fliiui.escci,ce of Quiiiirlirie Sulphte . . . . 93 Pliilips (L.). A Hornologue of Caffeine . . . . . . . 93 Felini (F.). Atro1)ine . . . . . . . . . . . 03 11x 11 S nl n 71 11 (U.). Bctulin . . . . . . . . . . 04 Weselsky (P ). GlJcyrretin . . . . . . . . . 96 B nrg (0.). Lignite Tar . . . . . . . . . . $16 Linderos (F.). Sonic Constituents of Adonis vernalis . . . . . 9(3 Fittig (R.). The Acids in Romaii Clinmoinilc Oil . . . . . 57 Soniienschein (’. L.). Some Constituents of Grelsemiunt sentpei*z~i~em .97 Physiological Chemistty . Chnmpio’n (C.) and H. Pellet. EqnivnlPllt Subsfitution of Bfineid Sub-staiiwb in Aiiininls nnd Phiits . . . . . . . . . 95 Wolf f Fitlike! and Ditt iiiann. Assimilation of different Sorts and 31iatiires of Food by Pigs . . . . . . . . . . . 95 v. Swiccic*hi*(IT.).Fo~inntionof I’epsin by Bstraehinns . . . . 100 M~~Iio~inil\off (117.). AcctoiiciuUI.ine . . . . . . . 101 Lorhiqcli (IT.F.}. Cl\eii,icnl Tnrcstjgntion of a Caw of Cjsttiniwin . . 101 Sch inic! t (-il). Relation uf Sodiunl Cliloricle to certain Aninxd Fei-mentn-t1on Proc.essrs . . . . . . . . . . . . 101 Podolinski H.).The Albuminous Ferment of the Pancreas . . . 103 iv CONTENTS. Chemistry of Vegefable Physiology and Agriculture.PbG4 hlercadante (M.). ModiGcation of Starch in Vegetables . . . . 104 Sch ul z e (E.). Formation of Sulphuric Acid in Seedlings . . . . 104 Schulze (E.). IT. Umlauf and A. Urich. The Gerniiration of Lupine Seeds . . . . . . . . . . . . . 104 Mercaclan te (&I.). Absence of Leucin in the Products of Gerinination of the IGraininaceae . . . . . . . . . . . 105 Saintpierre (C.) and L. Magnien. Gascs in the Fruit of the Bladder Senna . . . . . . . . . . . . 105 Rein d e Y s (G.) . Composition and Nutritive and Manurial Value of Kapok Cake . . . . . . . . . . . . . 105 Reinders (G.). Action of Ses-water upon Land . . . . . . 106 Joubert (J.)and C. Chamberland. Kotes on the Permenfation of Fruits plunged into Carbonic dnliydricle .. . . . . . 106 D uria (E.). Cellulose Fernlentation produced by Vegetable Organs and pro- babie Utilisation of Sugar for the Production of Cellulose in Vegetation . 106 BBchamp (A). The Microzynies of Germinated Barley and of Sweet Almonds asproducers of Diastase and Synaptase . . . . . 106 Traube (Moritz.). Pure Yeast . . . . . . . . . 107 Amalytical Chemistry. Puchot (E.) The Iodine and Stai-ch Reaction . . . . . . 107 Selini (F.). Detection of Traces of Phosphoric Acid in Toxicological Researelics ........... 108 D it t mar’s Method of Determining the Amount of Chromium in Chroine Ores . . . . . . . . . . . . 108 Davp (E. W.). A New Chemical Test for Alcohol . . . . . 108 Jacqnemin (E.). Rhodeinr a New Test for Aniline . . . . .109 Pellagri (G.). Phjllocy~~i;~ias a Reagent . . . . . . . 109 31ark 3 TV 11 i k o ff (W.). Determination of Theine in Tea . . . . 110 Selnii (I?.). Modification of the Process for Extracting the Poisonous Alka- loYds from the Viscera . . . . . . . . . . 110 Technical Cliemistry. Pnlineri (P.). Chemical Exaniiiiation of twelve Colours found at Poinpeii . 111 Piscli er (F.). Temperature and Coinposition of the Gases evolve3 fi.oin Ult Famarine Fnmaces . . . . . . . . . . 111 Jarolimek (A). Hardening of Steel . . . . . . . . 113 He s Y (P.). Eui-nishing of Iron . . . . . . . . . 114 Glanzmsnn (R.). The Uses of Patent Coloiirs . . . . . . 115 Lam-(A). The Present State of the Sugar Industi-y in France and a few Experiments on the Use of Lime in the Clnrifjing Process .. . 116 Use of Hydrochloric Acid in the Diffusion Process . . . . . 118 Xoeller (J.). Myall Wood . . . . . . . . . 119 Carbazotin. A New Explosive Substance . . . . . . . 119 von Henmen (F.)nntl IT.ran Hasselt. Manufacture of Yeast. . . 119 Terne (B.). The Maiiufitcture of Glue . . . . . . . 122 Vicdt (E.W.). Logwood Inks . . . . . . . . 123 Schiff (H.). Carbon Disulphide as an Antiseptic. . . . . 12.4 'IJI.-Study of Hydrogen Dioxide and of certain Peroxides in- cluding Experiments to determine the Heat of Formation of the Oxygen-molecule by T Fairley F.R.S.E. (COW tl'nuetl). . 125 1V.-The Alkalo'ids of the Aconites Part I. On the Crystal- lisable Alkalo'ids contained in Acoiaitzm Xapellu s by C. R.A.Wright D.Sc. . . 143 V.-Notes on some Experiments made with a view to nscertsin-ing the Practical Value of a Proposed Nethod of determin-ing the 3fineral Strength of Soils by means of Water Culture. By G. A. Hight . . 156 Colley (R.). On a case of Work produced by the Electric Current -. 160 13 er trand (A.). Electro-deposition of Aluminium Magnesium Cadmium Bismuth Antimony and Palladium . . . . . . . 161 Simon (E.). Ratio of the two SpecificHeats of a Gas . . . . 162 Atomic Weights and Tensims of Vaponrs . . . . 162 Tliomsen (J.). A pretended relation between the Mechanical Equivalent of Heat and the Molecular Weights . . . . . . . . 164 Mendelejeff (D.) and V. Hemilian. Compressibility of Gases at Pres- sures less than One Atmosphere .. . . . . . 164 Bruhl (J.W.). Determination of Vapour-densities . . . . . 165 Kommrath (H.). Chemical Affinity . . . . . . . . 165 Chevreul (E.). Capillary Affinity . . . . . . . . 166 Coquillon (J.J.). The Limits between whiclt Fire-damp can Explode ; and some New Properties of Palladium . . . . . . . 166 Inoygarzic Chemistry. Lelimann (A.). Note on Ultramarine . . . . . . . . 16'7 Passbender (R.). Some Double Salts of Calcium Sulphate . . . 167 Lecoq deBoisbaudran. Reactionsof Gallium . . . . . 167 Friedel (C.) and J. GuBrin. Titanium Compounds . . . . . 168 S key (W.). Evolution of Antimony from SLibnite . . . . . 174 Godeffroy (R.). Silicotungstates of Cmiuin and Ruhidium . . . 175 V1.-Observations on Fluid Cavities by Walter Noel Hartley .. 241 VI1.-On Potassium Tri-iodide by George Stillingf leet Johnson Daniel1 Scholar of Xing’s College London . . 249 VII1.-Researches on Colein by A. H. Church . . 253 1X.-On some Derivatives of Dithymyl-trichlorethane by Dr. Emil Jager . . 262 Heumann (Karl). Theory of Luminous Flames. . . . . . 265 Tollens (B.). Specific Rotatory Power of Glucose . . . . . 265 aarey-Lea (M.). Sensitiveness of Silver Bromide to the Green Rays a8 modified by other substances . . . . . . . . . 266 Fleming (A.). Polarisation of Electrodes in Water free from Air . . 266 Pettersson (Otto). Molecular Volumes of Sulphates and Selenates . . 267 Engler ((2.). An Tmprovement of Hofmann’s Vapour-density Apparatus 269 Leu b e (W.).Employment of Compressed Air in filtering Solutions. . . 270 Tollens (B.). Lecture Experiments :-1. Decomposit.ion of Glass by Boiling Water. 2. Demonstration of the presence of Alcohol in Beer or Wine. 3. Ascent of Water caused by Spontaneous Evaporation . . . . 270 Inorgamic Chemistry. ;;3 c ho big (Ern s t). Purification of Hydrogen Gas fop Analytical Pu~poses . 271 Yadiiii ((3.). Preparation of Iodic Acid . . . . . . . 271 Sansoni (M.) and G.Capellini. Precipitated Sulphur . . . . 272 Naumann (A.). Behaviour of Bromine and Sulphur Bromide to Hydrogen Sulphide . . . . . . . . . . . . 272 Hampe (W.). On Boron . . . . . . . . . . 273 Chambon (E.). Phosphorus Oxybromochloride . . . . . . a74 Geutlier (A.). On the Constitution of Phosphorus Bromochlorides and on “ Molecular Compounds ” .. . . . . . . . 274 Ponndnrf (A. I,.). Hypophosphorous Acid. . . . . . . 275 Qe ut h er (A.) . Constitution of Phosphorms and Hypophosphorous Acids . 2’76 Itammelsberg ((3.). Composition of the Phosphites . . . . 277 C!Iiiappe (P.) and 0. Malissi. Preparation of the Iodides of Potassium and Sodium and of Potassium Bromide . . . . . . . 277 B e r t helo t (M.). Potassium Thiosulphate .......278 Stahlschmidt (C.). Chemical Constitution of Chloride of Lime ...279 Leeds (A .R.). Zinc Hydride .Reduction of Silver Nitrate by Hydrogen .282 Gramp (F.). Action of Nitric Acid on Mercuric Sulphide ....282 Rammelsberg (C.). .Atomic Weights of the Metals of the Cerium Group .282 Bertrand (A.).Solubility of Lead Carbonate in Ammonium Butyrate .283 Thurach (Hans) .Preparation of Pure Bismuth and of Bismuth Com- pounds ... .........283 Neville (R.H.C.). A Compound of Chromium and Arsenic ...283 Soldaini (A.). Method of preparing Ferric and Cupric Oxides from the Sulphates so as not to obtain Basic Sulphates ......283 Mineralogical Chemistry . Cloud (J .C.). Atacamite ..........284 D a bney (C .W.). Cinnabar from Oregon . .....284 Typke (P .C.W.). A new Nickel Mineral from New Caled onia ...285 Harrington (B .J.). Pyrrhotite from Elizabethan Ontario ....285 Thurach (Hans) .On Substances which accompany Molybdenum-glance .285 Brush ((3.J.). Durangite ..........286 Hawes (G .W.). The Rocks of the "Chloritic Formation" on the western border of the New Haven Region .........286 Rchulze (E.).Analysis of the.Ash of Lignite ......287 Smith (J .L.). Gas-wells in Pennsylvania .......287 Boudier (M.). Foreign Bodies in Snow .......288 Smith (J .L.). Carbon-compounds in Meteorites ......288 Wright (A .W.). The Gases contained in Meteorites .....289 Shepard (C .U.). The Meteoric Stone of Waconda .....290 Organic Chemistry . ron Pieverling (L.). Selenium-compounds of Ethyl .....290 Barth (M.). Action of Bromine on Sodium Ethylate .....290 Klien ((3.). Action of Sodium Ethylate on Trichlomcetic Acid ...291 Elien (G.). Preparation of Monochlorodiethoxylethane ....291 Wurtz (A.). A Polymeride of Ethylene Oxide .. ...291 Laufer (E.). Epichlorhydrin .........291 Chambon (E.).Action of Ethoxyl-compounds of Phosphorus on Phosphorus Chlorides and Phosphorous Acid ........292 Balbino (L.). Inactive Fermentation Amylic Alcohol .....292 Leitzenmayer (0.). A correction relating to the preparation of Glycol .293 Krusemann (H.D.). Reduction of Levulose ......293 Muntz (A.) and E.Aubin .Optical Properties of Mannite ....294 Baily (W.). Optical Properties of Starch .......294 grey (0.). Chlorinated Acetals and some Derivatives .....295 Taubert (A.). Reactions of Acrolein Hydrochloride .....295 Meissner (F.). Polybasic Compounds of the Acids of Nitrogen ...296 Geuther (A.). Decomposition of Phosphorus-compounds ....296 Werner (H.). Action of various bodies on Nitroethane ....297 Backunts (H.).Action of Chlorine on Acetonitril .....297 Bac kun t s (H.) and R .0t t o.Action of Alkalis on the Chloriiiated Aceto- nitrils .............297 Backunts (H.) and R.Otto.a-Monochloropropionitril ....297 Backunts (H.) and R .Otto.Constitution of Dichloropropionitril ..298 A t t er b erg (A.). On the Ferrocyanides of Wyrouboff .....298 Jager (J.H.). Behaviour of Melam to Sulphuric Acid .....298 Nencki (M.). Constitution of Guaiiamine and Cyanuric Acid ...299 W y 8s ((2.).Glyoxaline...........299 Ruoff (G.). Results of an Exhaustive Chlorination of Aromatic Substances .299 CONTENTS. 111 PAUE Gessiier (33.). The Exhaustivc ddini of Bromine on aome Aromatic Bodies . . . . . . . . . . . . . 300 Ladenburg (A).Condensation in the Ortho-group . . . . . 302 6 c11i 11 e r (R.) au?t R. 0t t 0. Preparation of Benzene and Paratoluene Sulpliydrates . . . . . . . . . . . . 306 Schi ller (F.) and R. 0t t 0. Formation of Benzene and Paratoluene Disulphidcs . . . . . . . . . . . . 306 Gabriel (S.). Todo-:mcl Bromazacoiizpounds of Benzene . -. . 307 6iiej-er (11.). On tlie Yht1i:ilin and Yhthalidein of Phenol . . . 307 R e i c 111 (C.) . Soinc New Phenol-colours . . . . . . . 310 Scurati-Manzoni (G.). The Action of some Reagents on the principal 0rg:tiiic Colouring-matters . . . . . . . . . 310 rail Be ii L’ s s e (J.J.). Action of Silrer Nitrite on Benzyl Iodide . . . 310 x ail Re n e s s e (J. J.). Action of Potassium Cyanide on the Isomeric Ortho- nitronietabroniobenzoic Acids .. . . . . . . 310 Miohaelis (A.). Aromatic Arsenic-coml~ouiicls . . . . . 311 Schiller (R.) and R. Otto. Kew Method of Preparing Benzenesulphinic ilnd Toluencsulphinic Acids . . . . . . . . . 312 Pa uly (C.). Beiizenedisulphinic Bcid . . . . . . . . 312 Piccnrd (J.) and A. Huinbert. Resorciiidisulphonic Acid . . . . 31%Gijt iig (C.). Ethyl-coinpounds of Salicylic Acid . . .. . . 313 Suliiff (R.). A series of Compounds derived from Aldehyde-ammonia . . 313 Hepp (E.). Some Aldeliycle-compounds . . . . . . 314 Lippinann (E.) and J. Hawliczek Artificid Oil of bitter Almonds. . 315 Lippiiiaiiii (2.)aid J. Hawliczek. JSitrobenzoyl . . . . . 315 Gessncr (E.). On the Naphthalenesulphonic Acids . . . . . 315 l€ausmaiiii (0.).Some Derivatives of a-and ,&Naplithoic Acid .. . 31’7 Emiiierliiig (A.) and C. Engler Spthesis of Indigo-blue . . . 321 Englc~r((2.). Preparation of Indol . . . . . . . . 321 Eiigler (C.) and Janeclie. Properties of Iiidol . . . . . . 322 15’ur t z (A.) Rvsaniliiie and Fuclisine . . . . . . . 322 I)]*ap cr (J.C.). Effect of Temperature on the Power of Solutions of Quinine to Rotate Polarisecl Light and Suggestions regarding the Preparation to be used vheii Quinine is ernplojecl as a Medicine . . . . . 322 Kopp (A ). Transforniation of the Three Bromocinchonines into the corre- sponding Ox-jbases . . . . . . . . . . . 353 Bpugnatolli (T.) aiicl E. Zenoni. On an Alkalojid found in Damaged Turkey-corn nnd in Nilclewed Maize-bread . . . . . 323 Hardy (E.).Jnboraiicli (Pilocarps pitmatzts) . . . . . . 324 van Gelclern (€1.). A Substance in Ueerresenibling Colchicine . . . 325 Bizio (G.). Gelatin coilsidered as a Reducing Agent . . . . 325 Citzencuve (P.). Researches on €€Ematin . . . . . . . 326 cle Lucn (S.). Essence of Achillea agerattm. . . . . . 326 Y. Gerichten (E.). Apiol . . . . . . . . . . 326 Plzysiological Chemistry. P flugc 1’ (Z) lnflueiice of Temperature on tlie Respiration of Cold-blooded dizinials . . . . . . . . . . . . . 327 Sc1ia.a YZ (Hugo). Relation between Tissue-iiietamoi.~hosiR and Body-tcmpwature in Amphibia . . . . . . . . . . 327 c! olnsant i (Giuseppe). Influence of ttlie Surrounding Temperature on tlie Tissue-metamorphosis of Warm-blooded Animals .. . . . 327 Colasaiiti (Guiseppe). A Contribution to the Theory of Fever . . 328 S c 11r o cl t (M.) . Researches on the Bones of a Carnivorous Animal . . 328 Picart1 (I?.). Urea in tlie Blood . . . * ..... 339 Floyd (2’. B.). Clieiriical Charactcr of the Pigment of the Negro-skin . . 329 Yalkowski (K.). Phenol-forming Substance in Huniaii Urine . . . 330 Pecile (Doincnico). Guaniizeiii Pigs’ Urine . . . . . . 530 CONTENTS. v Manganese Bronze . . . . . . . . . . . . 384 van Slooten (W.). Ash of Hard Carbon from Coal-gas Retorts . . . 335 Paterson ((3.). Compositionof anIronDeposit . . . . . . 355 Graham (A. McD.). Effect of Aluminium Sulphate on Sewage . . . 355 Ballard. Experiments on the Alcohol from Barbary Figs . . . 355 Tibrans (0.).Use of Phosphoric Acid in the Manufacture of Beet-sugar . 357 Boussingault. Experinients to Demonstrate the Conversion of Sugar when added to Fermenting Must and Marc of Grapes . . . . . 358 Henniges (A.). Preparation of Anthraquinoue by the action of Chloride of Lime Solution and a Metallic Salt on Anthracene . . . . . 360 Abadie (A.). Black-blue Colour for Paper . . . . . . . 361 Rapid Destruction of Linen Cloths . . . . . . . . 361 Causes and prevention of Stains Spots and other defects in Dyed Cloths . 362 The Solution of Caoutchouc . . . . . . . . . . 363 Adlung (M.). The present state of the Rice-starch Manufacture . . . 363 Jobst (J.). Coto'in . . . . . . . . . . . 480 Jobst (J.) Coto-barks and their Crystalline Constituents .. . . 480 Lang (J.). Deriratives of the Bile-acids . . . . . . . 481 Physiological Ch.ernistry . Pfluger (E.). Influence of Respiration on the Metamorphosis of Tissue . 482 Finkler Dittmar and Ernst Oertmann. Influence of Respiration on the Metamorphosis or"Tissue . . . . . . . . . 482 Fink ler D it tma r. Isopepsin . . . . . . . . . 483 Schmidt (A). Experiments on the Coagulation of Fibrin . . . . 483 Wolffberg (S.). Origin and Accumulation of Glycogen in the Animal Organism . . . . . . . . . . . . 484 Bernard (C.). Critical Experiments on tlieForniation of Sugar in the Blood 485 Picard (P.). Urea in the Blood . . . . . . . . . 486 Banmann (E.) and E. Herter. BehaTiour of Phenols in the Animal Body 486 v. den Felden (R.) and E.Baumann. Behaviour of Terpenes in the Organism . . . . . . . . . . . . . 487 Felt z (V.) and E. Rit ter. Action of Fuclisine introduced into the Stomach and the Blood . . . . . . . . . . . . 487 Chemistry of Vegetable Physiology and Agriculture. Wittstein (G. C.). Examination of the Sunflowey . . . . 487 Pierre (I.). Sugar in the Leaves of Beet . . . . . . . 487 Wittstein (U.C.). Ash of Euphorbia anzygdalokles and of IIernziaria glabya . . . . . . . . . . . . . 487 Kosmann (C.). Study of the Ferments containd in Plants . . . 488 Analytical Chemistry. Chapman (E. J.). Blowpipc Reactions . . . . . . . 489 D i b bit s (H. C.). Decomposition of some Ammonium-salts by Potassium- and Sodium-salts . . . . . . . . . 490 Corue (M.).New Reaction of Iodides and Iodates .. . . . 491 Brugelmann (G.). Estimation of Sulphur in Coal-gas . . . . 492 Anniversary Meeting (March 29th 1877) . . 493 Balance-sheet (March 28th 1876 to March 27th 1877) . . . 529 PAPERS READ BEFORE THE CEEMICAL SOCIETY:-X1V.-On the Estimation of Urea by means of Hypobroinite By A. DuprB Ph.D. F.R.S. . . 534 XV.-On the Determination of Urea by means of Hypobromite of Soda by Dr. Maxwell Simpson F.R.S. and C. O’Keeffe F.C.S. . . 538 XV1.-The Derivatives of Di-isobutyl (Preliminary Notice) byW. Carleton-Williams . . 541 XVI1.-Dinitroso-orcin and Dinitro-orcin by John Sten-house LL.D. F.R.S. and Charles E. Groves . . 544 XVII1.-Note on Gardenin by John Stenhouse LL.D. F.R.S. and Charles E. Groves .. 551 X1X.-Isomeric Nitroso-terpenes by William A. Tilden,D.Sc. Lond. and W. A. Shenstone F.C.S. . . 554 XX.-Preparation o€ Copper-zinc Couples by J. H. Glad-stone Ph.D. F.R.S. and Alfred Tribe P.C.S. . . 561 ABSTR.ACT8 OF PAPERS PUBLISHED IN OTHER JOURNALS :-General and Physical Ckemistry. dckroyd (W.). Selective Absorption ........ 571 Abneg (Captain). Alkaliiie Development of the Photogmphic Image . . 572 Guerout (A.). Researches on thc Coeficient of Capillarity .... 573 Thomsen (J.). Thermochemical Researches ...... 574 B att a11 die r. I)ecomljositioii of a Solution of Potassium lodide by Light . 577 Corne (J.). Action of Phosphorus on Iodates in presence of AtmosphericOxygen .............. 578 Pellet (H.). Precipitation of Phosphoric Acid by Amnioiris in presence of Lime Baryta Alumina and Ferric Oxide ......578 Campani (G.).Mutual Action of Potassium Iodide and Lead Sulphate . 579 Emerson-Reynolds (J.). Glucinum its Atomic Weight a.ndspecific Heat 579 Mineralogical Chemistry . Field (F.). Ludlamite. a New Cornish Mineral ...... 580 Laspeyres (H.). Nickel Ores ......... 581 Schrauf (A.). New Minerals from the Graphite Deposit of Mugrau. in Bohemia ............. 581 Boricky (E.). On some Minerals from the Silurian Iron-stone Deposits and the Coal-formation of Bohemia. resembling Ankerite. and on the Chemical Constitution of the Minerals classed with Ankerite ..... 581 Klein (P.). Gypsum Crystals from Sutel ....... 582 How (H.). The Stilbite (desmine) of Nova Scotia ......682 Dana (E.). Staurolite Crystals from Fannin. Georgia ..... 582 Dana (Ed.). A Twin Crystal of Pyrrhotin ....... 583 v. Zepharovich (V.). Bournonite from Waldenstein. Carinthia and from Pribrani ............. 583 v. Zepharovich (V.). Red Vanadinite from the Lead-works on the Obir. near Kappel ............ 583 v. Zepharovich (T.). Sulphur from Cianciana and Lercara. in Sicily . . 583 D oel t er (C.) . The Mineralogical Composition of the Melaphyr and Augitic Porphyry of South Tyrol .......... 584 Organic Cliemisty-y . E hard (E). Action of Chlorochromic Acid on Organic Bodies ... 584 Claesson (P.). On the Mercaptides and certain Sulphides of Ethyl . . 585 v. Pieverling (L.). Mjrioyl Alcohol and some of its Derivatives . .586 \iTiurtz (A.). Somc Derivatives of Dialdol ....... 588 Miintz (A) cnd E. Aubin . Optical Propcrties of Maniiite .... 589 Lescoeur . Purification of Valeric Acid ....... 589 Erlenmeyer (E.). Normal Valerie Acid from Normal Caproic Acid . . 590 Champion (P.) and H. Pellct . Nitrostearic Acid ..... 590 Conrad (M.) xnd W. R . Hodgliinson . R-cw Method of Sjntliesis of Aromatised Fatty Acids .......... 590 Bottinger (C). ‘11k Acids C,H,O ........ 590 Pleischcr [E.). Citric Acid .......... 591 Erlenmeyer (E.). Simple nIcthocl of prepirii~gMetallic Cjanider . . 591 He in t z (\I-.).I)eli~ilrotriacctoi:amilie ........ 591 Heintz (W.). A Sixth Acetone-base ........ 592 Heintz (W.). Alcoholic Bases formed bj the IIjdrogeiiisation of Di-ad Ti4-acet onaniine ...........592 Heintz (W.). A New Platinum-salt containing two Ammonium-bases . . 592 Papasogli (G). Researches on Xssence of Turpentine ..... 592 Paternb (E.) and P. Spica. Cumol ........ 593 v. Zepb arovich . Crystallo-optical Investigation of certain Caiiiphor Deri-vatives ............. 594 Laubenhcimer (A.). Ortlio-dinitro-coml~oundu ...... 594 Limpricht (H.). Benzene-sulphonic Acid aiicl its Derivatives ... 595 Mazzara ((3.). Nitro-derivatives of Salicylic Alclehjde .... 59’7 Liebermaiiii (C.). Researches on the Naphthalene Group .... 597 Lieberniunn (C.). Studies in the Anthrnquinone Group .... 609 Eretzsch mar (A.). Action of Acetyl Chloride and of Benzoyl Chloride on certain Amides ........... 614 Bernthseii (A.). Tliiamides of Monobasic Organic Acids ....616 Fischer (E.). Aromatic Hydrazin-compounds ...... 619 Kirchmann (W.). Preparation and Estiniation of Amines .... 620 Xtard (A.). Preparation of Alkaline Nitrites ......685 Godeffroy (R.). Caesium and Rubidium Compounds . . . . . 685 Stein (W.). Ultramarine . . . . . . . . . . 666 Yhilipp (T.). Constitut. ion of LTltramarine .......68G Fremy (E.). Irisation of Glass . . . . . . 687 Gtlutzel (E.). The Oxide of Titanium obtained by the Solution of Titanium in Acids ;and some new Titanium Compounds ..... 688 Fre y (E.). Preparation of Earth-metals ......689 Eder (T.M.). Double HaloPd Salts of Cadmium ......689 Millot .A Crystallised Dicalcric Phosphate . . . . . . . 689 Friedel and Sarasin .Crystailine Phosphate and Areenate of Copper .690 Mu ir (M.M.P.).Action of Water and of Saline Solutions npon Lead .690 St olba (F.).Silicofluorides of Iron and Cobalt . . . . . 690 Stierlin.Sublimed Moljbdic Acid as an Object for the Polarising Micro- scope .............690 itirneralogical Chemistry. G ei n it z (F.E.). Mineral Pseudomorphs ....... 601 Seyms.The relation of Franklinite to the Spinel Group . . . . 701 A new Locality of Heavy Spar . . . . . . . . . '702 Brezina (A.). Strueverite . . . . . . . . . . '702 Wright (A.W.). Gases enclosed in Meteorites ......702 Planehard (E.). Formation of Natural Sulphuretted Waters . . . 704 Organic Chemistry . 9 ilvestri (0.). Hydrocarbons of the Paraffin Series found in a Lava from Etna .. . . . . . . . . . . . 704 N en b a ue r (C.) .Preparation of Chemically Pure Grape-sugar ...705 Salomon (G.). Occurrence of Grape-sugar in Alcohol ....705 Miguel (P.). Silicon Sulphocyanate . . . . . . . 705 Merz (V.) and G-.Ruoff.Action of Aromatic Substances on excess of Iodine Chloride . . . . . . . . . . . 706 Xeilstein (F.)and A .Kurbatow.Chlorinated Derivatives of Benzene .'706 Pateriid (E.) and P.Spica.Propgl-benzene and Propyl.pheno1 ...707 Ihle (R.). Cresols and Cresotic Acids . . . . . . . . 708 'rieniann (F.) and H.Herzfeld .Synthesis of Coumarin from Salicylic Aldehyde . . . . . . . . . . . . 708 Mi g u el (P.) .Action of Alcohols of the Fatty Series upon Benzoyl-sulpho- carbimide . . . . . . . . . . . . 709 Klin ger (H.).Action of Phosphorus Pentachloride on Phenyl- and Para-tolyl-oxamethane . . . . . . . . . . . 710 (2u ar e sc h i.Preliminary Note on Naphthalene Derivatives . . . . 712 Jorgerisen (S.M.). Herapathite and similar Periodides . . . . 713 Kirchmann (W.). Improved Method of obtaining Nicotine Conine and Sparteine . . . . . . . . . . . . 716 Mopp (A.). On the so-called Resina Guaiaci aroinatica v.odfxata ..716 v .Gorup-Besanez (E.). Ostruthin . . . . . . . . 717 Stenhouse (J.) and C.E.Grov es.Picrorocellin . . . . . 718 Yaternb (E.) and A .Oglialoro.Picrotoxin . . . . . . 719 Perier .The Insoluble Matter from Opium Extract . . . . . 720 Constituents of Tolu Balsam . . . . . . . . . . 720 Tltresh (J.C.). Capsaicin . . . . . . . . . . 720 G uichard .Xanthiunz bpinosurn .. . . . . . . . 720 J ohansen (E.). Chemi,itry of the Barks of the Oak Willow and Elm .720 Woiff (R.). Deroniposition of Ctintharidin in Cantharides . . . . 722 Se h u t z e n b e r g er (P.).New Derivative of Albuniino'id Substances ..725 CONTENTS. 111 Schmidt (A.). Coagulation of Fibrin . . . . . . . 726 H am m ar s t e n (01of) . Contributions to the Theory of the Coagulation of Fibrin . . . . . . . . . . . 726 v. Mering. Formation of Glyro en in the Liver . . . . . 728 Weiske (H.). Composition of 8orn and of Cmy-fish Shells . . . . 728 Selmi (F.). Some Volatile Products of the Putrefaction of Brain-matter . 730 Mu n k (Ira). On the Form of Combination of Urea in the Liver . . . 730 Haus (H.).A Levorotatory Substance in Normal Urine . . . . 731 Bill (J. H.). Double Decomposition of Potassium Bromide and Sodiuni Chloride in the Animal Organism . . . . . . . . 731 G e dl (M.). Influence of Salicylic Acid and Sodium Salicylate on Bodily Tem- perature . . . . . . . . . . . . . 732 Chemistry of Yegetable Physiology and Agriculture. Briosi (CX.). The Function of Chlorophyll in the Vine . . . . 732 Jellett (J. H.). Change of Composition in Potatoes during Disease . . 732 V o e 1 c k e r (A.) . Phosphatic Guanos . . . . . . .733 B o eh m (5.). The Plant-nourishing V alue of CRlcium Salts . . . . 735 B o u s s in g au 1 t. Influence of Soil on the Nitrification of Azotised Organic Substances in Manures . . . . . . . . . . 735 AaalyticuI Chemist?y.Wsring ton (R.). Determination of Nitric Acid by Indigo . . . 735 Berg (Paul). Estimation of Boric Acid by Baryta . . . . . 736 B ru g e 1ma nn ((3.). Volumetric Estimation of Sulphnric Acid by Barium Chloride Solution in Acid Liquids . . . .... 737 tained in Quantitative Analyses . . . . . . . . /3/Jean (F.). Determination of Alkaline Sulphates . . . 738 nium Molybdnte . . . . . . . . . . . C h ampi o n and P e 11 e t. Volumetric Estimation of Arsenic. . . . 739 as for the Estimation of Sulphur in Coal-gas . . . . . . 739B r ii gel m a n n ((3.). Volumetric Estimation of Arsenic Acid and Phosphoric Acid by Uraniuiri Solution . . . . . . . . . '741 Brugelmann ((3.). Estimation of Sulphur in Coal-gas . . . 741 €7 ino t (L.) and A.Bert rand. Estimation of Carbon Disulphicie in Alkaline Sulphocarbonates . . . . . . . . . . . 744 Per r o t (E.). Estimation of Sugar by Standard golutions . . . . 7'4 4 J,owenthal (J.). Estimation of Tannin . . . . . . . 745 K o p p en h a u e r (W.F.). Volumetric Estiniation of Phenol . . . 746 Guyot (P.) and R. Bidaux. Detection of Rosolic Acid in Presence of Fuchsine. . . . . . . . . . . . 747 B en n e t t (J.). New Tests for Anihracene . . . . . . . 748 Hager (H.). Testing of Quinine-salts for Strychnine and Morphine . . 748 Pape (0.). Some Reactions of Vegetable Poisons . . . . . 749 B 6 champ (A.) . Detection of Puchsine and other Colouring Matters . . 749 Fordos (a. M.). Detection of Fuchsine in Wines . . . . . 750 G a u t i er (A.).Dilution of Wines-I nfluence of Plastering Fining Brandy- ing &c. on the Weight of the Extract . . . . . . . '750 Hilger. Identification of Foreign Colouring-matters in Red Wines . . 751 Magnier de la Source (L.). Determination of the Residue of Wine. . 752 Strohl. Detection of Mineral Acids in Vinegar . . . . . . 752 Lev e s ie (0.). Composition of Coffees . . . . . . . . 752 Franz (A.). Testing Roasted Coffee for Chicory . . . . . . '752 Vohl (H.). Detection of Foreign Mineral Substances in Flour . . . 753 H u s son. Some Reactions of Hemoglobin and its Derivatives . . . 753 8chwarz (V.). Testing of Aqueous Liquids for Blood . . . . . 754 Analysis of Soap . . . . . . . . . . . . 755 Technical Chemistry. Rot t ier and Waldach.Photography-Researches on Iron Developers . 75 Ca p it a in e (F.). Preparation of Soluble Glass from Fossil meal . . . . 75 4 Grot he (H.). Use of Soluble Glass in the Textile Industry . . . . '757 Extraction of Sulphur . . . . . . . . . . . 759 E r 1 e nm eyer (E.). Extraction of the so-called "Soluble Phosphoric Acid " from Superphosphates . . . . . . . . . . 759 Gautier (4.)Dephosphorisation of Iron Ores . . . . . . 769 Blooring Slabs. . . . . . . . . . . . . 760 PAPERS READ BEFORE THE CHEXICAL SOCIETY :-PAGE ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS :-General and Physical Ohernistidy. Pictet (Raoul). Application of the Mechanical Theory of Heat to the Study of Volatile Liquids. Simple relations between the Latent Heats CONTEXTS.PAQR ‘li*evc and Ilnrnssicr. Action or ilcids on Troii . . . . . i75 Kimball (A4. S.). Some Clinngca in the 1’1iJsical I’roperties of Stccl 1)i.o- dacccl by Teruperiiig . . . . . . . . . 175 illheralogica1 Cliemistry. Gert t h (F.). Somc American TTacadium Xinerals . . . . . 175 Phipson (T. L.). ‘The Tripolite of Bnrb;docls . . . . . . 177 Bertrancl (E,). Crystalline form of illeliiiopl1ane . . . . . 178 Tscherinak ((3.). On the Foriiiatioii of’ Meteorites arid OH T’olcaiiic Agency . . . . . . . . . . . . . 178 Maskelyne (X. S.). TlicPittecl Surface of Metcoi*ites . . . . 18J Thorpe (T. E.). C’ontributioiis to the 11istoi-j- of the Old Sulphur IVell Harrogate . . . . . . . . . . . 181 Oi-ga?iic ClleiizL’striy.Behrcnd (P.). Actioii of Sulph[tryl Cl~loricleon Alcoliols . . . . 182 Cahours (A.) and E. Demarqap. Rccipocal Actio:i of Odic Acid and tlie 3Iontlto:nic Slooliola ...... .. 183 Kin gz e t t (C 11. T.). Limited OnicltLtioii of Essential Oils ad Pre1iiniiiai.y Rqort on the Ethers . . . . . . . . . . 183 Kriiger (F.). Isomeric Suiphine-c~iupoiiiids . . . . . 186 Curie (J.)and A. nlillctt. Culiibinatioli of’ Cliloral ~11‘1 Acctyl Chloride . 188 Michael (L4.). Action of I’ot‘issiuiii Sdi)li~drste on Clilcral Hydrate . 188 Dittmar (W.). Note on RebJiil’s pIToriii:il l’yrotartaric Acid . . . 188 Losseii (W.) slid J. Zaiiiii. Etlicrs of’ IIydroriLiiiic Acids Etliyl1i)di-oxyl- . aniine arid Blct~~lli~drosyla~iiiii~ .. . . . . . 188 WTrouboff (11.). Researches on the k’errocpaiiitles . . . . . 190 TY. R. 13. I’seu losulphocyanogon . . . . . . . . . 3 93 Baeyev (A,). The Coinpoiids of Plitlialic Acid nitli the Plienols. Part I 193 Grim aux (E.). Tere1)htlialic dldeh?;ile . . . . . . . 206 Baumauii (E ). a-Cres?lsulphuric Acid . . . . . . . 206 Ans chutz (R.) aiidQ. Hclinltz. Piew Mode of Formation of Azobenzcne . 206 TC’acliendorff ((2.). Halo d Derivatives of the Nitrotoluenes . . . 207 Clitre (P. ‘l‘.). Two Kew Modificatioiis of niiiit~.oiiaplitlialene . . . 207 Cl& ve (P. T.). Xitro-and dinido-iiaplithj 1sull)honic Acids aiicl their Deri-vatives . . . . . . . . . . . . . 208 Pei-kiii (W. H.). Eote on some Krn Deriiatires of Anthracene .. 209 Roseiist iehl (A.).Simultaneous formation of two ‘I’riox~antiir~iquirioiies axid Synthesis of a new IsomeriJe of Purpuriii . . . . . 209 Anscllutz (R.) and G. Schultz. Action of Quick-lime 011 Pheaantlirei~e-quiiioiic . . . . . . . . . . . . . 210 Anschutz (R) and G. Scliultz. ~iti,oplieiiantllreneyuiiioiie . . . 210 Jijrgeiiseii (S. 31.). Herapthite and similar Ad Periodides . . . 2 10 Tappciner (€1 ). Oiidation of Cliolic Acid vitli Potassium Biuliromate ad k3ulphuric Acid. . . . . . . . . . . 213 Fa ss b e ii de r (R.) The Fluorescent Body in Afrop Belladomta . . 213 . Van’t Hoff (J.I€.). StJmx . . . . . . . . 214 Mitchell (I€. W.).Kote 011 Litmus . . . . . . . . 214 Pliysiologicnl Cliemistiy. Bunge (G.). Quantitative Aiiuljsis ofBloocl .. . . . 215 Heiss (E.). Can Inorganic Constitueilts be witlidramin from the Bones by tlie introduction of Lactic Acid into the Iiitestiircs . . . . . 216 Tl-eislie (H.). Researchcs on the foriliation of Hippuric Acid in tlie Or-gsiiisiiis of Herbivorous*Aninials supl)liel n itli clifiercnt kinds of Fodder 21‘7 ... COKTESTS. i11 FAG E Ustimowitscli (C.). Alleged power of Glycerin to rcplace Sugar . . 22O K ultz (E.). 011 tlie liifiueiice which tjiug the Ductus chiledorht~sexerts upon the amount of‘ Glycogen in the Liver . . . . . . 221 v. Jaksch (R.). Occurrence of Nurlein in the Hornan Brain . . . 221 Laptschinsky (X) C‘liernistrj of the Crvstalliiie Lens . . . . 222 Bastian (H. (2.). The Feruientation of Urine in reference to a Coinm~uiica- 09.) tion by Pasteur .. . . . . . . . . . Clbemistry uj. TTtyef ab7e Flqsiulogy aI ~(1A 91’icidtiwe. Bert liclot (11.). ALorptioii of Free Kitrogen bj-the p~~xiiimte principles of Vegetables uiider the Influcncc. of Atniosplicric Electricity . . . 222 Stut zer (A.). Tile Mc+nmorphuses of tlie Groups COOH,C1-1.0H,CI12 and CH in the Living Plant . . . ...... 223 Peligot (E.). Action of Boric Acid and of Borates on Vqetntion . . 223 Kiilirieinann (G.). Oiyanic Constituents of U:Lrley niid Mult . . . 23 1. 130 ussingault (11.). Vcgctatim of Maize coiiiiiiciiceiliii ail Atiiio>plierefree from C’i1rboih R11h~dr~de . . . . . . . . . 234 Bro iv ri (\IT. 8.). Aid! sis of the -4sL of the G rouiiil Pcn (-iiachis hypga?n) as cultivated in Virginia .. . . . . . . . . 225 3out in. Coinparatire -&iialyscs of Roots of l*iiics. . . . . . 226 FitL (A). Alcoliolic Fer;!wiitatioii . . . . . . . . 236 . Fitz (A.). Fcriiiiw.aiioii of Gl~~~c~riu . . .. . . . . 226 Amlyticcc1 Clieft,,is tmj. Pellet (H.). Sevcriil M(~thods of Clleinical Analysis . . . . . 226 Kopfer (F.). Uae of 1’lati:ium lii the ultimate Aiialjsis of Carbon Com-poullas . . . . . . . . . . . . . 233 Champion (P.) and H. Pellet. Estimation of Nitrogen TetroxiJe in or- gaiiic Substances. Clieinical Composition of r:wious Gull-cottons . . 228 Bremy (E.). A general Method of Anal>& of Vegetable Tisaues. . . 229 Dittmai. (W.). Proximate Coinpositioii of Coal Gas . . . . . 230 . Wanklyn (J. A,).Detection of Aluiri in Bread niid F~JLI~* . . . 231 Cameron (C. A). Estiiiiation of Colour iii JTater . . . . . 231 Brown (J. T.). Anthraceiie Testiiig . . . . . . . . 232 Pattinson (T.). An Abnormal Sauiple of Sew Milk . . . . . 232 prl LI te r (J.). Ansly& of Butter . . . . . . . . . 233 Duprb (,k.j. lletectioii of Coloui=iiigAIattei-s in IViiie . . . . . 234 Uouilhoii (E.). Detection of FLucli~ine in Winc . . . . . . 23% Teclmical ClwmIstry. I’_eligot (Z.). Coniposition of Ancient Glass mLlCrjstd . . . . 232 hcrii (S.). Yrcwiice of Copper in Cast-iron . . . . . . . 235 Crenshaw (9.D.). Stove-pipe Deposit . . . . . . . 235 Kern (X.). Preparation of some Colom.ed Firm used in Fyrotecliiiy . . 235 Keates (T. W.). Mode of Generatiug Sulphurous Acid as a Disinfectant .236 Fis c her (I?.). On the Temperature required in Leblanc’s Soda-process and the Composition of the Gases evolred . . . . . . . 237 Alkali from Sen-meed . . . . . . . . . . . 237 Tlioiiison (IT.). Action of diffeiwit Oils upon Copper . . . . 237 Manufacture of Large Csstiiigs of Kichel iiud Cobalt . . . . . 238 V~PP mann (F.). Anthraceiie Procluction ... . * . 239 Correction relative to a Communiration 011 l’anification in tlie 8 ace (&I.). United States and tlie Properties of the Hop as it. Ferment . . . 244.0 Tollens (B.). I~ijuriousCliaracter ot runny Objects made of India Xubber 2.10 TVolffhugel. Effect of Sewers Sc. 011 the PuritF of the Soil . . . 210 CONTENTS. PAPERS READ BEFORE THE CHEMICAL SOCIETY :-PAQB ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNAI8:-General and Physical Chemistry... CONTENTS. PAGE ... iV CONTENTS. PAGE Morizzis (A.). The Natural Poison of the Human Corpse . . . 331 Vogel (H. W.). Spectroscopg of the Colouring Matters of Blood . . 331 Chemistry of Vegetable Physiology and Agriculture. Ri schawi (L.). Experiments on the Respiration of plants . . . . 331 M ay c r (A.). Dependence of Plant-respiration upon Temperature . . 334 Stutzer (H.). Action of Carbonic Oxide on Plants . . . . . 334 Fliche (P.) and L. Grancleau. Composition of Leares . . . . 334 Corenwinder. Presence of Sugar in the leaves of Beets . . . . 336 Wil son (P.B.). Silica in Grasses .. . . . . . . 336 Krusc. Analysis of roots of Pdix mas. . . . . . . . 336 Keller (J. L.). Chemical Examination of Piih-ling (L?/coprrlons6ZicZuni) . 337 v. Losecke-Hildbul*ghausen. Composition of Eat,able MushPooms . . 338 Amdyticnl Clze?nistfy. Stockmann (C.) Solution of Silicates . . . . . . . 3 40 Jacquemin (E.). Application of tlie Fcrrosopyrogallic Reagent to the Esti- mation of Bicarbonates in Wxtei. . . . . . . . 340 Wriglitson (F.). Quantitative Estimation of Metals bp Electroljsis . . 340 Kriiger (F.). Fluorcscein as an Indicator in Titration. . . . 341 Rosenfeld (Max.). Detection of Free Sulphur . . . . . 341 Casarnajor (P.). Estimation of Potassiiini as Acid Tartrate . . . 341 Bernard (C.) and L. Elirmann. On x Quick Method of Estimating Lime in presence of Maguesia and on tlie Application of Magiiesia to the Defecation of Sugar-liquors .. . . . . . . . 343 Jungcli (M.). Precipitation of Iron and Aluiiiina by Sodium Acetate . . 344 Al.essaiidri (L.) and C. Conti. Method fur detrcting tlie Adulteration of Lead Iodide . . . . . . . . . . . . 344 Pollacci. Phosphorus as a Test for Iodates. . . . . . . 344 Lepage. Method of Testing for Impurities in Potassiuin Iodide . . . 344 Jenkins (E. H.). Effect of Silicic Acid upon the Estimatjoii of Pho-phoric Acid by Ammonium Xolybdate . . . . . . . 344 Bohannon (R. D.) Zinc for AnalJtical Usc . . . . . . 34.5 Gawalorski (A.). Recovery of Ui-aiiinm Heaiclues . . . . . :545 Soldaini (G.A.). A New Reagent for the Lletection and Estiiiiatiori of Glucose .. . . . . . . . . . . . 345 Salleron (M.). Estimation of Alcohol by the Temperature of Ebullition . 343 Dott (D. B.). Davy’s Test for the purity of Cliloroform . . . . 346 Versmann (F.). Anthrileei1e Testing . . . . . . . . 347 Caspers (C.). Anthi.acenc Testing . ... 347 Prehault (A). Action of Iodine on Carininic Acid and on Haematin . . 347 Piiichoii (A.). Testing of Oils . . . . . . . . 348 Godeffroy (R.). Reagents for Aikalo’id Separations . . . . . 348 Pattinson and Stead. Estimation of Earleg-in Oatmeal . . . . 348 Estcourt (C.). Bntter Analysis . . . . . . . . . 348 Scutari-M anzoni (G.). liyposulpliita of Sodium (SO,Na,) as a Reagent in the Analysis of the Colouring Matters of Dyed Stuffs . . .349 Bayer (K. (3.). Estimation of Wool in Yarn . . . . . . 349 Technical Chemistry . Jurisch (K.).Deacon’s Process for the Preparation of Chlorine . . . 350 Extraction of Silver by means of Calcium Thiosulphate . . . . . 352 Nic t z k i (R.). Presence of Bulphocyanates in Cominercial Soda . . . 353 Alum-powder . . . . . . . . . . . . . 353 Bischof (0.).So-called Plastic Dinas-crjetitl . . . . . . 354 PAGE C 0 NT E NT S. .............................. PAPERS READ BEFORE THE CHEMICAL SOCIETY :-PAGE X.-On High Melting Points with special reference to those of Metallic Salts. Parts I1 and 111 by Thomas Carnelley D. Sc. . 365 XI.-On the Formation of Coummrin and of Cinnamic and other analogous Acids from the Aromatic Aldehydes by W.H. Perkin F.R.S. . 388 XI1.-Pignaentum 17,igrum the Black Colouring Matter of Hair and Feathers by W. R. Hodgkinson and H. C. Sorby . 427 XII1.-On the Corrosion of Lead by Water by G. Bischof . 488 . ABSTRACTS OE PAPERS PUBLISHED IN OTHER JOURNALS :-Ge.lzerd and Physical Chemistry. Heileseii (W.). The Effect of Heat on Voltaic Circuits completed by an Electrolyte ............ 429 Kohlrauscli (F.). Electric Conducting Power of Water .... 429 Aymon n et. Relation bctwecn the Absorbing Powers of Bodies for Heat and their Clieniical Equivalents ......... 4.30 Miiller (F. G. C.). Rise of Temperature occiisioned by passing Steam into Saline Solutions and on the Ten perature of the Vapours from Saline Solutions .. . . . . . . . . . ,-430 Miiller (F.G. C.). Specific Weights of Gases ...... 431 Troost (L.) and P. Hautefcuille. On theErrors resulting from the dppli- cation of the Law of Mixture of Vapours in the Deterinination of their Density ............. 431 Aymonnet. On the Quantity of Heat Absorbed by certain Substances . 438 Horatmnnn (A). Dissociation ......... 4.33 Pfaundlcr (L.). On t,hc Soft and Semi-fluid States of Aggregation and on Regelation and Recrystallisation ........ 433 Pf aundler (L.). The Application of the Principle of Dissinrilar Molecules to the Explanation of the Plienolvena of Supersaturated Solutions Super- fused Bodies Spontaneous Explosions and the Gradual Crystallisation of Amorphous Bodies ........... 435 Grenfell (J.G.).On Supersaturated Saline Solutions .... 436 Petterson (0.). Molecular Volumes of Sulphates and Selenates ... 437 Meg er (Victor). Lecture Experiment to show the Increase of Keight on Burning a Taper ........... 43’7 Woliler (P.). Beliaviour of Ptrlkidium in an Alwliol Flame. ... 437 Mignon and Rouart. Note on a Manometric Apparatus .... 437 .. 11 OONTENTS. PAGE Irtorgartic Chemistry. Berth elo t (M.). Does Ozone combine with Free Nitrogen in presence of Alkalis to form Nitrites and Nitrates . . . . . . 438 Miiller (F. G. C.). Synthesis of Water. Lecture Experiment . . . 438 Heuni ann (K.). Apparatus for Demonstrating the Manufacture of Sulphuric Acid . . . . . . . . . . . . . 438 Hensgen (C.). Action of Dry Gaseous Hydrochloric Acid on Sulphates at Various Temperatures .. . . . . . . . . 439 Urbain (V.). Dissociation of Sodium Bicarbonate at 100' . . . . 439 Bevan (E.). Note on a Crystallised Compound of Salt and Water . . 440 Wurtz (A.). Composition of Certain Phosphites . . . . . . 440 D it t e (A.). Action of Calcium Sulphate on the Sulphates of the Alkalis . 440 Filsinger (F.). Preparation of Lithium Carbonate and some new Coni-pounds of Lithium from Lepidolite . . . . . . . . 441 Pi sa n i (F.) . Crystallised Barium Silicate . . . . . . . 442 Lecoq deBoisbaudran. Crystalsof Gallium . . . . . . 442 Gourgeu (A). Capacity of Saturation of Manganous Acid . . . . 442 Deville (H. Sainte-Claire). Physical and Chemical Properties of Ru-thenium . . . . . . .. . . . . 4 $3 Mheralogical Chemistry. Daub r6 e. Simultaneous formation of Zeolites (Chabasite and Christianite) under the influence of Hot Springs in the neiglibourhood of Oran Algeria 4& Roscoe (H. E.). On two new Vandium Minerals. . . . . . 4'44 Dumas (E.). Composition of "Touchstone" ...... 445 Boussingault. Crystals of Magnetic Oxide of Iron formed in roasting a Spathic Mineral . . . . . . . . . . . 446 Bis c h o f (K.). Analysis and Determination of thc fusibility of three Bavarian Felspars . . . . . . . . . . . . . 446 Meiinier (S.). Devitrification of Vitreous Rocks . . . . . . 448 Vohl (H.). Carbonic Acid springs of the Kyll-Thal in theEifel (Preliminary Notice) . . . . . . . . . . . . . 448 Finot (E.). Analysis of the Gass of the Grotta del Cane .. . . 448 Organic Chemistry. Butlerow (A,). Di-isobutylene . . . . . . . . . 448 Balbiano (S.). Action of Sodium Hydrate on inactive Fermentation Aniylic Alcohol . . . . . . . . . . . . . 449 Bert oni (G.). Preparation of Ethyl Nitrate. . . . . . . 449 Bouchardat (G.). Rotatory Power of Mannite and its Derivatives . . 449 Prunier (L.). Action of Heat on Quercite . . . . . . . 450 Lound (L.). Effects of Heat on Cane-sugar in Aqueous Solution . . . 450 li'leury (M.). Researches on the Inversion of Sugar by Acids and Salts . 451 Villiers (A.). Researches on Melezitose . . . . . . . 451 B erthelo t (G.). Remarks on the preceding Paper . . . . . 451 Boussingault (?J.). Saccharine Matter cont,ained in the petals of Flowers .432 D obroslavine (A.). Differences in the Diastatic Reactions of' Starch from diff went Sources . . . . . . . . . . . 433 A be1 (F. A.). Composition of Gun-cotton . . . . . . . 453 Salkowsky (N.). Action of Bromine on Acetone . . . . . 453 Crommydis (C. 2.). Easy Method of preparing Glycollic Acid . . . 453 Idan of f. Diethyl-methjl-acetic acid . . . . . . . . 4-54 Cloez (S.). Modifications of Ehornargaric Acid produced by Liglit and Heat 434 Schalfeieff. Cerotic Acid from Beeswax . . . . . . 454 Bottiiiger (C.). Action of Hydrocyanic Acid on Pyruvic Acid . . . 455 Bunpe (N.). Electroljsis of Aqueous Solutions of Oxalic Acid . . . 455 ... CONTENTS. 111 PAGE Zay t z eff. Action of Iodide of Ally1 and Zinc on Ethyl Oxalate ... 455 Hunaus (P.). Citric and Aconitic Acids .. . . . ..455 Maurnen6 (M.) Observations respecting a Dextrogyrate Acid in Wine .456 Vi dau (M.) .Potassium Cuprocyanide and Potassium Palladiocyanide .4?16 Miguel (P.). Stains produced by Sulphocyanic Acid . . ...457 Gtuareschi (J.). Asparagine and Aspartic Acid .... ..437 Reym an (B.). Condensation-products of the Ortho-homologues of Benzene. 459 Staedel (W.) and L. Riigheimer. Action of Ammonia on Chloracetyl-benzene . . . .. . . ... ...459 Zagoumenny (A.). Diphenylcarbinol and some of its Derivatives ..459 Zincke (Th.). Action of dilute Sulphuric Acid on Kydrobenzoi’n and Isohydrobenzok .. . . .......460 Cahours (A.). Researches on the substituted Eugenols ....460 Schiller (R.) and R.Otto. Reactions of Aromatic Disulphides ...463 Schiller (R.) and R. Otto. Action of Sulphur trioxide on Sulphydrates .463 Pauly (C.). and R. 0tto. New formations of Benzene and Toluene Dioxy- sulphides .. . . . ... . . . . .463 Schiller (R.) and R. Otto. Ethyl Benzenesulphonate . ...463 Lieberman (C.). Constitution of Oxythymoquinone .. . . .463 Michael (A.) and T. H. Norton. Triiodoresorcin ... . .463 Thorner (W.). New Derivatives of Paratolylphenyl Ketone ...464 Pischer (0.). The l’hthaleins of Tertiary Aromatic Bases . ...4<65 B r un n er (H.). Action of Nitrils on the Haloid Ethers of Renzyl ..466 Wreden (F.)and Znatowich. Action of Hydriodic Acid on Naphthalene .466 Atterberg (A.). Derivatives of a-and /3-Diliitronaphthalene . . .466 At toer b e r g(A.).The Constitution of some Derivatives of Naphthalene .467 C 1 B v e (P.) .Dichlorinated Naphthalene corresponding with Nitronaphthyl- sulphurous Acid . . ... ..... .467 B aumann (E.). Phenylsulphuric Acids .. .... . 467 Klippert (L.). Paraxylenedicarbonic Acid .. ... ..468 B o t t inger (C.). Action of Zinc-dust on the Chlorides of Sulpharabromo-benzoic A cid ..........468 Sc h ill e r (R.) and R.01t 0. Plienyl Thiobenzoate and Paratolyl Thioben- mate ...........468 Schiller (R.) . and k.0tto. Experiments for Preparing the Thio ethers of Benzenesulphonic and Paratoluenesulphonic Acids . ....469 B1 at z b o c k e r (A.) .Benzyliboxylene and Benzoylisophthalic Acid ..469 Cleve (P. T,). Nitro- and Amidonaphthylsulphurous Acids and their Deri- vatives .. . . . . .. . . .. . 4 69 Cannizzaro (S.). Methyl Santonate . . . .. . ..470 Caniiizzaro (S ).Derivatives of Santonic Acid .....470 Sestini (F.). Photosantonic Acid . ... ... .47 1 S tr uever ((3.).The Crystalline Form of some Derivatives of Santonin .472 Graenvick (E ).The Action of Chlorocarbonic Ether on Amidophenol .472 Wi llgerod t. Action of a-Dinitrochlorobenzene on Acetamide ...473 Wi 11 g er o d t. Action of a-Dinitrochlorobenzene on Carbamidc ...4.73 Ueilstein (F.) and A. Kurbatow. Chlorinated Anilines .. ..473 Biedermann (R.). Disuccinylphenylenediamine .. ...474 Grie s s. New Researches on Diazo-compounds. Constitution of Compounds of Diazobenzoic Acid . .. . ... . . ,474 Mavin6 (W.). Taxine a Poisonous Alkalo’id contained in the Leaves and Seeds of Tuzus 6accafa (L.) ..... .. .476 Masing (E.). Alkalo’ids of Celandine (Chdido&zm majiis) ...477 Liebermann (C.) and M.Waldstein. Emodin from the bark of Rhznziius-frangula ... . .. . . . . . ..477 Nietzki (R.).A new Glucosicle in the Flowers of Ckhorium I/ityBus ..477 Van’t Hoff (J.H.) The Volatile Oil from Stjrax . . ...4.78 de Montgolfier (J.). Patchouli Camphor ... . . .4.78 Cec 11. Colouring-matter of Viridic Acid .... . ..478 Hertz (I.). Shell la(. and Sarcosinic Acid . . .. . . . 473 iv CONTENTS. PAGE C 0N T.E N T S. .............................. PAGE Ir~o rganic Chemistry. CONTENTS. PAGE CONTENTS. PAPERS READ BEFORE THE CHEMICAL SOCIETY:-PAGE XX1.-On the Coal-gas of the Metropolis.By T. S. Hum-pidge . 621 XXI1.-On the Theory of the Bunsen Lamp. By T. E. T h or pe, Ph. D. F.R.S.E. 627 XXII1.-On the Influence exerted by Ammonium Sulphide in preventing the Action of various Solutions on Copper. By F. W. Shaw Student and Thomas Carnelley D.Sc. . 642 XX1V.-On certain Bismuth-compounds. By M. M. Pat tison Muir F.R,S.E. 645 XXV.-Additional Note on a Process for Estimating Bismuth Volumetrically. By At. M. Pattison Muir F.R.S.E. . 658 XXV1.-On the Solveat Action of various Saline Solutions on Lead. By M. M. Pnttison Muir F.R.S.E. . 660 XXVI1.-Nohes on Madder Colouring Matters. By E daard Schunck Ph.D. F.R.S. and Hermann Roemer Ph.D. 665 ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS General and Physical Chemistry.v. L e pp el (F.). Spectroscopic Reactions of Magnesium Salts. . . . 676 Lommel (E.). Fluorescence . . . . . . . . . 676 Fuchs (F.). Division of the Positive Metal in the Galvanic Circuit between Two Acids . . . . . . . . . . . . 677 Herwig (H.). The Movements of Electrified Mercury. -... 677 Schiel (J.). Nobili’e Rings on Gold . . . . . . . . 677 Siemens (W.). Dependence of the Electric Conductivity of Selenium 011 Heat and Light . . . . . . . . . . . 677 Elsaesser (E.). Electrolysis with Evolution of Hydrogen at both Poles . 678 Winkelmann (A.). The Specific Heat of Mercury . . . . . 678 Tollin ger. Thermal Changes accompanying the Solution of Ammonium Nitrate in Wzter . . . . . . . . . . 678 Berth e 1o t and Lou g u i n i 11 e.Thermal Researches on Citric Acid . . 680 Thorner (W.). Apparatus for Fractional Distillation in Vacuum . . 681 Bu 1 k (C.). Simple Exhausting and Compressing Air-pump . . . 681 Stein (S.). Construction of Scientific Instruments of Rock Crystal . . 682 Landolt (H.). Use of the Magic Lantern in Chemical Demonstrations . 686 Inorganic Chemistry. Markoe ((3. F. H.). New Method of Preparing Phosphoric Acid . . 683 Re m s e n (Ira). Phosphorus Oxychloride . . . . . . . 685 CONTENTS. PAQE ..* Phpiological Chemistry. PA&R Briigelmann ((3.). Purification of the Bariuni Snlphate Precipitates ob. rr Kern (5.). Estimation of Phosphorus in the Form of Ammonio-phosphorno: lybdic Salt .. . . . . . . . . . . '738 C h ampi on and I' e 11 e t. Estimation of' Phosphorus and Arsenic by Ammo- B r ii ge 1 m an n ((3.). New Method for the Gravimetric and Volumetric Esti- mation oi Phosphorus Arsenic Sulphur Chlorine Bromine and Iodine in Organic Substances and in Vegetable and Animal Compounds as well Vogel (H. W.). A Delicate Spectroscopical Reaction for Alumina and Mag- nesia . . . . . . . . . . . . . Kern (B.). Calculation of the Percentage of Chemically combined Carbon in Analyses of Steels by Eggwtz's Colornetric Method. . . . . Berthelot (M.). AnaIgses of Illuminating Gas . . . . . . CONTENTS. PAGE

ISSN:0368-1769    

DOI:10.1039/JS87731FP001

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

BfUIR ON CERTAIN BISMUTE CONPOUNDS. II.-On Certain Bismuth Conqmds. Part 111. By M. 11.PATTISON MUIR,F.R.S.E. Assistant Lecturer on Chemistry The Om-ens College. 1. INa former paper (this Journal [2],xv 12) I have described four chromates of bismuth the production of one or other of which appears to be conditioned principally by the quantity of acid or alkali present by the temperature and by the time during which the action is main- tained. To one of the chromatm described in the above quoted paper I assigned the formula Bi2034Cr03.H,0or (BiO),Cr40,,H20. I have now to describe a new chromate obtained from this salt. 2. This salt was itself prepared from another chromate by treatment Trith strong nitric acid heating until the whole or almost the whole of the acid was expelled washing with water and drying.If however a considerable quantity of acid be allowed to remain in the salt and it be then repeatedly boiled with water a light orange-coloured salt is obtained the analysis of which dried at loo" gave the following results :-(a.) 0.639 gram gave 0.566 gram Bi,Os = 0.508 gram Bi. (b.) 0.3445 , 0.227 , . = 0.2037 , , (c.) 0.839 , 0.20 , Cr,03 = 0.150 , Cr. (d.) 0.3445 , 0.084 , , = 0.0575 , , Poulla. Calculated for A Y SBi,03.7CrOa. I. 11. 111. IV. Mean. Bismnth.. 59.85 60.55 59.13% -59-84 Chromium 17.35 -17.88 16.69 17-28 Tlie formula given above might be written (Bi,O3.5CrO3) 2{ (BiO) MUIR ON CERTAIN BISMUTH COMPOUNDS. CrO,) as if the salt were a compound of bisnzutl~ylpentacl~romate,and normal bismuthy1 chromatem 3.This chromate is of a light orange colour ; it is insoluble in water but is easily dissolved by dilute mineral acids especially by hydro- chloric acid. Strong hydrochloric acid dissolves it without heating with evolution of chlorine and formation of a very dark claret-coloured liquid. Cold caustic potash partially dissolves this chromate and partially converts it into a loose bulky light-yellow salt ; boiling potash converts it for the most part into a heavy dark brown-red salt' which is insoluble in water ; a portion of the chromate is at the same time dissolved with the formation of a greenish-yellow liquid. When heated this chromate becomes much darker in colour but the original shade is almost completely restored on cooling.4,In Part I1 of these researches I have described a chromate of bismuth having the formula Bi,O3.2CrO3 and prepared by boiling the precipitate obtained in a nearly iieutral solution of bismnthic nitrate by means of potassium chromate with an excess of the precipitant and a few drops of nitric acid. In attempting to prepare a fresh quantity of this salt (I had already prepared it on several distinct occasions) I found that the yellow colour of the original precipitate did not entirely give place to red even after very prolonged heating but that a heavy reddish-orange-colonred salt was obtained. On account of the great density of this salt it was extremely difficult to maintain the liquid in active ebullition hence for the greater part of the time during which the action was proceeding the teniperature of the liquid did not attain to 100".It is very probable-as already pointed out- that temperature materially conditions the formation of these chromates of bismuth. The dense salt was washed until perfectly free from acid dried at lOO" and analysed :-(a.) 0,4135 gram gave 0.275 gram Bi,03 = 0 2466 gram Bi. (b.) 0'509.5 , 0.336 , , = 0.3015 , , (c.) 0.4135 , 0.096 , Crz03= 0.0657 , Cr. (d.) 0.5095 , 0.120 , , = 0.0822 , , (e.) 1.023 gram heated gently over the Bunsen lamp lost 0.0315 gram. Found. Calculated for 5Bi,0311Cr036H20. 'I. 11. 111. A IT. 7. Mean. \ Bismuth . . 59.15 59.63 59-1.7 --59.40 Chromium. 16.17 -15.89 16.13 -16.01 Water . .. . 3.04 --3.08 3-08 The formula given above might be written 2(Biz03.4Cr03)3(BiO)2 Cr0,)6Hz0 as if the salt were a hydrated compound of bismuthyE tetracluomate and normal bisnzzctliyl cl~ro~nate.MUIR ON CERTAIN BISMUTH COMPOUNDS. 5. This salt appears as a finely crystalline very dense conipact powder of a brick-red colour inclining to orange. In its general reactions it comports itself in a manner similar to that detailed for the first chromate described. The action of hot caustic potash upon this salt appears to result in the production of the same chromate as was noticed in paragraph 3. I hope to prepare a quantity of this new chromate and to examine its properties. When heated the chromate now under consideration first becomes crimson then brown at which stage it is dehydrated and is finally conyerted before the blowpipe into a semi-fused grey-green mass.It was found that a temperature of 210-220" maintained for several hours was not sufficient to com-pletely dehydrate this salt. 6. I will now describe some investigations lately made upon bismuth salts other than chromates. 5 1. Actioyz of Chloriize on hot Biwmtlious Oxide. This action was carried out in the hope of obtaining an oxychloride of bismuth corresponding with POCl, VOCI, &c. as in the lower members of the nitrogen group this appears to be the best marked oxychloride. A quantity of pure dry bismuthous oxide was heated in a current of dry chlorine. Action began immediately and the only product appeared to be a white crystalline sublimate which was formed partly in the boat which had contained the trioxide partly in the colder part of the tube.The sublimate was deliquescent and closely resembled bismuth trichloride :-(a. 0.4192 gram gave 0-306 gram Bi,Os = 0.2747 gram Bi. (b.) 0.4192 )) 0.5425 , AgCl and 0.006 ) Ag. Calculated for BiC13. Found. Bismuth ............ 66.35 65.53 Chlorine ............. 33.65 32.47 This reaction is somewhat peculiar. 8 2. Action of Bromine on hot Bismuthous Oxide. 7. *4quantity of pure dry bismuthous oxide was gent'ly heated for several hours along with an excess of bromine in a long glass tube upon the end of which a small bulb had been blown. After. excess of bromine had been driven off the product was exposed to the air for some time and then analysed :- MUIR ON CERTAIN BISMUTH COMPOUSDS.27 (a.) 0.5778 gram gave 0.488 gram Bi& = 0.438 gram Bi. (b.) 0.5778 , 0.483 , , = 0,4335 ,) , (c.) 0.5778 , 0.222 , AgBrand0.008 , Ag. (a.) o 5778 , 0.235 , ,? , 0.008 , , 9 99 (B.) 0.661 0.259 ,? 3 0.010 > , Found. Calculated for F A \ BillBrjOll. I. 11. 111. 1v. V. Mean. Bismuth.. . 75.05 75.80 75-04 -75.42 L Bromine .. 18.19 -17.32 18.35 17.81 17-83 Oxygen . . 6.76 ---6-75 (by dif-ference.) 8. The new oxybromide presents the appearance of a cream-coloured amorphous powder it is non-deliquescent and is unaltered by ex-posure to the air. When heated it slightly darkens in colour but does not undergo decomposition; on cooling the original colour is regained.This salt is insoluhle in water whether hot or cold ; it is easily dis- solved by hydrochloric or nitric acid the addition of the latter if con-centrated causing disengagement of bromine. The formula of this oxybromide may be written as if the salt were a compound of bismuthyl bromide and bismuthous trioxide viz. 7BiOBr. 2Bi20,; or perhaps as an oxybromids of bisntutlzyl (Bi0)11Br702. Br-BiO \?BiOBr Br-BiO bio Br-BiO I Br-BiO BiOBr Br-BiO $iu BiO/O 9. By heating together bismuthous oxide and bismuthous bromide an oxybromide is formed which I believe to be bismuthyl bromide BiOBr. 9 3. Action of Ainnaonia on Oxybromidss and ON Oxide of Bisnzuth. 10. A quantity of the oxybromide Bi,Br,O,, described in a previous paper was heated to dull redness in a stream of dry ammonia.The salt darkened in colour a sublimate was produced which condensed in the colder portion of the tube in the form of a greyish-green powder while there remained in the boat semi-fused metallic-like globules. MUIR ON CERTAIN BISMUTH COMPOUNDS. 0.893 gram of the metallic globules gave 0.8929 gram bismuth ; there-fore this residue consisted of pure metallic bismuth. 11. A quantity of bismuthyl bromide BiOBr heated also to dull rcdness in dry ammonia yielded a smaller quantity of a similar sub- limate and a met'allic residue which was also shown on analysis to consist of pure bismuth :-@5735 gram gave 0.5743 gram bismuth. 12. Bismuthous oxide when heated to dull redness in ammonia was also reduced to metal:-O*678 gram of residue gave 0.675 gram bismuth.13. These reactions were carried out in the hope of obtaining a nitride of bismuth the results were unexpected. It is probable either that a nitride was produced at a lower temperature and was decomposed into metal and nitrogen at dull redness or that the ammonia being decomposed into nitrogen and hydrogen the nitrogen passed away and the phenomena noticed were the results of reduction in hydrogen. The production of water which was noticed during the process of heating showed that part of the ammonia at any rate had suffered decomposition. In order to ascertain whether a nitride was actually produced and was subsequently decomposed a further quan- tit(yof bismuthous oxide was gently heated in dry ammonia.The salt became darker in colour a small quantity of a yellow sublimate was produced and a dove-brown soft heavy powder remained in the boat. This powder was insoluble in water it was unacted upon by boiling caustic potash but was readily dissolved by strong nitric acid with copious evolution of lower oxides of nitrogen. (a,.) 0.456 gram gave 0.504 gram Bi203 = 0.4523 gram Bi. (b.j 0.737 , , 0.816 , , = 0.7323 , ) The heavy powder was therefore metallic bismuth. Hence it ap-pears that when bismuthous oxide is heated in dry ammonia to a temperature considerably below redness the ammonia is partly decom- posed and the metallic oxide is reduced in the hydrogen which is thus set free and that the nitrogen does not combine with the reduced metal.A similar reaction appears to take place in the case of the oxy-bromide of bismuth. I have already shown (this Journal 1876,ii 12) that the oxybromide Bi,Br6Ol5,is readilj reduced when heated in hydrogen. 14. The greyish-green sublimate produced when the oxybromide Bi8Rr6015, was heated in ammonia was submitted to analysis :-(a.) 0-53 gram gave 0.254 gram Bi,03 = 0.2279 gram Bi (b.) 0.322 , , 0.159 , , = 0.1427 , , (c.) 0.250 , , 0.262 , AgBr and 0.01 gram Ag. (d.) 0.5275 ,? boiled with KHO evolved KH, sufficient to neutralise 2.5 C.C. of standard acid (1C.C. = 0.049 gram H2S04). MUIR ON CERTAIN BTSXUTH COMPOUNDS. (e.) 0.518 gram boiled with KHO evolved NH3 sufficient to neutralise 2.2 C.C.of standard acid (1C.C. = 0.049 gram H2S04). Found. Calculated for cc 2BiBr3.5NH,. I. 11. 111. IT. V. Mean? Bismuth.. 42.68 43-00 44.32 --43.66 Bromine.. 48.79 -47.56 -47.56 Ammonia. 8.53 -I -8-06 7-22 7-64 15. This ammonio-bromide of bismuth is non-deliquescent nor is it decomposed by water it is readily dissolved by dilute acids. Strong nitric acid decomposes it with evolution of bromine. When heated fumes of bismuth tribromide are evolved and the salt is almost entirely volatilised a small quantity of what appears to be the oxybromide Bi,Br,O, remaining. A solution of this salt in hydrochloric acid allowed to evaporate over sulphuric acid deposited large very gale yellow tubular crystals. These crystals when dried by pressing between porous paper yielded the following numbers on analysis :-(a.) 0.2926 gram gave 0.117 gram Bi20s = 0.105 gram Bi., 0.456 , AgBr and AgC1. {o*f826 77” 99 0.294 Ag. 77 Calculated for 2BiBr3.5NH,C1.H20. Found. Bismuth ................ 35.43 33.82 Bromine ................ 40.49 40.19 Chlorine ............... 14.97 15.19 Deherain (Coinyt. rend. liv 724) has described a double salt analogous to this salt viz. 2BiC1,.5NH4C1. When added to water this double salt is at once decomposed with the production of a milky liquid probably containing oxychloride and oxybromide of bismuth. 16. The quantity of sublimate which was obtained when bismuthyl bromide (RiOBr) was heated in ammonia was too small to admit of much examination. It appeared to resemble the ammonio-bromide just described and the amoulit of bromine found in it closely corre- sponded with that required by the formula 2BiBr3.5NH, viz.48.79 per cent. 0.295 gram gave 0.3145 gram AgRr and 0.013 gram Ag = 48.69 per cent. bromine. § 4. Preparation of I€ypobismuthic Hydrate. 17. In a former paper (this Journal [el xiv 149) I have described the preparation of bismuthic hydrate Bi205.H20 by passing chlorine MUIR ON CERTAIN BISMUTH CORIPOUNDS. through very concentrated caustic potash kept at a boiling tempern- tnre in which bismuthous oxide was suspended. It'the caustic potash be somewhat less concentrated and the passage of chlorine be stopped when the suspended solid has been transformed into a chocolate-brown powder and if this powder after being washed free from alkali be boiled for a few minutes with a little concentrated nitric acid a reddish-yellow substance is obtained which when washed free from acid and dried over sulphuric acid presents the appearance of a brownish-yellow amorphous powder.A quantity of this powder prepared as just described gave the following results on analysis :-(a.) 0.5805 gram gave 0.545 gram Bi,Oa = 0.4891 gram Bi. (b.) 0,657 , , 0.614 , , = 0.551 , , (c.) 0.352 , ) 0.327 , , = 0.2935 , , (d.) 0,324 , , 0.302 , , = 0.271 , , (e.) 1.3135 , lost 0.056 after heating to 160" for some hours. Found. Calculated for I H20.Bi204. I. 11. 111. IV. V (mean). Bismuth .. 83.67 84.27 83.87 83-33 83.64 83.79 Water . .. . 3.58 --4-26 18. This salt to which I have given the name lzypobismuthic hydrate does not part with its water at 100" when heated to 130" for two hours 3.73 per cent. of water was given off the loss sustained at 160" (4-26 per cent.) was not increased when the temperature was raised to 190" and maintained at that point for an hour. After heating to 190" the colour of the salt had altered to a dark-brown. The colour did not further change on raising the temperature to 230° but decomposi-tion began at about 250° and on heating tlhe salt over a Bunsen-lamp the colour rapidly became light-yellow indicating the conversion of the bismutho-bismuthic oxide into bismuthous oxide. Hypobismuthic hydrate is insoluble in water whether hot or cold it is readily dissolved by hydrochloric acid with evolution of chlorine concentrated nitric acid very slowly dissolves this salt.19. I attempted to prepare a potassiam salt from this hydrate by boiling a quantity of it with strong caustic potash but no action appeared to ensue and the filtered liquid did not yield any salt containing a trace of bismuth either on evaporation or on neutralisation with acid. Schrader (Anw,.Ch. Pharm. exxi 204) has described a hypobis-muthic dihydrate Bi204.2H,0 obtained by a process similar to that described above.

ISSN:0368-1769    

DOI:10.1039/JS8773100024

出版商:RSC    

年代:1877

数据来源: RSC

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31 ABSTRACTS OF CHICRIIICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. The Absolute Weight of Atoms. By J. ANNAHEIM (Deut. Clienz. Ges. Be,.. ix 1151-1152) .-To show the divisibility of matter 0.0007 gram rosaniline hydrochloride C,,H,,N,,HCl was dissolved in alcohol and the solution diluted to 1litre. When a burette of 1cm. diameter is filled with this solution the red colour is clearly seen on a white background; and even if one drop be allowed to fall into a small test-tube which is held obliquely on a white paper the colour can still be perceived. Now as I cm. of the solution gives 35 drops it follows that 0~00000002 gram of the colour is perceptible and on dividing this number by the molecular weight of ihe hydrochloride we find that the absolute weight of 1 atom of hydrogen cannot be larger than 0~000000000059 gram.By using a solution of cyanine C28H35XJ,it was found that 0*0000000285 could be seen or that the weight of the hydrogen atom is not greater than 0~000000000054. c. s. Specific Heats of Saline Solutions. By C. MARIGNAC (Am. Chim. P7q.s. [5] viii 410-430).-This paper gives the numerical results of a long series of experiments undertaken with the view of determining. whether any relation could be traced between the specific heats of saline solutions and the nature of the contained acids and bases. The results show a certain parallelism in the various series of salts; the bases for example often range themselves in the same order.The exceptions however are numerous ; and calculations founded on the mean differences between the members of various series of acids and of bases do not fairly accord with the experimental figures in more than half the numberof cases. No relation was found between the specific heat and the greater or lesser tendency of the dis- solved salt to form definite and crystallisable hydrates. The experi- ments fully confirm an observation previously made by others as to the fact of the specific heat of a saline solution being usually less than the sum of the specific heats of the water and of the dissolved salt. In some cases however the inverse condition was noticed. The author admits the existence in the solution of definite and dissociatecl hydrates the proportions of which vary with the quantity of water and xxith the temperature ; and that these changes of constitution are accompanied by a disengagement or by an absorption of heat which diminishes or increases the apparent specific heat.R. R. Coefficient of Expansion of Gases. By D. MENDELEJEFF and N. KAJANDER (Deut. Chem. Ues. Ber. ix 1311).-Gases having ABSTRACTS OF CHEMICAL PAPERS. the same molecular weight have the same coefficient of expansion which increases with the increase of the molecular weight. C. S. Compression of Gases by Low Pressures. By HEMILIAN and BOGUSKY MENDELEJEFF (Deut. Chew,. Ges. Bey. ix 1312).-Air carbon dioxide and sulphur dioxide under a pressure of more t-han one atmosphere are more compressible than required by Boylc's law but less compressible under a diminished pressure ; such positive deviations are shown by air between 20 and 650 mm.by carbon dioxide between 20 and 180 mm. and by sulphur dioxide between 20 and 60 mm. Hydrogen always exhibits positive deviations from the law or contracts less than the law states. c. s. The Laws of the Compressibility and the Coefficients of Dilatation of certain Vapours. Py L. TROOST and P. HAUTE-F E u IL L E (Cowpi. rend. lxxxiii 333).-The vapours of silicic chloride carbonic chloride and phosphorous chloride even at temperatures far above their boiling points contract more under pressure than might be expected from Boyle's law. The following summary shows the contraction for each vapour that is to say the difference between the volume calculated from Boyle's law and that observed when the pressure is increased from + to 1atmosphere.Vapour. Contraction at 100". Contraction at 180°. Silicic chloride ...... 2.07 per cent. .... 0.455 per cent. Carbonic chloride .... 1.38 , .... 1.3637 , Phosphorous chloride. . , .... 1.548 ,, 7 From this it will be seen that the density determined at one tem- perature will vary according to the pressure for each of these vapours. The mean coeffieients of expansion as determined from experi- ments at different temperatures but at the same pressure are as follows :-Mean coefficients of expansion. n --. / Vapour. From 100" to 125O. From 125" to 180". Silicic chloride ......... 0.00449 ........ 0.00399 Carbonic chloride........ 0.00470 ........ 0.00414 Phosphorous chloride .... 0.00489 ........ 0.00417 These variations of the density of a given vapour with the tempe- rature at a given pressure and with the pyessure for a given tempe- rature exhibit the difficulties to be encountered when it is desired to calculate the elastic force which a vapour would acquire in a mixture. C. H. P. Migration of Gases. By F. BELLAMY (Compt. rend. lxxxiii 669-671).-The author has designated by the name of migration the passage of gases through minute channels or capillary tubes such as exist in a bundle of cotton threads a cotton cord a deal sharine &c. When a connection of this kind is made between vessels containing gases at different pressures the gas is aspired into the vessel where GENERAL AND PHYSICAL CHEMISTRY.the pressure is the less. Thus a cotton cord having one extremity passed up into a tube containing mercury inverted over the mercurial trough and the other extremity exposed to the air affords a cmduit for the passage of air into the tube. R. R. Determination of Vapour-densities. By L. T RO o sT and P. HAUTE FEUILLE (Cowpt. rend. lxxxiii 220-223).-The authors criticise the method which some chemists have adopted of deducing the vapour-density of a substance from results obtained with mixtures of the vapour with air or with some other inert gases or vapours. They point out that several causes of error affect these determinations arising from the known inexactitude of Dalton's Iaw the depctrture of the vapour from the law of compressibility and the variation of the coefficients of expansion.They animadvert upon the experiments of Wurtz for the determination of the density of pentachloride of phos- phorus-vapour in mixture with the vapour of the trichloride of which neither the coefficient of expansion nor the law of compressibility was accurately known. R. R. Determination of Vapour-densities in the Torricellian Va-cuum. By A. W. HOFMANN (Deut. Chern. Ges. Ber. ix 1304-1308).-Calibrated and graduated glass tubes are very liable to crack when exposed to a sudden change of temperature. The author has there- fore replaced these by plain tubes and determines the volume of vapour as follows. As soon as the mercurial column remains con-stant the pendulum cathetometer is brought to a level with it the apparatus allowed to cool and after removing the outer glass tube the volume of vapour is marked by a strip of paper.The barometer-tube is now inverted and filled to the mark with mercury the volume of which is ascertained by weighing it. In the usual form of the apparatus the whole column of mercury is not surrounded by the vapour and therefore two corrections have to be made on reducing the height to O" and in so doing it is assumed that the lower part of the column has the temperature of the sur-rounding air and the higher one that of the vapour which is not correct as the temperature of the mercury near the cork gradually changes from the lower to the higher temperature.This source of error is of little conscquence if the vapour-density be taken at a low temperature but at a high temperature it may influence the results. Wichelhaus has therefore proposed a modification of the apparatus by converting it into a syphon barometer which allows the immersion of the whole mercurial column in the vapour. The objection to this is that only one determination at a given temperature can be made whereas by using the conimon form the vaponr density can be ascer- tained at varying temperatures. To retain the latter advantage t,he barometer-tube may be surrounded by a long outer tube which dips into the mercury and to which at about 2-3 cm. above the level of the mercury a tube is sealed t,hrough which the vapour escapes.A much simpler method however is to retain the original form and to rest the barometer-tube on an india-rubber plate which is fixed on VOL. XXXI. D 34 ABSTRACTS OF CHEMICAL PAPERS. an iron disk to which an iron handle is attached On the side of the plate a groove is cut through which during the experiment the mer-cury can flow out. As soon as the height of the column remains con- stant the india-rubber plate is moved so that the groove is removed from the opening which is thus closed. The apparatus is now allowed to cool and the height of the column read off at the ordinary tem- perature. In the origisal form of the apparatus the steam is admitted at the top and this arrangement answers very well if the boiling point of the sub- stance does not exceed 150".But for higher temperatures it is more con- venient to allow the vapour to enter from below. For this purpose the cork of the outer tube as well as that of the copper boiler is provided with two holes. The tube through which the vapour enters begins just under the cork of the boiler and ends about 44-5 cm. above the cork of the outer tube while a second tube through which the condensed liquid flows back begins just above the cork of the outer tube and goes down nearly to the bottom of the boiler. Thus 100-150 ccms. of aniline or any other liquid are sufficient and if the outer tube is about 40 cm. longer than the tube a perfectly constant temperature is obtained in 20-25 minutes by using aniline ethyl benzoate or amyl benzoate.The connections between the outer tube and the boiler are conveniently made of metal and then the tube through which the vapour enters may be provided with a stop-cock which is closed when the boiler is heated. Thus the warm liquid is forced into the space between the outer tube and barometer-tube which is therefore gradually heated. As soon as the boiling point is nearly reached the cock is opened to allow the vapour to enter. In this way the tempera- ture can be kept constant for hours. c. s. A Method of Determining the Vapour-density of Substances boiling at High Temperatures. By VICTOR MEPER(Deut. Chern. Ges. Ber. ix 1216-1228).-The contents of this paper cannot be made intelligible in an abstract without the aid of the accompanying draw- ings.J. R. On the Separation of Mixed Liquids. By E. DUCLAUX (Ann. Chirn. Plays. [51 vii 264-280).-When two liquids dissolved one in the other are induced to separate by an external influence such as cold neither of the layers thereby formed consists of one of the liquids exclusively the other being a mixture but two new mix- tures are formed in which the two substances are distributed in other proportions. At the temperature of 15-20" glacial acetic acid and benzene may be regarded as soluble in all proportions one in the other; but when mixtures of these substances are cooled down to temperatures varying with the proportions of the constituents separa- tion into two layers takes place as shown in the following statement where the volume of the upper layer is placed above that of the lower :-Acetic acid.10 C.C. acetic acid separate at 20.1 c.c. containing 33.3 per cent. 15 , benzene } 15" into { 4.9 , 7 62.8 9 GENERAL AND PEIYSICAL CHEMISTRY. 35 Acetic acid. 10 c.c..acetic acid containing 33.6 per cent. 7, 10 , benzene 63.5 , 15 C.C. acetic acid containing 35 , 10 , benzene ? 62.5 9 A similar separation is effected by the addition to the above mix- tures of a small quantity of water. Mixtures of acetic acid and petro- leum also behave in the same manner. When amyl alcohol ethyl alcohol and water are mixed together in such proportions that the mixture just remains homogeneous at 20° the addition thereto of a slight excess of water causes separation into two layers having the composition shown in the following table where the letters U and L denote the upperand lower layers :--Amyl alcohol I Ethyl alcohol U *my1 ~thy' Water.-. 1 I alcohol. alcohol. L in U. in L. in U. in L. 1 I -1 -5.8 33 p. c. 33 '0 p. c. 2 -5 33 '8 ) 15% ) 30'3 , 30.9 , 0 *67 30.6 , 15.2 , 29'0 , 29'2 , 0 *40 31 *O , 14.4 ) 29.0 , 29'0 , -0 *18 33-0 , 14-8 , -0 -11 35-0 , 12'0 , 26.0 , ' 28.0 , The separation is effect'ed equally by the addition of excess of amyl alcohol instead of water. Such mixt'ures are very sensitive also to slight changes of temperature. The following table exhibits the tem- peratures at which mixtures of the liquids in the proportions there given separate into two layers :-~ ~~~_______ Amyl Ethyl Temp.of U Amjl alcohol alcohol. alcohol. Water. separation. -L' in U. in L. --~-I-100 C.C. 133 C.C. 246 C.C. 30" 0 *44 29.3 p. c. 16.1 p. c. 100 ,> 133 9 219 ?> 20 0.67 30% , 15-2 , 100 9) 133 191 9 10 1.2 . 31.3 , 14'2 ,, 39 100 7 133 9) 164 2 0 1-5 31% , 13.5 , looJ> 133 133 9 -14 1-8 34.4 , 10'3 ,, 97 Mixtures of methyl and am$ alcohol and water or of amyl alcohol acetic acid and water behave in exactly the same manner. A mixture of 5 parts of alcohol of 86" 10 parts of ether and 6 parts of water is perfectly homogeneous; but on adding a slight excess of water (A) the liquid becomes turbid and separates into two nearly equal parts both cont'aining the three liquids. This mixture resembles in its behaviour so far those previously described but it possesses the remarkable property of becoming turbid when heated.A difference of temperature of 0.1" at the critical point is sufficient to cause a sudden separation of the liquid into two laavers having the D2 ABSTRACTS OF CHEMICAL PAPERS. same composition as those produced by the addition of water. This property is exhibited also by a mixture of ether acetic acid and water. The author recommends the employment of mixtures such as are described above for thermometric purposes. The indications of ther-mometers made on this principle may be rendered more apparent by adding to the liquid a drop of red ink. So long as the liquid remains homogeneous it is uniformly coloured ; but when separation takes place the colouring matter becomes concentrated in the lower layer leaving the upper nearly colourless.Such mixtures might be used most advantageously as maximum and minimum thermometers. It is easy to prepare mixtures of nmyl and ethyl alcohol and water which will separate into two layers at any given temperature between -15" (or even lower) and 30". The two layers after separating do not mix again when the temperature rises owing to the difyerence in their densities. Such thermometers need be rery small only 1C.C.of the liquid sufficing for each so that a large number could be arranged in a small compass. J. R. Salt Solutionsand Attached Water. By PR E D E R I c K Gu T H RI E (PkiZ. Mag. [S] i 354-369 ; 446-455 ;and ii 213-225).--When a solution of a salt at or a little below 0" is further cooled one of three things must happen and which of them happens is determined by the strength of the solution.1. In all solutions weaker than the cryohydrate ice is formed at temperatures which are lower according as the solution is richer in salt. 2. In solutions of a certain strength (namely that of the cryohydrate) combination of the salt and water takes place in definite ratio and at a coilstant temperature. The solution is therefore a melted cryohydrate and solidifies as a whole. 3.When solutions stronger than the cryohydrate are cooled below O" either the anhydrous salt or some hydrate richer in salt than the cryohydrate separates. It follows therefore that the cryohydrate is ultimately obtained by cooling either a weaker solution or a solu-tion stronger than the cryohydrate since in the one case ice separates and the solution strengthens while in the other case anhydrous salt sepamtes and the solution becomes weakened.It is proposed (1)to trace the history of solutions weaker than the cryohydrates as they yield ice on cooling ; and (2) to examine the separation of such anhydrous salts or hydrates which separate when solutions richer in salt than the cryohydrates are cooled. A solution of a salt below O" which is weaker than the cryohydrate may be regqrded as a solution of ice in the cryohydrate and just as a given weight of water dissolves as a rule more of a salt t-he higher the temperature so a given weight of the cryohydrate dissolves more ice at higher temperatures below 0" than at lower ones.Again since at any given temperature the quantity of ice dissolved depends on the quantity of cryolijdrate present that is on the strength of the solution tlle stronger a solution is the lower must its tempera- ture be reduced before it can be made to yield up ice. In a similar GENERAL AND PHYSICAL OEIEMISTRY. manner anhydrous salt may be supposed to dissolve in the liquid cryohydrate and to separate therefrom at O" or at temperatures very little below. Solutions of various salts were prepared of known strength by dis- solving a weighed quantity of the salt in a weighed or measured quan- tity of water. Beginning with a 1 per cent. solution it was cooled the temperature noted and the nature of the solid which separated examined.The strength of the solution was then increased regularly by 1 per cent. examined as before axid the operation continually repeated until the solution solidified as a whole ; that is until the cryo- hydrate was obtained. While the solution is weak solidification begins and ice separates out at moderately low temperatures but when a certain degree of con-centration is reached the lowest temperature is obtained and t'he regular cryohydrate crystallises. On continuing to increase the strength of the solution a very slight alteration of temperature is sufficient to cause a deposit of anhydrous salt or of some hydrate containing less water than the cryohydrate so that as the concentra- tion proceeds the temperature at which salt separates may be 40" or more above 0" ; in fact the deposition of salt has then become only a case of ordinary crystallisation.Twenty-three complete tables are given containing the results of examination of as many different salts ; it is not however necessary to reproduce them here as the only point of special interest is the tem- perature at which the cryohydrate forms. The phenomenon of a solution undergoing fractional solidification by cooling may be considered physically as the homologue of the con- centration of a solution by boiling. Thus :-1. A solution weaker than the 1. A non-saturated solution re- cryohydrate loses heat; ice is ceives heat ; vapour is formed. formed. 2. Ice continues to form and 2.Vaponr forms and the tem- the temperature to fall until the perature rises until saturation is cryohydrate is reached. reached. 3. Water is thus withdrawn in 3. Water is thus withdrawn in the form of ice. the form of vapour. 4. At the point of saturation 4. When the solution is satu- ice and salt separate simulta- rated vapour and salt separate neously and the solid and liquid simultaneously and the same portions are identical in composi- ratio exists between the vapour tion. formed and the salt precipitated as existed previously between the water and the salt it held in solu- tion. Separation. of Ice from Mixtures of Salts.-20 per cent. solutions of silver nitrate and ammonium nitrate were mixed together in varying proportions; also 10 per cent.solutions of' ammonium nitrate arid ammonium sulphate and the temperature at which they began to give np ice wits noted. This appeared to be about a mean between the glacia- ABSTRACTS OF CHEMICAL PAPERS. tion temperatures of the constituents. It may be calculated from the equation-t=t,+ where n = grams of A m = grams of B of equal percentage strength and t, tz the temperatures at which A and B give out ice respec- tively. A few organic siibstances were experimented with. Cane-sugar gave a definite cryohydrate at -8.5",but from aqueous solutions of glycerin nothing but ice could be obtained. The results with tartaric acid were rather indefinite but like sodium iodide it appeared to yield two cryohydrates at different temperatures.Dry gum arabic was found to be powerless as a cryogen and in solution it also failed to produce a cry&alline compound on cooling. Albumin in form of white of egg began to separate ice at O" and froze into a solid mass at -0.5". No satisfactory results were obtained by cooling solutions of gelatin but ih was noticed that a strong solution of 50 per cent. boiled steadily at 97". J. W. On the Elasticity of Metals at Various Temperatures. By G. PISAT I (Gazzetta chi?nicaitaliana vi 23-32) .-After noticing the researches of Coulomb Wertheim Kupffer and Kohlrausch and Loomis the author describes the apparatus employed in which the elongation of two equal portions of the same wire under various ten- sions and at various temperatures could be accurately measured by means of a cathetometer.On examining an iron wire which had pre- viously been thoroughly annealed by heating it to dull redness and allowing it to cool very slowly in this instrument it was found that with a tension of lS00 grams and on gradually raising the tempera- ture to 300" the two halves expanded very irregularly and a similar phenomenon was observed on cooling However after the operation of alternate heating and cooling had been repeated several times the wire was reduced to the normal state ;that is the rates of expansion of the two halves of the wire coincided perfectly. The weight on one of the halves was now reduced by 1000 grams so that one was loaded with 800 the other with 1800 grams and the difference in elongation observed at 18.1" and at intervals of 50" from 50" to 300' ;the length of each half of the wire when stretched by a weight of 800 grams was 1778.22 millimeters and its diameter 0.4236 millimeters at 28.1".Similar experiments were made with a steel wire the two halves being loaded with 1000 and 4000 grams respectively the length of each half when stretched by a weight of 1000 grams was 1782.69 at 23*3" and its diameter at 14.8" was 0.4940 millimeter. The results obtained in these two sets of experiments were as follows :-Increase in length in millimeters. Temperature. Iron. Steel. ........ - 18" ................ 0.588 22 ................ -........ 1.510 50 ................ 0-590 ........ 1.519 100 ................ 0.594 ........1.589 GENERAL AND PHYSIOAL CHEMISTRY. Increase in length in millimeters. Temperature. Iron. Steel. 150 ................ 0.602 ........ 1.543 200 ................ 0.615 ........ 1.563 250 ................ 0.633 ........ 1.582 300 ................ 0.656 ........ 1.601 the readings giving the increase of length produced by the increased load on the one wire at the various temperatures. From the results it will be seen that the modulus of elasticity diminishes as the tempera- ture rises up to 300" C. whilst Wertheim (AY~ Chirn. Phys. [3] xii 385) found that it increased between -15" and ZOOo which is per- haps to be attributed to the latter not having brought the wire into the "normal state" previous to making measurements.If K be the modulus of elasticity of tension that is 10000 times the weight necessary to produce an elongation of 0.001 in a wire 1meter long and of section equal to 1millimeter square- I(=-P.L s.1 where the weight P produces an elongation Z in a wire whose length is L and section s. If moreover the wire be cylindrical and at the tem- perature 0" have a length of Lo,and its section a radius r0,its coeffi- cient of linear expansion being a we have- which gives the modulus of elasticity at the temperature to. Adopting Fizeau's values for the coefficient of expansion namely- a = 0.00001228 for iron a = O*OOOO1112for steel the following are the moduli of elasticity for iron and steel deduced from the author's results :-Temperature (cor.).Iron. Steel. 20" .............. 21441 ...... 18481 50 .............. 21364 ...... 18416 100 .............. 21212 ...... 18232 150 .............. 20895 ...... 18052 200 .............. 20458 ...... 17820 250 .............. 19871 ...... 17593 300 .............. 19175 ...... 17372 C. E. G. Elasticity ofTorsion. By G. P ISATI (Gazzetta chimica italiana vi 57-88).-After alluding to the labours of Kupffer Weber and others in this subject and to the fact that they had not examined the effects of torsion at temperatures above loo" the author describes the apparatus employed by himself and also gives the details of the methods. The apparatus a figure of which is given is very similar ABSTRACTS OF CHEMICAL PAPERS. to that used for the experiment on tension but the oil-bath and the tube containing the wire is only about 0.8 met.in length ; the wire for the experiment being about 0.65 met. long and 0.25 to 0.50 mm. in diameter. The met,hod employed was that of oscillations measuring the number and duration of the oscillations occurring whilst the ampli- tude of the oscillations gradually decreased from 90" to 10". In the first experiment a silver wire 0.468 mm. in diameter and 643.38 long was employed stretched by a weight of 309 grams obser- vations of amplitude being registered at the end of each 50 oscilla- tions. On repeating the experiment with the same wire a second third fourth time &c. it was found that the time occupied whilst the amplitude of the vibrations decreased from 90" to lo" .gradually aug- mented whilst the duration of a single oscillation diminished.After the twentieth experiment however no further change took place (the temperature remaining constant at 26.5"). From this it will be seen that a phenomenon took place similar to that observed in the experi- ments on tension namely that during the oscillations the wire gradually underwent alteration until finally it arrived at a normal state for the special conditions under which the experiment was made. In these experiments it was found that at first the time required to reduce the amplitude of thevibrations from 90" to 10" (vzt) was 15' '22.9"; n = 350 being the number of oscillations in this time and therefore the mean duration of an oscillation (t) was 2-637" whilst after the wire had reached the normal state these numbers were n = 450 vzt = 19' 42-1" and t = 2.6269'' respectively so that the mean duration of a single oscillation had been diminished in the proportion 1.0038 1.A fresh set of experiments was then made. The wire was heated to 100" for an hour allowed to cool and examined when it was found that the time required to reduce tlhe amplitude had again increased whilst the duration of a single oscillation had diminished. On repeat-ing this treatment several times these numbers at length became constant. An oscillation observation was then taken at loo" and also after the wire had cooled to 26". The numbers obtained at 100" were n = 100 m! = 4' 26*8" and t = 2.668" ; and at 26" n = 650 mt = 28' 09.7" and t = 2.5995".On now repeating the experiment several times the results obtained each time were found to be identical so that the wire had reached a second normal state differing from the first normal state in the same character and in the same direction in which the latter differed from the natural state. On increasing the temperature to 200° similar phenomena were observed the numbers for the normal state under these conditions being :-n. t. nt. At ........ 200" 30 2.7'50" 1',22.5" Cooled to . . 25.4" 1000 2.512" 41',52-0" It was then heated to 305" cooled to 26" and a series of oscillations observed these operations being repeated until constant results were obtained. The numbers at 25.8" for this third normal state were n = 1450 t = 2.417" (about).It wits found moreover that when the wire was relieved from the GENERAL AND PHYSICAL CHEMISTRY. tension to which it had been subjected even for so short a time as 30" an alteration in the elastic state was produced the duration and number of the vibrations being temporarily altered ; but that after the wire had been caused to oscillate for a long time stretched w-ith dif- ferent weights and at different temperatures it was finally reduced to a normal state such that wen when the tension was varied the same number of oscillations n were always observed the temperature remaining constant. A series of experiments was then made to ascertain the variation in the elasticity corresponding to variation of temperature the details of which are given.Under these circumstances the number of oscilla-tions 12 decreased rapidly up to 160" and then much more slowly up to 300° while the duration of a single oscillation gradually increased. On measuring the wire it was found to have slightly increased in length and diminished in diameter its dimensions now being 647.48 and 0.4661 millimeters. Modulus of the Elasticity of Torsion at Various Temperatures.-If E is the modulus of elasticity of torsion referred to a square millimeter in section where M is the moment of inertia of the tension (equal to 13608 grams per square millimeter in the experiment) ; t the duratioii of a single oscillation ; L and r the length and radius of the wire ; and g the accel- L leration of gravity expressed in millimeters.As -varies with the r4 temperature if a is the coefficient of linear expansion and T the tem- perature (1)becomes I?-M Lo 1 E=-.-. -g t" r,l' (1 +cxT)~ where Lois 647.48 and yo 0.233 millimeters and a = 0*000*0187+ 0*000~000~010 T. In the following table the number of oscillations during which the amplitude was reduced from 90" to 10" is given and also the modulus. Number of Modulus of Temperature. oscillations. torsion. 0" .......... -1644.5 10 .......... -1637.8 20 .......... -1630.9 30 .......... 1620 1623.8 40 .......... 1275 1616.4 50 .......... 1000 1608.6 60 .......... 780 1600.3 70 .......... 590 1591.5 80 .......... 445 1582-1 90 .......... 348 1572.0 100 ..........277 1560.9 110 .......... 218 1548.5 120 .......... 172 1535-0 ABSTRACTS OF CHEMICAL PAPERS. Number of Modulus of Temperature. oscillations. torsion. 130 .......... 135 1520.5 140 .......... 104 1502.5 150 .......... 80 1481.0 160 .......... 62 1456.0 170 .......... 48 1429.0 180 .......... 40 1400.5 190 .......... 32 1371.0 200 .......... 30 1341-2 210 .......... 28 1311.4 220 .......... 26 1281-6 230 .......... 24 1251.8 240 .......... 22 1222.0 250 .......... 80 1192.2 260 .......... 18 1162.4 270 .......... 16 1132.6 280 .......... 14 1102-8 290 .......... 12 1073.0 300 .......... 10 1043.2 Curves corresponding with these numbers and with their differences accompany the paper.C. E. G. Retardation of Chemical Reactions by Indifferent Sub-stances. By G. LUNGE(Deut. Chem. Ges. Ber. ix 1315-1316).-A mixture of equal volunies of fuming hydrochloric acid and glycerin (a) acts on ultramarine only after 45 seconds and bleaches it in 3 minutes while a mixture of equal volumes of water and acid (b) begins to act in 10 seconds and destroys the colour in 35 seconds. Mixture a dissolves zinc and iron much more slowly than b. Thus 10 C.C. of the latter dissolved 0.5 gram of nails in less than 24 hours while a left after 24 hours 86.2 per cent. undissolved and after 14 days 1.3 per cent. still remained. The cause of this is not that ferrous chloride is less soluble in glycerin than in water because the salt readily dissolves in the former and during the experiment none separated out.Mixtures of sulphuric acid and glycerin show a similar inactivity and in- stead of glycerin gum may be used. A mixture of acid and soot scarcely acts on metals but on removing the soot by filtration the filtrate acts like fresh acid. The retardation reaches a maximum by using a mix- ture of strong acid and glycerin with 5 per cent. of soot; iron nails lost in it-1. 2. In 3 days ...... 10.8per cent. ...... 21.2 , 6 days ...... 25.4 , ...... 13.0 , 14 days ...... 51.0 , -c. s. The Point of Combustion. By A. MITSCHERLICH (Deut. C7~em. Ges. Ber. ix 1171-1178).-By this term the author understands the temperature at which a body begins to take up free oxygen. This may be a simple oxidation or a decomposition may take place at the same INORGANIC CIFEMISTRY.time and the process may proceed only gradually with a slow evolu- tion of heat or quickly with a violent evolution of heat and light. The author describes the apparatus and the method which he used for these determinations but these can only be understood with the help of a drawing. The results which he obtained will be published afterwards. c. s. Contributions to the Theory of Luminous Flames. By KARL H E u MA N N (Liebig's Annalen 183 1-29) .-In this second contribu- tion the author considers specially the circumstances which determine the distance existing between a luminous flame and the orifice whence it issues. His principal conclusions are as follows :-1.The fact that a space occupied by unburned gas exists between a gas flame and the burner or between a candle flame and the wick as also the fact that a dame does not actually touch a cold body placed within it is due chiefly to the cooling action of the surroundings of the flame whereby the temperature of the gases is reduced below the ignition point. 2. The great distance existing between the flame and the burner in the case of a gas issuing under high pressure as in the case of a gas largely diluted with indifferent gases is to be traced partly to the cooling action already mentioned but more especially to the fact that the rate of propagation of ignition in t'he neighbourhood of t,he burner is less than the rate at which the gaseous stream issues.3. In order to remove other conditioning circumstances the rate of propagation of ignition shonld be maintained equal to the rate at which the gas flows at that point situated some distance from the burner at which the flame begins. The rate of propagation of igni-tion will be determined under such conditions for many gases and vapours ; and inasmuch as this magnitude is a function of the differ- ence between the temperatures of ignition and combustion of the com- bustible body it is hoped that much light m7ill be thrown on the relations existing between these two. 4. The rate of propagation of ignition may easily be determined for solids and liquids and comparative quantitative expressions for the liability to ignition of combustible substances may thus be obtained. M. M. P. M.

ISSN:0368-1769    

DOI:10.1039/JS8773100031

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

INORGANIC CIFEMISTRY. Ino rgani c Chemistry. Production of Ozone by the Pulverization of Water. By G. BE L LU c c I (Gazzetta chirnica itaZiana vi 88-9 7) .-Lender had noticed in the concentration of the brine springs of Kissingen by graduation that the air in the immediate neighbourhood of the columns gave the ozone reaction and Gorup-Besanez found that the quantity of ozone produced by the spray of water issuing under pressure was greater the more rapid the evaporation. Morin and Monte have also shown that in the pulverization of water as practised ABSTRACTS OF CHEMICAL PAPERS. at some thermal establishments ozone is produced in sensible amount. These facts induced the author to make observations in the neighbour- hood of the falls of Terni to ascertain if ozone was produced by the natural pulverization of the water especially as he had often noticed the characteristic odour of ozone there.He found that Schonbein’s paper was distinctly attacked in three hours the alteration being more marked in the immediate vicinity of the falls and especially at those seasons when the volume of water was greatest. Papers exposed at a distance from the fall within a radius of 80-100 meters were all more or less attacked but most strongly on the banks of the stream below the fall the current of air which invariably follows the course of a rapid stream closely shut in by rocks or in a narrow valley carrying along the ozone. The author infers from these results that ozone is generally pro- duced where water undergoes pulverization or is converted into finely divided spray whether this is effected by a cascade a torrent rushing over rocks the surf on the sea-shore or the rolling of the waves in the open ocean.It is noteworthy that the air over the surface of the ocean is richer in ozone than that collected on the land. After dis- cussing at length the various causes which might produce the ozone the author arrives at the conclusion that it is due to the electrical state induced by the friction of the minute drops of water against one another which is increased by the mineral matter suspended or even dissolved in the water. C. E. G. Prismatic and Octohedral Sulphur. By D. G E RN E z (COmpt. rend. lxxxiii 217-220) .-When the contact of solid particles is pre-vented fused sulphur may be indefinitely maintained in the liquid state at a temperature much below its point of fusion.Under these circumstances solidification may be induced without the introduction of a crystal of sulphur by either rapidly cooling a part of the liquid as by touching the exterior of the containing tube with a cold body or rubbing the interior of the tube with a glass rod left in the liquid. In either case the sulphur solidifies at temperatures above 60” in the prismatic form and at ordinary temperatures these prismatic crystals break up into minute octohedrons. The octohedral crystallisation may however be induced in the fused sulphur even at the tempera- ture at which the prismatic occurs spontaneously as just described.This result is obtained by the introduction of an octohedral crystal which determines a crystallisation in the octohedral form throughout the mass but at a much slower rate than when the prismatic forms are produced. On fusing sulphur in a U-tube with proper precautions the two kinds of crystallisation can be simultaneously set up by the introduction of different crystals into each branch. R.R. and The Atomic Weight of Selenium. By 0. PETTERSSON G. EKMAN (Deut. Chem. Ges. Ber. ix 1210-1212).-The authors have attempted to arrive at the atomic weight of selenium by a variety of methods of which two only proved practicable namely (1) heating silver selenite and weighing the residual silver and (2) reducing selenious anhydride dissolved in water by means of INORGANIC CHEMISTRY.sulphur dioxide and weighing the precipitated selenium. The atomic weight was found to be by the first method 79.01 and by the second 79.08. The authors place more reliance on the results obtained by the second method J. R. Action of Halogen Acids on Selenious Oxide. By A DITTE (Compt. red lxxxiii 223-225) .-The compound Se02. 2HBr ener-getically absorbs bydrobromic acid gas with evolution of heat giving rise to a crystalline compound corresponding with the formula 2Se02.5HBr. This is decomposed at 65" with formation of water and disengagemenh of bromine but at lower temperatures it is trans- formed into Se022HBrand hydrobromic acid. The following are the values of the tension of dissociation of the compound 2Se02.5HBr at various temperatures :-At -25'...... At 30'. .....287 mm. , -6" ......lo:"$' 1 , 41" ......335 , , 0"......135 , , 54". .....404 Traces of bromine , $11"......191 , , 62".. ....404 } vapour. , 14"......209 , , 70°.. .... Decomposition with i abundant vapour of bromine. Hydriodic acid reacts with selenious oxide even at -lo' the products being water iodine and selenium. Selenious oxide also combines with anhydrous hydrocyanic and hpdrofluoric acids. Selenious oxide and hgdroselenic acid in presence of water decompose each other with separation of selenium. This result is always the same whether the solutions be concentrated or dilute hot or cold; and no compound corresponding with pentathionic acid has been obtained.The re-action is a convenient means of obtaining selenium soluble in sulphide of carbon. R. R. Action of Halogen Acids on Tellurous Oxide. By A. DITTE (Compt. relid. lxxxiii 336).-Tellurous oxide whether crystallised or amorphous behaves in the same manner to hydracids. Anhydrous tellurous oxide absorbs hvdrochloric acid with extri- cation of heat. If the vessel in which the reaction is occurring be cooled to -lo" the absorption of the hydrochloric acid ceases after a while. The substance has become light brown and the quantity of hydrochloric acid absorbed is that which corresponds with the formula 2Te02.3HC1. A slight elevation of temperature decomposes this compound hydrochloric acid is evolved and a body having the formula Te02.HIC1 remains.When this substance is heated at about 110" drops of waterappear and are deposited on the cool parts of the vessel. These increase in quantity by increased heat; the liquid becomes darker and at about 300" the production of the water (which should be removed as fast as it forms) ceases and if the heat be stopped so soon as white vapours begin to appear indicating the volatilisation of the substance left in ABSTRACTS OF CHEMICAL PAPERS the vessel this on cooling solidifies to a crystalline mass which con- sists of tellurous oxychloride TeOCI,. The oxychloride melts to a deep-coloured liquid which when boiled gives off bromine-coloured vapours and these on condensing deposit white crystals which consist of tellurous chloride while a great portion of the substance is not volatile at about 400° and consists of tellurous oxide.The oxychloride therefore splits up under the action of heat in the manner shown by the equation- 2TeOC12= TeOz + TeC14. No compound of the formula Te02.2HC1 analogous to the selenium compound could be obtained. C. H. P. Thermic Formation of Hydroxylamine or Oxyammonia. By M. B ERTHELOT (Cowzpt. rend. lxxxiii 473-478).-This paper contains a study of the thermic and chemical phenomena attending the formation and decomposition of oxyammonia leading the author to the conclusion that this compound belongs to a special and hitherto unrecognised type to which among bodies already defined the oxide of triethylphosphine offers the nearest analogy.The thermic observa- tions confirm and specify the conditions which determine the insta- bility of the compound. R. R. Phosphorus Pentafluoride. By T. E. T H ORYE (Liebig’s Anmden clxxxii 201-205) .-When phosphorus pentachloride is added pa- dually to arsenic trifluoride (obtained by heating arsenic trioxide with fluor-spar and snlphuric acid) a violent reaction takes place resulting in the formation of arsenic trichloride and phosphorus pentafluoride in accordance with the equation- 5AsF3 + 3PCl5= 5AsC1 + 3PF,. Phosphorus pentafluoride is a colourless gas having a very pungent odour and attacking the mucous membranes. It fumes in the air reacting with water to form phosphoric and hydrofluoric acids. Its density was found to be 63.23 that o€ hydrogen being 1 (theory re- quires 63).Under the pressure of 12 atmospheres at 7” it exhibits no marked deviation from Boyle’s law. The gas neither burns nor supports combustion. It is not affected by the passage of electric sparks through it when pure nor when mixed with hydrogen or oxygen. It combines with dry ammonia to form a yellowish-white solid body represented by the formula 2PF5.5NH3. A solution of the gas in aqueous ammonia deposits on evaporation crystals of ammonium phosphate (H,NH,PO,) and ammo- nium and hydrogen fluoride (HF.NH,F). J. R. Formation of Phosphonium Iodide. By K. LISSEPU’RO (Dezd. Chem. Ges. Rer. ix 1313).-The author believes that this compound is formed by the action of hydriodic acid on hypophosphorous acid for when the latter is fused and saturated with hydriodic acid a pro-duct is obtained which when heated in a current of carbon dioxide yields non-inflammable hydrogen phosphide hydriodic acid and phos- Ih'ORQANIC CHEMISTRY.47 phonium iodide while phosphoric acid remains behind. When 1part of phosphorus and 2 parts of iodine are dissolved in carbon sulphide and the latter distilled off a red mass is obtained which is a mixture of several compounds. On adding water the odour of hydrogen phosphide is given off and the solution first contains hypophospho- rous acid but on standing also phosphoric acid. The orange residue which remains appears to be solid hydrogen phosphide. c. s. Action of Hydrochloric Acid on Potassium Chlorate. By G. Sc HA c K E R L (Liebig's Annah clxxxii 193 -201) .-Pebal showed that the action of hydrochloric acid on potassium chlorate results in the formation of chlorine and hypochloric acid (C102) in varying pro- portions (see this Journal 1875 1157).The author's experiments on this subject have led to the conclusion that the action is represented primarily by the equation- 1CC103+ 2HC1 = CIOz + C1 + KCl + H20; or when sulphuric acid and potassium chloride are employed by the equation-KC103 + KC1 + 2H2SO4 = ClOz + C1 + 2KBSO4 + HZO; but that in most cases there occurs a secondary action of free hydro- chloric acid on the hypochloric acid first formed whereby the pro- portion of chlorine is increased. The extent to which this secondary action takes place was found to depend upon the amount and strength of the hydrochloric acid preseiit in the liquid from which the gases were evolved.Thus when a solution of potassium chlorate was run into hot hydrochloric mid of sp. gr. 1-19 the proportion by volume of the hypochloric acid and chlorine evolved was 2 35.6 ; but when finely-triturated potassium chlorate was decomposed with hydrochloric acid diluted with twice its bulk of water the two gases were in the proportion of 2 1.71. Again when a mixture of 1mol. of potassium chlorat'e and 5 mol. of potassium chloride was decomposed by sul- phuric acid the hypochloric acid and chlorine evolved were in the proportion of 2 5.54; but when a mixture of 4 mol. of chlorate and 1mol. of chloride was decomposed in the same manner the two gases were in the proportion of 2 1.27.Numerous other experiments were made all leading to the same conclusion. In no case was pure chlorine obtained. The gases were analysed by Pebal's method. J. R. The Dissociation of the Vapour of Calomel. By H. DEBRAY (Compt. rend. lxxxiii 330) .-The results of the author's experiments upon the dissociation of the vapour of calomel at 440" do not coincide with those of Odling and Erlenmeyer according to whom the disso- ciation is complete as determined from the vapour-density and the fact that a strip of gold plunged into the vapour becomes amalga- mated and also incrusted with corrosive sublimate. This experiment with the strip of gold can only be of use if it is established that at 440"the tension of dissociation of the amalgam of gold is inferior to ABSTRACTS OF CHEMICAL PAPERS.one-half an atmosphere which is the tension of the vapour of mercury in the mixture of equal volumes of mercury and corrosive sublimate supposed to exist by Odling's hypothesis if it is beyond half an atmosphere the strip of gold could not amalgamate in such a mixture ; but it is shown by direct experiment that a strip of gold heated to 440° does not become whitened in the vapour of mercury at the ordi nary atmospheric pressure ; it could not therefore become amal-gamated in the globe used for determining the vapour-density. When calomel is heated to 440"in a platinum vessel and a curved silver-gilt tube through which cold water is circulating is plunged for a few seconds into the vapour it becomes coated with a greyish deposit consisting of a little mercury interspersed in a powder of calomel PO fine that the mercury has not been able to attack the gold.Therefore althongh calomel heated to 440° and maintained at that temperature for some time suffers some decomposition it cannot be considered as established that the dissociation is complete. c. H. P. A New Process for the Extraction of Gallium. By LECOQ DE Bo ISBAUDRAN (Cornpi. h end. lxxxiii 636-638).-The gelatinous precipitate obtained by treating acid solutions of the gallium-bearing mineral with excess of zinc is dissolved in hydrochloric acid; sul-phuretted hydrogen is passed through the liquid; and after the gas has been expelled from the filtrate the latter is fractionally precipitated by sodium carbonate until gallium ceases to be thrown down and the precipitate no longer yields the characteristic spectrum of the metal.The precipitates are dissolved in sulphuric acid and the solution is evaporated until vaponrs of sulphuric acid cease to be evolved. The residue is treated with cold water and after dilution the solution is heated to boiling when a sub-salt of gallium is precipitated and separated by filtering while the liquid is hot. This basic salt is dis-solved in a small quantity of sulphuric acid a slight excess of caustic potash is added and the filtrate is treated for some time with a current of carbonic acid gas by whkh gallium oxide is precipitated. This is dissolved in the smallest possible quantity of sulphuric acid a small excess of slightly acid ammonium acetate is added and sulphuretted hydrogen is passed through the liquid which is then filtered diluted and heated to boiling.The greater part of the gallium is now pre-cipitated and is separated by filtering the hot liquid. The precipitate is dissolved in sulphuric acid caustic potash is added in slight excess and the solution is filtered and submitted to electrolysis. The metallic gallium is easily separated from the platinum pole by pressing with the fingers under warm water and the product is purified by treatment with nitric acid free from chlorine. R. R. On the Physical Properties of Gallium. By LECOQ DE BOISBAUDRAN (Conzpt. rend. lxxxiii 611-613).-The author has prepared more than half a gram of gallium; when liquid it has a silver-white liistre but when crystallised it shows a tinge of blue and loses its brilliancy.Its crystalline form is octohedral. Its melting-point averaged from six determinations is 30.15. It is hardly acted INORGANIC CHEMISTRY. on by nitric acid diluted with its om volume of water. Its specific gravity is 5.956 ;when crystallised under water it decrepitates slightly when melted. W. R. 2RC1 . PtCI,. 2TlC1 . PtC1,. BRbC1 . PtCl,. 2NaC1. PtCl2 4-4H,O. 2csc1 . PtCI,. 2LiC1 . PtC12 + 6HzO. 2AmCl . PtC1,. 2AgC1. PtCI2. BeC1 . YtCl + 5H,O NiCl . PtCl + 6H20. MgCI . PtCl + 6H,O. CUCI . PtCl + 6HZO. MnC1 . PtCI + 6H,O. ZnCl . PtC1 + 6H,O. CoC1 . PtCl + 6H20.PeCl .PtCl f 7H20. ITI. Tehad iwetals. ZrOC1,. PtCl + 8H20. I 2ThC14 .3PtC12 + 24 HZO. IV. Heread Netab. A12C16 . 2PtC1 + 21H,O. I ErzGl6 . 2PtC1 + 27H,O. Y,C& La2CI6 . SPtCI + 24HzO. . 3PtC1 -+-18Hz0. I Di2CI . 3PtC1 + l8H,O. CezC16 .4PtC1 + 20H20. 1 Di,Cl . 4PtC1 + 20H,O. The chloroplatinit,es of the monad and dyad metals are all normal salts ; the mercuric salt and that of cadminm could not be obtained. The metals having a higher quantivalence form chiefly basic salts and a few also acid salts and it is very remarkable that in the case of the VOL. XXXI. E ABSTRACTS OF CHEMICAL PAPERS. cerite and gadolinite-metals the normal salts crystallise only from basic and the acid salts from normal solutions. Ferric chromic and indium chloroplatinites could not be obtained.The following chloroplatinates were also prepared :-SnC14+ PtC14 + 12H,O forms glistening thin four-sided yellow plates. ZrOC1 + PtC1 + 12H20 crystallises in sma,ll oblique four-sided honey-yellow plates. Clet-e has already described the salt ThC14 + PtCl + 12H20,which is further proof that thorium is a tetrad. c. s. The Specific Heats and Atomic Weights of Cerium Lan- thanum and Didymium. By W. F. HILLEBRAND (Pogg. Ann. clxiii 71-87).-The paper describes the method by which the author determined the specific heats of cerium lanthanum and didymium operating with masses of the metals electrolytically prepared by Norton and himself. The figures obtained for the specific heats were cerium ,04479 ; lanthanum *04485 ; didymium -04653.Mul-tiplied by the hitherto-accepted atomic weights the respective pro-ducts are 4.12 4.15 and 4.40 by which the elements would appear as exceptions to the law of Dulong and Petit. But as these atomic weights have been estimated by indirect methods based upon hypo- thetical assumptions the author prepared the several oxides and sub-mitted them to a rigorous analysis. The results show that when instead of CeO Lao and DiO as heretofore the formulae of these compounds are taken as Cez03 La203 and Di203 the atomic heats exhibit a satisfactory accordance with Dulong and Petit’s law; for they severally become 6.18 6.23 and 6.60. The atomic weights as thus determined are Ce = 138; La = 139; Di = 144.78.X R.R. New Salts of Bismuth and their Use in the Detection of Potash.By A. CARNOT(Cowyt. rend. lxxxiii 338).-The new salts are the double thiosulphates of bismuth and alkalis. When to a faint’ly acid solution of bismuth chloride a rather strong solution of sodium thiosulphate is added the liquid becomes yellow but remains clear ; water may then be added in any quantity without producing any alteration if the amount of tbiosulphate which should be about three times as much as the bismuth is sufficient. This double salt with sodium is also soluble in alcohol. The aqueous solution decom- poses on standing the more rapidly in proportion to its concentration ; heat also assists the decomposition the double salt splitting up into bismuth sulphide and sulphuric acid.Potassium chloride added to an alcoholic solution of the sodium * Mendelejeff from considerations deduced from the “ periodic law ” of the ele- ments likewise regards the oxides of cerium aid didymiuin as sesquioxicles Ra03 assigning to both these metals the atomic weight 138. He has also made a deter-miiiatioii of the specific heat of cerium for which he finds the number 0.050 agree-ing nearly with that found by Hillebrand. On the other hand he regitrds Ianthanuni oxide as Lao, and estimates the atomic weight of lantliai~ulvat 180. (See this Journal rol. xsvi p. 1004.)-[E~.] INORGANIC CHEMISTRY. salt affords a yellow precipitate which rapidly coheres on agitation. The reaction succeeds equally well with a mixture of potassium chloride and nitrate but not with sulphate.No precipitate is formed by the chlorides of ammonium and the ordinary metals which are not precipitated by sulphuretted hydrogen but the chlorides of barium and strontium afford a white precipitate in either aqueous or alcoholic solutions of the double salt. The potassium precipitate is soluble in water but nearly insoluble in alcohol; it keeps well when dry but rapidly alters when moist particularly when in contact with the mother-liquors which themselves soon decompose bismuth sulphide being ia all cases deposited. The composition of the potassium salt is expressed by the formula Bi,03.3S,0 + 3K2S,03+ 3H,O. It is crystalline the crystals being the more marked in proportion as they are more slowly produced.Some very good crystals were obtained by redissolving in water some of the precipitated salt (after filtering off the mother-liquors) and adding alcohol till precipitation was on the point of occurring and then plunging into the solution a dialyser containing strong alcohol. As the alcohol diffused the salt slowly crystallised out chiefly on the membrane of the dialyser. These crystals keep in the air without alteration. C. H. P. Researches on the Solution of Gases in Iron Steel and Manganese. By L. TROOSTand P. HAUTEFEUILLE (Am. Chinz. Phys. [5],vii 155-1i"7).-This is a reprint of several papers which have appeared in the Comptes mndus de Z'dcade'rnie des Sciences and in abstract in this Journal (1873 729 ; 1875 610 and 790). Appended is the following summary of the general results arrived at :-1.Whenever cast iron is kept in fusion in contact with silica or silicates it evolves carbon oxide resulting from the action of iron carbide on silica ; the iron consequently becoming poorer in carbon and richer in silicon. 2. Melted cast iron dissolves considerable quantities of hydrogen the solubility of the gas being diminished by the presence of silicon and much increased by the presence of manganese. 3. Carbon oxide is much less soluble than hydrogen in the different varieties of cast iron. Its solubility is diminished or even annulled by the presence of manganese. 4. Pig iron after cooling retains gases which may be extracted by heating the metal to a temperature not exceeding 800'. Hydrogen is always more abundant than carbon oxide both in the solid and the fused metal and is more persisteutly retained by the metal.Man-ganiferous iron retains more hydrogen than does ordinary cast iron. 5. Steel dissolves less gas than cast iron hydr0g.n predominating over carbon oxide and being more forcibly retained by the metal. 6. Soft iron on the contrai-y dissolves more carbon oxide than hydrogen and retains it more forcibly. 7. Finely-divided pure iron deprived of gases decomposes water slowly at the ordinary t'emperature and rapidly at loo" the decom- position being more rapid the finer the state of division of the iron. J. R. E2 ABSTRACTS OF CHEMICAL PAPERS. Salts formed by Manganese Peroxide. By E. FRE MY (Cornpi. rend.Ixxxii 1231-1237) .-Manganese peroxide in the anhydrous state is very commonly considered as an indifferent oxide ; sometimes however it behaves like a saline oxide and less frequently as a metallic acid ; in the present instance the author wishes to show that it is also capable of functioning as a trne base. He has succeeded in combining the peroxide with sulphuric acid by acting directly on the hydrate Mn02.2H20 ; but the best method of operating seems to consist in decomposing potassium permanganate with a considerable excess of sulphuric acid. 100 grams of perman-gannte are treated with a cold mixture of 500 grams of sulphuric acid and 150 grams of water whereupon an oily layer of permanganic acid separates which gradually decomposing forms at the end of a few days a deep yellow liquid from which crystals can be obtained.This salt the author first!regarded as a sulphate of the sesquioxide but the following considerations induced him to alter his opinion and to look upon it as a salt of the peroxide. It is deliquescent soluble in sulphuric acid and decomposed by water forming at the same time a hydrate of the peroxide MnO2.2H2O. The liquor resulting from this decomposition contains no manganese. The yellow liquor exposed to the air or saturated with potassium snlpbate deposits a black subsulphate of the composition Milo2.SOS which when redissolved in sulphuric acid reproduces the yellow sul-phate. Certain salts such as manganous sulphatle potassium sulphate &c. combine with the yellow sulphate and form well-crystallised double salts The analysis of the new compound was effected by making it react upon an acidulated solution of ferrous chloride of known strength and then titrating the residual iron by means of a solution of perman-ganate.Experiment. Theory. Manganese. ................... 63.62 63.28 Oxygen ...................... 37-00 36.72 Five new compounds have been prepared from the yellow liquid before mentioned an amorphous hydrate ; a crystalline hydrate ; two subsulphates ; and a double sulphate containing both protoxide and peroxide of manganese the analyses of this latter salt led to the formula MnOz(S03)2.Mn0( S03).9H,0. This double salt may be pro- duced by the careful addition of reducing agents such as alcohol to the solution of the yellow sulphate ; it is of a rose colour and easily decomposed by water.It is possible of course to regard this compound as containing manganese sesquioxide but the existence of a corresponding potassium salt and the fact that when decomposed by an alkali it gives a pre-cipitate which yields a quantity of msnganous oxide to ammonia leaving a residue of peroxide are sufficient to show that the manganese exists in the salt in two different states of oxidation. Manganese sesyuioxide does not break up under the action of ammonia. Manganese peroxide does not appear to be the only oxide of the MINERALOGICAL CHEMISTRY. formula RO which can unite with acids to form salts inasmuch as the author has obtained several definite combinations of stannic oxide Sn02,with sulphuric nitric and hydrochloric acids. J. w.

ISSN:0368-1769    

DOI:10.1039/JS8773100043

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. Mineralogical and Crystallographical Notices (continued). By A. TON LASAULX (Jahrb. f. Min. 1876 353-368).-Aerinite a new mineral is characterised by its intense and brilliant colour vary- ing from dark-blue to light sky-blue. It possesses a dense indistinctly fibrous foliated structure being at the same time of a thoroughly earthy nature a crystalline structure being scarcely discernible. A thin section still exhibited a deep blue colour and was distinctly pleochromatic the colours varying from dark sky-blue light-blue to yellowish-blue. In polarised light the section appeared almost uni- formly of a dark-green colour thus differing from lazurite which still retains its blue colour in polarised light.The crystal-system is probably either rhombic or clinoaxial. Hardness 3 to 4; some parts can be scratched with the finger-nail others only with a knife. Streak-light bluish-grey. Binds together before the blowpipe forming eventually a grey blistered slag containing here and there small metallic magnetic grains proving the presence of iron. Acids attack the mineral easily in the cold quickly removing the blue colour and causing a depositim of powdery silica. From these reactions it is evident that the mineral is neither vivianite crocydolite nor lazulite. A portion of the mineral was fused with sodium carbonate and analysed when its percentage composition was ascertained to be as follows :-Si&. Al,OS. Fe,O:;&FeO. Mn203. CaO. MgO. H,O. 48.528 7.551 32.785 1.167 3.586 0.900 6.158 = 100,675 A previous spectroscopic examination had proved the absence of alkalis.It is evident that the mineral must be a hydrated ferroso- ferric silicate (ferric oxide predominating) belonging either to the same class of minerals as gillingite or to the chloropals. Specific gravity 3.0185. Prom a microscopical examination the author observed that aerinite is the cement or binding material of a great mass of what are apparently cleavage- pieces of quartz olivine felspar and augite which are regularly embedded in it sometimes in clumps and round masses and occasionally separated by broad zones of the blue mineral. The quartz occupies only a secondary position exhibiting at times however a hexagonal section and containing very large fluid enclo- sures which are moveable.The felspar is often observed slightly decomposed into serpentine. From the manner in which the particles of olivine occur in agrinite the author considers it highly probable that the latter is a secondary product from the former as portions of olivine which are near one another but separated by agrinite possess uniform polarisation thus showing that they all probably belonged to ABSTRACTS OF CHEMICAL PAPERS. the same individual originally. Magnetite also occurs in the mass with apatite which is often intergrown with quartz and plagioclase. Hollow spaces are observed not only in the aerinite but also in the embedded minerals sometimes containing a finely fibrous radiating zeolitic mineral.This zeolitic mineral appears to exert some influence upon the colour of the aerinite as the latter has a leek-green colour at the points of contact with it. Pilinite a new mineral occurs in hollows in the granite of Striegau as a felt-like formation of extraordinarily fine colourless or white flexible needles. The straight needles never exceed 0.01 mm. in breadth and have a tabular appearance owing to the predominance of two faces in the zone of prismatic development indications of other faces in this zone being very rare. Indistinct sections appeared to be elongated rhombs. A very distinct cleavage was observed at right angles to the direction of prismatic development no doubt being a basal cleavage as all the larger prisms are closed by this cleavage face ; in addition to the basal cleavage there is also a less complete prismatic cleavage.Examined in polarised light the mineral proved to be double refractive the principal directions of vibration being parallel to and at right angles to the vertical axis or coincident with the cleavage directions. Total darkness was observed when the edges of a cleavage plane (a long prismatic edge and a short basal edge) are parallel with the "chief section " of one of the crossed Nicol's prisms. Extremely small rhombic sections were obtained and measured (approximately) and found to have angles of 120" and 60" and from the other optical properties of the mineral von Lasaulx concludes that it crystallises in the rhombic system. It melts very easily in the flame of a Bunsen lamp with intumescence becoming eventually a transparent and nearly coloarless glass.In the matrix it gives off water. An analysis showed it to have the following composition :-Si02. A1203.Fe203. CaO. Li20. Mg0,Na20,K20. H20. -d -. v / 55.70 18.64 19.51 1-18 traces. 4*97=100.00 Specific gravity at 15" C = 2.263. From the analysis the formula 2CaO.A1,0,.5LiO2 + 2H,O is obtained which does not agree with the formula of any known zeolite unless it is supposed that the sodium oxide of analcime is replaced by calcium oxide when it would nearly agree wit,h the formula for that mineral but against this is interposed the crystallographic system of the new mineral. The author prefers to give it a distinct name as it does not agree with any known mineral species.The genesis of pilinite stands in direct connection with the occurrence of calcite in the hollows of the Striegau granite. Note on Ardennite.-A small brownish-yellow transparent crystal of this mineral was characterised by the predominance of the macrodome Po0 ,which was easily measured and the angle found to be 112" 15' thus agreeing very closely with the angle calculated by vom Rath viz. 112.12". The angle of-the prism was ascertained by measuring over the marcropinacoid mPm and found to be 130" 20' the angIe calculated by vom Rath being 130' 0'. The faces of a brachydome which could not be measured were observed on one crystal whilst MINERALOGICAL CHEMISTRY. another crystal nearly two inches in length and three lines in breadth was strongly vertically striated on COPand mpm.At the same time the macrodome (which was partially attached to quartz) was strongly striated parallel to the combination-edges with the pyramid. The prism of this crystal was much bent and evenly broken through at right angles to the vertical axis thus adding a basal cleavage to the other three cleavage directions already described (Pogg. Ann. 149 242; Juhrb. f. &!in. 1872 930). Impressions of the striation are observed on the quartz similar to those observed with tourmaline and microscopical apatite ; from this fact it may be safely inferred that ardennite is the primary formation. Pisani stated that ardennite always contained arsenic but the author has repeated the analysis of the specimen first described by him (Jahrb.f.Min. 1874 276) and confirms his statement that it was free from arsenic. Since then an improved method of separating vanadic acid in presence of alumina discovered by Dr. Bettendorff has enabled the author thoroughly to examine this mineral andas the result of ihe analyses it appears that there are two varieties of ardennite viz. (1)arsenic-ardennite ; (2) vanadium-ardennite the first having a very pale sulphur-yellow colour and the second a colophonium-brown colour the colour becoming darker as the percentage of vanadic acid increases and lighter as the percentage of arsenic acid increases. Bettendorff separates vanadic acid from alumina by precipitating them from their solution with ammonia as vanadate of aluminium an excess of ammonia having no influence.The precipitate is then digested with ammonium phosphate on a water-bath when the yellow precipitate becomes white a double decomposition having taken place viz. aluminium phosphate remains insoluble and ammonium vanadate is in solution. Ferric oxide does not interfere with this reaction. Two analyses were made of (1) light coloured ardennite; and (2) colophonium-brown ardennite resulting as follows :-SiO,. A1,03. Fez03. MnO. CaO. MgO. CuO. V05. AS~,.H2O. -No. 1.. 2'7.50 22.76 1-15 30.61 1.83 1.38 0.1'7 053 9.33 5*13=100*39 NO.2.. 27.84 24.22 26.70 2.17 3.01 -9-20 2.76 5.01=100*91 It is found that the percentage amounts of vanadic acid and arsenic acid vary considerably showing that they replace each other vicari- ously.Some of the arsenic-ardennites appear to have a dark colour but it is owing to an outward film of earthy pyrolusite which is easily removed by hydrochloric acid. The primary ardennite is undoubtedly vanadium-ardennite as it is always perfectly clear and transparent whilst the lighter arsenic-ardennite is completely opaque and appears rather porous thus favouring the assumption that it is a secondary product of the decomposition of vanadium-ardennite C. A. R. Analysis of Chrysocolla and Copper-pitchblende. Bp HUTCHINGS (Chern. News.,xxxiv l4l).-The minerals are from Mexico and are imported into England in large quantities for copper smelting. The chrysocolla bas a light bluish-green colour ; hard-ness 4.0.The copper-pitchblende is dark brown almost black; ABSTRACTS OF CHEMICAL PAPERS. hardness 6.0. 'It contains large quantities of gypsum intermixed and here and there copper carbonates. When large lumps are broken open they orten show drusy cavities in which the chrysocolla occurs botryoidal. This botryoidal chrysocolla is always coated over with a thin layer of quartz sometimes amorphous but more frequently betiutifully crystallised in very minute crystals. The minerals were very pure and were dried at 95" for some hours previous to analysis :-Chrysocoua. Copper-pitchblende. Silica soluble in Na&O,. . 62.42 20.63 Silica insoluble in Na2CQ3. 3.83 7.35 Copper oxide .......... 25.69 28-59 Lead oxide ............ 0.12 0.41 Ferric oxide ............0.26 10.94 Alumina .............. I 0.15 Manganous oxide. ....... trace 17.53 Oxygen ................ -3.60 } Cobalt oxide. ........... trace 0-35 Zinc oxide.. ............ 0.34 1-54 Lime .................. 0.74 0.92 Magnesia .............. 1.06 Water ................ 6.13 8.30 100.59 100.31 D. B. A Lithia-bearing Variety of Biotite. By G. W. HAWES (A.m. J. of Xci. [3] xi. 431).-This mineral is from felspar quarries in the large granite veins near Portland and Middlet'own in Connecticut. It is black and lustrous but in thin plates transparent brown anti uni- axial. Specific gravity 2.96. Results of analysis :-Silica 35.61 ; alumina 20.03 ; ferric oxide 0.13 ; ferrous oxide 21.85 ; manganous oxide 1.19 ; magnesia 5.23 ; potash 9.69 ; soda 0.52 ; lithia 0.93 ; titanic acid 1.46 ; fluorine 0.76 ; water 1.87 with a trace of chlorine.The ratio of R €k Si is 1 1 2 and thus the analvsis shows that this mica is an iron biotite in which lithia replaces par of the potash. R. R. Note on a New Cornish Mineral. By FREPERICK FIELD (Chem. News xxxiv 147).-This mineral has the formula 3FeO.P2O,. 4H,O ; it is green transparent and crystallises in rhombs ; dissolves in hydrochloric acid and loses water and turns black when heated per se. Hardness 3.5. W. R. A Sulphantimonide of Lead found at Arnsberg Westphalia. By F. PISANI(Compt. rend. xxxiii 747-749).-The mineral examined by the author was of a steel-grey colour and carious struc- ture with cavities filled with crystals.Hardness 2.5 ; density 5.73. Examination and analysis showed itl to be a true crystallised hetero- morphite. R. R. ORGAN10 CHEMISTRY. (Compt. rend., Origin of Crystalline Rocks. By A. M. L~VY lxxxiii 749-752) .-The results of a microscopic examinat'ion-which the paper describes-of certain petrosiliceous rocks invalidate in the author's opinion the theory which regards crystalline rocks as formed from vitreous rocks by a process of devitrification. R.R. Experiments and Observations on Vitreous Rocks. By MEUNIEEK STAN. (Conzpt. rend. lxxxiii 616-619).-As each group of vitreous rocks resembles in composition a group of crj-stalline rocks they might be supposed to be simply fused crystalline rocks ; but this supposition cannot be maintained on careful examination for they are found to contain water and other volatile substances.Various facts one of which is the existence of spherulitic obsidian lead to the supposition of a true devitrification. The author experimented on small fragments of obsidian in order to discover if by application of heat they would become devitrified and found that when heated for eight days to a temperature below their fusing point some samples remained practically unaltered while in others white grains of felspar and prisms of augite were developed. These crystals were probably present before application of heat. It is probable therefore that de- vitrification does not take place in obsidian and gallinace below their point of fusion.Even in a pasty condition as shown by another series of experiments these rocks are not devitrified. Nevertheless when they were fused for 36 or 48 hours and then exposed for eight days to a temperature favourable to devitrification some particles which acted on polarised light were observed showing a commencement of crystallisation. In some cases the angles of fracture were rectan- gular or hexagonal analagous to those of felspars. On analysis their composition was found to resemble that of orthose. The conclusions at which the author has arrived are that vitreous rocks are not a pro- duct of fusion of crystalline rocks but that crystalline rocks are derived from vitreous rocks by devitrification ; that obsidian and allied rocks cannot be directly devitrified owing to the escape of gas bubbles but that this devitrification takes place after they have been fused so as to expel all volatile matter. W. R.

ISSN:0368-1769    

DOI:10.1039/JS8773100053

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

ORGAN10 CHEMISTRY. Organic Chemistry. Formation of Tertiary Alcohols. By D. PAWLOW (Deut. Chem. Ges. Ber. ix 1311).-In the formation of these alcohols 2 mol. of the zinc-compound act on 1mol. of the acid chloride. At the same time condensation-products of acetones are formed because the latter are also a product of the reaction- /CH3 CH3.COC1 + Zn(CH& = CH3.C-C1 \0ZnCH3 /CH3 CH3.C-Cl + CH3COC1 = 2CO { EE + ZnClz. \OZnCHs ABSTRACTS OF CHEMICAL PAPERS. The acetone is then further acted upon by the zinc methide for on adding the latter body to acetone mesityl oxide is formed while among the products of the action of zinc methide on propiouyl chlo- ride the oxide C,H,,O boiling at 167-168' could be isolated. Ethylisopropyl ketone boils at 117-119' and is oxidised to acetone and propionic acid.By acting on butyryl chloride with zinc methide and ethide the tertiary alcohol C,H,( CH,) (C,H,) COH was obtained which boils at 135-138" and yields a heptylene boiling at 90-95'. Methylethyl-isopropyl carbinol which was obtained by an analogous reaction boils at 124-127" and its heptylene at 75-80". c. s. Conversion of Acid Chlorides into Alcohols. By D. DJA-KONOW (Deut. Chem. Ges. Ber. ix 1312).-A better yield is obtained by employing sodiixm instead of its amalgam which Saytzeff used. c. s. Cholesterin. By W. E. WALITZKY (Deut. Chem. Ges. Ber. ix 1310) .-Cholesterin from brain yields the chloride C,,H,,Cl. This chloride was heated with the acetates of potassium sodium and silver in presence of alcohol or acetic acid under varying conditions but Berhhelot's acetate was not formed the chloride remaining either un- changed or losing chlorine and being converted into a resin.Alkalis sodium sulphite potassium cyanate and cyanide mercuric cyanide and silver cyanide gave similar results. When the chloride is heated with sodium ethylate the hydrocarbon C,H, is formed which is sparingly soluble in alcohol more readily in ether and crystallises in transparent needles melting at 80'. On heating the chloride with alcoholic ammonia a resin is formed together with the compound (C26H42)2HCI. The iodides of potassium and aluminium do not convert the chloride into an iodide and aniline does not act on it whereas when sodium amalgam is added to its boiling alcoholic solution the hydrocarbon CZGH44 is formed crystallising from ether-alcohol in large pointed pyramids melting at about 90".Aqueous hydriodic acid and iodine and phosphorus convert cholesterin into impure CQ6H4,. According to Latschinoff cholesterin yields with potassium perman- ganate the acid C26H4207, which forms amorphous salts ; only those of the alkalis are soluble in water the others are insoluble in water alcohol and ether but dissolve in benzene. c. s. (C0172pt.rend., Action of Water on Glycols By M. NEVOLE lxxxiii 228-229) .-Bromide of isobutylene when heaked with water in a sealed tube is transformed into the corresponding aldehyde. The author explains this reaction by supposing that the glycol is first formed and then changed into aldehyde by elimination of the elements of water thus :-CHS CH CH CH \/ CBr + 2Hz0 = \C.<E + 2HBr; I 1 C'H2Br CH,OH 59 ORGANIC CHEMISTRY.CH CH CH CH \/ \/ COH = CH + HZO. I I CHZOH CHO For he found that when the glycol prepared from bromide of isobuty-lene was heated with water for some hours at 200," isobutyric aldehyde was in fact formed. The parallel reaction took place with ethylenic glycol at a somewhat higher temperature. R.R. Preparation of Trimethylene Bromide. By J. L E R M oN T o F F (Liebig's Aizrbalen clxxxii 358-362) .-The author prepares this sub-stance as follows:-Ally1 bromide is saturated at -10" to -15" with dry hydrogen bromide and afterwards heated to 165-170" in the same vessel for 24 hours.Nearly the whole of the product boiling at high temperatures is trimethylene bromide. About one-third of the ally1 bromide remains unaltered after this operat'ion but if the liquid be again saturated with hydrogen bromide and heated for 24 hours the whole enters into combination. The product is purified by distil- lation with steam. J. R. Preparation of Dichloracetic Acid. By 0. WA L LA c H (Deut. Cher12. Ges. Bey. ix 1212).-This substance may be prepared as follows :-Ethyl dichlora.cetate (obtained by the action of potassium cyanide on alcoholic chloral) is dissolved in alcohol and mixed with an equal number of molecules of potash. The cryst,als of sodium dichloracetate thereby produced are dried placed in a long combustion tube and submitted to the action of a current of hydrogen chloride so long as the gas is absorbed.The dichloracetic acid resulting from this operatiori is then distilled off in a slow stream of hydrogen chlo- ride. The acid boils at 189-191" solidifies at O" and yields a crys-talline poiassium salt. J. R. Action of Potash on Trichlorobutyric Acid. By K. GAR-ZAROLLI-THURNLAK (Deut. Chern. Ges. Ber. ix 1209).-The author has obtained by this reaction an acid having the same composition as Gottlieb's dichlorocro tonic acid but differing therefrom in properties. The investigation is not yet complete. J. R. A Simple Method of preparing Glycollic Acid. By RUDOLPH PITTIG (Deut. Chem. Ges Ber. ix 1198).-When chlwacetic acid in moderately strong aqueous solution is boiled for a few hours it is almost completely converted into glycollic and hydrochloric acids.On distilling the product and evaporating the residue over the water-bath there remains a syrupy liquid containing only a trace of chlorine from which it may be freed by again evaporating with water. The calcium salt obtained from the residue is pure glycollate. J. R. Action of Chloral and Bromal on Oxy-acids. By 0. WAL- ABSTRACTS OF CHEMTCAL PAPERS. LACH (Deut. Chem. Ges. Ber. ix 1214-1216).-The following bodies are obtained by heating chloral with the respective acids :-Chloralide of mandelic acid 10-7 C6H5CH/ )CHCC13 Snow-white crystals melting at 59" boiling at 305-310' with partial decomposition soluble in alcohol and ether insoluble in water.Chlornlide of tartaric acid /0-HC\ )CHCC13 HC<VOO)CHCC13 I coo 0-Small crystals melting at 122-124" insoluble in water soluble in warm alcohol and ether. Cldoralide of rnalic acid CHP.C00H I CH 1'0 ~OO)CHCC13. A monobasic acid forming fine crystals which melt at 137"and dissolve freely in hot water. The corresponding bromalides are obtained by precisely similar re- actions. J. R. Synthesis Of a-Oxybutyric Acid. By s.PRSCHIBITEPK (Deut. Chem. Ges. Ber. ix 1312).-This acid is formed by the action of hydrocyanic and hydrochloric acids on propionic aldehyde. C. S. Action of Ally1 Iodide and Zinc on Ethyl Oxalate. By E. YATERN~ (Guzzettn chimica italiana vi 38-39).-0n and P.SPICA gently heating a mixture of one molecular weight of ethyl oxalate and 4 of ally1 iodide with granulated zinc an energetic action is set up which must be moderated by affusion of cold water. On adding water tu the product and distilling an oil passes over which when sub-jected to fractionation may be separated into ally1 iodide and a com- pound boiling at 207-209'. This by analysis gave numbers corre-sponding with the formula CIOH1603, so that there can be no doubt the substance is ethyl-diallyloxalate H0.C(C3H,),.CO(OCzH5). From this ether the acid may be obtained by saponification but the authors have not yet examined it. They thought it probable that the acid CeH,oO might be obtained by Prankland and Duppa's method of treating the ether with phosphorus trichloride but the results were unsatisfactory.C. E. G. ORGANIC CHEMISTRY. 61 On so-called Non-saturated Compounds. By R UDOLPH PITTIG (Reut. Chem. Ges. Ber. ix 1191-1195).-This is a continua-tion of a previous paper on the same subject of which an abstract has already appeared in this Journal (1,976 i 897). 'It was stated before that maleic acid and its anhydride when dis- solved in fuming hydrobromic acid are converted into fumaric acid. Further exaxmination of this reaction has shown that monobromosuc- cinic acid is formed at the same time. The two products are formed in about equal numbers of molecules whatever the proportion of hydrobromic acid employed. Furnaric acid when heated to 100" with a sufficiently large excess of hydrobromic acid is rapidly and completely converted into mono- bromosuccinic acid identical with that obtained from maleic acid.A strong solution of monobromosuccinic acid prepared in the cold is almost completely decomposed by boiling for a few hours the praduct being pure fumaric acid. Citraconic acid and its anhydride dissolve in fuming hydi-obromic acid to a clear liquid which in the coiirse of a few days deposits small hard crystals of bromopyrotartaric acid. This acid when recrystallised from hot water forms large transparent monoclinic crystals melting at 148" with decomposition. It is resolved by prolonged boiling with water into methacrylic and hydrobromic acids and carbon dioxide and the same decomposition is brought about instantaneously by dissolving the acid in excess of sodium carbonate aud heating the solution to the boiling point.The reaction affords a satisfactory means of preparing methacrylic acid. Itaconzic acid dissolves in fuming hydrobromic acid and forms with it a crystalline addition-product melting at 133" which is still under investigation. Crotonic and isocrofonic acids dissolve in hydrobromic and hydriodic acids forming solutions which deposit substituted bromobutyric acids after standing a few days. These products are completely converted into normal butyric acid by treatment with sodium-amalgam. Cinizanzic acid combines with hydrobromic and hydriodic acids in the cold. Bromhydrocinnamic and iodhydrocinnamic acids both form pearly laminq the former melting at 128" and the latter at 120",with decomposition.J. R. On the Isomeric Pyrotartaric Acids. By W. MARKOWNIKOFF (Liebig's AnnaZen clxxxii 324-346) .-The author's investigation of these acids has led to the following results :-1. Pyrotiwtnrzic Acid from Pvopylene Bvomide.-This acid was pre- pared by heating to 150" a mixture of propylene bromide with excess of potassium cyanide and alcohol and afterwards heating the propy- lene cyanide thus formed to 100" with fuming hydrochloric acid. The product, when purified by crystallisation melted at 112". The neutral ammonium saZt forms crystals very easily soluble in water arid sparingly soluble in alcohol. The caZciunz saZt forms small prismah crystals. The acid when heated to 200" gives off water and is converted into the anhydride C511603 which is a colourless oily liquid boiling at ABSTRAOTS OF CHEMICAL PAPERS.244.9" (cow.) tasting sweet and sour and combining but slowly with water. Pyrotartaric acid prepared from tartaric acid behaves in the same manner so that the two acids are identical. 2. Isopyrotartaric Acid from a-Bromobutyric Acid.-This acid termed by the author a-isopyrotartaric acid was prepared by acting on ethyl bromobutyrate diluted with alcohol with potassium and mercury cyanide at 130" and heating the ethyl cyanobutyrate thus formed to 100" with hydrochloric acid. It crystallises when pure in rhombic prisms which melt at 111.5" and dissolve easily in water alcohol and ether. At 160"it begins to decompose into carbon dioxide and butyric acid.The potassium salt forms small crystals easily soluble in water in- soluble in alcohol. The sodium salt crystallises in granular masses more freely soluble in cold than in hot water. The silver salt dissolves sparingly in boiling water. It does not blacken at 100". The zinc saZt formed by saturating the acid with zinc carbonate is sparingly soluble in cold and hot water. At 150" it begins to decom- pose into butyric acid carbon dioxide and water. The lead salt is a heavy white precipitate which is not affected by boiling. The ethyl-ether of this acid formed by the action of ethyl iodide on the silver salt is a colourless liquid of faint aromatic odour boiling at 199-201". 3. Isopyrotartaric Acid fyom Isobutyric Acid (fl-hopyrotartaric Acid) .-This acid crystallises in transparent four-sided prisms sparingly soluble in alcohol and moderately soluble in water.At 120" it sub- limes in white needles and at 170" begins to melt and decompose into carbon dioxide and isobutyric acid. The sodium saZt crystallises in small needles easily soluble in water. The barium salt is less easily soluble and crystallises in stellate groups of thin needles. The caZcium salt like that of the a-acid is moderately soluble in cold water and is deposited from the solution on warming. It crys-tallises in nodules. The magnesium snlt is crystalline and easily soluble in water. The zinc saZt C5H,04Zn.3H,0 obtained by saturating the acid with zinc carbonate dissolves in 106 parts of water.It resembles the zinc salt of the a-acid and decomposes in the same manner. The lead saZt produced on adding lead acetate to a hot solution of the sodium salt forms white scales insoluble in hot and cold water. The silver saZt crystallises in small needles insoluble in water and not affected by boiling. 4. Normal Pyyotartaric Acid.-This acid obtained by acting on pro- pylene bromide with potassium cyanide at loo" and then proceeding as in the preparation of cc-isopyrotartaric acid crystallises from water in large transparent four-sided prisms which melt at 97.5". It distils for the most part at 215" the distillate forming a white crystalline mass melting at 82". ORGANIC CL-TEMISTRY. The calcium salt which is more freely soluble in cold than in hot water crystallises in stellate groups of thin needles.The magnesium salt is crystalline and easily soluble in water. The zinc salt dissolves very sparingly in cold and still less freely in hot water. This acid appears to be identical with Dittmar's pyrotartaric acid obtained by the reduction of glutanic acid the salts of the two acids behaving in the same manner. The foregoing results set at rest the question of the isomerism of the dicarbon acids of the formula CjHS04. The four theoretically possible isomerides are now all known. Their structural formuh are as follows :-CHzCO2H CHZCOZH CH(COZH), I I I CH2 CHCO2H CH, I I I CHZCOZH CHs CH3 Normal Methylsuccinic acid Ethylmalonic acid pyrotartaric acid.(from tartaric acid). (from butyric acid). Dimethylmatonic acid (from isobutyric acid). J. R. On Normal Oxypyrotartaric Acid (Glutanic Acid) and its Isomerides. By w. MARRORNIKOFF (Liebig's AnnaZen clxxxii 347-358).-The author prepares glutanic acid by the action of nitrous acid on glutamic acid the best result being obtained by adding potassium nitrite in the required quantity to a dilute solution of glutamic acid mixed with hydrochloric acid. Glutanic acid being very soluble is obtained in crystals with difficulty. The crystals melt at 72-73' and solidify on cooling in a clear amorphous mass. The acid appears to form with bases two classes of neutral salts differing in solubility. The zinc salt obtained by saturating the acid with zinc carbonate crystallises from a syrupy solution on standing in transparent four- sided tables which when dissolved in hot water are transformed into a pulverulent sparingly soluble salt.It crystallises from a hot satu-rated solution in nodules agreeing in composition with the formula C5H,O5Zn+ 3Hzo. The mag?zesiz~wadt C5Hs0,Mg + 4H20 obtained in the same manner as the zinc salt is sparingly soluble in cold water and crys- tallises from hot solutions in tramparent microscopic rhombic tables. Glutanic acid when heated to 190" is converted into an anhydride which dissolves in water reproducing the acid Glutanic acid is converted by reduction into normal pyrotartaric acid. It is isomeric with Maxwell Simpson's oxypyrotartaric acid ABSTRACTS OF CHEMICAL P-4PERS.from dichlorhydrin. The structural formula of these bodies are as follows :-CH(OH)CO,E CH&O,H I I CH2 CH(OH) I I I CHzCOzH CE,CO,H Glutanic acid. Oxypyrotartaric acid. The aut,hor discusses also the probable formula of itamalic and citramalic acids two other isomerides of glutanic acid but as yet the constitution of these bodies cannot be determined with certainty. J. R. Conversion of Citraconic Anhydride into Xeronic Anhy- dride. By R. FITTIG (Deut. Chew. Ges. Ber. ix 1189).-The author formerly described as xeronic anhydride a body formed in the distilla- tion of citric acid. Further investigation of this body has shown that it is a product of the decomposition of citraconic anhydride (see this Journal 1876 i 898).When pure citraconic anhydride is gently heated in a ret,ort it begins to evolve carbon dioxide at 160" and on continuing the heating till the temperature gradually rises to 190" the contents of the retort become converted into a brown very viscid mass which when distilled yields first a small quantity of citraconic anhydride and afterwards at 220-270° a brown oil insoluble in water a carbonaceous residue being left in the retort. The brown oil when distilled with water yields a distillate of xeronic anhydride the amount of which is com-paratively small. J. K Product of the Oxidation of Glycogen with Bromine Silver Oxide and Water. By R. H. CH[TTE N DEN (Liebig's AnnaZen. clxxxii 206-213).-The author has obtained by the action of bro-mine on an aqueous solution of glycogen at loo" and subsequent treatment of the product with silver oxide an acid which he proposes to call glycogenic acid.It forms when pure an intensely sour syrupy liquid the aqueous solution of which dissolves carbonates forming salts having the general formuIa C6H,,M'O7 and mostly crystalline. The calcium barium cadmium cobalt manganese and lead salts have been analysed. In all but the last (C6H,Pb20,) the acid appears to be monobasic. The formation of the acid by the oxidation of gly-cogen may be represented as follows :-C6HI0O5 + H20 + Br2 = C6H1206Br,; C6H1206Brz+ Ag20 = C,HlZO7+ 2AgBr. J. R. Glycosamine Hydrochloride. By G. LEDDERHOSE (Deut. Chem. Ges Ber. ix 1200).-When purified chitin is heated for half an hour with pure strong hydrochloric acid it dissolves completely forming a blackish-brown solution which when evaporated leaves a large quantity of brilliant crystals mixed with a black amorphous mass If chitin be similarly treated with addition of metallic tin ORGASIC CHEMISTRY.the solution formed has only a slight yellowish-brown colour and the formation of the amorphous substance is entirely avoided. The crys- tals amount to about 40 per cent. of the chitin employed. Their composition agrees with that of a carbohydrate in which HO is re-placed by NH2 combined with hydrogen chloride. COH.(CH,OH) . CHZ . NHZ + HC1. The crystals which have a decidedly sweet taste dissolve freely in water sparingly in alcohol forming acid solutions.They give with soda-ley and copper sulphate a dark-blue solution which deposits cuprous oxide on warming. The substance is being further examined. J. R. New Derivatives of Mucic Acid. By R,UDOLPH (Deqct. PITTIG Chem. Ges. Ber. ix 1198).-Muciu acid is decomposed by fuming hydrobromic acid when heated therewith for some days in the water- bath. The chief product of the reaction is an acid crystallising from water in long silky needles and from alcohol in lamin= and agreeing in composition with the formula C6H405. Its formation may be repre- sented by the equation- in accordance with which the author calls it deRydromucic acid. The bnriumsalt C6H20,Ba + 2+Hz0,crystallises in tufts of needles sparingly soluble in cold water. The calcium salt C6H205Ca + 3HL0 forms colourless laminae or small transparent needles.The silver salt CsHz05Ag,,is a white precipitate insoluble in water. The eth?y7 ether C6Hz05( C2H5)z crystallises from alcohol in colour- less rhombic prisms dissolving easily in alcohol aud ether and melting at 46-47'. It is not affected by heating with acetic anhydride. The acid is converted by the action of sodium-amalgam into a new acid which is crystallisable and easily soluble and melts at about 140'. Dehydromucic acid when carefully heated distils for the most part undecomposed without melting ; but when distilled in a bent tube it breaks up almost entirely into carbon dioxide and pyromucic acid. Cs?&05 = C5H50 + C02. J. R. On the Preparation of Levulinic Acid and on Caragheen-sugar.By F. B ENTE (Deut. Cl~em. Ges. Ber. ix 1157-1158).- This acid is formed not only by boiling cane-sugar or inulin with dilute sulphuric acid but is also obtained from filter-paper wood Caragheen-moss and left-handed gum-arabic. The latter yields att the same bime a small quantity of Scheibler's arabinose and caragbeeii an kactive sugar which reduces copper and silver salts and is oxidised by nitric acid to oxalic acid. The isomeric silver levulinate whicn the author formerly described does not exist being only the impure ordinary salt (see this Jouriial 1875 1005). c. s. Spontaneous Alteration of Anhydrous Hydrocyanic Acid ; VOL. xxxr. F ABSTRACTS OF CHEMICAL PAPERS. and a New Case of the Complete Transformation of that Acid.By J. DE GIRARD (Compt. red. lxxxiii 344).-It is kno\\-n that anhydrous hydrocyanic acid sometimes suffers decomposition in a very short time whereas at other times it may be kept for moiitlis without change. This difference arises from the calcium chloride used in drying the acid. If tlie calcium chloride is neutral the acid obtained will be pure ; but if the chloride is alkaline as it is when ignited in the open air the acid rapidly decomposes spontaneously. The expla- nation is that on the contact of the acid with the lime contained in the ignited calcium chloride calcium cyanide is formed ; this with the water contained in the hydrocymic acid gives rise to the for- matmion of calcium formste and animonia arid it is known that a trace of ammonia is sufficient to determine ihe decouiposition of the anhy- drous hydrocyanic acid.If some pure anliydrons acid be heated in a sealed tube for four or five hours the liquid solidifies to a compact bli:ck mass. On opening the tube there is no evolution of gas and the black substance has the total weight of the acid employed and the same centesimal coni- position. 011 heating it in a tube open at one end ammonium cyanide is at first formed then cyanogen and a carbonaceous residue is left ; but it niay be lieated to 50" without alteration. 011 treating the black substance with ether a crystallisable body is obtained upon which further experiments are in progress. C. IS. P. Decomposition of Potassium Cyanide Zinc Cyanide and Potassium Formcte in Carbonic Acid Air and Pure Hydro-and F.DE MONTIIOLON gen. By L. NAUDIN (Cowpt. reid. lxxxiii 345) .-Carbonic acid completely decomposes potassium cyanide in aqueous solution. With a solution containing abont 3 per cent. of the salt and a regular cui-rent of carbonic acid the quantities of cyanide decomposed were found to be equal for equal intervals of time. Deconipositio~~ of Potassium Cyaiiicle iiz Pure Hylroge?~,and iv Air Deprived of Cadhzic Acid.-A solution containing 2.1'7 per cent. of the salt as HCy was employed through which hydrogen was passed. After 36 hours the loss of HCy amounted to 5.8per cent. The decomposition still proceeded but so slowly that tlie loss of hydro- cyanic acid was undeterminable.The limit of 5.8per cent. was attained more rapidly in proportion as the current of hydrogen was itself more rapid. At a temperature of 15" no formic acid was pro-duced ; biLt at 60-80" a notable quantity of potassium formate was obtained but as this body decomposes at that temperature the pro- gress of the reaction could not be followed. Air gave identical results. The decomposition of potassium cyanide in an inert gas is limited only by the alkalinity of the remainder due to the potash liberated ; with carbonic acid there is no limit because the alkali is iieutralised as rapidly as it is produced. Decouiposition oj' ZirLc CyawXe aiid Potc~ssiwibFomnclte in Ci~rbo?iic Acid Pure Hyclrogeiz t~ndPure Air.-Zinc cyanide suspended in dis- ORGANIC CHEMISTRY.tilled water suffered slow decomposition by a rapid current of car-bonic anhydride. With air deprived of carbonic anhydride a very slight but noticeable decomposition occurred. No trace of decom-position was noticed in the cases of uranium and nickel cyanides even by the prolonged action of carbonic anhydride; but that gas decomposes potassium formate as also do pure hydrogen and air though in a less degree. C. H. P. The Structure of Cyanic and Cyanuric Acids. By A. C~aus (Dent. C'heliL. Ges. Bw.,ix 1165-1167) .-The author maintains against Nencki and Fleischer that these acids are hj-droxyl-compounds. c. s. Chloral Cyanide-cyanate and its Derivatives. By C. 0.CE c H (Deut. Chem Ges. Ber. ix. 1253-1255).-The formation of this sub- stance has been described by the author in a previous paper (see this Journal 1876 i 376; also ii 66).It dissolves sparingiy in cold and easily in hot water being completely decomposed thereby with formation of hydrocyanic and formic acids. On heating it with water in sealed tubes hydrocyanic acid is eliminated and the liquid yields ammonium chloride on evaporation. The substance dissolves in dilute acids and cry stallises therefrom unaltered but when heated with dilute hydrochloric acid it yields ammonium chloride. When dis- tilled with water it is resolved into hydrocyanic arid hydrochloric acids carbon dioxide and formic acid. Heated pel. se in a closed tube it sublimes partially in long needles at loo" and carbonises at i9no In the reaction of chloral potassiunz cyanide and potassium cyanate there is formed together with the foregoing compound a body having the formula C1H2C12NZ02, and therefore differing from it by the elements of 1mol.of hydrogen chloride. This substance previously described by Wallach (see this Journal 1876 i 376) forms small yellow needles soluble in alcohol ether and water. The author has found that it is formed whenever chloral cyanide-cyanate remains suspended in a solution of potassium cyanide. It dissolves in soda- ley and is precipitated unaltered by acids. When heated with alkalis it evolves animonia. Heated with dilute hydrochloric acid it is con-verted into fine lamixm of a substance which dissolves in water alcohol and ether and crystallises therefrom in yellow needles agree- ing in composition with the formula C4H,C1,NOa.The formation of this substance may be represented thus C,H,CIJV,@ +HC1 +2HZO =CaH,Cl,NO* +NHACI. The needles melt at 154" sublime partially in beautiful rhonibic tables dissolve in ammonia and dilute acids and crystallise from the latter unchanged. J. R. Action of Bromine on Phenyl Sulphocyanate. By B. PROS-KAUER aiid EUG.SELL(Deut. Chem. Ges. Ber. iv 1262-1266).-When a solution of bromine in chloroform is added to phenyl sulpho-cyanate diluted with chloroform an orange-red crystalline sub-F'i ABSTRACTS OF CHEMICAL PAPERS. stance is formed the composition of which agrees with the formula C14Hl,NzS3Br2.At the same time some phenyl isocyanide is formed. The reaction is probably represented by the equation- 3(C6H5NCS)+ Br = CIaHloN,S,Br2+ C6H,NC.The former product dissolves quietly in water in the cold but at looo a riolent reaction occurs in which large quantities of carbon dioxide and hydrogen sulphide are evolved and aniline hydrobromide and the hydrobromide of another base C6H5N0,are formed. The reaction is as follows :-The base C6H5N02,crystallises in white needles which dissolve sparingly in water and easily in alcohol. It forms with platinum tetrachloride a crystallisable double salt. Its melting point is 156'. With alcohol the orange-red body behaves quite differently. At the boiling heat a violent react'ion takes place in which ethyl bromide and hydrobromic acid are formed and part of the alcohol is oxidised.The liquid on cooling deposits beautiful sulphur-yellow needles agreeing when purified with the formula ClaH,,N2S3,melting a.t 152" and dissolving freely in hot alcohol but not in water. The same product is formed by the action of glacial acetic acid on the orange-red body. Its constitution is not yet determined. The authors are continuing t,heir investigation. J. R. Action of Alcoholic Potash on the Mustard Oils (Sulpho- carbimides). By R. SCHIFF (Deut. Chem. Ges. Ber. ix 1316).-By this reaction the same sulphocarbamic ethers are formed that Hofmann obtained by heating the sulpliocarbimides with absolute alcohol to 110". Thus a mixture of phenylic sulphocarbimide and alcoholic potash becomes hot and then the compound CS { :E:Hs separates out.Allylic sulphocarbimide is even more readily acted upon by alcoholic potash. c. s. Action of Phosphorus Pentabromide on Amides. Fy 0. WALLACH (Deut. Chem. Ges. Ber. ix 1213). -Diethyloxamide reacts with phosphorus pentabromide at a gentle heat to form two crystalline bodies which may be represented by the formule. CBr2NHC2H CBrNC2H I and I C:Br2NH C,H CBrNC2H These substances are decomposed by water and react with ammonia to form diethyloxamide. When heated they give off hydrogen bromide 3nd yield a brown mass from which potash liberates the base broiri-oxaZ&hyZin. This last is a solid body,-which distils with difficulty. J. R. ORGANIC CHEMISTHY. On Salts of Hydroxylurea and Double Salts of other Hy- droxarnates.Ry N. D. C. HOD GE s (Liebiy's L4nnalen clxxxii 214-220).-Dresler and Stein who first investigated hydroxylurea were unable to obtain compoands of that substance with acids. Derivatives of hydroxylamine corresponding with smides having since been shown to possess acid properties it is improbable that hydroxylurea is capable of combining with acids it might rather be expected to contain hydrogen replaceable by metals and the results of experiments made by the author seem to show that such is the case. Sodium ard Potassium Salts of Hydr.oxylurea.-When a solution of hydroxylurea in absolute alcohol is mixed with a sollition of potassium hydrate or of metallic sodium in absolute alcohol a colourless pre- cipitate is thrown down which rapidly becomes pasty and absorbs moisture greedily from the air.On one occasion the potassium com- pound was obtained as a crystalline powder which after careful drying in a current of air was found to contain 17.94 per cent. of potassium. By analogy with other hydroxamates the formula of the potassium salt should be NzCH3K02+ N2CH402 which requires 20.56 per cent. of potassium. Lead Salt of Hydroxylurea and Acetic Acid.-When to an aqueous solution of the sodium salt obtained as above an excess of neutral lead acetate is added the solution deposits on standing small colourless crystals agreeing in composition with the formula (CJ&02)J'b + (N&H,02)J'b + NzCH402 or Lend Acetate awd A.nishydrnxamn,ate.-Acid potassium anishydrox- amate added to excess of a strong solution of neutral lead acetate throws down a dense white precipitate the composition of which after drying agrees with the formula.CZH302 b<N( c,H,o,)Ho' Lead Acetate and Benzhydroxamate.-Obtained in the same manner as the preceding compouiid. A dense white precipitate agreeing in composition with the formula. N(C,H,O)HO + Pb' 'N(C,H,O)HO 'N(C,H,O)HO' J. R. Decomposition of Uroxanic Acid. By L. MEDICUS (Deut. Chem. Ges. Ber. ix 1162-1164).-0n boiling this acid witlh water no allanto'ic acid is formed as Mulder has stated the products consisting of urea carbon-dioxide and glyoxalyl-urea. C,H,N,O = CONZH + CO + C3H43,Os. ABSTRACTS OF CHEMICAL PAPERS. This decomposition confirms the views which the author held as to the constitution of uric and uroxanic acids.Uric acid. Uroxanic acid. Glyoxaljl- urea. OH I /NH-C-CO-NH \NH-CO I OH c. s. Two new Thiocarbamides (Sulphureas). By PSI.DE CLER-MONT and E. WEHRLIN (C0777pt. red. lxxxiii 347).-These were produced by a reaction similar to that signalised by one of the authors for the preparation of phenylthiocarbamide which consisted in heating aniline hydrochloride with ammonium suiphocyanidc. C'resyZthiocarbnniide CS.NH2.NH.C7H7.-Hydrochloride of paratolui-dine is heated with ammonium thiocyanide on the water-bath in presence of water. After a brief space an insoluble substance sepa- rates. This is washed on a filter until the washings afford no reaction with a ferric solution and then dissolved in boiling alcohol which on cooling deposits the cresylthiocarbamide in crystals.These crys- tals are colonrless plates which melt at 188",have a persistent bitter taste and are scarcely soluble in water or ether. Ncl;whtyZfl~iocnr0lnmz'cle.-Prepared in the same manner as the last substituting naphtylamine for the toluidine. It crystallises in small prisms with rhombic base which melt at 198" are slightly soluble in water and ether and very soluble in boiling alcohol. They have a bitter flavour and become brown on exposure to the air. Heated with lead oxide in boiling alcohol the substance is completely desulphurised and a crystalline body is produced which is under examination. If to a solution of napht~lthiocarbamide in sulphuric acid a little nitric acid is added nitrous vapours are evolved and a flocculent yellow substance produced which is slightly soluble in water but very soluble in alcohol.It has an intense tinctorial power and dyes silk a beautiful yellow. The formula of naphtylthiocarbamide is CS.NH2.N€I.CloH7. C. H. P. On Fluorene and Pyrogenic Hydrocarbons. By PII r L I P P E BARBIER (Ann. Chim. Yhys. [5] vii 472-546).-The author com-mences by briefly referring to the results of various chemists who have isolated or otherwise examined the hydrocarbons fluorene anthracene phenanthrene and tolane the last-named three isomerides may all be formed sjdhetically from toluene and may legitimately be considered as derived by dehydrogenation from the hydrocavbons C14H,,.Fluorene isolated some years ago by Bertlielot f'rom the heavy oils of coal tar boiling between 280 and 340",has been prepared in some qiiantity by the author and carefully examined. It is best prepared .horn the heavy oils from which anthracene and naphthalene have ORGANIC CHERTISTRY. 71 separated by first submitting them to fractional distillation and col- lecting. the portion passing at 290-340" (the distillate at 270-290 contains milch acenaphthene) ; by a further series of fractionations a portion passing at 300-320" is isolated. To obtain a good result enough oil should have been originally employed to allow of 15 or 20 liters of this distillate being collected. By the action of cold this fraction becomes nearly solid ; the mass is pump-filtered and the solid residue pressed in blotting paper and then again distilled collecting what passes at 290-310".Above this temperature little but phenan- threne passes over this hydrocasbon being thus obtained in an almost pure state ; it constitutes about one-half of the pressed crystals. On again distilling and collecting at 295-305" a yellowish-white mass is obtained containiiig a little oxidized substance and some acenaphthene ; these are eliminated by successively crystallising from a mixture of benzene and alcohol alcohol alone and glacial acctic acid. The last-named solvent removes the oxidized substance. but the same result can also be obtained by exposing to sunlight a solution of the crude fluorene in benzene. Absolutely pure fluorene may be prepared from the nearly pure substance thus obtained by dissolving it in ether.and adding the re-quisite quantity of picric acid. On slow evaporation fine red needles of the picric acid compound of the hydrocarbon separate melting at 80-82" ; by treating these with ammonia the hydrocarbon is set free ; and by repeating the combination with picric acid and regeneration sereral times a perfectly pure body melting at 113" is obtained Fluorene thus olhined boils at about 305O ; it sublimes with difficulty in very small white plates agglomerated so as to look like small white granules. It is very soluble in ether benzene carbon disulphide and hot alcohol; in cold alcoliol it is onlj sparingly soluble. The crystallised product has a beautiful violet fluorescence.On analysis it gives numbers leading to the formula ClsHlo*-a result confirmed by the quantity of picric acid contained in the picrate and by the analysis of ~lib~on? ojluorene-a well- crys tallised cb:tracteristic derivative obtained by adding the calculated quantity of bromine dissolved in carbon disulphide to a solution of fluorene in the same menstruum. By distillation a residue is left which is freed from a red bye-prodnct by washing with ether ; the insoluble substance is then crystailised twice from carbon disulphide by spontaneous evaporation The crystals belong to the clinorhombic or nionoclinic system and melt at 166-16i" ; they distil unchanged at a high temperature and are not attacked by boiling alcoholic potash.They are nearly insoluble in ether and in alcohol but dissolve readily in carbon disulphide and in chloroform. This bromo-derivative is formed by the reaction. C,,H, + 2Br2 = 2HBr + C1,HeBr2. When heated with red-hot lime it forms clkhenyl melting at 60" and produces lemon-yellow rhomboidal plates with Fritzsche's re-* The author throughout liis paper employs the combining numbers C = 6 and 0 = 8 and adheres to the system of formulz used by Berthelot of whom he is a disciple. He accordingly rLpresents fluorene by the formula C2sHloand fluoreiiic dcohol by C~,~HB(H~O~). ABSTRACTS OF CHEMICAL PAPERS. agent (dinitranthraquinone) hence the author regards fluorene as it ,ene1y12-met1yhew,ipd C12H8,CH2 i.e. as "diphenyl in which H is replaced by an equal volume of meth ylene." If an excess of bromine be employed in the production of dibromo-fluorene or if that body be heated with bromine hydrobromic acid is evolved and tribrornofiuorene formed thus :-CI3H8Br,+ Br = HBr + CI3H7Br3.It is somewhat difficult to obtain this body free from the dibromo derivative ; when pure it melts at 161-162". A tetrabro.rl2o~/~ore?ze and a dibroniide of rnonobromofluorene CI3H9Br(Br,) have also been obtained the latter by avoiding all heating when fluorene and bromine are brought together this being accomplished by passing air charged with bromine rapour slowly into a solution of fluorene in carbon disulphide. This body forms silky yellow needles soluble in benzene but decomposed on frequent crystallisation forming hydrobromic acid and dibromofluorene ; this result is instantly brought about by contact with alcoholic potash.The production of this addition-product is according to the author quite in accordance with the constitution assigned to fluorene ; bromodiphenyl-methylene should be capable of taking up Br ; thus C13BrH7[(CHZ)( -)] +BrZ = C,2BrH,[(CHZ)(BrZ)]. When nitric acid acts on fluorene mono-nitrcfiuorene and &nitro-Jluorene are produced ; the former is a red powder not easily obtained in the crystalline state ; the latter a reddish-yellow mass of needles diffi- cultly soluble in ordinary solvents but crystallisible with difficulty from a mixture of nitrobenzene and light oils when treated with reducing agents it forms an alkalojidal substance (Diumine of JEuowne?).Sulphuric acid forms with fluorene a snlpho-acid the salts of which are either non-crystalline or crystallisable only with difficulty. Chromic acid dissolved in acetic acid or a mixture of pot'aesium dichromate and sulphuric acid attacks fluorene only with difficulty ; after long action there are formed besides formic oxalic and phthalic acids two new bodies-$u orene- quinone and di$ he71yI eiLe carhonyI. These are nearly insoluble in water and are separated by means of a warm mixture of alcohol and benzene. On cooling grains of the former separate whilst the latter remains in solution ; by recrystalli- sation of these grains from benzene fluorenoquinone is obtaiiied pure ; it is formed by the reaction CnHio + 30 = CuHSOz + HZO.Fluorenequinone melts at 181-182" sulphurous acid solution at 100" gives a crystalline product probably fluorene-hydroquinone ; when it is heated to 180" with iodine and phosphorus fluorene is regenerated. CO melts at 81-52". When treated Diphenylene-carbonyl C12H8. with melting potash it forms diphenyZfoywiic acid C,,H8.CH202,the cal- cium salt of which gives rise to diphenyl by dry distillation. Sppar- ORGANIC CHEMISTRY. ently. therefore this oxidation-product of fluorene is identical with the "diphenylenacetone " of Fittig and Ostermayer prepared from diphenyl-oxalic acid (an oxidation-product of phenanthrene) . Hence the relationships between fluorene diphenyl and phenanthrene are expressed by the formuh- By acting on diphenylene-carbonyl (prepared from phenanthrene which is easier) with nascent hydrogen fEuorenic aZcohoZ is formed ;after crystallisation from benzene this alcohol forms hexagonal plates melt- ing at 153" ; it is soluble in alcohol and ether more so in benzene ; oxidising agents convert it into diphenylene-carbonyl i.e.it behaves like a secondary alcohol. The following equations represent the for-mation of the alcohol and its subsequent reconversion into diphenylene carbony1:-By the action of acetic anhydride at loo" fluorenic alcohol forms Juoyeriic acetate a crptallisable body melting at 75" and capable of saponification by baryta-water at 120° with formation of barium acetate and reproduction of the alcohol. When heated to a tempera-ture a little below it's melting point either alone or preferably with ace tic anhydride fluorenic alcohol loses water and forms $uore?zio etkey-~CIJL(H,C))= CiJ&(CuHioO) + HaO.The ether thus formed is a nearly colourless resinous body melting at about 290" very soluble in benzene but only sparingly soluble in alcohol and ether These properties of fluorenic alcohol result accord- ing to the author from the double functions it possesses arising from its being noc only a hydrogenised carbonyl (i.e. an incomplete ketone) but also a derivative of a lion-saturated hydrocarbon ; wherefore it exerts t'he functions of a pseudo-alcohol of incomplete character and is capable of parting with water whilst it can also polymerise the two actions taking place simultaneously.Together with fluorenic alcohol there is formed on hydrogenising diphenj-lene carbonyl with sodium amalgam a small quantity of a body somewhat more soluble in benzene and crystallising in fine needles. Not improbably this body is the relatively complete body of the series formed by the fixation of 2Hz on diphenylene carbonyl and bearing to fluorenic alcohol the same relation as pseudo-propylic alcohol to allylic alcohol. When fluorene is heated to about 275" with ten times its weight of a solution of hydriodic acid saturated at 0" carbon is set free together with various hydrocarbons of less complex character than fluorene ; benzene and toluene are thus produced together with a hydrocarbon boiling near 220° and entirely soluble in fuming nitric acid.If a larger quantity of hydriodic acid be used (40 parts) hexane and hep- tane and a tridecane Cl,Hz, are formed together with a minute quantity of a hydrocarbon volatile at about 360". The tridecane thus produced is not attacked either by nitric acid cold bromine or fuming ABSTRACTS OF CHEMICAL PAPERS. sulphuric acid ; it can also be formed by hsating to 200" fluorene and red phosphorus with hydriodic acid of sp. gr. 1.5. In the hope of synthesizing fluorene from a mixture of benzene and toluene at a red heat in virtue of the reaction- C,H + CsH,.CH = C,H1(C,H,.CH?[-]) + 2H2 Benzene. Toluene. Fluorene. the author passed the vapour of a mixture of these hydrocarbons through a red-hot tube but with no decisive result ; a minute quan- tity of a body boiling near 301" and possessing fluorescent properties mas formed but the greater portion became converted into diphenyl and anthracene.With the same object in view the isomeric hydrocarbons C13H12,diphenyl-methane and phenyl-toluene (frorn liquid bromo- toluene and phenyl bromide by the action of sodium) were heated in sealed tubes wrapped in wire gauze to a dull red heat the air in the tubes having been withdrawn by a pump before sealing the tubes ; no fluorene however was produced in either case. The phenyl-toluene used was found to boil at 255-260" after purification by fractional distillation. Like its isomeride diphenyl-methane it yielded benzene and toluene in the sealed tube ; a viscid hydrocarbon boiling at about 300" was also formed with phenyl-toluene whilst diphenyl-methane gave rise to much anthracene.The author considers that flnorene is formed in coal-tar by an altera- tion of phenanthrene which he supposes first to assimilate hydrogen forming phenanthrene hydride C14H12 which then splits up into acetylene hydrogen and fluorene thus :-2CirHiz = C2H2 + H2 + 2C13H10-No experimental evidence in support of this view is hovrrever adduced. Action qf Heat on Hydrocarbons derived from a Double Ndeczcle of Toluene by elimination of HycZrogen.-The isomerides C14Hll,dibenzyl ditolyl and benzyl-toluene are represented thus- Dibenzyl ...,. . ,.. . .. C6H1.CHz[CH2.C6H,] Ditolyl ... . . ...... . .. CHz.C6&LC6H4.C~H~] Benzyl-toluene........CH2.C6H,[CH2.C6H6] all these being capable of being regarded as being formed from toluene by elimination of hydrogen thus :-2C7Ht3 = Ci4Hi4 + H2. In order to trace out the relat,ivnships between these substances and the three isomerides CIIH1O,anthracene phenanthrene and tolane the former hydrocarbons were heated to 500-60(3" in sealed empty tubes as above described. In this way dibenzyl gave rim to tolzwbe and stilbene C14H12 thus :-2C11H14 = Cl4H1z + 2CTHe. Dibenzyl. Stilbene. Toluene. ORGANIC CHERIISTRY. By the same means stilbene gave rise to tolmne and phe~aant?mme-3Ci4Hiz = ~C~~HICI + 2c7H8 no tolane being found although the production of that body would seem ci p riori probable since the relationships of dibenzyI stilbene and tolane are represented by the formule- Dibenzyl...... C6H4.CH,[CH,.C6H6] Stilbene ... . .. C6H4.C[CH,.C6H,] Tolane ...... C6H4C[C.C,H,] ; phenanthrene being C.CH,[ C,H,.CH,] since the author finds that on heating tolane with hydriodic acid and red phosphorus to 180” stil-bene is formed. The phenanthrene therefore is produced on heating stilbeiie by a sort of “intramolecular movement ” analogous to that whereby ethyl-benzene becomes transformed into dimethyl-benzene at a high temperature (Berthelot). Tolane itself when heated in sealed tube to 509” is almost wholly carbonised a little benzene and traces of what seems to be diphenyl being formed but no phenanthrene or other hydrocarbon. Ditoly1 prepared from solid bromotoluene and sodium gave rise when heated to 500-600° in a sealed tube to no decomposition at all during a short exposure; but after the lapse of a longer time it was wholly destroyed hydrogen being evolved and carbonisation taking place but neither anthracene nor phenanthrene being formed.Simul-taneously with the crysta’llisable di tolyI prepared from solid bromo- toluene the author found that a liquid isomericle called by him p-ditolyl is formed in small quantity. This is different from the ditolyl previously known prepared from liquid bromotoluene inasmuch as when heated in a sealed tube it is wholly destroyed like the solid ditolyl whilst ditolyl from liquid bromotoluene (a-ditolyl of the author) forms under the same conditions toheiie anthracene and phei?n?ithe~ze, the second hydrocarbon constituting the grcatcr portion of the product.The niixture of anthracene and yhenanthrene thus produced was found to give with Pritzsche’s reagent brown rhomboidal plates exactly resembling those assigned to the “phorene” of that chemist whilst the pure hydrocarbons separated by repeated crj-stalli- sation from this supposed phorene gave entirely different products anthracene forming rose-violet plates and phenanthrene clear yellow ones hence the author concludes that “phorene ” is not as Fritzsche supposed a single hydrocarbon isomeric with anthracene but is simply a mixture of phenanthrene and anthracene the more SO as a mixture of perfectly pure anthracene with pure phenanthrene formed brown rhomboidal plates with Fritzsche’s reagent.Benzyl-toluene as prepared by acting on benzyl chloride with zinc in presence of toluene is a mixture of two isomerides both represented by the formula CH,.C&[CH,.C,H,] (just RS the three ditolyls above mentioned are all represented by CH2.C6H4[ CH4.CH4]) the author did not attempt to separate these two but heated the mixture boiling at 277” in a sealed tube. The products were toluene and aizthracene formed from one modification of the benzyl-toluene while from the other mod$cation which rernai~zedunaltered under the conditions of the expe- ABSTRACTS OF CIIEMICAL PAPERS. riment a minute amount of phenanthrene was apparently also formed as the plates thrown down by Fritzsche's reagent were not of a pure rose-violet colour but consisted of a mixture of rose-violet plates with brown ones.To complete the history of the pyrogenic derivatives of the hydro- carbons CIJHIJ the au tlior synthesized a new isomeride pheryl xyZene by Zincke's method viz. acting on tolyl chloride (prepared by the action of chlorine on xylene vapour and boiling at 192-196") with ziuc in presence of benzene. After several fractionations a pro-duct was obtained boiling between 270" and 280" and giving numbers agreeing with the formula CIPHI1. To this body the author assigns the formula (CHz.C6H,.CHz)(C6H,) regarding it as being formed by the reaction- CH,.C,H,.CH + C~HE= H + (CH,.CsH,.CHZ)(C6Hs) Xylene. Benzene. (Phenyl-xylene). whilst benzyl toluene is formed by the reaction- 2(C,H,.CH4) = Hz + (C~H~.CH,)(C~H,.CHP).Toluene. Benzyl- toluene. On heating this phenyl-xylene to 500-600" in a sealed tube there were obtained benzene xylene and anthracene apparently containing a little phenunthrene as brown plates were obtained with Fritzsche's reagent. It hence appears that in pyrogenic actions anthrncene may be formed not only by the dehydrogenation of a double molecule of toluene (or of a hydrocarbon such as benzyl-toluene of the same degree of carbon condensation) but also by the similar reaction between benzene and xylene. A fraction of hydrocarbons boiling at 245-250" was isolated from coal-tar and deprived of solid hydrocarbons by methodical precipi ta- tion with picric acid. The liquid thus obtained consisted of a mixture of saturated hydrocarbbns of high boiling point (paraffins ?) and other hydrocarbons of clinracter analogous to the C14H14 hydrocarbons.On heating this mixture to 500-600" in sealed tubes there were obtaiiied aceiiaphthene and a little benzene and naphthalene whence it is manifest that the coal-tar hydrocarbons of mom saturated character split up under the influence of heat into less condensed carbon groups just as do the hydrocarbons above examined. Phenunthrene. Regarding this hydrocarbon as diphenyl in which H is replaced by acetylene the author tried to synthesize it by passiug through a red-hot tube a mixture of diphenyl vapour and ethylene. The products of the reaction were benzene styrolene and nuphthalene arising from the condensation of the acetylene formed by the action of the heat on the ethylene the first also arising from the decomposi- tion of diphenyl.In addition unthracene and p7tenuntlmme were formed the latter constituting the main portion of the whole product. Hence the reaction was-c12H6(H'2) + CZHZ= HZ+ CJ%(CHZ)Z* Diphenyl. Acetylene. Plienanthrene. ORGANIC CHEMISTRY. In the hope of preparing. the phenanthrene hydride described by GrEbe. the author heated together to 210-240" phenanthrene and hydriodic acid but without any result. At 260" a liquid was formed consisting of unaltered phenanthrene and a paraffin CI4HJo,not attacked by nitric acid cold bromine or sulphuric acid. Hence the author concludes that &=be's product was not a single hydrocarbon C14HIZ, but only a mixture of this tetradecane and unchanged phenan- threne ; although he thinks phenanthrene hydride is formed in small quantity when sodium amalgam acts on an alcoholic solution of phe-nanthrene.The mixture of phenanthrene and the product of its hydrogenation by hydriodic acid was heated in a sealed tube to 500" ; diphenyl hemene and a little phenanthrene were formed by the inverse reaction of that by which phenanthrene is synthesized viz. :-The acetylene thus produced however becomes forthwith polymerised into benzene. Phenanthrene and anthracene are formed simultaneously not only in the above-described cases but also by the pyrogenous reaction of benzene and styrolene and of ethylene and benzene. The anthracene formed by acting on benzyl chloride with water forms with Fritzsche's reagent the brown compound characteristic of a mixture of anthracene and phenanthrene as does also the anthracene produced by reducing alizarin with zinc powder.The only reaction in which phenanthrene is formed without the production of anthracene is when stilbene is heated. When benzyl sulphide is distilled a body expressed by the formula C,J3,,S is formed to which the author applies the term sulphostdliene. This substance forms light white plates melting at 168-169" and readily subliming at a higher temperature. With Frit,zsche's reagent it forms light yellow rhomboidal plates and with picric acid it pro-duces very unstable fine red needles. By oxidation it forms benzylic alcohol.C. R. A. W. Synthesis of Propyl-isopropyl-benzene.Bg E. PATE and RN~ P. SPICA (Qmzetta chimica itaZia,na vi 99-100) .-The authorp find that a powerful reaction takes place when either benzyl chloride or cumeiiyl chloride is treated with zinc-ethyl it being necessary to cool t,he zinc-ethyl with snow and add the chloride drop by drop. With benzyl chloride a hydrocarbon was obtained closely resembling in its properties the cumene from cuminic acid but which if Jacobsen's results are correct must be isomeric with it. Cumenyl cliloride gives a hydrocarbon C3H7.C6H1.CH2.C2H5 It is 231^0~yZ-i.so~~roiP2/1-be'l"%zene. lighter than water and boils at 205°-208*. The authors have not vet carefully examined these reactions but have observed tha,t con- &ensat?ion-p;oductsof high boiling point are formed at the same time.C. E. G. Action of Carbon Tetrachloride on Phenol in Alkaline and FERD.TIE~IANN Solution. By K. REIMER (Deut. Chem. Ges. Bey. ix 1285-l'LW) .-Carbon tetrachloride is but very slowly acted ABSTRACTS OF CHEMICAL PAPERS. on when heated with an aqueous solution of phenol in excess of alkdi but in alcoholic solution the reaction proceeds more rapidly. The products are sali cylic and paraoxybenzoic acids the formation of which is represented by the following equation :-COONa C6H,0Na + CC1 + 5NaHO = C,H,( t 4NaC1+ 3H20. 'ONa The authors employed in their experiments 28 parts of sodium hydrate or 36 parts of potassium hydrate dissolved in a small quantity of boiling water and mixed with so much alcohol that carbon tetra- chloride produced no turbidity in the solution together with 10 parts of crystallisect plienol and I7 park of carbon tetrachloride the mixture being heated to 100" in sealed tubes for two or three days.The relative amounts of salicylic and paraoxybenzoic acids pro-duced were apparently not influenced by the nature of the alkali employed. This reaction of carbon tetachloride on phenol in alkaline solution corresponds exactly to that of chloroform since it produces directly the same acids that are obtained by the oxidation of the aldehydes formed in the chloroform reaction. J. R. Preparation of Hydroquinone. By P. WESELSKI and J. SCHULER (Deut. Cliem. Ges. Bel-. ix 1159-1161).-When diazo-phenol nitrate which is obtained by the action of nitrous acid on a solution of phenol in ether is dissolved in dilute sulphuric aid and the solution mixed with alcohol and ether the sulphate crystallises out which by means of barium chloride is readily converted into the hydrochloride.The diazophenol is identical with that which Schniitt obtained from the nitrophenol melting at 110". When the sulphate is boiled with water a resinous body is formed but on using dilute aulphuric acid (1 5-90 per cenr.) hydroquinone is produced a pure product yielding 46.2 per cent. instead of 50. c. s. Rotatory Powers of the Isomeric Camphols. By J. DE &I o N 'r G o L F IER (CYompt. 1-encl. lxxxiii :341) .-The cainphols of dif-ferent origin natural or artificial differ from one another only by their rotatory power.This is explained by the fact that borneol con- sists of a mixture of an active and an inactive variety the maximum rotation for the active one being + 3'7" for the ray D. It is easy to produce the variety having a high rotatory power but the production of the other is by no means so certain and as yet all efforts have failed to obtain a borneol wholly inactive. By the action of alcoholic potash on camphor a borneol of very low rotatory power is obtained such as 1" 41' 3" and 5" 15'. By using alcohol more and inore dilute the rotatory power of the borneol is progressively increased but other circumstances also affect the results the study of which is not xet completed. By tshe act of combination the rot,atory power of borneol is augmented.Some pure boriicol liaving a rotation of 14" 35' ORGANIC CHEMISTRY. was treated with stearic acid for ten hours at 200'. The portion not combined was removed and found to have a rotatory power of 15" whilst that obtained by decomposing the stearic borneol had a rotatory power of 22" 18'. This is evidently not a separation of the active from the inactive variety. The augmentation of rotatory power is effected by the temperature at which the etherification takes place ; the higher that temperature the greater the rotatory power of the borneol subsequently elimi- nated. Is this really a creation of rotatory power ? The author thinks not because the camphors produced by the action of iiitric acid on borneols of any rotatory power always exhibit the same rotation namely about 44" 40'.These results cannot be explained on the hypothesis of an active and an inactive variety without supposing a partial destruction of the inactive variety by the action of stearic acid and its total destruction by conversion into camphor. But this is not borne out by experiment because there are no products of destruction by the action of stearic acid and the transformation of a nearly inactive borneol such as of I" 30' rotation ought to give only about one-twentieth of active camphor whereas the quantity really obtained was far larger. The hypothesis of an ordinary inactive variety should therefore be aban- doned. It is a new type ; an active body in which the rotatory power is so to speak hidden and is ready to be reproduced by the first action to which it is subjected such as etherification especially at high temperatures.Thus the borneols whether natural or artificial tvoulcl be mixtures of this particular inactive and of the active varie- ties. C. H. P. Crystalline Form,Specific Gravity and Molecular Volume of Oxysulphobenzide. By J. ANNAHEIM (Deut. Che.rn. Ges. Ber. ix 1148-11 50).-To obtain well defined crystals of oxysulphoben-zide (CsH1.OH),SO, it is dissolved in boiling glacial acetic acid and the nearly saturated solution placed in a water-bath which is heated to 100". A second larger inverted beaker is then put over it the whole covered with a cloth and left to itself for 24 hours.The crystals are often 2 cm. long and 5-6 mm. thick and belong to the orthorhombic system being combinations of 00 PG c;o €'g OP P. Axial ratio a b c = 0,53419 1.2829 1. The specific gravity at 15"is 1.3663 corre- sponding with the molecular volume 182.9 which number agrees very closely with that calculated from the atomic volumes of the elements; that of amorphous carbon = 7.5; of rhombic sulphur = 15.6 ; of hydrogen 6.5 ; and of oxygen 5 ;. the two latter being calcu- lated from the molecuiar volume of water. The specific gravities of the following derivatives were also deter-mined :- Spec. grav. Temp. Mol. rol. Tetrachoroxysulphobenzide . . . . . . 1.7774 Tetrabromoxysulphobenzide . . . . . . 2.3775 Tetraiodoxysulphobenzide .. . . . . . . 2.7966 16" 17 19 218.2 238.0 269.5 c. s. 80 ABSTRACTS OF OHEMICAL PAPERS. Two Benzenedisulphonic Acids and their Relations. By W. KOERNER (Gazzetta chimica itnliana vi 133 and G. MONSELISE -142).-Most chemists now consider the relation between the dihy- droxyl and dicarboxyl derivatives of benzene to be that represented by the formuh- C6( OH) (On)% C6( OH)H(OH)& C6( OH)H,(OH)H,. Pyrocatechin. Resorcin. Hydroquinone. C,(CO,H)(CO,H)H,. C6(CO,H)H( COzH)H,. C,(COzH)H,(CO,H)Hz. Phthalic acid. Isophthalic acid. Terephthalic acid. One of the greatest dificulties in the acceptance of this hypothesis is the fact that the benzenedisulphonic acid discovered by Hofmann and Buckton yields both resorcin and terephthalic acid.It seemed not impossible however that the disulphonic acid hitherto considered as homogeneous was really a mixture of two isomeric acids C6(S03H)H(sO3H)H3 and C6(SOsH)Hz(SO:jH)H,. This supposition has been fully confirmed by experimental evidence. The benzenedisulphonic acid was prepared by dissolving two parts of pure benzene in three parts of a mixture of ordinary (1vol.) and fuming (2 vols.) sulphuric acid and heating the product with three- fourths its volume of the fuming acid to 200-245" for 3-5 hours. The black mass was then dissolcred in water and neutralised with calcium carbonate the calcium salt was converted into the potassium salt and the solution evaporated. By this means crystals of two kinds were obtained which had to be separated mechanically.One of these potassium ol-benxenedisu~honccte,C6(S03K)H(S03K)H3+HzO,corre-sponding with isophthalic acid forms large colourless sharply- defined prisms very soluble in water but insoluble in alcohol ;whilst the other potassium P-be~2zenediszLlphoizate,c6(S03K)Hz(S0,K)H,+ H,O corresponding with terephthalic acid was obtained in ill-defined thin iridescent plates less soluble in water than the a-compound. The acids were liberated from the purified potassium salts by adding a con- siderable excess of sulphuric acid precipitating the potassium sulphate by alcohol and finally removing the excess of sulphuric acid with barium hydrate. Both acids are deliquescent crystalline substances closely resembling each other. Derivatives of a-Benzeuedisulphofiic Acid.-The bnritut?t-sfilt C,(S@,,H(S03)H3 -t'2Hz0 crystallises from a dilute solution in Iarge \/ Ba colourless prisms which are sometimes quite transparent whilst from 8 concentrated solution it separates in nodules consisting of colourless needles. The lead salt C,(SOdH(SO3)H3 +2H20 appears to be 'Pb/ isomorphous with the barium salt. The copper saZt c6(S03)H(S03)H3 \/ cu +6H30,forms blue needles ;the sodiwn salf c6(SC),Na)H( S03Na)H + crystallises in colourless needles and the cadinium salt iu small colourless prisms. ORGANIC CHEMISTRY. a-Dicyanobenzene C,(CN)H(CN)H, is obtained together with ammoniuni carbonate bj distilling a mixture of the potassium a-disul- phonate with potassium cpnlde. It is readily purified by washing with water and crystallisation from alcohol in which it is very soluble.It forms needles which melt at 156". It is readily decomposed by boiling with potassium hydrate solution yielding potassium isophtha- late with evolution of ammonia. The isophthalic acid melts above 320" and yields the characteristic soluble barium salt. a-Be?Lzenediszc~?l~oi2ic clhride C,( SO,Cl)H( SO,Cl)H, formed by the action of phosphorus perchloride on the potassium salt of the a-acid crystallises from ether in large colourless prisms which melt at 6:3" ; it is converted into the corresponding nmide C6(S02NH2)H( S02NH2)H3 by the action of ammonia-solution. The amide crystdlises in needles resembling snblimed benzoic acid and melts at 229". Tkioresomhz is formed by the reducivg action of tin and hydrochlo- ric acid on the chloride and after beizlg purified by distillation in a current of steam forms a crystalline mass of aromatic odour resem- bling that of the leaves of some species of geranium.It melts at 27.1" and distils unaltered at 24.5". It readily yields metallic derivatives. DeTivatives of P-ne?2z~nedisu~ho?aicAcid,-The barium mlt C,(S03)H,(S03)H + H,O forms crystalline crusts? consisting of \/ Ba microscopic needles much less soluble in water than the corresponding a-compound. The lend sdt c,(so,>&(so,)H,+ H,O forms small 'Pb' graniilar crystals which under the microscope are resolved into nodules of minute needles. This also is somewhat less soluble than the a-compound.p-Dicyrcnobeizzeizs is readily prepared in a manner similar to the a-compound the yield being considerably greater. It crystallises in large lustrous needles which melt at 222" but begin to sublime at 153". It is very slightly soluble in alcohol even when boiling and is deposited again almost entirely when the solution is cold. By the action of a boiling solution of potassium hydrate the cyanobenzene is converted quantitatively into terephthalic acid. P-Benzened?~~su~ho?~~c SO,Cl)H,. The action chZoride C,( S02C1)H2( of phosphorus perchloride on the ,B-disnlphonate is much less violcnt than with the a-compound the product being obtained at once in the crystalline state. It is less soluble in ether than the a-dicyanobcnzene crystallising in long transparent needles which melt at 131".l'hc rcmide C,(S02NH2)€I,(SO?NH,)H, crystallises from water in very thin scales and fkom alcohol in small plates which melt at 288". T721:07~ycZroqi~ino?~e is formed from ('3-benzenedisulphonic chloride hy the action of tin and hydrochloric acid subliming in lustrous hex-agonal plates. It is purified by distillation in a current of steam and crystallisation from boiling alcohol in which it is but slightly solublc~. The colourless crystals become oxidised on exposure to the air with formation of a yellow powder. Thiohydroqninone melts at 9S" and possesses an aromatic odour distantly resembling that of the tropmtZut,i. YOL. XXXT. G ABSTRACTS OF CHEMICAL PSPERS. It yields metallic derivatives the lead compound being an orange-red precipitate which is unaltered by a concentrated solution of potassium hydrate even when heated wit11 it at 200" for several hours.C. E. G. Sulphoparachlorobenzoic Acid. By T H. C OL L E N and C. BO T-TINGE R (Deut. Cheru. Ges. Ber. ix 1247-1251).-The preparation and properties of this acid and some of its salts were described in a former paper (see this Journal 1876 ii 412). Some other compounds have now been examined. The acid sodizm sn7t crystallises in tufts of needles which contain 2 mol. of water and are easily soluble in water. The inccyiiesizm sn7t forms needles containing 6 mol. of water which is given off at 150". The anhydrous salt absorbs moisture with avidity. The zinc salt is very soluble and crystallises from concentrated solutions in long shining needles containing 4 mol.of water. The neutral silver salt forms brilliant pointed needles containing 1 mol. of water which it gives off at 120" the salt decomposing at a somewhat higher tempe- rature. It dissolves in water. The potassium salt is not converted into dioxybenzoate by fusion with potash. When fused with potassium formate it yields benzoic isophthalic aiid terephthalic acids. The free acid when treated with sodium-amalgam is deprived of chlorine and at the same time reduced. No definite products of the reaction have been obtained. Phosphorus pentachloride acting on the acid forms a chloride which crystallises from ether in long needles melting at 150" and agrees in composition with the formula C6H~Cl.C0.S02.0H.Cl.This body when dissolved in alcohol is converted into the efh~~Z-co.nyioi~nd C6H3CICOS020HOC2H5 which forms long needles melting about 150". The chloride when treated with alcoholic ammonia yields the ammonium salt of the amide C6H3C1.CO.SO2.ONH4.NH2,whicli crystallises in hair-like needles melting at about 230". J. R. Sulphoparabromobenzoic Acid. By C. BOT T I NO E R (Deuf. Chenz. Ges. Bey. ix 125l).-In a previous paper the author stated that this acid yields a chloride melting at 155" with decomposition. Further examination of the reaction has shown that various mono-chlorides are formed according to the temperature. The chloride formed in the cold (that previously described as above) melts at -* i/6" and is convert'ed at a higher temperature into another chloride melting at 108".The former of these is designated a-chloride the latter P-chloride. The a-chloride has an acid reaction. The ethyZ-coTnpomd melts at 165". The amide melts at 252-254' and crystallises in long needles its ammonium salt melts at 203". The @-chloride forms an ethyl-compound melting at go" and crys-tallising in laminm which sublime nndeconiposed. The amicle melts at 829-230" aiid fornls an ammonium salt crystsllising in needles and melting at 125-126". J. R. ORGANIC CHEMISTRY. Action of Chloroform on Aromatic Oxy-acids in Alkaline Solution. By K. RE~MER TIEIIANN and FERD. (Deut. C?zenz. Ges. AcrD.-'Cvhen pure salicylic acid Be?-.,ix 1268-lE78).-S~~rc~~rc (14 parts) and solid sodium hydrate (25 parts) dissolved in water (50 parts) are boiled with chloroform (15 parts) for some hours and the product of the reaction is clissolved in water arid strongly acidified with hydrochloric acid a yellow precipitate is thrown down which dissolves readily in ether and is taken up therefrom almost entirely by an aqueous solution of acid sodium sulplzite.The latter solution when boiled with dilute sulphuric acid deposits a crystalline precip- itate scparabIe by crystallisation from water into the two following bodies :-/COOH 1. Paraldeh?ldosalic?lZic acid C,H,'OH .-This substance crystal- \CON lises first in long delicate yelIowish needles melting when pure at 248-249" and dissolving freely in et8her and hot alcohol but very sparingly in water and chloroform.The aqiieous solution produces a deep cherry-red coloration with ferric chloride. It decomposes car- bonates with efferrescence and combines with acid sodium sulphite thus behaving both as an acid and an aldehyde whence it appears that it is formed by the introduction of the aldehyde-group into sali- cylic acid. Its calcium salt when submitted to dry distillation with calcium hydrate yields paraoxybenzoic acid. The author concludes therefore that the aldehyde-group occupies the para-position in re-lation to the hydroxyl. 2. Ortlcots~cleh~jrlosalic~jll~c acid,-This body is contained in the mother- liquor 9f the preceding and is taken up therefrom by ether which leaves it on evaporation in the form of a white crystalline mass.When pure it crystallises in delicate needles which melt at 166" and sublime without decomposition at a somewhat higher temperature. Its aqueous solution is coIoured yellow by soda and red by ferric chloride. It decomposes carbonates with effervescence and combines with acid sodium sulphite like the preceding compound with which it is iso-meric. Its calcium salt when distilled with calcium hydrate yields pure salicylic aldehyde whence it is concluded that the aldehyde- group occupies the ortho-position in relation to the hydroxyl. The formation of the foregoing compounds is represented by the equation-COONa C&< + 3NaHO + CHCI = ONa ,COONa C,H,-ONa + 3NaCl + 2H,O. 'COH PARAOXYBENZOJC acid when treated with sodium hydrate Acm-This and chloroform in the same manner as salicylic acid (see above) yields the two following products :- ABSTRACTS OF CHEMICAL PAPERS.XOOH 1. Ort~aoaldehydo-oxydraeyZic acid C,H LOH .-A substance 'COH crystallising in thin yellow prisms which melt at 243-244" and sublime in long white needles at a somewhat higher temperature. It dissolves sparingly in chloroform and water easily in alcohol and ether. The aqueous solution is coloured an intense yellow by soda and brick-red by ferric chloride. It decomposes carbonates with effervescence and combines with acid sodium sulphite and must therefore be regarded as an aldehydo-oxybenzoic acid. Its calcium salt when submitted to dry distillation yields salicylic aldehyde and a small quantity of phenol showing that the aldehyde residue and the hydroxyl-group occupy the same positions as in salicylic aldehyde.Hence the above name. COH 2. Pamoaybenzaldehyde C6H4/ .-This substance which is se-'OH parated from the preceding with difficulty melts at 115-116'. Its aqueous solution has an acid reaction and gives with ferric chloride a faint bluish-violet coloration. Its formation from paraoxybenzoic acid is represented by the equation- ,COONa + CHCI + 4NaHO = C6H4<ONa COH C&d + Na2C03i-3NaC1 + 2H,O. 'ON% J. R. Rufigallic Acid. By W. K LOB uK o w s R I (Dezd. Chenz. Ges. Be,-. ix 1256-1262).-The author has continued his experiments on the reactions of this acid. (For an abst'ract of a previous paper see this Journal 1876 i 259).Rufigallic acid dissolves in cooled fumin,q nitric acid and in weaker acid on warming evolving large quantities of gas-chiefly carbon dioxide. The solution yields oxalic acid when evaporated. Fuming sulphuric acid dissolves rufigallic acid with dark purple- red colour and deposits it unaltered on dilution. The solution evolves sulphur dioxide when heated. Sulphuric anhydride mixed with the acid converts it into a thick violet-coloured pulp from which the acid is recovered unchanged on addition of water. Bromirie and phosphorus pentachloride both act on rufigallic acid but no definite products of the reaction have been obtained. Rufiigallic acid submitted to dry distillation with lime or baryta is mostly carbonised a slight sublimate only apparently of naphthalene being formed and an inflammable gas evolved.Rufigallic acid heated with h-j-driodic acid and phosphorus yields a yellow crystalline body the composition of which agrees -71th the formula, C14€Ilo07.This substance is not soluble without decompo- sition. Distilled with zinc-dust itJ yields anthracene. When heated ORQANIC CHEMISTRY. with acetic anhydride it is converted into a crystalline compound agreeing in composition with the formula- CZ6H22013 = C,,H,( C2H,O)sO,. The action of hydriodic acid on rufigallic acid ClaH,O, is there-fore to replace an atom of oxygen by two atoms of hydrogen. Now if rufigallic be regarded as a body formed from two substi- tuted benzene-nuclei united by two GO-groups the acid and the re- duction-product may be represented thus H C (H0)aHC /i\ 0 CsH(OH), \A/ H and the acetyl-compound thus H c (CH,OO),HCs /I\ O C~E(OC,H,O),.\A/ H These formule however are based on the assumption that the acid is capable of taking up six acetyl-groups the presence of which has not yet been demonstrated experimentally in the acetyl-compounds of either. the acid or the reduction-product. J. R. Action of Phosphorus Pentachloride on Nitronaphthalenes. By ALBERT (Dezct. Chenz. Ges. Ber.. ix 1187-1189).- ATTERBERG Nitrochloronaphthalene melting at Go,when heated with an equi- valent quantity of phosphorus pentachloride yields a dichloronaph-thalene which crystallises in long brittle needles melting at 66" and is identical iii properties with the /3-dichloronaphthalene of Faust and Saame.Nitro-ydichloronaphthalene similarly treated yields a trichloro-naphthalene crystallising in long colourless needles which melt at 129". This product is not identical with any of the known trichloro- naphthalenes all of which melt at lower temperatures. a-Dinitrochloronaphthalenemelting at 106" is only partially acted on by phosphorus pentachloride the product being a trichloronapli-thalene apparently identical with that just mentioned. a-Dinitronaphthalene heated to 217" with phosphorus pentachloride yields a chloronaphthalene which crystallises in fine laminae melting at 107" and is identical in properties with the y-dichloronaphthalene pre- viously described by the author.@-Dinitronaphthalene heated to 170" with phosphorus pentachloride ABSTRACTS OF CHEMICAL PAPERS. yields a trichloronaphthalene melting at 129" and identical with that obtained from nitro-y-dichloronaphthalene and a-dinitrochloronaph-thalene (see above). a-Nitronaphthol wheu heated with phosphorus pentachloride yields a small quantity of P-dichloronaphthalene melting at 6i". Hence P-di- chloronaphtlialene a-nitronaphthol and nitrochloronaphthalerie are corresponding and similarly constituted bodies. Naphthoquinone must also belong to the same series Liebermann having obtained it from a-nitronaphthol. J. R. An Isomeride of Dibromanthracene. By 0swA L D M IL L E R (Liebig's Aiimaleiz clxxxii 366).-Dibromanthraquinone when heated to 150" with hydriodic acid and red phosphorus yields by reduction a substance isomeric with dibromanthracene.The new body is ex-tracted from the products of the reaction by benzene. It cr,ystallises from alcohol in brilliant golden-yellow rectangular tables which melt at 190-192". It dissolves sparingly in alcohol and benzene. Strong sulphuric acid dissolves it easily forming a reddish-brown solutioii from which water throws down unaltered dibromanthracene. By oxidation it is converted into dibromanthraqninone. The investi- gation is being continued. J. R. Anthranol. By C. LIEBXRMANN and TOPF(Deut. Chern. Gcs. Ber. ix 1201-1203) .-Anthraquinone when treated with hydriodic acid and phosphorus in excess yields anthracene dihydride C,,H,, which may thus be obtained with ease in large quantities.It crystal-lises from alcohol in large lamin= melting at 108". But when the reducing action is allowed to proceed for a short time only the product is a body intermediate in composition between anthraquinone and anthracene dihy dride. This substance called anthrarzol by the authors crystallises from alcohol in yellow necdles. Its formation is represented by the equation- Anthranol forms with acetic anhydride yellow needles of a monacetyl- compound CI4H,( C,H,O)O melting at 126-131" ; whence the authors conclude that if the constitutioii of anthraquinone be represented by the first of the following formulze that of the new substance must be expressed by the second Anthraquinone.Anthranol. Anthranol is reduced to anthracene by zinc-dust at a red-heat and is oxidised to anthraquinone by nitric or chromic acid. Fuming nitric acid in the cold converts it into a nitro-compound crystallising in needles. It does not dissolve completely in alkalis on prolonged boiling of the solutions it is partially converted into anthraquinone. ORGASIC CHEMISTRY. 57 It melts at temperatures varying between 163" and 170° and at higher temperatures turns green and carbonises without volatiljsing. J. R. Xanthopurpurin. By H. PLATH (Dezit. Clienz. Ges. Ber. ix 1204-1206) .-Xanthopurpurin is best obtained by the reduction of purpurin with stannous chloride in alkaline solution. It sublimes mheLi pure in yellowish-red needles which melt at 262".It crystallises from glacial acetic acid in brilliant short needles. Xanthopurpurin forms crystalline sodium bnriu172 and caZcium siilts the last named crgstallising in dark reddish-brown needles which agrm in composition with the formula C1,H6(02Ca)0,. Di1?Leth~Z~uir;tho~uipzL,.in7 C,,H (CR,O),O,. -This substance is ob-tained by heating to 120" a mixture of xanthopuypurin methyl iodide and potash in molecular proportions. The product crystallises from glacial acetic acid in small pale-yellow needles melting at 178-180". n,btli~Zxa,iil~c~u,p111"i72, C,,H,(C,HjO),O, obtained in the same manner as the preceding compound forms yellow needles easily soluble in alcohol and glacial acetic acid but insoluble in water. It melts at 170".TJibi.oitioxa~itlio~~i~~2~rirz~ is formed by tlie direct action C14HGB~*204 of bromine on xanthopurpurin. It crystallises from glacial acetic acid in orange needles melting at 227-230O. Its ai??riroir.;unz-co~?~ozLll(~, Cl&IF1Bra(@.NHl)202, formed by boiling it with a solution of ammo-nium acetate crystallises in red matted ncedles having a fine metallic lustre. D.ilLitroxa.ntht~u,puri?z is formed by the action of C14H6(K02)20$ nitric acid of sp. gr. 1.48 on xanthopurpurin in the cold. It dissolves in water ether alcohol and glacial acetic acid and crystallises froin the last in bright-red needles melting at 249". The bariUm-ConZplJzL~~~ ClIH4(NOz),(O,Ba)O, formed ~iiadding baryta-water in excess to an aqueous solution of dinitroxant hop urpurin crystallises in dark-red needles.The anz~t~o~i'i~~i~~-~o~~~oz~~~d, C14H4(N02)2( OH) (0.NH4)O, is obtained in bright-yellow silky needles by dissolving the nitro-corn- pound in a boiling solution of ammonium acetate. When xanthopurpurin is dissolved in strong sulphuric acid and nitrous acid is passed into the soliltion a substance is formed which crystallises from glacial acetic acid in steel-blue needles appearing reddish by transmitted liglrt. This substaiice dissolves easily in water ether and other solvents melts at 249" and has the composition of dinitroxantliopurpurin ; but whether it is identical or only iscmeric with the compound described above is not yet made out. J. R. Constitution of Compounds of the Coniferyl and Vanillin Series.By PERD.TIEMBNK (Deut. Chem. and B. MEXDELSOHN Ges. Ber. ix 1278-1284).-Wlzen 1 niol. of vanillic acid is boiled for some hours with 1 rnol. of chloroform and an aqueous solution of 5 mol. of sodium hydrate and the product of the reaction is dissolved in water and acidified with hydrochloric acid a sparingly soluble body is thrown down which proves on examination to be aZdehydovadZic mid whilst vanillin remains in solution. as ABSTRACTS OF CHEMICAL PAPERS. The former product dissolves in ether and is taken up from the solution by acid sodium sulphite. It crystallises from boiling water in yellow silky needles melting at 221-222" dissolves easily in alcohol and ether and decomposes carbonates with effervescence. The reactions by which these products are formed may be repre-sented thus /COONa C6H3-OCH3 + 4NaHO + CHCI = 'ONa C6H3LOCH + 3NaCl + Na,C03 + 2H,O.'ONa (Sodium-vanillin). ,COONa CGH3LOCH + 3NaHO + CHC1 = \ONa COONa C6H2'~$~3+ 3NaC1 + 2Hz0. \COH (Sodium aldehydoranillate) . This behaviour of vanillic acid is perfectly analogous to that of paraoxybenzoic acid under the same circums tances whence the authors conclude that in the molecule of vanillic acid the carboxyl-group occupies the para-position in relation to the hydroxyl ; and accordingly \Tanillic acid is to be regarded as metamethoxyl-paraoxybenzoicacid and vanillin as metamethoxyl-paraoxy benzaldehyde. Aldehydovanillic acid must for the same reason be regarded as a derivative of salicylic aldehyde and in fact it exhibits the characteristic behaviour of such derivatives giving an intense yellow solution with soda and a distinct reddish-violet coloration with ferric chloride.J. R. The Constitution of Veratric Acid and Veratrol. By G. KOERN E R (Gaxxetta chimicu itnlium vi 142-148).-1t VI as found that veratric acid yielded prot30catechuic acid when submitted to the action of fused potassium hydrate a result in accordance with the author's idea that this rare acid was a trisubstitution derivative of benzene resembling anisic acid. He was thus induced to study the action of hydriodic acid on veratric acid and found that when the two were heated together for some time at 150-160" niethyl iodide was formed together with protocatecliuic acid (m.p. 199") and a small quantity of another acid which again heated with hydriodic acid at 170" yielded methyl iodide carbonic anhydride aiid pprocatechin. This result distinctly proved that veratric acid is identical with di- methylprotocatechuic acid but in order to obtain additional evidence tile author prepared dimethylprotocatechuic acid synthetically. Pure protocatechuic acid (from essence of cloves) mas converted into methylic dinietliylpro t ocatechuate by treating it with sodium methylate and ORGANIC CHEMISTRY. methyl iodide. The ether when pure crystallises in colourless needles melting at 58" and possessing an agreeable although feeble aromatic odour. It is easily saponified by treatment with solution of potassium hydrate and the solution on the addition of hydrochloric acid deposits the dimethylprotocatechuic acid in needles which have the same melting point as veratric acid namely 179*5",and is identical with the latter in all its properties.Veratric acid is therefore closely allied to vanillin being identical with methyl-vanillic acid the formulse C6(OCH,) (0CH,) H(C0OH)H3 and c6(OCH,) (0CHS)Hi representing veratric acid and veratrol respectively. The author thinks that the different results obtained by Koelle (Am. Chew €'harm. clix 240) are probably due to his dimethyl- protocatechuic acid being contaminated with a small quantity of monomethylprotocatechuic acid. C. E. G. Usnic Acid. By E. PATE ~wi,(Gazzetta chimica italiann vi 113-l33).-The research described in this paper has already been briefly noticed (this Journal 1876 vi 202 and Deut.Chem. Ges. Ber. ix 345). The memoir commences with an historical summary after which the method of preparation of the acid from Zeoia sordidu is fully described and its principal reactions given. Treated with sulphuric acid and potassium dichromate it yields acetic acid. Acetyl chloride I has no action on usnic acid even when boiled with it whilst at 100" in sealed tubes the acid is converted into carbonaceous products. Decayb-z~slzicacid Cl5HI6O5,is formed not only by the actioii of ethyl alcohol at 150' on usnic acid but also by the action of methyl alcohol and ally1 alcohol. Water also acts in the same manner but very slowly owing probably to the slight solubility of the acid in it.Amongst the products of the action of a solution of potassium hydrate on usnic acid the author has verified the presenrje of carbonic anhydride acetic acid and acetone so that the equation- C18H1607 + 3HzO = Ci,H,,Oj + C02 + C2H402 + C3IZjO really represents the formation of pyrousnic acid Cl2HL2O5, from mnic acid C,,H1,O7. It is not improbable that decarbusnic acid is formed as an intermediate product which becomes transformed into pyrousnic acid thus- Ci5Hi~05-I-H2O = CizHnO + C3H60-The formation of acetone renders it highly probable that usnic acid and perhaps decarbusnic acid contains the group C(CH,),. When pyrousnic acid is heated it decomposes yielding a crystalline sublimate which melts at 175" ; but in order to obtain a satisfactory result the operation should be conducted in a current of hydrogen the residue left is then very small.This new substance which not oiily melts 20" lower than pyrousnic acid but is also much less soluble in water appears to be formed without elimination of wfiter. Its solu-tion in potash absorbs oxygen from the air and becomes green. If usnic acid be treated with potassium hydrate in a manner similar to that for the preparation of pyrousnic acid but instead of boiling the solution it be merely heated to loo" acetone is produced and on 90 ABSTRACTS OF CHEMICAL PAPERS. adding hydrochloric acid to the alkaline solution a yellow flocculent pre- cipitate is obtained. This after being purified by washing with ether and crystallisation from alcohol is obtained in colourless micaceous plates quite different from decarbusnic acid and from pyrousnic acid.It is but slightly soluble in water and its alkaline solution alters readily in contact with the air but does not turn green. It melts at a lower temperature than pyrousnic acid and when heated in a current of hydrogen yields a cr-ystalline sublimate meltiiig at about 160" the alkaline solution of which does not become green on exposure to the air. The memoir concludes with some criticisms on Salkowski's paper on usnic acid. C. E. (3. Ethyl Santonate. By F. SE sT I K I (Gazzettic chimica itnliam vi 148-150) .-This compound is most conveniently prepared by heating silver santonate with excess of ethyl iodide distilling off the excess of iodide and extracting the residue with ether.On the evaporation of the ether the ethyl santonate is left in large prisms. It may also be prepared by saturating an alcoholic solution of santonic acid with hydrochloric acid and heating but is then difficult to purify. The ether which has the composition C,,H,,( C2Hj)04,melts at 88-89'. It is readily decomposed by boiling with a dilute solution of sodium hydrate with formation of sodium santonate ; also by prolonged contact with nitric acid santonic acid being liberated. C. E. G. Oxidation of Aromatic Acetamines by Pot*assium Perman- ganate. By A. W. HOFMANN (Deut. Chem. Ges. Ber. ix 1299-1303).-\Then a concentrated solution of potassium permanganate is added to a hot aqueous solution of the acetoxylide melting at 127-128" a product is formed which appears to be a mixti1i.e of at least two acids.Orie of these which can easily be isolated as it forms an insoluble blue copper salt is ucetwiz idoplithalie acid It is very sparingly soluble in water more freely in alcohol and separates from dilute alcohol in small white crystals melting with decomposition at 270-280". The acet,yl-group is not removed by heating with hydrochloric acid to ?20" whereas at 200" carbon dioxide is given off and probably an amiclobenzoic acid and perhaps also aniline is formed. Acetoparatoluide yields with potassium permangannte an acetamido- benzoic acid which crystallises from alcohol in needles melt'ing with partial decomposition at 250" and easily converted by boiling hydro- chloric acid into the hydrochloride of paramidobenzoic acid.c. s. Action of a-Dinitrochlorobenzene on Amido-compounds. By WILLGERODT (Deut. Chenz. Ges. Ber. ix 1178-1181).-While aniline acts already in tlie cold on a-dinitrochlorobenzene metani- traniline does not even at 150" ; but on heating an alcoholic solution with magnesia to 200' the following reaction takes place :- ORGANIC CHEMISTRY. 2(HzN.C,H,.N0,) + ZC,EIs,(NO,),Cl + MgO = The a-dinitrophenylnletanitraniline thus formed is sparingly soluble in boiling alcohol and less so in water ether dilute hydrochloric acid and dilute potash but freely in boiling acetic acid from which it crys-tallises in short yellow needles. When a-dinitrochlorobenzene is heated with oxamide and alcohol for six hours to 200-230" dinitraniline is formed C2Oz(NH,)2 + C,H,(NO,)ZCl + 2(C?H,.OH) = HzN.C,H,(NOz)z + (CzH,),O + CO2 + CO + NH.iC1.But when magnesia is added the reaction takes place at 150' and requires only two hours Aniline-black. By R. NIETZKI(Deut. Chem. Ges. Bey. ix 1168 -1170) .-When aniline is heated with aniline-black a blue colouring matter is formed which is obtained pure by boiling out the crude black with alcohol and treating the residue with soda to obtain the base which is converted into the acetate by moistening it with acetic acid. The dry acetate is then heated with 8-10 times its weight of aniline to 160-180" for 6-8 days. The product is then treated with an excess of dilute hydrochloric acid which does not dissolve the hydrochloride of the new base.The latter was obtained in the free state by the action of soda and purified by dissolving in ether precipitating this solution with hydrocl~loric acid and repeating this process. The free base which has either the formula CB6HB3NS but probably or C36H31N5 the former dissolves in ether with a magenta-red colour. C36H34N5.c1H crystallises from hot alcohol in needles having a coppery lustre while by precipitating the ethereal solution of the base with hydrochloric acid it is obtained as a crystalline violet powder with little lustre. C3,H3,N5.1H is a very similar compound and CZ6H3,IIU',. C6H3(NOZ)~O is obtained as a crystalline precipitate by adding an aqueous solution of picric acid to an alcoholic solution of the hydrochloride.(C3,H3,N,. CIH),PtC14 is a violet crystalline precipitate which is sparingly soluble in alcohol and insoluble in water. c. s. Action of Phosphorus Pentachloride on Acetotoluidide. By 0. WALLACH (Deut. Chena. Ges. Be)-. ix 1214).-Amongst the products of t'his reaction is the imido-chloride CH3CC1NCsH4CH3,a crystalline easily decornposible substance yielding with aniline tolui- dine and naphthylamine the following amidines :-Ethe?c,yij~ henyltoly 1arnidiqie. White needles melting at 86-88'-CH,C// NC6H4CH3 \NHC,H ABSTRACTS OF CHEMICAL PAPERS. Et~Le"iL1/lditolylamidine,a crystalline substance melting at 117-118O-CH,C //Nc6H4CH3 'NH C6W,CH3' EtJze~~ylna~Z~thyltol~la;l~iidi.ne, a body not yet obtaincd in definite form-CH,C//NcBH4CH3 \NHC,,H The imido-chloride when heated evolves hydrogen chloride and yields the hydrochloride of a base C18H,,C1N, which melts at 71-72" and decomposes at 130° the hydrochloride of a new base being formed.J. R. Xylidines. By A. W. HOFMANN (Deut. Chem. Ges. Rer. ix 1292- 1299).-The author has isolated from the crude oils of high boiling point obtained in the manufacture of aniline a xylidine which forms sparingly soluble salts with nitric and hydrochloric acids. This he calls provisionally a-xylidine to distinguish it from an isomeride occurring together with it (p-xylidine) which forms a sparingly soluble nitrate but an easily soluble hydrochloride.The two isomerides were separated by repeatedly crystallising from hot water the mixture of acetyl-compounds obtained by boiling them with glacial acetic acid the a-compound being the less soluble was thus obtained pure. a-AcetoxyZidide forms large flat white needles which melt at 127- 128" and dissolve easily in alcohol. When boiled wit,h strong hydro- chloric acid it is converted into xylidine hydrochloride. The base separated from this salt is an oil colourless at first but rapidly turning dark its boiling-poilit is 212" and its sp. gr. 0.9184 at 25". Analysis of the platinum salt agrees with the formula [C6H3( CH3),HC1],PtC14. A xylidine having the same properties as the foregoing is obtained by the action of methyl alcoliol on toluidine hydrochloride ah 300".The following derivatives of a-xylidine have been prepared. U~;eylyZsu?p/tocnI-Zln iilide CS[ NH.C,H,(CH,),], was obtained by digesting xylidine with carbon bisulpliicie till hydrogen sulphide ceased to be evolved. It is insoluble in water and but sparingly soluble in boiling alcohol from which it is deposited in dazzling-white hard crystala melting at 152-153". XyZyI sulpl~ cyccwate is formed by distilling the preceding compound with phosphoric anhydride. It is solid at the ordinary temperature but melts very easily. DixyZyZgua?ziditie CNH[NH.CsH,( CH3)& is readily formed by the action of lead oxide on xylylsulpliocarbamicle in presence of alcoholic ammonia. It crystallises from hot alcohol in delicate white needles which melt at 156-158" apparently undergoing decomposition.It is insoluble in water. NitracetoxyZidide C,H (CH3),( NO,) NH( C,II,O) formed by the action of strong nitric acid on acetoxylidide crystallises from hot water or alcohol in ye!low needles melting at 172-173". ORGANIC CHEMISTRY. Nitromylicline (Nitramidoxylene) CsH2(CH,)2(N02)NH2,is formed by boiling the last compound with strong hydrochloric acid till the liquid acquires a deep-red colonr. It crystallises from hot water in fine orange-red needles melting at 69" and dissolving sparingly in water and more freely in alcohol. It is only very slowly attacked by boiling soda- ley. Xylene-diarnine (Diamidoxylene) C6H2(CH,),(NH,), is formed by the action of tin and hydrochloric acid on nitroxylidine.It forms glittering laminae or delicate white needles which melt at 74-75". It is a faintly alkaline base and forms crystallisable salts. J R. Fluorescence of Quinidine Sulphate. By E. S CHAE R (Deut. Chenz. Ges. Ber. ix 1314).-A solution of Pasteur's quinidine sulphate (Hesse's conquinine) in chloroform after standing in the diffused light for some months assumed a splendid green fluorescence resem- bling that of certain uranium-salts. c. s. A Homologue of Caffeine. By L. PHILI PS (Deu,t. Chem. Ges. Ber. ix 1308-1310) .-When theobromine-silver is heated with ethyl- iodide ethyl-theobi-omine C7H7(C2H,)Na02is formed which separates from alcohol in white prismatic cryst,als which are somewhat freely soluble in boiling water. It is a weak base forming with nitric acid and hydrochloric acid crystallised salts.Its aqueous solution gives with silver nitrate a precipitate C7H6Ag(C2H5)N402.Ethyl-theobro-mine melts above 2$0" and sublimes without decomposition. With chlorine-water and ammonia it gives the same reactions as caffei'ne. c. s. On Atropine. By F. SELMI (Gazzetta chimicn italiana vi 153-156).-Si??zpli$ed Method of Eztracting tha Poisonouts Al?;aloi'ds) .-The alcoholic extract of the viscera acidified and filtered is evaporated at 65" ; the residue taken up with water filtered to separate fatty mat- ters and decolorised by means of basic acetate of lead leaving the solution in contact with the air for 24 hours. It is then filtered the lead precipitated with sulphuretted hydrogen arid the solution after concentration repeatedly extracted with ether.The ethereal solution is then saturated with dry cai.bonic anhydride which generally causes a precipitate of minute drops adhering to the sides of the vessel and containing some of the alkaloids. The ethereal solution is then poured into a clean vessel mixed with about half its volume of water and a current of carbonic anhydride passed for 20 minutes which may cause the precipitation of other alkaloids not precipitated by dry carbonic anhydride. Dsualljy the whole of the alkaloids present in the ether are thrown down by these means but if not the solution is dehydrated by agitation with barium oxide and then a solution of tartaric acid in ether added to the clear liquid taking great care not to employ excess of acid ; this throws down any alkalo'id that may remain.In order to extract any alkaloids that may still remain in the viscera they are mixed with barium hydrate and a little water and agitated with 2mi-i$ed aniylic alcohol ; the alkaloids may subsequcntly be extracted from the alcohol by agitation with very dilute sulphuric acid. ARSTRACTS OF CHEMICAL PAPERS. Af~opine.-As atropine is readily decomposed into tropine and atropic acid and might become altered in the process of extraction the author studied the action of various reagents on the alkaloid. Boiled with a solution of barium hydrate in contact with the air it gave a pleasant odour of hawthorn flowers ;but no odour was observed on distilling the mixture.The residue contained tropine which was extracted with ether. Atropine was decomposed when boiled with dilute sulpliuric acid or with a solution of tartaric acid but no odour was developed ; a substance (A) being obtained from the solution on treatment with ether very different in its reactions from tropine. The action of ammonia on atropine yields two substances of the nature of an alkaloiid ; one (B) precipitable by carbonic anhydride from the ethereal solution ; the other (C) Eot precipitable. Their reactions are as follows :-Tropine. A. B. C. Tannic acid.. .................. Whit,e White White - Iodised hydriodic acid .......... Brown drops -Brown Brown Platinum perchloride .......... Turbidity None Kone None Picric acid ....................-Id. Id. Id. Meyer's reagent.. .............. White Id. Id. Id. Gold chloride.. ................ Yellow Yellow Ycllow Yellow Brominated hydrobromic acid. ... None -Yellowish Id. Mercuric chloride .............. Straw yellow White White T;CThite Sodium phosphotungstate. ....... -Id. Ia. -Iodide of potassium and bismut,h 3range-yellcw Yellow Yellow Iodide of potassium and cadmium White White From experiments made on the putrified viscera of an animal poisoned with atropine and on the alkaloids generated by the putre- factive process in the viscera themselves tthe author finds that one of those formed in the latt,er case and which may be extracted by the use of amylic alcohol (although not by ether) closely resembles atropine in its action on the animal organism.Atropine may be dis- tinctly recognised however by the characteristic odour of hawthorn given off during evaporation with baryta; by the bitter taste of the ethereal extract ; and by the poisonous action of the ethereaZ extract accompanied by dilation of the pupil. C. E. G. Betulin. By U. HAUSXANN (Liebig's AnnoZen, clxxxii 368-380).-The author prepares betulin a's follows :-The outer bark of the birch tree previously boiled with water and dried is boiled for three or four hours with 20 times its weight of 90 per cent. alcohol ; the extract is strained while hot and at once mixed with alcoholic neutral lead acetate so long as a precipitate is produced thereby. The mixture again heated to the boiling point' is filtered and the filtrate is freed from lead by means of ammonium carbonate and allowed to cool whereupon it deposits a mass of crystals of impure betulin.This pro- duct is purified by treatment with ether arid crystallisation from boiling alcohol. ORGANIC CHEMISTRY. 95 Pure betulin forms long thin colourless prisms which when dry present the appearance of asbestos. It is inodorous and tasteless. It melts at 258" (corr.) to a colourless liquid which solidifies in a glassy amorpilous mass; at a somewhat higher temperature it begins to sublime in long extremely delicate needles. When strongly heated it gives off vapoiirs smelling strongly of Russia leather. It is insoluble in water sparingly soluble in cold alcoliol ether chloroform and benzene but freely soluble in the hot liquids.It dissolves also in glacial acetic acid oil of almonds and turpentine. Its composition agrees with the formula C,,H,,O,. Betulin is dissolved and acted on by strong sulphuric acid in the cold and by hydrochloric and hydriodic acids when heated therewith in sealed tubes. It is attacked also by chlorine bromine arid iodine but as yet no definite products of these actions have been obtained. Betulin yields by dry distillation a number of volatile products amongst which is one of thick oily consistence boiling at 243" of sp. gr. 0.951 and having the composition of an anhydride of betulin -C36H560. Betzslin D2'ncetafe.-This body was obtained by heating to 1%"a mixture of betulin and acetic anhydride.It crystallises in long colour- less prisms which melt at 223" (corr.) and solidify in a crystalline mass on cooling. It dissolves easily in benzene sparingly in alcohol and ether. Its composition agrees with the formula C4,,H6,05. RefuZi?.linnzaricAcid.-The author calls by this name a bocly obtained by adding betulin gradually to nitric acid of sp. gr. 1.51. The yeilow liquid thus formed leaves when evaporated a residue which after washing with water is pure betulinamaric acid. Dried over sulphuric acid it has the composition represented by the formula C36HgJ016,but when dried at ll.OO it loses 2 mol. of water yielding the anhydride C36H18011. The acid and anhydride both dissolve easily in alkalis forming bitter salts whence the name. They are nearly insoluble in water to which they impart a yellow colour and faint acid reaction.They disscilve in all proportions of alcohol and ether and are soluble also in concentrated acids. The anhydride melts at l85" undergoing decomposition. The acid forms two classes of salts one containiiig 4H20less than the other their general formuh bcing C36H1001ZR'4, and C36H480,6R'4. These are regarded by the author as salts of two different acids sus-ceptible of transformation one into the other by elimination or assimi-lation of water. The potassium snZf C36H&12K4 obtained by evaporating a solution of the acid and potassium carbonate in water exhausting the dry mass with alcohol and evaporating is a yellowish-brown hygroscopic mass. From it are derived the calcium salt C3,HloOl2Ca2; the barium salt C36H100L2Ba2 all yellowish-white pre- ; the lead salt C16H10012Pb2 cipitates ; and the copper salt C36H48016C~2, which is a green precipi- tate.The cahium salt C36HJ8016Ca2, was obtained by evaporating a solu-tion in water of the acid and calcium carbonate. The Zead saZt C36H48016PbZ, was precipitated by neutral lead acetate from an alcoholic solution of the acid. ABSTRACTS OF CHEMICAL PAPERS. When betuli~amaric acid dissolved in alcohol is saturated with hydrogen chloride and heated to 120" in sealed tubes a compound is formed agreeing in composition with the formula C44H64014, which is that of the neutral ethyl ether of the acid mimes 2 mol. of water (C,,H,,o1,(C,H,),-2H,o).It melts at 119" (con-). BetuZinic Acid.-This acid is formed together with resinous products on adding chromic anhydride to a solution of betulin in glacial acetic acid and gently warming the liquid. It forms when pure a white powder nearly insoluble in water but easily soluble in alcohol It melts at 200" (corr.) and gives on analysis numbers agreeing with the formula C,,H,,O,. Its alcoholic solution gives with neutral lead acetate an amorphous precipitate agreeing in composition with the formula (C,6H5,06),Pb3 whence it would seem that the acid is hi-basic. J. R and R. BENEDICT Glycyrerretin. By P. WESELSKY (Iie.u;t. C'hem. Ges. Ber. ix 1158-1159) .-This compound which is formed together with sugar by boiling glycyrrhizin with dilute acids J-ields when fused with potash only paroxybenzoic mid.c. s. Lignite-tar. By 0. BURG(DeuLt. Chem Ges. Ber. ix 1207-1209).-The heavy high-boiling oils of lignite tar contain a substance capable of combining with picric acid to form a compound which crys- tallises €rom benzene in long needles and gradually decomposes in the air. When the crystals are decomposed with ammonia and the oil thus liberated is dissolved in carbon bisnlphide or chloroform and saturated with bromine or chlorine pale-yellow crystals of a bromine- or chlorine-compound are deposited. These compounds are insoluble in water alcohol ether chloroform carbon bisulphide and benzene and soluble in xylene and the high-boiling oils of coal-tar only on pro-longed boiling. They are deposited from their solutions in small needles agreeing in composition with the formula Cl,H,Brl or Cl8H*CL.The same compounds may be obtained by treating the crude oils directly with bromine or chlorine. They are not acted on by sodium- amalgam or by potash. When heated with zinc-dust they yield a hydrocarbon crystallising in lamin% which melt at 122" and dissolve in alcohol glacial acetic acid ether chloroform and carbon bisulphide forming greenish-yellow fluorcscent solutions. The boiling point of the hydrocarbon lies above 360". Its formula deduced from ana3pis is C,sH,z. A solution of the hydrocarbon in chloroform gives on addition of bromine a yellowish-white precipitate of a broniine-compc,uncl, Cl,H,Br3 which dissolves in boiling benzene and crystallises therefrom in small needles.The hydrocarbon is converted by oxidation with chromic acid into a quinone-like body of reddish-brown colour agree-ing in composition with the formula Cl0H6O2. J. R. Some Constituents of Adonis Vernalis. By F. LINDEROS (Liebig's Ann~17er~,, clxxxii 365).-Accorcling to the authoZ"s iuvestiga- tion the leaves of this plant gathered at the time of flowering contain ORGANIC CHEMISTRY. 9i 18 per cent. of their weight (when dry) of aconitic acid in the form 0f calcium and potassium salts. J. R. On the Acids inRoman Chamomile Oil. R~RUDOEPH FITTIC; (Deect. Clmn. bes. Bey. ix 1195).-The author has obtained from this oil an acid melting at 45" and boiling at 185" and a second acid melt- ing at 65" and boiling at 198.5'.These acids are present in about equal proportions. Both agree in composition with the formula @,H,O,. Besides these the oil contains another wid boiling at 360". The investigation is being continued. J. R. Some Constituents of Gelsemiurn Sempervirens. By F. L. SONNENSCHEIN (Dezcf. Chem Qes. Be?*.,ix 1182-1186).-The root of this plant which in North America is used for medical preparations contains according to Wormsley a peculiar acid which he calls ye7-semic mid. This body is however idelltical with Esculin. Besides this compound the root contains also an alkaloid gelseinine which was obtained as an amorphous colourless or slightly pinkish mass melting below 100" to a colourless liquid. It dissolves but sparingly in water pllore readily in alcohol and freely in ether and chloroform.Its solu-lution has a very bitter taste and a strongly alkaline reaction. Its h-j-drochloride is amorphous neutral readily soluble in water and the solution is precipitated by tannic acid solution of iodine in potassium iodide gold chloride phosphomolybdic acid &c. Platinic cliloridc prodnces an amorphous lemon-yellow precipitate which dissolves 011 warming and crystallises on spontaneous evaporation in transparent quadyatic octohedrons which on the addition of water are changed into the amorphous compound while platinic chloride goes into solu-tion. The composition of gelsemine is C,,H,,NO,; that of the hydro-chloride (C1,H,,KO2),ClH and of the amorphous platinum-salt- 2[C,lH19N02),HC1] + PtC14.The pure alkalo'id dissolves in coneenti-ated nitric acid wit11 a greenish-yellow and in sulphnric acid Tith the same colour which however soon changes into a reddish-brown and dirty-red. When potassium dichromate is added to the sulpharic acid solution the liquid changes first into cherry-red and then into bluish-green whilc by using cerosoceric oxide a bright cherry-red colour is produced. On administering 0.012 gram of the h-j-drochloride to a large pigeon it died with convulsions in 36 minutes and frogs exhibited the same symptoms. c. s. VOL. XXXI.

ISSN:0368-1769    

DOI:10.1039/JS8773100057

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

98 ABSTRACTS OF CHEMICAL PAPERS.. Physiological Chemistry. Equivalent Substitution of Mineral Substances in Animals and Plants. By P. CHANPIONand H. PELLET (Compt. wnd. lxxxiii 48.5-488).-A table of analyses of the ash from the flesh of various animals and from eggs is given to show that while there is considerable variation in the relative amounts of soda potash lime and magnesia the quantity o€ sulphuric acid required to saturate the whole of the bases in each case varies within narrow limits and the quantity of phosphoric acid present in the ashes is nearly constnmt. R.R. Assimilation of different Sorts and Mixtures of Foods by Pigs. By WOLFF,FUNKE (Ladw. Versuchs-Stat., and DITTMANN xix 241-313).-This paper contains an account of some experiments carried out at the Experimental Station of Hohenheim during 1872-1873 of which the chief novelty is an enquiry into the nutritive value of cockchafers.Some of the results have already been published in the Wiirttemb. Wochenblcrft fir Land. zc. FomtzrirtkschaJt 1873 No. 49 and they have also been briefly noticed by Wolff in a paper read at the meeting of the German Natural Philosophers at Wiesbaden Sept. 1873 (Jour. Chen2. Soc. xxvii 384) but the puhlication of a complete and classified report has hitherto been unavoidably delayed. Four young pigs of half English breed were selected two and two from the same litters those mentioned as Nos. 2 and 4 being about twelve weeks old and the other two Nos. 1and 3 between five and six months old at the commencement of the experiments.They were fed always three times a day their food being mixed with lukewarm water generally in the proportion of about a liter to every 200 grams. The more important results are shown in the following tables :-Composition of dried Feeding Materials the Digestibility of zchich could Be determined with tolerable accuracy. I I Non-Protein Fibre. jnitmgenowl Ash. substance. extractive Cockchafers .............. 64.09 16'06 4*?3 7 *83 Cocoa-nut cake ............ 26.69 13'66 44.93 6 *12 Barley meal (a) ............ 14 *05 6 '13 '74 *78 2 a97 , , (6) ............ 12.65 4-28 '77'10 2 -79 Indian-corn meal .......... 10 -59 2'18 80-18 2 -08 Pea meal.. ................ 26 '03 8.67 59.78 3 -40 PHYSIOLOGICAL CHENISTRP.Coqjicients o,f Digestibility. ~~~ ~ ~ Protein. Fat. Extractive matter. I-Cockchafers .................... 68 *97 83 -04 - Cocoa-nut cake .................. '73 -44 83 -20 89 -24 90.09 Barley meal (a,).................. 78 -00 65 '92 .. , (tl).. ................ 79 -11 72 *28 91 +17 Indian-con1 meal ................ 84 '53 76.46 92.81 Pea meal.. ...................... 84 *43 66.52 94 9'6 The amount of actual nourishment i.e. constituents actually diges- tible contained in a hundred parts of dried food is therefore as follows :-Estractivc Protein. Fat. Hibre. matter . ---I Cockchafers .................... 44 '20 6 -05 ,* -Cocoa-nut cake .................. 19 -60 7-16 8'24 40.10 Barley meal (a)..................10-96 2 -02 0.96 67.3'7 ,) )) (6) .................. 10-01 2 -30 -'70 -29 Indian-corn meal ................ 8.95 3 -80 0.41 74-41 Pea meal.. ...................... 21.98 1-41 5.36 56-65 It will be seen that the protein substance of cockchafers and cocoa- nut cake is less digestible than that of barley meal whilst the protein of maize and pea meal is more so ; but that the fat of cockchafers and cocoa-nut cake is better digested than that of pea and barley meal the coefficient for Indian-corn meal being about the mean. The following table shows the daily increase in the weight of the animals and the quantity of dry food and of actually digestible con- stituents required for the production of 100 kilograms of live weight :-* Chitin is quite iiidigestible to pigs.ABSTRACTS OF CHEMICAL PAPERS. -*G Increase For the production of 100 kilo-;$ OEl .nTeight grams of live nqeight. .3 .A u51 Discription of Food. da2 per h cad __ 22 per day. Dry Carbo-F;w food. hydrates. -~-Kilos. Pigs 1 and 2. Days. Kilos. Kilos. Barley meal ............... 16 0 *369 441 48.4 9.3 334 *s 2 barley + 1 cockchafers .... 16 0 -393 413 90.0 13 .7 194 -5 1 barley + 1 cockchafers .... 15 0 ‘332 458 133.4 195 172-5 Barley meal .............. 24 0 *451 452 43 3 10 .4 317.7 )) ) .............. 28 0 -495 4.33 42-4 9.2 301 -6 )) )) .............. 16 0 -492 422 42’1 30.9 297 -1 )) , .............. 12 0 -461 450 4; ‘4 11.6 317 -0 Pi<qs3 and 4. Barley meal ..............16 0 ‘375 377 41.0 7.0 251.9 1 barley + 1cocoa-nut cake.. 16 0 925 437 60.2 16.2 267 ‘0 2 barley + 1cockchafers .... 15 0 -357 430 92.2 13.7 197-7 Barley meal .............. 24 0 -3P8 439 43.9 10.1 30s .G 8 barley + 1cockchafers .... 28 0 *430 394 56.2 10.1 2%4-0 6 barley + 1 starch ........ 16 0 -411 454 39.5 9.6 333 *I Pigs 2 and 4. 3 barley + 1starch ........ 12 0 ‘504 373 25.0 5.6 285.8 Maize meal.. .............. 16 0 ’278 649 55.0 24 6 484 * 8 Pea meal.. ................ 15 0.411 367 80.8 5.5 227 -3 The mean of 14 of the above experiments shows an increase of 100 kilograms in weight to have been produced by the consumption of 432 kilograms of dry barley or 358 kilograms of actually digestible organic substances. H..H. B. S. Formation of Pepsin in Batrachians. By H. VON SWTECI CK I (Pffjger’s Archiv. f. Pliysinloyie xiii 444-452) .-A microscopical examination of the stomach of the frog reveals in its cardiac end. as also in the esophagus peculiar glands which have not hitherto been described and concerning whose physiological importance nothing is known. These glands which stretch in thick layers from the commence-ment of the msopliagus to the cardiac dilatation of the stomach present distinct differences according to the stage of digestion. They are of a ramified tirbular form possessing dull cylindrical cells which exhibit an ordinary eccentric nucleus. Though varying in size the cells show a clear outline and a tendency to coloration (carmine haematoxylin).Both-sized cells are found together the larger being in excess in that portion of the membrane richest in pepsin. Chemical experiments show that during digestion the cells are larger and contain more pepsin than during fasting; also that the quantity of pepsin in the cesophagus exceeds that of the stomach whilst the pyloric region always contains the least. This fact led to PHYSIOLOOICAL CHEMISTRY. other experiments which show that the formation of pepsin takes place almost entirely in the cesophagus whilst the cells of the stomach form the acid. The quantity of pepsin formed increases during the first 6 to 10 hours of' digestion then decreases until about the 20th hour whe~ it attains its minimum and again increases. These results have been verified upon other batrachians.F. J. L. Acetone in Urine. By W. MARKOWXIKOFF (Liebig's Amalen clxxxii 362-364).-The author found in 73 litcrs oP the urine of a boy of 16 suffering from diabc>tes complicated with other disorders 30 grams of acetone and nhut 3 grams of alcohol ; ad in 82 liters of the urine of a girl affected with diabetes alone 5 grams of acctone and a very small quantity of alcohol. He believes that acetone and ethyl alcohol are constant constituents of the urine in diabetes and that they are the product of a peculiar fermentation of glucose such fermentation being consequent on the formation in the organism of a special acetone-ferueiit. J. It. Chemical Investigation of a Case of Cystinuria. By W. F. L o E B I Y c H (Lkbifs Amuxlen clxxxii 231-240).-The author has determined the aniounts of area uric acid cystine and sulphuric acid contained each day during 14 consecutive clays in the urine of a young man affected with cystinuria.The urine when first voided was per-fectly bright of yellow colour without peculiar odour and always acid except on one day when vegetable food alone was eaten. On standing for 10 or 12 hours the cystine was deposited in fine loose graiiules on the sides and bottom of the containing vessel and pre- seiited much the same appearaiice as calcium oxalate deposited from acid urine. The analytical results showed the presence on the average of 3328 grams of urea 0.5545 gram of uric acid 0.3930 gram of cystine and 2.439 grams of sulphuric acid in the 1296 C.C.of urine vbided daily. The author concludes from these results that the secre- tion of' the nibrogenous d~composition-proc3uctsof albumiiiotids is not affected by the formation of cystine. J. R. On the relation of Sodium Chloride to certain Animal Fermentation-Processes. By AL E XA N D E R Sc H M I D T (P'u~w's Archiv. f.Phys. xiii 93-14G).-In this paper the author gives the results of his experiments on the coagulation of milk with rennet the digestion of albumin with pepsin and describes more fully the influ- ence of neutral salts on the coagulation of' fibrin. 1. The CoaguJatiom of LlIilk by RenrLet.-By entire removal of the soluble salts the author attained the highest degree of activity of the casein ferment whence it follows that the alkali-salts contained in the milk and in the gastric juice especially sodium chloride influence the coagulation of casein only by hindering its progress.2. Uigestiow of Albuininous Bodies by Pepsin arLd Hydrochloric Acid.- The author found iii confirmation of previous experiments that by the addition of -5to *6of sodium chloride to gastric juice containing little or no salt the fermentative activity is greatly diminished the time ABSTRACTS OF CHEMICAL PAPERS. of solution often increasing in length from 3 to 10 times. Egg albumin boiled in the shell and therefore containing all the salts is he found much less soluble than that coagulated by dilution with acidulation and boiling in which case only a part of the soluble and insoluble ash components is retained in the coagulum.For the same reason the latter is dissolved more slowly than albumin coagulated after dialysis. He finds that the transformation into peptone occurs more rapidly in the case of casein than of albumin. The author shows that in the new-born calf less pepsin is formed than in one six weeks old. He thinks however that this smaller quantity suffices for its wants. 3. The Congulation of l?iibrin.-The author expresses the relation subsisting between the soluble salts and the fibrino-plastic substance in a coagulable fluid as follows :-1. The proportion of soluble salts remaining constant the weight of fibrin increases in a diminishing ratio with the proportion of fibrino-plastic substance within certain limit8s beyond which it diminishes until coagulation is entirely absent.2. The proportion of fibrino-plastic substance remaining constant the weight of fibrin increases in a diminishing ratio with the content of salts within certain limits beyond which it diminishes until coagula- tion is prevented. The first law the author has previously demonstrated; in proof of the latter he describes numerous experiments in this paper. By increasing the amount of fibrino-plastic substance and salts in a coagulable fluid the quant'ity of fibrin may be increased up to a certain point this being limited by the quantity of fibrinogenous sub-stance present. The author found tbat if a coagulable transndation did not coagulate on the addition of fibrin-ferment it never did so on the further addition of sodium chloride.In those coagulable transudations which coagulated on the addition of fibrin ferment the addition of from -2 to -5per cent. of sodium chloride always dimin- ished the amount of fibrin formed. As regards the mpidity of coagulation the author's observations confirm those of Heidenhain with regard to the digestion of albumin by pancreatin. They are to the effect generally that with an equal proportion of salt the rapidity increases with the content of ferment up to a certain limit not to be exceeded and with a constant proportion of ferment it rises with an increase of salt up to a certain point beyond which it sinks on increasing the salt. With regard to the fibrinogenous substance the author finds that the amount contained in the pericardial fluid of the horse and in human hydrocele fluid is greater than that of the fibrin obtained from the same fluids under the most favourahle circumstances.The anionnt of the produet of decomposition is therefore less than thatl of one of the component albuminous substances. The author concludes that the quantity of fibrin obtainable from a given fluid is variable and depends on the concurrence of the following conditions :-1. Con-tent of fibrin generators. 2. Content of salt. 3. Content of alkali. 4. Temperature of coagulation. 5. And to a limited degree the con- tent of ferment and hemoglobin (?). From experiments described the author draws the following con- clusions :- FKYSIOLOQICAL CHEJfISTRY.103 1. In B satmated alkaline solution of the fibrin generators free from salt and not containing an excess of the dissolving agent there is formed by the action of fibrin ferment a product insoluble in water and soluble in an excess of alkali which is not fibrin but in pre- sence of neutral alkali-salts in the alkaline solution becomes converted into fibrin. Provided there is no excess of alkali present almost &liewhole of the globulin-like substances contained in the fluid become converted into this body. 2. Having shown in previous experiments that in solutions of the fibrin generators in nentral alkali-salts in presence of fibrin-fer-men$ coagulation occurs (provided there he no excess of the salt) the author thinks that in this case a similar transformation occu~s.The same agent whieh causes the solution of the fibrin generators gives rke also in. this case to the conversion of the transformation-product into fibrin. 3. By a suEciently great excess of alkalis and neutral salts this transformation of the coagulation substratum is prevented ;this sub- stance retains the characters of the globulin-like bodies. 4. The blood contains in its alkalis and salts of alkaline reaction done sufficient dissolving agents to dissolve the globulin-like coni- ponents. The excess however of dissolving agents is not so great as to prevent entirely the action of the ferment ; a part of the substtratum is therefore transformed the rest remaining in solution as globulin-like body. Ordinarily this residue consists only of fibrino-plastic substance and can therefore not be converted into fibrin.The trncw-jkrmed portion which is at first retained in solution by the alkaline components of tile fluid is converted by the action of the neutral salts into fibrin. Experimenting with horse-blood plasma the author found that satu-ration with sodium chloride precipitated not only the globulin sub-stances but also the fermentative product of its transformation. The fibrin-substances precipitated by sodium chloride from one and the same plasma resemble true fibrin more the nearer the time at which they are precipitated is to the moment of spontaneous sepam- tion of the fibrin. The author applies the term fibrin to those only which are insoluble in a solution of sodium chloride whether more or less soluble in soda.Sodium chloride he finds hinders to a certain degree the enclosure of fibrin-ferment by fibrino-plastic substance. With regard to the action of alkalis on the intermediate product of coagulation the author finds that this consists in a further transfor- mation of the same into a slimy mass having the same characters as that obtained by Semmer and the author from the stroma and nuclei of amphibian blood-corpuscles by means of dilute soda. In conclusion the author likens the coagulation of fibrin to an inverted digestion. E. C. B. The Albuminous Ferment of the Pancreas. By S. PODO-L I N sK 1 (PJZuger’s Archiv. f.Ph~j.siologie,xiii 422-443) .-Heidenhain found that the albumin-dissolving ferment of the pancreas does riot exist in the living gland but appears first in the secretion.It can however ~QITTI itself in the tissue of the gland after death and this conversion t,akesplace (a) on exposing the organ to the atmosphere ; (b) on diluting the glycerin extract of the fresh gland with water; (c) on tiwatirag the substance of the gland with acids- This paper describes B series of experiments made with the view of accuratdy discovering the cause of this yost-nzoi-kiu formation of pan-creatin. And the experiments show this conversion to be in all three instances dne to the action of oxygen onthe substance contained 41~the living gland viz. zpogen.* F. a. La

ISSN:0368-1769    

DOI:10.1039/JS8773100098

出版商:RSC    

年代:1877

数据来源: RSC

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Chemiabry of Vegetable Physiology and Agriezrlture. B!Idificatian af Starch in Vegetables. By M. 3%E Ec ADA N T K (G'mzetta chimica itnlzana vi 97-98).-The author does not agree wit11 Trank that the starch iu the cells of the medulla and the medul-1;ir-y rays is transformed into gnm without any change of aspect or foim for he finds that the gum first appears in tlie cells coiltemp- miieously with the starch the latter occnpying the centre of the eelluIsr mas whilst the gum forms colaceniric layers outside it. 111 tlie spring the starch gradually dissolves whilst the gum increases and now forma a deposit in the interior of the cells ;with the progress of the vegetation the starch disappears serving 8s food for the young growth and leaving the cells empty.That this starch is converted into soluble starch is ghown by the cold aqueous extract of the medullae giving a precipitate with baryta-water. 6.E. G. Formatian of Sulphuric Acid in Seedlings. By E. SCHCLZE (Lmdw. Verszcchs-Stat. xix 172-1 16).-Plants are known tJo possess the power of p-rtilising the sulphnr of aulphates for tbe prodaction of snlpho-organic cornpounds a process by which the sulphate un-doubtedly undergoes reduction. It was however discovered during some researches conducted by the author in conjnnction with Urnlauft and Urich that during the growth of lupine seedlings in the dark exactly the contrary takes place viz, that the amount of slxlphnric acid increases at the expense of snlphnr pre-existing in organic corn-binations in the seed.Subsequent experiments confirm this and show that the increase in sulphur is most probably due to the clteeompo-sition of sulpho-albumindid csmpoands. M. H. B. s. The Germhation of Lupine Seeds. By E. SCHPCLZE IV. UMLAUF (Deut. Chew. Ges. Ber. ix 1314).-Kon-and A. URICH germinated seeds of lupines contain 45 per cent. of conglutin and albu-min but after germinating for 15 days in the dark only 8 per cent. of nlbuminoids remain and 60 per cent. of their nitrogen is found as * This paper was written before the appeamllce of Kiihne's research upon the albumin-ciissolviiig ferment of the pancreas termed by him Trypsirz. (Yerhalpdl. d. Heidelberg. naturhists. Ges. 5 i.) VEGETABLE PHYSIOLOGY ASD AGRICULTURE. 105 asparagine ; other amides and ammonia are also formed but only in sniall quantit,y while the sulphur is converted into sulphates.c. s. Absence of Leucin in the Products of Germination of the Graminacea By 31. MERCADANT E (Guzzetta chimica ittcliana vi lOU-101) .-The germinated seeds of Triticzcnz scctivum €Ior~de.umvzd-gm-e Avena satiua and Zew 3!Iais were each boiled with water and the clear liquid filtered and concentrated. Ontesting the solution for leucin by nitrate of mercury no precipitate was obtained neither did the liquor give any coloration with sodium hypochlorite in presence of phenol as it would have done had leucin been present. This result affords f urthcr evidence of the dfierence between the nitrogenous principles of the Graminaceae and those coiitained in the LeguminosE.C. E. G. Gases in the Fruit of the Bladder Senna. By C. SAINT-PIERH E and L. ~XBGNIEN (Compt. red. lxxxiii 490).-The gas in the fruit of Colideu arburescens is not comrnoii air but a mixture poorer in oxygen and containing 0.50 to 2.32 per cent. of carbonic acid. The authors have found that in these fruits although their colour is green oxygen gas is absorbed and carbonic acid gas given out by night as well as by day; and that the amount of carbonic acid produced is greater than the oxygen absorbed would furnish. In this plant there are therefore green organs which act like the animal tissues and the coloured parts of other vegetables. It. R. Composition and Nutritive and Manurial Value of Kapok-cake. By G. REIKDERS (Latdzu.Versuclzs-Stat. xix 161-164).- The kapok-tree (Eriodeizdi-o9b ajfmctuowinj of Java and the Indian Archipelago bears a seed resembling in many respects that of the cotton-plant. Like cotton-seed it is covered with a wool which though less suited for spinning yet has long been used in India and the Netherlands for filling bolsters &c. The following analyses show the composition of a trial-cake made from this seed as compared with that made from seed of the cotton- plant :-Kapok cake. Cotton cake. Water.............................. 13.28 12.60 Nitrogenous (albuminous) compounds .. 26.34 20.62 lht.. .............................. 5.82 6-33 Non-nitrogenous extractive matter .... 19.92 35-42 Woody fibre ........................ 28.12 '20.36 Ash............................... 6-52 5.64 It is probable that kapok-seed may be employed in the Netherlands for adulterating linseed-cake although it is not mentioned by Voelcktx (Jour. Roy. Agricultural Soc. vol. ix Part I) among the seeds dis-covered by him to have been used for this purpose. The ash of the seed contains 28.5 per cent. phosphoric acid and 24-6per cent. potassa ; it would consequently have about the same manurial value as linseed or rape. H. H. B. S. ABSTRACTS OF CHEMICAL PAPERS. Action of Sea-water upon Land. By G. REINDERS (Land. Verstcchs-Xtat. xis 190-214) .-Land that has been submerged by sea- water generally proves sterile for some time and indeed in some cases has remained so for 10 or even 20 gears.This sterility can be traced to the co-operation of the three following chemical causes in adciition to the injury produced mechanically by the inundation :-lst to the introduction of too great a proportion of chlorine salts; 2nd to the hygroscopic property communicated to it preventing it from properly drying ; and 31.61 to the formation of ferrous sulphate which is known to exert a very prejudicial effect upon plant-growth. This salt is produced in the soil thus the calcium and magnesium sulphates becoming reduced to sulphides by the organic matter react upon the iron compounds forming iron sulphide which is then oxidised to sulphate by exposure to the air. Land which has been thus damaged should be drained as quickly as possible and sown with grass or clov(.r and allowed to rest.Expe-rience shows that it recovers its fertility sooner if treated in this way than if cultivated all the year round as arable land. H. H. B. S. Notes on the Fermentation of Fruits plunged into Car- bonic Anhydride. Rg J.JOUBERT (C~mpt. and CH. CHAMBERLAND red lxxxiii 354).-A number of fruits (cherries plums goose- berries &.) chosen as perfect as possible were placed in tubes partially filled with carbonic anhydride over mercury-one fruit only in each tube. When tlze volume of gas ceased to augment the fruits were withdrawn and the interior pulp extmcted every precaution being taken to prevent its contact with the outw skin. The micro- scopic examination of the pulp nevcr showed the presence of ferments.Certain round granulations were seen but they may be found in fruits which have not been planged into carbonic anhydride ; moreover the pulp extracted in the manner mentioned does not cause the fermen- tation of grape must into which it is introduced. This difference of results from those obtained by Premy is considered to be due to the lengthened washing to which he subjected his specimens and to their being piled together in a flask. C. H. P. Cellulosic Fermentation produced by Vegetable Organs ; and probable Utilisation of Sugar for the production of Cel-lulose in Vegetation. By E. DURIN(Compt. rend. lxxxiii 355).-It is shown that plants contain some substance capable of exciting cellulosic fermentation from which it appears that the sugar assists in the production of cellulose in vegetation.C. H. P. The Microzymes of Germinated Barley and of Sweet Almonds as producers of Diastase and Synaptase in refer- ence to a Note of Pasteur and Joubert. By A. B~CHAXP (Corn@. red,lxxxiii 358).-The microzymes of the pancreas of barley natural or germinated of almonds and of yeast possess the same chemical functions as pancreazymose diastase synaptase and the zymase of beer-yeast. C. H. P. ANALYTICAL CHEMISTRY. On Pure Yeast. By MORITZ (Deut. Chern. Ges. Ber., TRAUBE (ix 1239-1244).-When ordinary beer-yeast is added to a filtered decoction of yeast to which sugar-candy and alcohol have been added the products of the action thereby set up vary with the proportions of the ingredients more especially with the proportion of alcohol.A decoction of 40 grams of yeast in 200 C.C. of water made up to 1 liter wit,h water holding in solution 100 grams of sugar-candy (Pasteur's liquid) undergoes alcoholic fermentation almost com-pletely on addition of a small quantity of' yeast. But if t'he proportion of sugar be reduced to one-half the formation of yeast-cells goes on with difficulty whilst bacteria develope rapidly and in a few days the liquid becomes putrid. The effect of alcohol added to the fermentable liquid is very striking. From numerous experiments with varying proportions of this liquid the author arrives at the following con- clusions :-1. The development of bacteria and of all other disease-ferments as well as of Xyccldermn wind,is considerably retarded by a small quan- tity of alcohol (2.8 per cent,) and is entirely prevented by a larger quantity (5.6 per cent.).2. The development of yeast is also retarded by alcohol but it still 3. Hence pure yeast is developed in appropriate solutions contain- goes on in solutions containing 8.2 per cent. ing from 5.6 to 8.2 per cent,. of alcohol.* It appears to be unnecessary to boil fhe liquid to be fermented before adding yeast provided it contains the necessary proportion of alcohol. It is evident that when once a small qumtity of pure yeast has been obtained as above it may be used to obtain a larger quantity by introducing it into a previonsly boiled fermentable solution free from alcohol. Pure yeast may thus be developed even in solutions yich in alburriinous matters and the fact that it can be so developed is the best possible proof of the purity of the yeast added. J. R.

ISSN:0368-1769    

DOI:10.1039/JS8773100104

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. The Iodine and Starch Reaction. By E. PUCHOT (Conzpt. vend. lxxxiii 225-226) .-The sensitiveness of the iodine and starch reaction is greatly impaired by the presence of certain organic nitro- genous bodies. Thus albumin introduced into t,he water which holds iii suspension iodide of starch causes the disappearance of the colour ; and if albumin be mixed with a solution of starch the addition of a saturated aqueous solution of iodine produces no coloration unless the iodine be added in great excess. As albumin added to an aqueous solution of iodine causes the colour to vanish there probably is in the above-described cases a direct combination between the iodine * This is true only at teiiiperatures not exceeding 15".Subsequent experiments at 25" showed that the yeast developed in solutions containing as much as 10.6 per cent. of alcohol is not quite pure. LO8 ABSTRACTS OF CHEAIICAL PAPERS. and the albumin. If a little albumin be mixed up with starch in rz mortar and iodine drop by drop be allowed to fall upon the mixture each drop produces a temporary blue stain which disappears as the liquid by spreading meets with a sufficient quant,ity of albumiu. 1%.1%. Detection of Traces of Phosphoric Acid in Toxicological Researches. By F.S E LMI (Gaxxetta chimica itnliana vi 34-35).-The method consists in bending the cxtremity of a platinum wire into a ring dipping it into the liquid suspected to contain phosphoric acid and then inserting it into the centre of a hydrogen flame at a point somewhat nearer to the orifice than to the apex of the flame.The minutest trace of phosphoric acid immediately communicates a green tinge to the flame. In using this test sodium must be absent,* and the phosphoric acid in the free state. C. E. G. Dittmark Method of Determining the amount of Chromium in Chrome Ores. (DingZ. yolyt. J. ccxxi 450).-!L’his method is based on the knowledge of the fact that powdered chromium ores are readily dissolved in a flux consisting of B parts of borax fused toge- ther with 3 parts of alkaline carbonates. The mixture formed absorbs oxygen during the fusion and also while in contact with the air and this results in a conversion of the oxide of chromium to a chromate. 0.5 gram of the ore is fused with 5-6 grams of the above- mentioned flux in a covered crucible for about five miiiutxs.?’he lid of the crucible is then removed and the mass heated very strongly ~rithconstant stirring until the whole of the ore has been dissolved %\-lienthe fusion is still continued for about three-quarters of an hour. The fused mass is digested with water heated over a water-bath with the addition of a few drops of alcohol so as to reduce any manganates if present; the liquid is filtercd and the residue washed with hot water. The filtrate contains the whole of the chromium present in the ore in the form of a chromate which is determined according to Penny’s method by dissolving a certain quantity of iron wire in hot dilute sulphuric acid cooling the solution very quickly and adding the chromate.The mixture is then titrated back with potassium bichromate. Experiments have shown that one fusion suffices to dissolve the whole of the chromium present in the ore ; the utmost difference when two fusions were made was not more than 0.3 per cent. of oxide. Althougli the platinum crucibles employed showed no signs of alte-ration the residue after fusion gave a notable quantity of a platinum salt when dissolved in dilute sulphuric acid. It is therefore not adi&,ble to simplify the above method by dissolving the whole fused mas4 in dilute acid and then titrating the solution. D. €3. A new Chemical Test for Alcohol. By EDMUND W. DAVY (Proceediiays of tlie Boyal Irish Academy [2] ii 579-582) .-A solutioii of 1part of molybdic acid in 10 parts of strong pure sulphuric acid * The difficulty occasioned by the presence of sodium may be overcome by examining the flame with the specfroscope.-iYote by Abstractor..ANALYTlCAL CHEMISTRY. 109 is warmed gently in a porcelain capule and a few drops of the liquid to be tested are allowed to fall gently into the capsule. If alcohol be present a blue coloration becomes apparcnt either imme- diately or after a few moments. This coloration disappears after exposlire to the air but onlyin consequence of absorption of moisture for on evaporation thc colour again appears. This colour is also pro-duced by methyl propyl butyl arid amyl alcohols ether and alde- hyde. The test is especially useful for detecting alcohol in chloroform or in chloral hydrate.Its sensitiveness is so great that alcohol may be detectcd in one drop of a mixture of 1part of alcohol with 1,000 of water. W. R. Rhodeine a New Test for Aniline. By E. JACQUENIN (Cowp. ~enc7. lxxxiii 226-229). -The sensitiveness of the well-known reaction of aniline with hypochlorites is such that one part in 10,000 may be detected. With a greater dilution hypochlorites give orily a very slight brown tint if they produce any visible effect at all. But the author has found that the further addition to the brown or colourless solution of a few drops of a very dilute solution of ammonium sulphide (one drop in 30 cc. of water) develops a mag-nificent rose colour by which so small a proportion as one part of aniline in 250,000 may be recognised.This new colour which is very fugitive and disappears immediately if an excess of sulphide be added the author proposes to designate as s-hodeiqae. He did not obtain similar results with oxidising or reducing reagents other than those above-named nor did toluidine &c. produce any such effects. R. R. Phyllocyanin as a Reagent. By G . PEL LAG RI (GnxPtia chimica italicma vi 35-38) .-The blue colouring matter of flowel's p.hy110-eyanin is extremely sensitive to minute traces of free alkali and although the blue solution cannot be preserved yet when a small quantity of sulphuric acid is added the red solution thus produced may be kept for a long time without' undergoing alteration. The quaxitity of acid added should not be so large as to give a distinct red colour but merely enough to change it to a dark purple intermediate between the blue and red.In this state it is capable of showing dis-tinctly the alkaline reaction caused by the presence of Smmonia in rain-water or by the plumbic hydrate in water which has been in contact with metallic lead. Added to a solution of one part of potassium hydrate iu 1,200,000 parts of water it produces a per-manent blue colour whilst with a solution in 200,000 parts of water a permanent green is obtained. It is therefore a much more delicate test than litmus which scarcely gives any reaction with the last-mentioned solution. Paper prepared with a solution of phyllocjranin mast be kept in well-closed vessels ; for although unaEected in a vacuum or by air which has been exposed over sulphuric acid yet when it is exposed freely to the air the ammonia present in it turns the colour blue.The phgllocganin is best obixained from the iris the violet or the purple verbena by treating the petals with a small quantity of warm ABSTRACTS OF CHEMICAL PAPERS. water ; sulphuric acid is then added until it assumes a purpie coiour and the solution is preserved in a closed vessel excluded from the light. c'. E. (3. Determination of Theine in Tea. By B. W. MARKOWNIKOFF (Deut. Chena. Ges. Ber. ix 1312-1313).-15 grams of powdered tea 15 grams of magnesia usta and 500 cc. water are boiled and filtered ; the residue washed with hot water ; and the filtrate after addition of magnesia and sand evaporated to dryness.The residue is ex- hausted with hot benzene which is then evaporated and the residue weighed. Young leaves contain more theine and less ash than old ones. The author believes that the quality of tea does not depend on the quantity of theine but on that of tannic acid esseiltial oils &c. c. s. Modification of the Process for Extracting the Poisonous Alkaloi'ds from the Viscera. By F. SELMI(Gazzetta chiqnicn itaZiana vi 32-34).-As it has been found that the acidulated alcoholic extract containing the alkalo'ids frequently undergoes altera- tion when evaporated in the ordinary way the author concentrates the solution in small portions at a time at about 65" in a porcelain dish accelerating the evaporation by means of a fan.The aqueous liquid thus obtained is filtered concentrated and agitated with ether after the addition of barytn. If the ethereal solution is coloured it must be evaporated mixed with basic acctate of lead exposed to the air for 24 hours and then filtered from the carbonate of lead and the coloured lead lake. The excess of lead is then removed by sulphnretted hydrogen the solution evaporated and the alkaloids again taken up by ether after the addition of baryta ; even then the ethereal solution may contain foreign matters which modify the reactions or impede crystallisation. If however an ethereal solution of tartaric acid be added a white precipitate is formed which usually contains the whole of the alkalo'id as tartrate.In some cases the alkdoi'ds may be pre- cipitated as carbonates by passing a current of dried carbonic anhy- dride into the ethereal solution ; if not on adding about one-third or one-fourth of the volume of distilled water and continuing the passage of the gas the carbonates of the alkaloids are dissolved by the water whilst the foreign matters remain in the ethereal solution. Amylic alcohol extracts may with advantage be treated in a similar manner. The coloured precipitate above mentioned should also be carefully examined suspending it in water and decomposing it by sulphuretted hydrogen. In the case of volatile alkalo'ids the author separates them by dis- tilling them off in the vapour of absolute alcohol and condensing the vapours in a receiver containing an alcoholic solution of tartaric acid. C. E. G.

ISSN:0368-1769    

DOI:10.1039/JS8773100107

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

111 TECHNICAL CHEMISTRY Technical Chemistry. Chemical Examination of Twelve Colours found at Pompei. By P. PALxE R I (Gazxetta c7Limica itrcliaiza vi 39-45) .-Of these colours three were yellow one consisting of a yellow ferruginous earth mixed with white clay to make it paler ; another a limonite (hydro- carbonate of iron) mixed with gypsum; the tliird a yellow ochre mixed with calcium carbonate. Of the two greens one a bright g.reen was found to contain ferrous and ferric oxides alumina lime silica and carbonic anhydride. It is apparently identical with “ terra zrertle,” which Pliny mentions (xxxv 29). “ Sunt etiamnum novitii duo colores et vilissimi; viride quod Appianum vocatur. . . . Fit et ex creta viridi.” The other green contained copper but from its state of aggregation the author thinks it must have become considerably altered in the lapse of time.Five red and red-brown colours were found to be ochres ; one probably “mhio faZso,” the “9ni71iuwb secun-da~i~?z’’ of Pliny; another sample was a mixture of fragments of various descriptions and the twelfth whicli was of a rose colour was found to consist of a white clay mixed with a little chalk and phos- phate and coloured with a rose colour of organic nature. ItlForms a purple lake with alumina and its reactions when compared with those of cochineal and madder lakes exhibit a marked discrepancy in several instances especially under the action of chlorine and bromine the Pompeian colour being exceedingly stable. The author is of opinion judging from various statements in Pliny the text of which he quotes that it is not improbable that this extremely solid and fast rose-colour employed by the Pompeians may Lave been obtained by saturating a white clay with the compound colour produced from Tyrian purple (from Pzcrpura or Jfurex) extract of Kermes (Coccus ILicis from Querczis coccijera) and madder extract This point he hopes to deter- mine experimentally.C. E. G. Temperature and Composition of Gases evolved from Ultra-marine Furnaces. By F. FISCHER (Dhzgl. pol@ J. ccxxi 468-473).-The temperatiire of the ovens mas ascertained with a Siemen’s electric pyrometer (Dingl. J. 1875 217 29l) and the composition of the gases escaping determined by Orsat’s apparatus which has been recently improved by Aron.The fact that the absorption and the measurement of the gases take place i3 two distinct tubes by which the determination of the separate constituents in the gas after it has been measured is greatly facilitated renders this apparatus more suitable for analysis than the use of Winkler’s burette. The sul- phurous acid was determined with normal iodine solution. The acids absorbable by potash were determined by Orsat’s apparatus using oil as the indicator so as to prevent the solution of sulphurous acid in water. The difference of the two determinations is calculated as carbonic acid but since the gases are always coloured more or less white from the presence of sulphuric anhydride which is also absorbed by potash lye the percentage of carbonic acid will be somewhat high.ABSTRACTS OF CHEMICAL PAPERS. The following fable gives the results of analyses made with ;Icrucible furnace :-Crucible Furnaces lighted at 6 a.m. -No. of Experi-Time. sop coz. 20 0. N. Cempera Remarks. ture. ment. ----_ --4th Jnly our. min 1 90 2 -67 9 *93 0 6 *4 81 .o Fire burnt down. White vapours. 2 9 30 2 -5s 10 -12 0 7'1 80 2 473 Ditto. Ditto. Dampers 3 10 30 3.28 12 '12 0 4 '8 79 -8 522 { partly closed. 4 11 0 2 *89 10 '01 0 6 '2 80.9 696 Ditto. -5 11 30 3.04 8 -26 0 8 .7 80 .O Ditto. 6 12 0 2 *'76 10 -5.4 0 6.2 80 .5 -Ditto. 7 12 40 2 '10 10.80 0 6 *O 81-1 700 Ditto. 8 2 50 2 '27 12.63 0 3 '0 82 .1 Air shut off by -{ layers of brichs. Immediately after 9 3 40 3 *12 17.88 0 0 79 .o -il stoking.Vapoiirs not white.Upper layer of bricks removed 10 3 47 2.95 13*05 0 2'1 81 *9 733 { thus allowing more air to pass tl1rough. Imniediatelg aft er stoking. Slight 11 40 3 *25 -0 * 0 -4 81 -1 -{ separation of f soot. Not stoked ;there-I fore burnt com-12 4 20 1 '48 -0 0 -4 82 *5 pletely. Vapou1-s white not trans- -1 L p:irent . About 10 minutcs 13 4 40 1*40 -0 4 .8 82 '6 714 { after stoking. 14 5 10 0 '73 -0 3 .8 81 -7 Completely burnt. Vnpours white. Ditto. Air slint 15 5 45 0 -34 -0 6.3 SO -8 668 { Off. 16 6 10 0 '47 -0 1 -1 82 -5 -Ditto. 17 G 16 1*11 -0 3.4 81 '1 Immediately after stoking. -i R'ot stoked ;burnt 3.8 6 30 0 *64 -0 0 *1 83-1 '30 { 5th July completely.Not stoked for 0 p.m. hours ; all open- 19 50 0.01 -0 7.9 80 *4 627 ings shut off by clay. -It seems that the temperature of the furnaces during the ultramarine process is about 700". The gas analyses show that the process is more quickly conducted in crucible furnaces than in mufHe furnaces. It is next to impossible to use the gas mixture profitably for the lead- TECHNICAL CHEMISTRY. chamber process as the gases are very much diluted and are not evolved regularly. The reason why a crucible furnace requires 50 kilos. and a muffle furnace 146 kilos. of best Westphalian coal for every 100 kilos. of blue charge is sufficiently explained by the fact that through the latter form of furnace a larger quantity of air is always passed.Carbonic oxide is mostly absent in these gases. D. B. MEK (Dingl. YoZyt. J. ccxxi, Hardening of Steel. By A. JAEULI 436-446).-1t is stated that boiliiig water does not form tlhe only cooling liquid which hardens steel but that under circumstances water at a temperature of 150" or more will do so and that boiling hot oil fluid lend fluid tin and even fluid zinc-a cooling liquid of about 400" of heat-will also give similar results. This latter fact is worthy of notice as it has in general been assumed that steel cannot be har- dened unless it be brought down very quickly to a much lower tem- perature and that hardened steel softens considerably when exposed to a temperature of 300" ; but experiments have shown that the hardness of steel depends upon the quickness with which it is reduced from a temperature of about 500" to one somewhat under 500".Although the above-mentioned metals are able to harden steel it was iiever- theless found that their hardening property could not at all be compared with that of water this property being in fact influenced not merely by the temperature and the conductivity of the cooling substance but also by its capacity for heat its boiling point and in the case of a low boiling point by the amount of latent heat tvhicl.1 the vapour contains. For instance alcohol vaporises very readily and as it contains but little iatent heat hardens steel but very badly. Now it is well known that a metal which is heated to a temperature of 1000" or even only to 500" must be surrounded by a temperature which renders the existence of water of an ordinary pressure quite impossible.So long as hardened steel possesses this temperature-which it in fact retains until its hardening commences- it cannot be in immediate contact with water and when plunged into that liquid must be surrounded by a layer of vapour which is apt to hold back portions of water near the steel and thus prevent a regular liardening of the latter. It is of course improbable that under these circumstances the steel would give up its heat to the water by direct conduction and as the layer of steam between the metal and the water cannot be superheated to any material extent at so slight a pressure we must suppose that the water becomes heated by radiation the layer of water separated by the steel evolving a constant stream of vapour which condenses on the upper portions of the layer of water.It is shown by calculation that one kilo. of steel requires about 0.2 kilo. of water at 20" to lower its temperature from 1000" to 300'; but the reason why a much larger quantity of water is actually required is sufficiently explained if we consider that (I) the steel has to be moved about in the water ; otherwise the formation of vaponrs would prevent its hardening. (Relying on this fact it was possible to harden steel under hot water alcohol or turpentine.) (2.) The vapours con- dense in the water and heat a small quantity of it too strongly. Thus it seems that it would be possible to harden steel with a small VOL.XXSI. I ABSTRACTS OF CHEMICAL PAPERS. quantity of water could the vapour escape as quickly as it is formed. S~ich however is not the case and the above condensation can there- fore be facilitated only by the following Gperations :-(1.) By pluiqing the hot steel slowly into the water the surface of the latter 1s cliietly acted upon the vapours having easy access of escape in the air. This method is applicable in cases where the metal above the water remains sufficiently hot to be hardened ey. files and other similar articles are easily hardened by this process. (2.) A hot and powerful stream of water escaping from a steam-boiler or an ordinary stream of water facilitates the hardening by carrying off the vapours as quickly as they are formed.(3.) The most satisfactory method is that by which the steel is hardened by means of a thin spray. In this con-dition the water is largely mixed with air which having a very quick and strong action not only occasions a quick vaporisation but also c*aiTiesoff the vapour formed in a much more complete way than any of the above-mentioned agents. In practice the degree of hardness of steel depends upon the annealing of the lntter-a process which alwnps follows the hardening operations. In order to obtain a medium hard- ness the steel is cooled slowly throughout the whole of the operation or it is cooled very quickly to 400° and afterwards slowly. The former method did not answer in practice a quick cooling being almost indispensable if satisfactory results are to be obtained.The resulting steel was either of a very hard or of a very soft nature. With regard to the annealing methods similar experiments were undertaken the results of which seemed to show that the mosi pro-fitable form of applying the cooling liquid was when a spray of water 51-as blown on to the steel. In conclusion it is stated that fused metals especially tin answer very well for hardening small articles. The author was able to harden a steel wire 3 mm. thick in a tin bath of 400" of heat the wire again becoming soft when it was left in a bath of 350". On account of the smaller heat-capacity of tin a large quantity of it is re-quired. One part of steel requires about 45 parts of tin to cool it from 1000" to 300° if the temperature of the bath before use is 250° aid has not to be raised over 300".In another paper a description of tlie fusion of the steel before it is hardened and further results with regard to the above operations will be given. D. B. Burnishing of Iron. By P. HESS(Dingl. polyt. J. ccxxi 94-95).-The surface of the iron is painted over with linseed oil and heated whereby together with separated carbon ferroso-ferric oxide appears to be produced which forms the essential protecting layer. Articles which cannot be heated may be dipped into an acidulated solution of ferric chloride whereby a black layer of ferroso-f erric oxide is formed which when dipped into hot water becomes firmly fixed on the iron SO that after drying it can be rubbed with linseed oil.The formation of this layer takes place by the reducing action of the iron on the oxide and its salts 4Fe203+ Fe = 3F304. The advantages of burnishing with ferroso-ferric oxide (magnetic iron ore or smithy scale burnishing) consists in the fact that it is done much more quickly than the burnishing with ferric oxide and that it TECHNICAL CHEMISTRY. 115 is more beneficial to the iron than the latter. By using cuprous snl-phide a fine bluish-black layer is obtained which forms a good protec- tion against rusting. The iron has only to be placed in a solution of cupric sullphate for a few minutes until a fine copper coating is formed on its surface which after having been washed with water is treated with a solution of sodium hyposulphite (thiosulphate) slightly acidu- lated with hydrochloric ncid when a bluish-black coating of cuprous sulphide is obtaiued which is unaffected by air and water.The sur- face is then washed with water dried and polished. D. €3. The Uses of Patent Golours. By R. GLANZMANN (Dim$. po&. J. ccxxi 4i3-47 7) .-On accouut of their simple application their perfect coloration and their cheapness the patent colours described by Croissant and BrdxmniBre are now largely used in the dyeing of yarns. These organic colours containing large quantities of sulphur are manufactured by various firms and under differelit names. The author described (BUZZ de Bown 1876 61) a prepara-tion which was broiight into commerce by Poirrier under the name of "Cachou de I~aval." It seems to be prepared from sawdust and is in the form of large blackish-blue very porous lumps which are very hygroscopic smell strongly of sulpliuretted hydrogen and contain 14 to 2 per cent.of water. It is very readily soluble in water its aqueous solution having a strongly alkaline reaction and being pre-cipitated by acids with evolution of sulphuretted hydrogen elimina- tion of sulphur and formation of a darkish brown precipitate difficiiltly soluble in alkalis. In spite of the valuable property which this colouring matter shares with the other patent colours of being fixable on cotton without the use of a mordant or even without steam and in spite of their resistance to the action of light acids and soaps the author has nevertheless come to the conclusion that this category of colours will not find much application to the printing on cotton.These colours are easily acted upon by chlorine and do not form shades which are much valued for cotton prints. Glanzmann has made several dye experiments with Poirrier's " Cachou de Laval," and has obtained very good results from the " dark cachou " which he produced in a bath of 50 grams of colouring matter fixed by a solution of 5 grams of potassium bichromate in 1 liter A bath containing 3 gmms of colouring matter in 1 liter yields after treatment with potassium chromate a light grey colour with a yellow tinge. By dissolving 10 grams of the cachou in water mixing the solution with 20 grams of real cachou (dissolved in 10 C.C.of soda-lye of 1.208 sp. gr. and 500 C.C. of water) and making the total up to 1000 c.c. yarn acquires a fine dark bronze colour when it is left in this bath at 7.5" for a quarter of an hour and aft'erwards fixed with the chromate or still better with a nitric acid bath of 2" B. The various shades resulting from the colouring bath are greatly influenced by the fixation bath. Potassium bichromate gives the darkest sliade of colour ; nitric acid and nitrate of iron with lead acetate give a grey colour having a slight yellow tinge; ferrous sulphate (5 grams in 1liter) with sul-phuric acid of 1.004 sp. gr. or better copper vitriol (5 grams in 1liter) give a pep with a blue tinge. This shade forms the main use 116 ABSTRACTS OF CHEMICAL PAPERS.of the patent colours serving as a ground colonr for indigo blue by which a considerable saving of valuable colouring matter is occasioned whereas the stability of the blue is not in the least injured. In Ger-many this colour is sold in the form of a liquid under the name of "Indigoersatz " (indigo substitute). In the Deutsche Ind?c.styie-Zeitzbng 1876 43 a description of a second use of this shade as a finishing colonr for chemical blues is given. Yarns either white or steeped are passed through a solution of nitrate of iron rendered blue by yellow prussiate of potash and finished with indigo substitute. The yarn patt,erns dyed in this manner obtain either a deep black or a very fine bluish-black colour. The former colour is obtained by leaving 25 kilos.of boiled yarn in a bath of sumach (-5 kilos.) for 12 hours and then in a bath of nitratle and lignate of iron (2 kilos. of nitrate of 1.525 sp. gr. and 3 kilos. of lignate of 1.133 sp. gr.) for half an hour. The yarn is brought into a chrome bath (350 grams of red potassium chromate) and lastly dyed in a hot bath of indigo substitute (2.5 kilos.) to which 250 grams of quercitron extract has been added. After washing with soap the yarn is washed with water and dried. The bluish-black shade is obtained by allowing the same quantity of yarn to remain in a bath of 5 kilos. of sumach for 12 hours then in a bath containing 5 kilos. of nitrate of iron. It is brought into a bath of 1.5 kilo. of yellow potassium prussiate to which 0.5 kilo. of hydrochloric acid are added and having passed it though this bath 2.5 kilos.of nitrate of iron are added to the latter and the yarn treated therewith. Its further treatment in the chronie bath and the indigo-substitute baths (3 kilos.) is analogous to that of the black dye. D. B. The Present State of the Sugar Industry in France and a few Experiments on the Use of Lime in the Clarifying Process. By A. LAMY (Dingl. yo7yt. J. ccxxi 64-68).-After point-ing out thatl the manufacture of sugar in France has of late years become less profitable than formerly in consequence of the great excess of production over home consumption and the keen competition in foreign markets the author proceeds to indicate the methods which appear to him best adapted to remedy the evil.These are :-1. The endeavour on the part of the cultivator to produce roots containing a large percentage of sugar rather than roots of great size. 2. Increased attention to the methods of extracting and purifying the juice. The French beetroot contains onlyfrom 5 to 6 per cent. of its weight of sugar whereas from German and Austrian roots 7 to 8 per cent. are obtained ; but experience has shown that with proper care a root of the same richness in sugar can be produced in France. Manufacturers have until recently bought the root according to its weight alone without taking into consideration the percentage of sup- and to increase their crop many farmers have employed seeds or chemical manures which were favourable to the formation of large roots.In Germany how- ever the mode of levying the duty does not induce farmers to obtain a large bulk of material but to obtain a large percentage of sngar in comparatively a small quantity of roots. The second and third conditions which require improvement in that country are the TECHNICAL CHEMISTRY. extraction and the chemical purification of the sap. In a recent paper M. Phsier discussed the excessive use of lime in the clarifying process. The considerable increase in the weight of the scum which contains about 50 per cent. of the sap occasions a loss amounting to 200 kilos. for every 100,000 kilos. of roots. To justify the use of this excess of lime it is usual to allege the fineness of the white sugar of first crystallisation thereby obtained the quick and complete decolori- sation of the sap and the necessity of fixing with the lime the total quantity of sugar in the form of a saccharate.But although the existence of a lime saccharate at a temperature of 35" has been generally assumed it has never been proved. PBsier has made a large number of alkalimetric determinations the results of which seemed to show that at a temperature of 35" a saccharate does not exist still less therefore at 60" or 70" at which temperature the acldi- tion of the lime takes place. With the view of clewing up these contradictions Lamy undertook the following experiments. In the first place the quantity of lime was determined which would dissolve 100 parts of a 10 per cent. sugar-solution at SO" 50° GO" 70" and loo" if 1to 2 per cent.of lime were added a proportion generally taken in practice. The slaked lime and the sugar-solution were mixed at the hrial temperature and left in contact for three hours with frequent shaking. The same quantities of lime were added at SO" GO" and iO" the temperature allowed to rise gradually to loo" and the liquid filtered very quickly at this temperature. The lime in solution was then titrated. The results are shown in the following table :-Solubility of Lime in a lop. c. Sugar Solution using 2 yarns of Liwe for 100 parts of the &olution. . _c_- 100 grams. 15-5 gimns. + 139.5 70 23 *O + 133 -9 50 53 -0 + 105'6 30 120-0 + 80-7 15* 215 -0 -53.0 0 250 *O -87.0 50-100 18*5 -I-136*5 60-100 17 *O + 138 '0 70-100 16'0 + 139 .0 * The numbers corresponding with the temparatures 15' by saturating the sugar-solutions with an excess of lime.and O" were obtained I2 ABSTRACTS OF CHEMICAL PAPERS. The conclusions to be drawn herefrom are :-(1.) The quantity of lime dissolved in the sugar-solution increases in the same ratio as the temperature decreases. The same applies to the solution of lime in pure water. (2.) By deducting the quantities of lime dissolved in sugar-water (col. 2) from those dissolved by pure water (col. 3) at the same temperature numbers are obtained which correspond with the absorp- tion of the lime by the sugar alone. It is strange however that these numbers vary with the temperature and are much higher than those corresponding with the solution of lirne in pure water.(3.) By comparing the numbers in column 4with 149 of column 5-a number which gives the quantity of lime to be dissolved so as to form a monobasic saccharate-we find that tbey are lower than tliis and so much the more the higher the temperature is than 30". The slight differences of the numbers in colnmn 6 which correspond with the temperatures loo" 50-100" 70-lOO" are suEciently explained by the difference of time during which the solutions were kept at loo" and by the difficulty 3f obtaining a saturation at this temperature. (4.)The quantity of lime absorbed by the 10 per cent. sugar solu-tion may rise with the fall of the temperature so mnch that at O" for example it surpasses the quantity necessary for the formation of a monobasic saccharate more than 50 per cent.With regard to pure sugar-solutions therefore the quantity of fixed lime is larger than that which pure water disswlves at the same temperature and even at 100" ; but it is much lower than that necessary for forming a monobasic sac- charate at 30-70". In conclusion Lamy gives a description of Marot's new method which is based on the idea that it is not the true mineral salts which hinder the manufacture of sugar but rather the salts with mineral bases which are combined with organic acids and neutral bodies. The organic substances left in the sugar through faulty treatment have in- duced Marot to give up the use of lime and baryts salts in order to carry out the refining with a minimum of lime (5 per cent.).Marot boils the solution after having added the lime until its volume has been reduced to one-fifth expecting thereby to decompose the nit'ro- genous substances and to liberate the resulting ammonia. Witli regard to the probable success of this process it is to be observed that soluble lime salts and lactates must remain behind after the purification of the juice by this treatment and it is by no means proved that all the nitrogen is thereby removed. Analyses of the juices thus treated and of the boiled masses are the only means of judging whether the yield is increased and whether the method is to be pre-ferred to the ordinary process. D. B. Use of Hydrochloric Acid in the Diffusion-process. (Dingl. yotyt.J. ccxxi 92) .-At several sugar refineries the so-called "bad pressing," i.e. a more difficult and slow circulation of the sap hhrough the layers has already been noticed during the diffusion and Erk showed last year how after a normal working of two months this bad pressing came on to such an extent that instead of 125 tons only 42.5 tons of bectroots could be worked in one layer. TECHNICAL CHEMISTRY. 119 For every pan of 3,000 liters of contents or 2,500 kilos. of charge, 1.5 to 2 liters of 40 per cent. hydrochloric acid diluted with an equal bulk of water was added which at once produced a normal pressing. This action seems to depend on the fact that certain organic sub-stances coagulate and are rendered insoluble by the acid. D.B. Myall-wood. By J. MOELLER (DingZ. poZyt. J.,ccxxi 153- 156).-At the present time a species of wood imported froni Australia is largely used in commerce under the above name and forms a substitute in the manufacture of the well-known briar pipes. At the ordinary temperature this wood smells very strongly of yiolets ; it is very hard and heavy and does not split regularly. Its spec. grav. is 1.578. When dried at loo" it yields 11.25 per cent. of ash containing the following percentage ingredients :-Silicic acid .................... 0.401 Carbonic acid .................. 43.721 Sulphuric acid ................ 0.488 Phosphoric acid. ............... 0.103 Chlorine ...................... 0.0'38 Potash. ...................... 2.621 Soda ........................2.054 Lime ........................ 47.533 Magnesia. ..................... 3.879 100.893 Deduct the quantity of oxygen equivalent to the chlorine.. .... 0-022 100.876 D. B. Carboazotin a new Explosive Substance. (DiizgZ. polyt. J. ccxxi 94).-hccording to Cahuc and Soulages a mixture of-50-64 parts of potassium nitrate (sodium or lime), 13-16 , sulphur 14-16 , tan 9-18 , soot lampblack &c. 4-5 , iron vitriol is heated with a corresponding quantity of water at 110-120" the liquid cooled the solid mass dried and brought into forms &c. According to the English patent of Faure and Trench a mixture of 1part of charcoal 16 parts of barium nitrate and 1part of uitro-cellulose are made up with water to a pulp then formed into cakes and dried.D. B. Manufacture Qf Yeast. By F. VAN HEUMEN VAN and W. €I. HASs E Lrr (Dingl. polyt. J. ccxxi 451-465).-Yeast is now prepared according to one of the following methods :-1. Dutch Xethod.-In Holland a tax is levied on the spirit pro-duced whereas the coops and apparatus are free from ltaxes ; hence in that country it is advantageous to carry on the fermentation in a ABSTRACTS OF CHEJUCAL PSPERS. large number of vessels. The raw material is always rye- and barley- malt. These substances are ground to a fine powder and washed with hot water until a temperature of about 65" has been reached. The mixture after the lapse of 1-2 hours is cooled to 37" with clear brewer's wash and then to 30-33" witli water at wliich temperatures the yeast is added.The fermentation commences gradually and goes on so slowly that the returns and the other insoluble substances are deposited. After three hours' standing the liquid is rim off and pumped into a shallow square vessel whereby the temperature is lowered to about 20". The actual fermentation and formation of yeast takes place in this vessel two layers of yeast being formed the one on the surface of the liquid and the other at the bottom of the vessel. The clear liquid between the two layers is after the termi- nation of this fermentation drawn off and brought back to the first mashing vessel where its fermentation is completed with that of the returns left behind. The yeast is brought into smaller vemels -"vhere after depositing it is sifted washed and pressed.The vessels used hold about 2,200 liters in which 93 kilos. of rye and 95 kilos. of malt are mashed. From 100 kilos. of flour 10 to 12 kilos. of yeast and 26-28 liters of spirit of 100 p. c. are obtained. The mash obtained varies from 62.5 to 67 per cent. 2. German Xethod.-In Germany spirits are not taxed but vessels and apparatus taxed very heavily which circumstance renders it necessary to occupy as little space as possible for fermenting vessels and other apparatus. Besides rye and malt maize is also used which on account of its hardness requires to be boiled in water for 1-2 hours before it can be used. The hot maize is added to the mash of rye and malt at a temperature of 65" and after saccharification cooled to 37".The mass is then run into the fermenting vessels cooled with clear wash and treated with yeast. After the fermentation has ter- minated the mass is separated from the returns by sifting and mixed with water. The mixture is again filtered and washed and the yeast after sett'ling is pressed while the cold mash on the top of the yeast is again pumped into the fermenting vessels and allowed to stand for two dnye. After this the fernientation is finished. The liquid can now be distilled off. In one hectoliter of space 13.88kilos. of flour (70 p. c. maize and rye and 30 p. c. malt) are mashed; 50 litres of wash are required for cooling purposes and the mash obtaiiied is equal to 67 p. c. of extract. 100 kilos. of raw material give from 9 to 10 kilos.of yeast and 28 to 30 liters of spirits of 100 p. c. 3. Afethod with Clear MaslL.-By this method a product of great purity and strength is obtained which has proved to form an excellent article in panary fermentation and is of' great importance to bakers wlio very often have orily a limited space at their disposal and require a substance which raises the dough very readily. 20 p.c. of rye 30 p. c. of maize and 50 p. c. of barley-malt are mashed in a vessel at the bottom of which a perforated plate is placed under which a cock is fixed for letting off the liquid. After the sacctiaritication is finished the clear mash is drawn off at the bottom of the vessel and the returns are washed with hot water. The filtrate is then cooled to 2T" and the yeast added.The mash after fermentation is pumped TECHNICAL CHEMISTRY. into a shallow vessel where the yeast is deposited. The clear mash is then taken back into the fermenting vessel and the yeast obtained is washed and pressed. For 1 kilo. of grain about 7.5 liters of mash are obtained equal to about 56 p. c. of extract. The yield of yeast is calculated at 9 p. c. that of spirit (100 p. c.) at 24-25 p. c. With regard to the raw material the method (2) is the most profit- able as less malt is reqiiired and the composition of the mash can be chosen in such a manner that the grain which is the cheapest at the time shall predominate in it. With regard to the apparatus used and the space required for fer-mentation the method (1) is the most expensive and suitable only for places where no duty has to be paid on vessels and other apparatus.Regarding the labour attached to the three methods it is shown that methods (1) and (3) reqnire only a very small staff of workmen. Method (2) requires more workmen. The largest yield of yeast is obtained from method (1); most spirit fi-om (2) ; this difference is due to the composition of the mash and can be decreased by mashing less maize and more rye in method (2). The reason why the method (3) gives a low percentage of siiirit is that the extraction of starch from the grain is never effected completely with malt alone but that the process is continued when t.he mash is allowed to ferment with the returns as is the case with methods (1) and (2).In the working of method (3) however. the clear mash is alone employed so that a portion of the starch is not dissolved but remains behind with the returns when sifted. Method (1)gives the finest quality of spirit its purity being due to the absence of' maize whose fatty and oily ingredients give the spirit a bad taste which is difficult to remove. The small yield of yeast in method (3) is due to an analogous cause. The niash obtained from methods (1)and (2) is generally turbid when it is pumped from the fermenting vessel into the boxes. This turbidity is caused by admixtures of albuminous substances finely divided cellular tissues &c. which are probably dissolved during the fermentation and thus increase the yield of yeast.The yeast obtained from method (3)is perfectly white and very pure. The authors experimented on the above-mentioned methods with the view of disco\-ering a new method combining with method (3)all the advantages of the other two methods. The following are the results obtained. In the first place the grain is well trimmed and ground into a fine powder. In order to prepare the mash tu-o-thirds maize and qe and one-third malt are used. After having boiled the maize and rye with steam the mixture is saccharificd with malt and tlie mash pumped into filter-presses. By boiling the former substances with steam before using them it is possible to increase the quantity of rye used and to work with larger quantities of the latter. The advantages which are gained by using filter-presses are that tlie returns require less water for washing purposes and therefore yield a clearer and more con-centrated mash.The returns after pressing are washed with hot water. The clear mash is cooled brought into the fermenting vessel the necessary quantity of wash added and the wliole treated with yeast. By passing filtered air though the mixture a more ready and ABSTRACTS OF CHEMICAL PAPERS. a larger formation of yeast is resulted. During the time allowed for fermentation tlie filter-presses are opened the pressed cakes taken out put into boxes treated with water and boiled with dilute acid in a copper still. The reason why acid is used is that it extracts a larger quantity of product from the returns than water alone.After one hour’s boiling the still is opened and the resulting mash brought into the filter-presses. ‘I’he clear mash is cooled mixed with water and added to the fermentiug mash. After the end of the fermen-tation the clear mash is syphoned off and pumped into retorts where the washings are redistilled while the residual yeast is washcd and pressed. The returns remaining in the press are dried as completely as possible and are then ready for use. The aclvantages of this method are that (1.) All kinds of grain (and probably even potatoes) can be worked up in yarious proportions and the addition of malt can be decreased. (2.) By working the clear concentrated mash the space for fermen-tation is thoroughly utilised. (3.) The shallow cooli~g and fermenting vessels are not rcqnired.(4.) The mash becomes clear without being boiled. (5.) The yield of yeast and spirit is high the yeast pure and white and the spirit from rye of a fine quality. (6.) ‘I’he costs for labour &c. are but slight. (7.) The consumption of coal is small. D. B. Manufacture of Glue. By B. TE KNE (Diwg7. pZyt. J. ccxxi 251-258).-The author contradicts the assertion of Gintl that “the quality of the glue is not impaired by the use of high pressure steam ;” on the contrary he finds that tlie inferiority of the prodnct is directly proportional to the pressure of the employed steam till at length all the gelatin is destroyed. The same material which at a pressure of 10 to 20 lbs. per square inch yields a tolerably good product yields at a pressure of 30 lbs.or orer (duration of boiling being in both cases equal) a perfectly white substance quite innocent of gelatin. The author states that the liquors obtained on steaming the slaughter- house refuses may besides being valuable for glue production be looked upon as a source of ammonia. Seeing that a high temperature is injurious to the gelatin in the extractive liquors to be boiled down the author proposes the use of vacuum-pans for this boiling down pro-cess. It is asserted that a glue factory is no more prejudicial to the health of a neighbourhood tlian a starch or yeast factory. The raw materials used for glne-makii:g in the United States are comprised in two classes-(I) Slaughter-house refuse and remains ; (11) Kefuse of tanneries.The preparation of bone-glue by extraction of the mineral constituents of bones by means of hydrcchloric acid thus leaving the gelatin pays only in those neighbourhoods where hydrochloric acid is to be had cheap. Use qf Blauyhter-house R<fuse.-According to thcir value as a source of glue the varieties of the raw materials are arranged as follows :-(1) Feet of oxen; (2) pig’s feet; (3) feet of calves and sheep; (4) fresh bones; (5) heads of sheep and oxen. The raw material is TECHNICAL CHEMISTRY. freed from blood as much as possible and rednced to as fine a condition of division as practicable the flesh being torn to pieces and the bones broken by a suitable machine and then m-ashed free froin dirt and blood.The matter is then ready for the boiling operation in the ordi- nary course hut the author here introduces a process for bleaching by meaus of sulphurous acid. This is done in wooden vats closely covered and a saturated sulphurous acid solution is used. The time required for the bleaching depends greatly upon the condition of the material. By means of this important process an extractive liquor is obtained nearly as clear as water which by evaporation in the vacuum pan yields a glue unsurpassed for clearness and lustre by tlie very first qualities. The bone-fat is likewise clearer and free from objectionable odour and commands a considerably improved price. In order to pre- pare the concentrated sulphurous acid solution a sulphur-burner from the roof of which a stoneware pipe passes supplies a reservoir with sulphurous oxide gas.This gas afterwards passes up a coke tower (connected with the upper part of the reservoir by a series of short stoneware pipes) and meets a slow current of water which trickles down amongst the coke and is supplied by a cistern from ahore. The result'ing concentrated solution accumulates in the reFervoir below. The action of the acid is very Characteristic. The particles of skin and flesh swell out and finally assume the lustre of silk and the trans- parency of gelatin. The mass is also rendered much more porous and thus can be far more quickly converted into glue. The boiling pro- cess then follows and the advantage of the previous bleacliing is made evident in the short time and low pressure required in this boiling which gives a good concentrated liquor.The melted fat is removed by taps. The liquor free from fat is now passed through a filter con- tairiiiig bone-charcoal but the author believes that a filter-press manufactured by Wegelin aud Hubner of Halle would answer the purpose better. From the filter tlie liquor passes to the vacuum-pan where it is evaporated down till of siicli a consistency that the resulting glue may be easily cut or if cast in moulds easily detached therefrom and in a short time. For the pouring plates of tinned sheet iron are genetdly used but recently glass tables have been introduced by the use of which an extraordinary gloss is conferred upon the glue. These tables are however liable to frequent breakage.When moulds are used they are cooled down by cold water and ice and when the temperature falls to within 0" and 5" the glue niay be removed. A process bas been recently patented for America in which benzene is used for removing the fatty portions of the raw material for glue-making. w. s. Logwood Inks. By E. U. VIEDT(Pharm. J. Trans. [3] vi 1004).-Inks prepared from logwood are of four classes viz. with logwood and chrome with alum with copper or with iron. Runge's ink prepared from logwood with a small quantity of potassium chro- mate is good and cheap easily penetrating the paper ;but on exposure to air it deposits black flakes leaving a colourless liquid above. This may be prevented by the addition of a little sodium carbonate ; the following ink is therefore recommended.Dissolve 15 parts of log- 124 ABSTRACTS OF CHEMICAL PAPERS. wood extract in 900 of water ; leave the liquid to deposit and decant ; heat and add 4 parts of crystallised sodium carbonate; lastly add drop by drop a solution of 1 part of potassinin chromate in 100 of water. Inks prepared from chrome-alum have little depth of colour. Under the influence of air reaction takes place between the metallic salts and the colouring matter ; sulphuric acid is therefore added and this attacks the pens. If metallic salts are used cupric sulphate is preferable. One of the best formulas for this kind of ink is the following given in proportions for a manufacturing scale :-20 kilograms of extract of logwcod are dissolved in 200 litres of water and the solution clari6ecl by subsidence and decantation.A yellowish-brown liquid is t.hns obtained. In another vessel 10 kilograms nf ammonia-alum are dis- solved in 20 litres of boiling water; the two solutions are mixed there being also added 200 grams of sulphuric acid and finally 16 kilogram of sulphate of copper. The ink should be exposed to thc air for a few days to give a good colour after which it shonlcl be stored in well-corked bottles. Boettger gives the following formula :-30 grams of extract of log-wood are dissolved in 250 grams of water; 8 grams of crgstallised carbonate of soda and 30 grams of glycerin of density 1-2.5are added ; and lastly 1 gram of yellow chromate of potassium and 8 grams of gum arabic reduced to a powder arid dissolved in several grains of water.’ This ink does not attack pens does not mould and is very black. E. IV. P. Carbon Disulphide as an Antiseptic. By HUGOSCH~FF (Dezct. Chew,. Ges. Ber. ix 828) .-Cocoons of silkwornis which had been killed by exposure to the vapours of carbon disulphide under- went no change during six months’ keeping in flasks in the laboratory. The bodies of some pigs which had been used for physiological experiments were put into a stoppered vessel with a few c.c’s. of carbon disulphide in 1869 and have been perfectly preserved without decomposition. The same result was obtained with a lizard 35-45 centimeters long which had been suffocated accidentally in 1869 and was bottled whole.In this case a small quantity of liquid collected at the bottom of the vessel and the green hue of tlie skin became a dirty greyish-green but not the slightest putrefaction occiirred. Similar results were obtained with the intestines of poultry im- mersed in water in 1872 with a little carbon disulphide in a bottle with a greased stopper ; with a lump of beef weighiny 200 grams ; and witli the body of a finch killed by paraconine. The bcef yielded a normal flesh fluid and was eaten by a dog without hesitation even after several months. C. R. A. 17.

ISSN:0368-1769    

DOI:10.1039/JS8773100111

出版商:RSC    

年代:1877

数据来源: RSC